WO2011121910A1 - 溶融亜鉛系めっき鋼板の製造方法 - Google Patents
溶融亜鉛系めっき鋼板の製造方法 Download PDFInfo
- Publication number
- WO2011121910A1 WO2011121910A1 PCT/JP2011/001481 JP2011001481W WO2011121910A1 WO 2011121910 A1 WO2011121910 A1 WO 2011121910A1 JP 2011001481 W JP2011001481 W JP 2011001481W WO 2011121910 A1 WO2011121910 A1 WO 2011121910A1
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- Prior art keywords
- rolling
- steel sheet
- zinc
- less
- roll
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 46
- 239000010959 steel Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title abstract description 19
- 238000005096 rolling process Methods 0.000 claims abstract description 112
- 239000011701 zinc Substances 0.000 claims abstract description 62
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 62
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000007747 plating Methods 0.000 claims abstract description 36
- 230000003139 buffering effect Effects 0.000 claims abstract description 19
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 239000003929 acidic solution Substances 0.000 claims description 58
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 42
- 239000008397 galvanized steel Substances 0.000 claims description 42
- 238000011282 treatment Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 15
- 238000005275 alloying Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000005246 galvanizing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 14
- 239000003513 alkali Substances 0.000 abstract description 12
- 238000012545 processing Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 238000007781 pre-processing Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 4
- 239000011787 zinc oxide Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 59
- 239000011324 bead Substances 0.000 description 17
- 238000004090 dissolution Methods 0.000 description 12
- 239000002344 surface layer Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012670 alkaline solution Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- RQALKBLYTUKBFV-UHFFFAOYSA-N 1,4-dioxa-7-thiaspiro[4.4]nonane Chemical compound O1CCOC11CSCC1 RQALKBLYTUKBFV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- 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
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—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 only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
-
- 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
- C23C28/34—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
- B21B2001/228—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length skin pass rolling or temper rolling
Definitions
- the present invention relates to a method for producing a hot-dip galvanized steel sheet that is excellent in press formability and handling properties when formed into a steel sheet coil.
- Hot-dip galvanized steel sheets are widely used in a wide range of fields, mainly for car body applications. In such applications, they are used after being press-formed.
- the hot dip galvanized steel sheet has a disadvantage that the press formability is inferior to that of the cold rolled steel sheet. This is because the sliding resistance of the hot dip galvanized steel sheet in the press die is larger than that of the cold rolled steel sheet. That is, there is a problem that the hot-dip galvanized steel sheet hardly flows into the press mold at a portion where the sliding resistance between the mold and the bead is large, and the steel sheet is easily broken.
- the hot dip galvanized steel sheet may or may not be subjected to an alloying treatment after plating. In the present invention, these are collectively referred to as a hot dip galvanized steel sheet. In order to distinguish between the two, it is referred to as GA when alloying is performed after plating, and as GI when alloying is not performed.
- Patent Document 1 and Patent Document 2 describe that GA is temper-rolled, brought into contact with an acidic solution having a pH buffering action, left for 1 to 30 seconds after contact is completed, and then washed with water and dried.
- a technique for improving the press formability by forming a zinc-based oxide on the surface layer of GA is disclosed.
- a small amount of Al is added to the molten zinc bath to adjust the alloying reaction between the base iron and zinc, and Al oxide derived from Al in the bath exists on the surface of the molten zinc-based plated steel sheet. . Since GI has a higher surface Al oxide concentration than GA, GI has particularly low surface activity.
- Patent Document 3 as a method for forming the zinc-based oxide on GI having particularly low surface activity, the surface is activated by removing Al oxide on the surface by contacting with an alkaline solution before contacting the acidic solution. A method for promoting oxide formation is disclosed.
- an alkali such as contact with an alkali solution is used as described in Patent Document 3 to remove the surface Al oxide.
- Pre-processing is required. It is indispensable to newly install an alkali pretreatment in a production facility that does not have an alkali pretreatment facility, and on the line layout, a GI with a zinc-based oxide formed on the surface cannot be installed in an alkali pretreatment facility. Can not do it.
- the thickness of the zinc-based oxide layer on the surface and increase the generation area ratio from the viewpoint of improving the sliding characteristics during press molding for both GI and GA, but no alkali pretreatment is performed.
- the oxide is thin and the generation area ratio is also low.
- the first problem of the present invention is to improve the above-mentioned problems and form a zinc-based oxide layer having excellent sliding characteristics without performing alkali pretreatment even for GI having a low surface activity. It is providing the manufacturing method of the hot dip galvanized steel plate which can be performed.
