WO2014136417A1 - 高強度溶融亜鉛めっき鋼板およびその製造方法 - Google Patents
高強度溶融亜鉛めっき鋼板およびその製造方法 Download PDFInfo
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- WO2014136417A1 WO2014136417A1 PCT/JP2014/001108 JP2014001108W WO2014136417A1 WO 2014136417 A1 WO2014136417 A1 WO 2014136417A1 JP 2014001108 W JP2014001108 W JP 2014001108W WO 2014136417 A1 WO2014136417 A1 WO 2014136417A1
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- Prior art keywords
- steel sheet
- dip galvanized
- hot
- oxide
- galvanized steel
- Prior art date
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 59
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 20
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 133
- 239000010959 steel Substances 0.000 claims abstract description 133
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 63
- 230000003647 oxidation Effects 0.000 claims abstract description 62
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 49
- 238000000137 annealing Methods 0.000 claims abstract description 31
- 230000009467 reduction Effects 0.000 claims abstract description 23
- 238000005246 galvanizing Methods 0.000 claims abstract description 15
- 238000007747 plating Methods 0.000 claims description 99
- 238000005275 alloying Methods 0.000 claims description 45
- 239000010410 layer Substances 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 20
- 239000002344 surface layer Substances 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 11
- 230000001590 oxidative effect Effects 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/76—Adjusting the composition of the atmosphere
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0478—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular surface treatment
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
- C21D9/561—Continuous furnaces for strip or wire with a controlled atmosphere or vacuum
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- 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
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- C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
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- 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
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- 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
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- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
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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
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- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
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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
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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
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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
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- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
- C23C8/14—Oxidising of ferrous surfaces
Definitions
- the present invention relates to a high-strength hot-dip galvanized steel sheet using a high-strength steel sheet containing Si, Mn and B as a base material and a method for producing the same.
- hot dip galvanized steel sheets use thin steel sheets obtained by hot-rolling or cold-rolling slabs as the base material, and the base steel sheets are recrystallized and annealed in a CGL annealing furnace, and then hot-dip galvanized. Manufactured. Further, the alloyed hot-dip galvanized steel sheet is manufactured by further alloying after hot-dip galvanizing.
- Si or Mn is effective.
- Si and Mn are oxidized even in a reducing N 2 + H 2 gas atmosphere where Fe oxidation does not occur (reducing Fe oxide), and Si or Mn oxide is formed on the outermost surface of the steel sheet.
- reducing Fe oxide reducing Fe oxide
- the oxides of Si and Mn reduce the wettability between the molten zinc and the underlying steel sheet during the plating process, non-plating frequently occurs in steel sheets to which Si or Mn is added. In addition, even when non-plating is not achieved, there is a problem that plating adhesion is poor.
- Patent Document 1 discloses a method of performing reduction annealing after forming a steel sheet surface oxide film.
- Patent Document 1 the effect cannot be stably obtained.
- Patent Documents 2 to 8 the oxidation rate and reduction amount are regulated, the oxide film thickness in the oxidation zone is measured, and the oxidation conditions and reduction conditions are controlled from the measurement results to stabilize the effect.
- Such a technique is disclosed.
- Patent Document 9 describes an alloyed hot dip galvanized steel sheet of an oxide containing Si present in a plating layer and in a ground iron. It defines the content rate.
- patent document 10 about the hot dip galvanized steel plate and the alloyed hot dip galvanized steel plate, the content rate of the oxide containing Si which exists in a plating layer and a ground iron is prescribed
- patent document 11 the amount of Si and Mn which exist as an oxide in a plating layer are prescribed
- Japanese Patent Laid-Open No. 55-122865 JP-A-4-202630 Japanese Patent Laid-Open No. 4-202631 Japanese Patent Laid-Open No. 4-202632 JP-A-4-202633 Japanese Patent Laid-Open No. 4-254531 JP-A-4-254532 JP-A-7-34210 JP 2006-233333 A Japanese Patent Laid-Open No. 2007-21112 JP 2008-184642 A
- Patent Documents 9 to 11 Although good fatigue resistance can be obtained with a hot-dip galvanized steel sheet that is not subjected to alloying treatment, it is sufficient for the alloyed hot-dip galvanized steel sheet that has been subjected to alloying treatment. It was found that fatigue resistance characteristics may not be obtained. In Patent Documents 9 and 10, the wettability of plating and phosphate treatment are improved, and fatigue resistance characteristics are not considered.
- the present invention has been made in view of such circumstances, and provides a high-strength hot-dip galvanized steel sheet excellent in plating adhesion using a high-strength steel sheet containing Si, Mn and B as a base material and a method for producing the same. For the purpose. Furthermore, it aims at providing the high strength hot-dip galvanized steel plate which performed the alloying process excellent in the fatigue resistance, and its manufacturing method.
- the addition of solid solution strengthening elements such as Si and Mn is effective for increasing the strength of steel. It is also known that the addition of B improves the hardenability of the steel and can obtain a good balance between strength and ductility even in high-strength steel. Particularly for high-strength steel sheets used for automobile applications, since press forming is required, there is a great demand for improving the balance between strength and ductility. However, it has been found that when B is contained in steel in addition to Si, the oxidation reaction of Si on the steel sheet surface is promoted in the annealing process.
- the surface temperature of Si can be controlled by controlling the heating temperature in the oxidation treatment and the oxygen concentration of the atmosphere by the contents of Si and B.
- a sufficient amount of iron oxide to suppress oxidation can be formed, and as a result, a high-strength hot-dip galvanized steel sheet with stable quality and good plating adhesion can be obtained without non-plating. I understood.
- a high-strength hot-dip galvanized steel sheet that undergoes an oxidation treatment at a heating temperature T ° C. that satisfies the following formula for steel containing Si, Mn, and B, followed by reduction annealing and hot-dip galvanizing treatment Manufacturing method.
- the component composition of the steel is, by mass%, C: 0.01 to 0.20%, Si: 0.1 to 2.0%, Mn: 1.0 to 3.0%, B: 0
- oxides of oxides of 0.05 g / m 2 or more and Mn in the amount of Si in terms is included 0.05 g / m 2 or more in the amount of Mn in terms, high-strength galvanized steel sheet.
- oxides of Si from the steel sheet surface layer of the under plating layer in the steel sheet 5 ⁇ m is 0 in the amount of Si in terms .01g / m 2 oxides of less and Mn is 0.01 g / m 2 or less in the amount of Mn in terms, high-strength galvanized steel sheet.
- the high strength in the present invention is a steel plate having a tensile strength TS of 440 MPa or more.
- the high-strength hot-dip galvanized steel sheet of the present invention includes both cold-rolled steel sheets and hot-rolled steel sheets.
- a steel plate in which zinc is plated on the steel plate by a hot dipping treatment is generically called a hot dip galvanized steel plate. That is, the hot-dip galvanized steel sheet in the present invention includes both hot-dip galvanized steel sheets that have not been subjected to alloying treatment and galvannealed steel sheets that have been subjected to alloying treatment.
- a high-strength hot-dip galvanized steel sheet having excellent plating adhesion using a high-strength steel sheet containing Si, Mn and B as a base material.
- a high-strength hot-dip galvanized steel sheet that has been subjected to alloying treatment is also excellent in fatigue resistance.
- FIG. 1 is a diagram showing the relationship between the oxidation furnace outlet temperature and the heating temperature obtained by the equation (1).
- the annealing conditions before the hot dip galvanizing treatment are changed, Si and Mn are oxidized inside the steel sheet, and the oxidation on the steel sheet surface is prevented, thereby improving the plating property. It was found that the reactivity can be increased and the plating adhesion can be improved.
- oxidation treatment is performed before the annealing process, and then reduction annealing, hot dipping, and alloying treatment are performed as necessary. It was found that it is effective and that it is necessary to obtain a certain amount or more of iron oxide by oxidation treatment.
- oxidation is suppressed by an increase in Si content, so that it becomes difficult to obtain a necessary oxidation amount.
- B contained it turned out that the oxidation on the steel plate surface of Si in an annealing process is accelerated
- the oxidation furnace exit side temperature that is, the temperature reached by heating and the oxygen concentration in the atmosphere were regulated by the contents of Si and B, and appropriate oxidation treatment was performed to obtain the necessary oxidation amount.
- FIG. 1 shows a comparison between the oxidation furnace outlet temperature described in Table 1 and the heating temperature obtained using the above formula (1).
- a correlation coefficient R 2 is about 0.98, it is seen that very high correlation is observed.
- the coefficient related to the B content is a very large value, and although B is a trace amount added element, the influence thereof is great, and it can be seen that it is a particularly important factor in determining the oxidation conditions.