- the second problem of the present invention is to provide a method for producing a hot-dip galvanized steel sheet that can increase the generation area ratio of the zinc-based oxide layer on the surface and increase the thickness of the oxide layer for both GI and GA. Is to provide.
- the present inventors applied hot dip galvanizing to a steel sheet, subjected to temper rolling, and then contacted with an acidic solution having a pH buffering effect.
- temper rolling is performed by rolling using a dull roll and rolling using a bright roll. It has been found that the surface can be activated by performing both, and a sufficient amount of zinc-based oxide can be formed without performing alkali pretreatment.
- the present invention is based on this knowledge. Means of the present invention for solving the above-described problems are as follows.
- Hot dip galvanizing is applied to the steel sheet, subjected to temper rolling, brought into contact with an acidic solution having a pH buffering action, held for 1 to 60 seconds after completion of contact, and then washed with water to form an oxide layer on the plating surface.
- temper rolling is performed using a dull roll having Ra of 2.0 ⁇ m or more and rolling at a reduction rate of 5% or less, and then using a bright roll having Ra of 0.1 ⁇ m or less.
- the acidic solution having a pH buffering action is at least one of acetate, phthalate, citrate, succinate, lactate, tartrate, borate, phosphate, and sulfate.
- the method for producing a hot dip galvanized steel sheet according to the present invention by performing an appropriate temper rolling, excellent sliding properties can be achieved without performing alkali pretreatment for GI having a low surface activity.
- the zinc-based oxide layer can be stably formed by the zinc-based oxide layer forming step performed after temper rolling, and the surface roughness Ra of the hot-dip galvanized steel sheet can be made appropriate. It has become possible to provide hot-dip galvanized steel sheets that are excellent in press formability and handling properties when made into steel sheet coils.
- the surface area of the zinc-based oxide layer can be increased, and the thickness of the oxide layer can be increased. It becomes possible to manufacture plated steel sheets.
- FIG. 1 It is a schematic front view which shows a friction coefficient measuring apparatus. It is a schematic perspective view which shows the shape and dimension of the bead in FIG. It is a schematic perspective view which shows the shape and dimension of the bead in FIG.
- the steel sheet is usually subjected to temper rolling in order to secure the material after hot dip galvanizing.
- the temper rolling was temper rolling using a dull roll. This is because GI, which is not alloyed after plating, has a smooth plating surface, poor retention of lubricating oil during pressing, and inferior moldability. This is to improve the retainability.
- the oxide on the plating surface layer is worn out and scraped away. Therefore, if the contact area between the mold and the workpiece is large, a sufficiently thick oxide layer exists on the plating surface with a high coverage. It is necessary to do.
- a thin continuous Al oxide layer is formed on the surface layer of the hot dip galvanized steel sheet, but this thin Al oxide is not sufficient to obtain good slidability and is thicker than that. Must be formed.
- Hot-dip galvanized steel sheet, temper rolled, contacted with acidic solution with pH buffering action, held for 1-60 seconds after contact completed, then washed with water to form zinc-based oxide layer on plated surface can do.
- the Al oxide layer on the surface layer of the hot dip galvanized steel sheet is relatively stable in an acidic solution and inhibits the zinc dissolution reaction during the treatment with the acidic solution described above, so that the portion where Al oxide is present It is difficult to produce a zinc-based oxide. Since GI has a high concentration of Al oxide on the plating surface layer, this problem becomes more prominent. Therefore, in order to produce the zinc-based oxide, it is necessary to remove the Al-based oxide layer before contacting with the acidic solution.
- the temper rolling is performed when manufacturing the hot dip galvanized steel sheet, and at this time, the Al oxide layer on the plating surface in the part in contact with the rolling roll is physically removed.
- temper rolling using a dull roll has been performed, and the dull roll has Ra with a surface roughness of several ⁇ m, so that the convex portion of the roll surface mainly contacts the steel sheet surface.
- the surface of the hot dip galvanized steel sheet is activated only at the contact portion with the dull roll, and the surface is not activated except at the contact portion.
- the part where the convex part on the roll surface is in contact exists as a concave part compared with the surroundings, and the part where the convex part on the roll surface is not in contact exists as a convex part compared with the surroundings. Therefore, in conventional temper rolling using dull rolls, when contacted with an acidic solution, a zinc-based oxide is generated only in the concave portion whose surface is activated, and the convex portion whose surface is not activated is zinc. Generation of the system oxide is suppressed.