- the oxidation treatment is performed at the heating temperature T that satisfies the above formula (1).
- the present invention is characterized by the fact that the oxidation condition considering the influence of B is defined, and is an important requirement. And it heats up with an oxidation furnace to the temperature which satisfy
- the Fe oxide is peeled off in the reducing atmosphere furnace in the subsequent reduction annealing step, which causes pickup, so the heating temperature T when performing the oxidation treatment is 850 ° C. or lower. It is preferable. Moreover, if the heating attainment temperature satisfying the formula (1) is reached, iron oxide is formed on the surface of the steel plate, so that it is not necessary to maintain at that temperature. However, when heated at an extremely high temperature increase rate, before the necessary iron oxide is formed, the process proceeds to the subsequent reduction annealing step. Therefore, the average temperature increase rate during the oxidation treatment is 50 ° C. / Sec or less is preferable. On the other hand, from the viewpoint of production efficiency, the average temperature rising rate during the oxidation treatment is preferably 1 ° C./sec or more.
- the atmosphere of the oxidation furnace during the oxidation treatment controls the oxygen concentration as described above.
- the oxygen concentration during the oxidation treatment satisfies the formula (1), and the oxygen concentration is preferably 0.05% or more. If it is less than 0.05%, a sufficient amount of iron oxide may not be obtained even if the formula (1) is satisfied, and 0.05% or more is preferable in order to stably obtain a sufficient amount of iron oxide.
- N 2 , CO, CO 2 , H 2 O, unavoidable impurities, and the like are included in the atmosphere, a sufficient effect can be obtained as long as the oxygen concentration and temperature are within the specified range. .
- the type of oxidation furnace for performing the oxidation treatment is not particularly limited, but it is preferable to use a direct-fired heating furnace equipped with a direct-fire burner.
- a direct fire burner heats a steel sheet by directly applying a burner flame, which is burned by mixing fuel such as coke oven gas (COG), which is a by-product gas of an ironworks, and air, to the surface of the steel sheet.
- COG coke oven gas
- the direct fire burner has an advantage that the furnace length of the heating furnace can be shortened and the line speed can be increased because the heating rate of the steel sheet is faster than that of the radiation type heating.
- the direct fire burner has an air ratio of 0.95 or higher and the ratio of air to fuel is increased, unburned oxygen remains in the flame, and the oxygen can promote oxidation of the steel sheet. Therefore, the oxygen concentration in the atmosphere can be controlled by adjusting the air ratio.
- COG, liquefied natural gas (LNG), etc. can be used for the fuel of an open fire burner.
- the steel sheet After the steel sheet is subjected to the oxidation treatment as described above, it is subjected to reduction annealing.
- the conditions for the reduction annealing are not limited, it is preferable that the atmospheric gas introduced into the annealing furnace contains 1 to 20% by volume of H 2 in general and the balance is N 2 and inevitable impurities.
- H 2 volume% of the atmospheric gas When the H 2 volume% of the atmospheric gas is less than 1 volume%, H 2 is insufficient to reduce the iron oxide on the steel sheet surface. If it exceeds 20% by volume, the reduction of Fe oxide is saturated, and excess H 2 is wasted.
- the dew point exceeds 0 ° C., oxidation by H 2 O in the furnace becomes remarkable and excessive internal oxidation of Si occurs. Therefore, the dew point is preferably 0 ° C.
- the reduction annealing is preferably performed in the range of the steel plate temperature from 700 ° C. to 900 ° C. from the viewpoint of material adjustment.
- the soaking time is preferably 10 seconds to 300 seconds.
- hot dip galvanizing is performed.
- the hot dip galvanizing treatment is performed by using a plating bath having a dissolved Al amount of 0.12 to 0.22 mass% when the alloying treatment of the plating layer is not performed, and when the alloying treatment is performed after the hot dip galvanizing.
- a plating bath having a dissolved Al amount of 08 to 0.18 mass% the steel sheet is infiltrated into the plating bath at a plate temperature of 440 to 550 ° C., and the adhesion amount is adjusted by gas wiping or the like.
- the temperature of the hot dip galvanizing bath may be in the normal range of 440 to 500 ° C.