- the actual contact with the press die during press molding is mainly due to the convex part of the plated steel sheet and not the concave part where the zinc-based oxide layer is formed. The effect of improving sex was small and insufficient.
- the plating film is mainly ⁇ 1 unlike the GI ⁇ layer, the plating film is hard, and even in the temper rolling using a conventional dull roll, the convex part on the roll surface is convex on the plating surface. There is a large proportion of contact with the part, and the surface is activated to some extent by the contact, but the degree of activation is weaker and the thickness of the oxide film becomes thinner than when the alkali treatment is performed.
- temper rolling includes both rolling using a dull roll and rolling using a bright roll.
- the concave portion of the plated steel sheet to which the concave and convex shape is given by rolling is activated by removing Al oxide, but the convex portion other than the concave portion is made of Al oxide. It is not activated because it is not removed.
- the convex part of the plating surface comes into contact with the roll surface of the bright roll, and the Al oxide is physically removed.
- the Al oxide layer is removed and activated on almost the entire surface of the concavo-convex shape on the surface of the plated steel sheet.
- a thick zinc-based oxide layer can be formed on the plating surface with a high coverage area ratio.
- hot dip galvanization is applied to the steel sheet, or alloying treatment is further applied after hot dip galvanization, followed by temper rolling.
- Hot dip galvanizing and alloying treatments may be performed by conventional methods.
- Temper rolling is rolling (dull rolling) in which Ra is rolled at a reduction rate of 5% or less using a dull roll having 2.0 ⁇ m or more, and rolling at a reduction rate of 3% or less using a bright roll having Ra of 0.1 ⁇ m or less.
- Bright rolling may be performed after dull rolling, or dull rolling may be performed after bright rolling.
- Ra of the dull rolled dull roll is specified to be 2.0 ⁇ m or more is that when Ra becomes less than 2.0 ⁇ m, the Ra of the hot-dip galvanized steel sheet after temper rolling becomes small and melts when handling the steel sheet coil. This is because the coefficient of friction between galvanized steel sheets is reduced, coil collapse and the like are concerned, and handling properties are significantly reduced.
- the upper limit of Ra is not specified, but is preferably 5 ⁇ m or less from the viewpoint of sharpness after coating.
- the reason why the rolling reduction of the dull rolling is specified to be 5% or less is that when the rolling reduction exceeds 5%, the elongation of the steel sheet is lowered and adversely affects the press workability. Although the lower limit is not specified, 0.1% or more is preferable in order to eliminate the yield point elongation.
- the bright roll Ra of the bright roll is defined to be 0.1 ⁇ m or less, when the bright roll after the dull roll, when the bright roll Ra exceeds 0.1 ⁇ m, the portion that did not contact the dull roll in the dull roll, When the area ratio of the portion that comes into contact with the bright roll during the next bright rolling is reduced, and the dull rolling is performed after the bright rolling, when the Ra of the bright roll exceeds 0.1 ⁇ m, the portion that does not come into contact with the bright roll during the bright rolling.
- the minimum of Ra is not prescribed
- the reason why the rolling reduction of bright rolling is specified to be 3% or less is that when the rolling reduction exceeds 3%, the elongation of the steel sheet is lowered and adversely affects the press workability.
- the lower limit is not specified, 0.1% or more is preferable in order to eliminate the yield point elongation.
- Ra is the arithmetic average roughness Ra of JIS B0601-2001.
- the hot dip galvanized steel sheet After the temper rolling, the hot dip galvanized steel sheet is brought into contact with an acidic solution having a pH buffering action, held for 1 to 60 seconds after completion of the contact, and then washed with water and dried to form a zinc-based oxide layer on the plated surface.
- the acidic solution is a solution having a pH buffering action, a zinc-based oxide layer having excellent sliding characteristics can be stably formed on the plating surface flat portion.
- This zinc-based oxide layer formation mechanism is not clear, but can be considered as follows.
- dissolution of zinc occurs from the steel sheet side.
- This dissolution of zinc causes a hydrogen generation reaction at the same time.
- the concentration of hydrogen ions in the solution decreases, resulting in an increase in the pH of the solution, and zinc is mainly present on the surface of the hot dip galvanized steel sheet. It is thought that an oxide layer is formed. If an acidic solution that does not have a pH buffering action is used, the pH of the solution rises instantaneously, and zinc cannot be dissolved sufficiently to form an oxide layer. An oxide layer does not form.
- the pH of the acidic solution is too low, the dissolution of zinc is promoted, but it is difficult to form an oxide. Therefore, the pH is preferably 1.0 or more. On the other hand, if the pH is too high, the reaction rate of zinc dissolution becomes low, so the pH of the solution is desirably 5.0 or less.
- the acidic solution having a pH buffering action is more preferably one having a pH buffering action in a pH range of 2.0 to 5.0. This is because, when an acidic solution having a pH buffering action in the above pH range is used, the oxide layer targeted by the present invention can be stably obtained by holding the acidic solution for a predetermined time after contact. is there.
- Examples of such an acidic solution having a pH buffering action include acetates such as sodium acetate (CH 3 COONa), phthalates such as potassium hydrogen phthalate ((KOOC) 2 C 6 H 4 ), sodium citrate (Na Citrates such as 3 C 6 H 5 O 7 ) and potassium dihydrogen citrate (KH 2 C 6 H 5 O 7 ), succinates such as sodium succinate (Na 2 C 4 H 4 O 4 ), and lactic acid At least one of lactate such as sodium (NaCH 3 CHOHCO 2 ), tartrate such as sodium tartrate (Na 2 C 4 H 4 O 6 ), borate, phosphate and sulfate, It is preferable to use an aqueous solution containing 5 to 50 g / L.
- acetates such as sodium acetate (CH 3 COONa)
- phthalates such as potassium hydrogen phthalate ((KOOC) 2 C 6 H 4 )
- sodium citrate Na Citrates such as 3 C 6 H 5 O 7
- the concentration is less than 5 g / L
- the pH of the solution rises relatively quickly with the dissolution of zinc, so that an oxide layer sufficient to improve the slidability may not be formed, and 50 g / L. This is because the dissolution of zinc is accelerated and the formation of the oxide layer not only takes a long time, but also the plating layer is severely damaged, and the original role as a rust-proof steel sheet may be lost.
- the method of bringing the hot dip galvanized steel sheet into contact with the acidic solution is not particularly limited.
- the method of immersing the plated steel sheet in the acidic solution the method of spraying the acidic solution onto the plated steel sheet, the acidic solution via the coating roll Is applied to the plated steel sheet, and it is desirable that the acidic solution is finally in the form of a thin liquid film on the surface of the steel sheet.
- the amount of the acidic solution present on the surface of the steel plate is more than 15 g / m 2 , the pH of the solution does not increase even if zinc dissolution occurs, and only zinc dissolution occurs one after another.
- the lower limit of the amount of liquid film present on the steel sheet surface is not particularly limited, but if the amount of liquid film is too small, an oxide layer having a desired thickness cannot be formed on the plating surface.
- the lower limit of the amount is preferably 1 g / m 2 or more.
- the liquid film amount can be adjusted by a squeeze roll, air wiping or the like.
- the end of contact is “dipping end” in the case of the method of immersing in the acidic solution, “spray end” in the case of the method of spraying the acidic solution onto the plated steel plate, and “in the case of the method of applying the acidic solution via the coating roll” It means “end of application”.
- a zinc-based oxide layer can be efficiently and stably formed on the surface of a hot-dip galvanized steel sheet.
- the Al oxide on the surface layer is destroyed by contact with the rolling roll, but a part of the Al oxide may remain.
- the Al oxide layer remaining on the surface layer can be removed to further activate the surface.
- the pH is preferably 10 or more. If it is pH within the said range, there will be no restriction
- a treatment for neutralizing the acidic solution remaining on the surface of the steel sheet may be performed by contacting with the alkaline solution by a method such as immersion in an alkaline solution or spraying the alkaline solution.
- the alkaline solution preferably has a pH of 12 or less in order to prevent dissolution of the zinc-based oxide formed on the surface. If it is in the said pH range, there will be no restriction
- the zinc-based oxide in the present invention is an oxide mainly composed of zinc as a metal component, a hydroxide, and a case where the total amount of metal components other than zinc such as iron and Al is less than zinc.
- a case where the total amount of anions such as sulfuric acid, nitric acid and chlorine is less than the number of moles of oxygen and hydroxyl groups is also included in the zinc-based oxide of the present invention.
- the zinc-based oxide layer may contain anionic components such as sulfate ions used to adjust the pH of the acidic solution. However, the zinc-based oxide layer has an anion component such as sulfate ions and a pH buffering action.
- Impurities such as S, N, P, B, Cl, Na, Mn, Ca, Mg, Ba, Sr, and Si contained in the acidic solution, S, N, P, B, Cl, Na, Mn, Ca, Mg
- a compound composed of Ba, Sr, Si, O, and C may be contained in the zinc-based oxide as long as the effects of the present invention are not impaired.