- the degree of alloying (Fe% in the film) should be 7 to 15% by mass. If it is less than 7% by mass, unevenness in alloying will occur and the appearance will deteriorate, or the so-called ⁇ phase will be generated and the slidability will deteriorate. If it exceeds 15 mass%, a large amount of hard and brittle ⁇ phase is formed, and the plating adhesion deteriorates.
- the high-strength hot-dip galvanized steel sheet of the present invention is manufactured.
- the high-strength hot-dip galvanized steel sheet manufactured by the above manufacturing method will be described.
- the unit of the content of each element of the steel component composition and the unit of the content of each element of the plating layer component composition are “mass%”, and are simply represented by “%” unless otherwise specified.
- C 0.01 to 0.20% C makes it easy to improve workability by forming martensite or the like as a steel structure. For that purpose, 0.01% or more is preferable. On the other hand, if it exceeds 0.20%, the weldability deteriorates. Therefore, the C content is preferably 0.01% or more and 0.20% or less.
- Si 0.1-2.0% Si is an element effective for strengthening steel and obtaining a good material. If Si is less than 0.1%, an expensive alloy element is required to obtain high strength, which is not economically preferable. On the other hand, if it exceeds 2.0%, the heating attainment temperature that satisfies the above-described formula (1) becomes high, and thus problems in operation may occur. Therefore, the Si content is preferably 0.1% or more and 2.0% or less.
- Mn 1.0 to 3.0% Mn is an element effective for increasing the strength of steel. In order to ensure mechanical properties and strength, it is preferable to contain 1.0% or more. On the other hand, if it exceeds 3.0%, it may be difficult to ensure the weldability and strength ductility balance. Therefore, the amount of Mn is preferably 1.0% or more and 3.0% or less.
- B 0.0005 to 0.005%
- B is an element effective for improving the hardenability of steel. If it is less than 0.0005%, it is difficult to obtain a quenching effect. If it exceeds 0.005%, the temperature on the outlet side of the oxidation furnace that satisfies the above-described formula (1) becomes high, and thus an operational problem may occur. Therefore, the B content is preferably 0.0005% or more and 0.005% or less.
- Al 0.01 to 0.1%
- Mo 0.05 to 1.0%
- Nb 0.005 to 0.05%
- Ti 0.005 Requires one or more elements selected from -0.05%
- Cu 0.05-1.0%
- Ni 0.05-1.0%
- Cr 0.01-0.8% It may be added depending on.
- Al is most easily oxidized thermodynamically, it is oxidized prior to Si and Mn, thereby suppressing the oxidation of Si and Mn on the surface of the steel sheet and promoting the oxidation inside the steel sheet. This effect is obtained at 0.01% or more. If it exceeds 0.1%, the cost increases. Therefore, the Al content is preferably 0.01% or more and 0.1% or less.
- the Mo content is less than 0.05%, it is difficult to obtain the effect of adjusting the strength and the effect of improving the plating adhesion at the time of composite addition with Nb, Ni or Cu. On the other hand, if it exceeds 1.0%, cost increases. Therefore, the Mo amount is preferably 0.05% or more and 1.0% or less.
- the Nb content is preferably 0.005% or more and 0.05% or less.
- the Ti content is less than 0.005%, the effect of adjusting the strength is difficult to obtain. If it exceeds 0.05%, the plating adhesion may be deteriorated. Therefore, the Ti content is preferably 0.005% or more and 0.05% or less.
- Cu is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual ⁇ phase and the effect of improving the plating adhesion when combined with Ni or Mo. On the other hand, if it exceeds 1.0%, the cost may increase. Therefore, Cu is preferably 0.05% or more and 1.0% or less.
- Ni is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual ⁇ phase and the effect of improving the plating adhesion upon the combined addition of Cu and Mo. On the other hand, if it exceeds 1.0%, the cost may increase. Therefore, Ni is preferably 0.05% or more and 1.0% or less.
- the Cr content is preferably 0.01% or more and 0.8% or less.
- the remainder other than the above is Fe and inevitable impurities.
- hot-dip galvanized steel sheets are annealed in a reducing atmosphere in a continuous annealing facility, and then immersed in a galvanizing bath, galvanized, and then pulled up from the galvanized bath and coated with a gas wiping nozzle. It is manufactured by adjusting. Further, it is manufactured by subjecting the plating layer to alloying treatment in an alloying heating furnace as required. In order to increase the strength of the hot dip galvanized steel sheet, it is effective to add Si, Mn, B, etc. to the steel as described above.