- the thickness of the oxide layer in the plating surface layer By setting the thickness of the oxide layer in the plating surface layer to 10 nm or more, a hot-dip galvanized steel sheet having good slidability can be obtained, but the thickness of the oxide layer is 20 nm or more, more preferably 30 nm or more. It is preferable that stable sliding characteristics can be obtained. This is because, in the press molding process in which the contact area between the mold and the workpiece becomes large, even if the oxide layer on the surface layer is worn, it remains and does not cause a decrease in slidability.
- the upper limit of the thickness of the oxide layer is not particularly set, but if it exceeds 200 nm, the surface reactivity tends to decrease, and the amount of zinc-based oxide film produced tends to decrease. desirable.
- the additive element components other than Al are not particularly limited. That is, in the case where a zinc-based oxide is produced even if a small amount of Pb, Sb, Si, Sn, Mg, Mn, Ni, Ti, Li, Cu, etc. is contained or added in addition to Al, the present invention is used. The effect of is not impaired.
- a steel sheet having a thickness of 0.7 mm annealed after cold rolling was subjected to hot dip galvanizing or alloying after hot dip galvanizing, and then subjected to temper rolling.
- the zinc plating amount was adjusted to 45 g / m 2 per side, and the Fe content of the plating film after the alloying treatment was adjusted to 10% by mass.
- For temper rolling either or both of dull rolling using a dull roll and bright rolling using a bright roll were performed. After temper rolling, in an acidic solution tank, containing 30 g / L of sodium acetate, immersed in an acidic solution at 50 ° C.
- the amount of liquid film to be adhered to was adjusted.
- the amount of liquid film was adjusted by changing the pressure of the squeeze roll. After adjusting the amount of the liquid film, it was allowed to stand (hold) for 1 to 60 seconds, then sprayed and washed with hot water at 50 ° C. and dried with a dryer to form a zinc-based oxide layer on the plating surface. Some are left (held) for a predetermined time after adjusting the amount of liquid film, then sprayed with an alkaline solution (sodium hydroxide aqueous solution) having a pH of 10 and a temperature of 50 ° C.
- an alkaline solution sodium hydroxide aqueous solution
- the oxide layer thickness, oxide generation area ratio, sliding characteristics during press molding, and handling properties of the plating surface layer of the hot dip galvanized steel sheet prepared above were investigated.
- the sliding characteristics during press molding are the oxide layer thickness measurement method, oxide generation area ratio measurement method, press moldability (sliding characteristics, mold caulking properties) evaluated by the friction coefficient and mold caulking properties.
- the evaluation method of the handling property of a coil is as follows.
- a silicon wafer on which silicon oxide films having a thickness of 96 nm, 54 nm, and 24 nm cleaved to an appropriate size were measured at the same time, and the intensity of the measured OK- ⁇ ray and the film thickness of the silicon oxide film on the silicon wafer were measured. From this, the thickness of the zinc-based oxide layer was calculated.
- FIG. 1 is a schematic front view showing a friction coefficient measuring apparatus.
- a friction coefficient measurement sample 1 collected from a test material is fixed to a sample table 2, and the sample table 2 is fixed to the upper surface of a slide table 3 that can move horizontally.
- a slide table support 5 having a roller 4 in contact with the slide table 3 is provided.
- the slide table support 5 is pushed up to bead onto the surface of the friction coefficient measurement sample 1. 6 is pressed.
- a first load cell 7 for measuring the pressing load N applied to the friction coefficient measuring sample 1 by the bead 6 is attached to the slide table support 5.
- a second load cell 8 for measuring a sliding resistance force F for moving the slide table 3 in the horizontal direction in a state where the pressing force is applied is attached to one end of the slide table 3.
- a rust preventive cleaning oil (Preton R352L, Preton is a registered trademark) manufactured by Sugimura Chemical Industry Co., Ltd. was applied to the surface of Sample 1 and tested.
- FIG. 2 and 3 are schematic perspective views showing the shape and dimensions of the beads used.
- the bead 6 slides with its lower surface pressed against the surface of the sample 1.
- the bead 6 shown in FIG. 2 has a width of 10 mm, a length of 12 mm in the sliding direction of the sample, and lower portions at both ends of the sliding direction are curved surfaces having a radius of curvature of 4.5 mm. It has a plane with a moving direction length of 3 mm.
- 3 is 10 mm in width, 69 mm in the sliding direction length of the sample, the lower part at both ends in the sliding direction is configured with a curved surface having a curvature of 4.5 mmR, and the lower surface of the bead to which the sample is pressed is 10 mm in width and sliding It has a plane with a direction length of 60 mm.
- the coefficient of friction was measured under the following two conditions.
- Sample No. 1-31 Sample No. 1 is an example of the present invention in which temper rolling was performed by dull roll and bright roll by the method of the present invention, and then contacted with an acidic solution to perform oxide formation treatment. Comparative Examples in which 12-15, 17-20, 22-24 and 26-31 were all subjected to temper rolling with dull rolls and temper rolling with bright rolls, and thereafter no oxide formation treatment was performed. Sample No. Sample Nos. 1 and 6, which were comparative examples in which either one of temper rolling using dull rolls and temper rolling using bright rolls were performed, and then contacted with an acidic solution to perform oxide formation treatment. Samples Nos.
- Sample No. No. 25 was inferior in handleability, although the press formability was equivalent to that of the present invention example.
- Sample No. 1 is an example of the present invention in which temper rolling was performed by dull roll and bright roll by the method of the present invention, and then contacted with an acidic solution to perform oxide formation treatment.
- Samples Nos. 33 to 36, 42 to 44, and 46 to 51 are comparative examples in which only one of temper rolling with dull rolls and temper rolling with bright rolls was performed, and no oxide formation treatment was performed thereafter.
- Samples Nos. 37 and 39 which are comparative examples in which either one of temper rolling with dull rolls and temper rolling with bright rolls was performed and then contacted with an acidic solution to perform oxide formation treatment. 38 and 40, and Sample No. which is a comparative example in which the oxide forming treatment was not performed after both temper rolling with dull roll and temper rolling with bright roll.
- Sample No. No. 45 was inferior in handling property, although the sliding characteristics were at the same level as the example of the present invention.
- the method for producing a hot dip galvanized steel sheet according to the present invention by performing an appropriate temper rolling, excellent sliding properties can be achieved without performing alkali pretreatment for GI having a low surface activity.
- the zinc-based oxide layer can be stably formed by the zinc-based oxide layer forming step performed after temper rolling, and the surface roughness Ra of the hot-dip galvanized steel sheet can be made appropriate. It has become possible to provide hot-dip galvanized steel sheets that are excellent in press formability and handling properties when made into steel sheet coils.
- the surface area of the zinc-based oxide layer can be increased, and the thickness of the oxide layer can be increased. It becomes possible to manufacture plated steel sheets.
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Abstract
Description
酸化物層の厚さ測定方法、酸化物生成面積率の測定方法、プレス成形性(摺動特性、型カジリ性)およびコイルのハンドリング性の評価方法は以下の通りである。
酸化物層の厚さの測定には蛍光X線分析装置を使用した。測定時の管球の電圧および電流は30kVおよび100mAとし、分光結晶としてTAP(Thallium Acid Phthalate)を用い、O-Kα線を検出した。O-Kα線の測定に際しては、そのピーク位置に加えてバックグラウンド位置での強度も測定し、O-Kα線の正味の強度が算出できるようにした。なお、ピーク位置およびバックグラウンド位置での積分時間は、それぞれ20秒とした。また、適当な大きさに劈開した膜厚96nm、54nmおよび24nmの酸化シリコン皮膜を形成したシリコンウエハーも同時に測定し、測定したO-Kα線の強度と、シリコンウエハー上の酸化シリコン皮膜の膜厚から、亜鉛系酸化物層の厚さを算出した。
極低加速走査型電子顕微鏡(SEM)を用い、加速電圧3kVで表面を35μm×45μmの視野を任意の10点観察し、得られたSEM像(反射電子像)において観察される、酸化物が生成している部分と、酸化物が生成していない部分の明度差から、酸化物が生成している部分の面積率を測定し、その平均値を酸化物生成面積率(%)とした。
プレス成形性を評価するために、各供試材の摩擦係数を以下のようにして測定した。
図1は、摩擦係数測定装置を示す概略正面図である。同図に示すように、供試材から採取した摩擦係数測定用試料1が試料台2に固定され、試料台2は、水平移動可能なスライドテーブル3の上面に固定されている。スライドテーブル3の下面には、これに接したローラ4を有する上下動可能なスライドテーブル支持台5が設けられ、このスライドテーブル支持台5を押し上げることにより、摩擦係数測定用試料1の表面にビード6が押し付けられる。ビード6による摩擦係数測定用試料1への押付荷重Nを測定するための第1ロードセル7が、スライドテーブル支持台5に取付けられている。上記押付力を作用させた状態でスライドテーブル3を水平方向へ移動させるための摺動抵抗力Fを測定するための第2ロードセル8が、スライドテーブル3の一方の端部に取付けられている。なお、潤滑油として、スギムラ化学工業(株)製の防錆洗浄油(プレトンR352L、プレトンは登録商標)を試料1の表面に塗布して試験を行った。
[条件1]
図2に示すビードを用い、押し付け荷重N:400kgf、試料の引き抜き速度(スライドテーブル3の水平移動速度):100cm/minとした。
[条件2]
図3に示すビードを用い、押し付け荷重N:400kgf、試料の引き抜き速度(スライドテーブル3の水平移動速度):20cm/minとした。
供試材とビードとの間の摩擦係数μは、式:μ=F/Nで算出した。
GIは、摺動距離が長い部位において金型へめっきが付着し摺動抵抗が増加する型かじりが問題となる。そこで、GIについて、図1に示した摩擦係数測定装置を用いて、摩擦係数の測定とは別に、摺動試験を50回繰り返し実施し、摩擦係数が0.01以上増加したときの繰り返し数を調査し、この繰り返し数を型かじり発生の限界繰り返し数として、型カジリ性を評価した。試験条件は上記[3]摩擦係数の測定方法と同様に上記の条件1および条件2で実施した。
コイルのハンドリング性をシミュレートするための評価方法として、引張り試験機にロードセルにより一定の押し付け荷重を負荷したビードで供試材を挟み、引き抜き荷重を測定し摩擦係数を算出した。なお、このとき供試材と同一のサンプルをビードに貼り付け、供試材と供試材が接触する部分の摩擦係数を測定した。30mm(幅)×35mm(長さ)の形状のビードを用いて、接触面圧を0.5MPaに設定し、50mm/minの速度で引き抜いた。過去の知見から、摩擦係数が0.08以上であれば、コイルのハンドリング性に問題がないことが知られているので、摩擦係数が0.08未満を×(不良)、0.08以上を○(良好)と判定した。
調質圧延を、ダルロールによる圧延とブライトロールによる圧延を本発明法で行った後、酸性溶液と接触させて酸化物形成処理を行った本発明例であるサンプルNo.12~15、17~20、22~24および26~31はいずれも、ダルロールによる調質圧延およびブライトロールによる調質圧延のいずれか一方だけを行い、その後酸化物形成処理を行わなかった比較例であるサンプルNo.1および6、ダルロールによる調質圧延とブライトロールによる調質圧延のいずれか一方を行った後、酸性溶液と接触させて酸化物形成処理を行った比較例であるサンプルNo.2~5および7~10、およびダルロールによる調質圧延とブライトロールによる調質圧延の双方を行った後、酸化物形成処理を行わなかった比較例であるサンプルNo.11および16に比べて、酸化物生成面積率が高く、酸化物膜厚が厚く、そのため、摩擦係数が低く、型カジリ発生の限界繰り返し数が大きく、プレス成形性に優れ、また、ハンドリング性の評価も良好であることから、コイルつぶれの問題もない。一方、ダルロールによる調質圧延とブライトロールによる調質圧延の双方を行った(但し、ブライトロールによる調質圧延条件は本発明の範囲外である。)後、酸性溶液と接触させて酸化物形成処理を行った比較例であるサンプルNo.21は、酸性溶液との接触終了後、水洗までの保持時間が同じ(30秒)である本発明例と比べてプレス成形性が劣り、また、ダルロールによる調質圧延とブライトロールによる調質圧延の双方を行った(但し、ダルロールによる調質圧延条件は本発明の範囲外である。)後、酸性溶液と接触させて酸化物形成処理を行った比較例であるサンプルNo.25は、プレス成形性については、本発明例と同等レベルであるものの、ハンドリング性が劣っていた。
調質圧延を、ダルロールによる圧延とブライトロールによる圧延を本発明法で行った後、酸性溶液と接触させて酸化物形成処理を行った本発明例であるサンプルNo.33~36、42~44および46~51はいずれも、ダルロールによる調質圧延およびブライトロールによる調質圧延のいずれか一方だけを行い、その後酸化物形成処理を行わなかった比較例であるサンプルNo.37および39、ダルロールによる調質圧延とブライトロールによる調質圧延のいずれか一方を行った後、酸性溶液と接触させて酸化物形成処理を行った比較例であるサンプルNo.38および40、およびダルロールによる調質圧延とブライトロールによる調質圧延の双方を行った後、酸化物形成処理を行わなかった比較例であるサンプルNo.32に比べて、酸化物層の厚さが厚く、酸化物生成面積率が高く、そのため、摩擦係数が低く、また、ハンドリング性の評価も良好であることから、コイルつぶれの問題もない。一方、ダルロールによる調質圧延とブライトロールによる調質圧延の双方を行った(但し、ブライトロールによる調質圧延条件は本発明の範囲外である。)後、酸性溶液と接触させて酸化物形成処理を行った比較例であるサンプルNo.41は、酸性溶液との接触終了後、水洗までの保持時間が同じ(30秒)である本発明例と比べて摺動特性が劣り、また、ダルロールによる調質圧延とブライトロールによる調質圧延の双方を行った(但し、ダルロールによる調質圧延条件は本発明の範囲外である。)後、酸性溶液と接触させて酸化物形成処理を行った比較例であるサンプルNo.45は、摺動特性については、本発明例と同等レベルであるものの、ハンドリング性が劣っていた。
2 試料台
3 スライドテーブル
4 ローラ
5 スライドテーブル支持台
6 ビード
7 第1ロードセル
8 第2ロードセル
9 レール
N 押付荷重
F 摺動抵抗力
Claims (4)
- 鋼板に溶融亜鉛めっきを施し、調質圧延を施した後pH緩衝作用を有する酸性溶液に接触させ、接触終了後1~60秒保持した後に水洗することによりめっき表面に亜鉛系酸化物層を形成する溶融亜鉛系めっき鋼板の製造方法において、
調質圧延は、Raが2.0μm以上のダルロールを用いて圧下率5%以下で圧延し、次にRaが0.1μm以下のブライトロールを用いて圧下率3%以下で圧延する、
又は、
Raが0.1μm以下のブライトロールを用いて圧下率3%以下で圧延し、次にRaが2.0μm以上のダルロールを用いて圧下率5%以下で圧延する、
ことを特徴とする溶融亜鉛系めっき鋼板の製造方法。 - 前記pH緩衝作用を有する酸性溶液は、酢酸塩、フタル酸塩、クエン酸塩、コハク酸塩、乳酸塩、酒石酸塩、ホウ酸塩、リン酸塩、硫酸塩のうちの少なくとも1種を含有し、pHが1.0~5.0の範囲にある酸性溶液であることを特徴とする請求項1に記載の溶融亜鉛系めっき鋼板の製造方法。
- pH緩衝作用を有する酸性溶液に接触終了時のめっき鋼板表面の液膜量を15g/m2以下にすることを特徴とする請求項1又は2に記載の溶融亜鉛系めっき鋼板の製造方法。
- 溶融亜鉛めっきを施した後めっき層の合金化処理を行い、その後請求項1記載の調質圧延を施すことを特徴とする請求項1~3のいずれかの項に記載の溶融亜鉛系めっき鋼板の製造方法。
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EP11762163.1A EP2554707B1 (en) | 2010-03-31 | 2011-03-14 | Method of manufacture for molten zinc-plated sheet steel |
US13/638,188 US9260774B2 (en) | 2010-03-31 | 2011-03-14 | Method for manufacturing hot dip galvanized steel sheet |
KR1020127028365A KR20130026435A (ko) | 2010-03-31 | 2011-03-14 | 용융 아연계 도금 강판의 제조 방법 |
CN2011800224882A CN102884219A (zh) | 2010-03-31 | 2011-03-14 | 热浸镀锌系钢板的制造方法 |
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EP2947180A4 (en) * | 2013-01-16 | 2016-01-20 | Jfe Steel Corp | MANUFACTURING METHOD FOR ZINC PLATED STEEL SHEET |
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HUE042725T2 (hu) * | 2017-05-18 | 2019-07-29 | Grob Gmbh & Co Kg | Eljárás és készülék bevont felületek minõségének vizsgálatára |
DE102020200326A1 (de) * | 2020-01-13 | 2021-07-15 | Thyssenkrupp Steel Europe Ag | Verfahren zur Herstellung eines oberflächenveredelten und oberflächenkonditionierten Stahlblechs |
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CN1207424C (zh) * | 2000-04-24 | 2005-06-22 | 杰富意钢铁株式会社 | 合金化热镀锌钢板及其制造方法 |
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KR20060033811A (ko) * | 2003-08-29 | 2006-04-19 | 제이에프이 스틸 가부시키가이샤 | 용융아연도금 강판 및 그 제조방법 |
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EP2554707B1 (en) | 2017-07-26 |
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KR20130026435A (ko) | 2013-03-13 |
US9260774B2 (en) | 2016-02-16 |
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