- the added Si, Mn is added to the steel sheet surface.
- Si and Mn are oxidized inside a steel plate by oxidation treatment before reduction annealing on the oxidation conditions according to Si and B content, and the oxidation on the steel plate surface is prevented.
- the plating property is improved, the reactivity between the plating and the steel plate can be increased, and the plating adhesion can be improved.
- the internal oxide composed of oxides of Si and Mn formed during reduction annealing remains in the steel sheet under the plating layer.
- the internal oxide is dispersed in the plating layer. Therefore, in the hot-dip galvanized steel sheet without alloying treatment, the amount of internal oxide in the surface layer of the steel sheet under the plating layer is improved, and in the hot-dip galvanized steel sheet subjected to alloying treatment, the amount of internal oxide contained in the plating layer is improved in plating adhesion. It is thought to be related.
- the present inventors pay attention to the oxides present in the steel sheet under the plating layer and the oxides present in the plating layer, and the oxides of Si and Mn contained therein, and the plating adhesion The relationship was investigated. As a result, in the hot dip galvanized steel sheet that is not subjected to alloying treatment, the oxides of Si and Mn contained in the 5 ⁇ m steel sheet from the surface layer of the steel sheet under the plating layer, It has been found that when the Si oxide and Mn oxide contained in the plating layer are each 0.05 g / m 2 or more, the plating adhesion is excellent.
- the effect on each 1.0 g / m 2 exceeds is saturated, 1.0 g / m 2 or less.
- the oxide of Si is 0.05 g / m 2 or more and 0.05 g / m 2 or more that in the Si amount conversion, the oxides of Mn 0.05 g / m 2 or more, Mn amount It is 0.05 g / m 2 or more in terms of conversion.
- the oxide of Si and the oxide of Mn can be quantified by the method of Examples described later.
- the fatigue resistance is closely related to the oxides of Si and Mn existing in the surface layer of the steel sheet under the plating layer. From the surface layer of the steel plate under the plating layer, it was found that the fatigue resistance is improved when the oxide of Si and the oxide of Mn contained in the 5 ⁇ m steel plate are each 0.01 g / m 2 or less.
- the mechanism by which the fatigue resistance is improved by controlling the oxide present in the steel plate under the coating layer of the hot-dip galvanized steel sheet that has been subjected to alloying treatment is not clear, but the oxide present in this region is due to fatigue. It is thought that this is the starting point of the crack that occurs.
- the Si amount and Mn amount of the oxide existing in the 5 ⁇ m steel plate from the steel plate surface layer satisfy 0.01 g / m 2 or less, the cracks generated in the plating layer propagate to the inside of the steel plate. It is thought that the fatigue resistance is improved.
- the manufacturing method for realizing the state of the oxide as described above is not particularly limited, it is possible to control the steel plate temperature and the processing time in the alloying process.
- the alloying temperature is low or the processing time is short, the progress of the alloying reaction of Fe—Zn from the interface between the plating layer and the steel sheet is insufficient, so that the oxide remaining on the steel sheet surface layer increases. Therefore, it is necessary to secure an alloying temperature and a processing time for obtaining a sufficient Fe—Zn alloying reaction.
- the heat treatment is preferably performed at an alloying temperature of 460 to 600 ° C. and a treatment time of 10 to 60 seconds.
- the hot dip galvanized steel sheet not subjected to alloying treatment, even when the Si amount and Mn amount of the oxide contained in the 5 ⁇ m steel plate from the surface layer of the steel plate under the plating layer are 0.01 g / m 2 or more, respectively. Good fatigue resistance can be obtained.
- the plated layer is not alloyed and is substantially made of zinc, so that it is more ductile than the plated layer of the galvannealed steel sheet. For this reason, since no cracks are generated even when a tensile stress is applied, it is considered that the influence of oxides existing in the steel plate under the plating layer does not appear.
- a slab obtained by melting steel having chemical components shown in Table 2 was hot-rolled, pickled, and then cold-rolled to obtain a cold-rolled steel sheet having a thickness of 1.2 mm.
- the CGL having a DFF type oxidation furnace was appropriately changed in the oxidation furnace outlet side temperature, and the cold-rolled steel sheet was heated for oxidation treatment.
- the direct flame burner used COG as the fuel, and adjusted the oxygen concentration in the atmosphere by adjusting the air ratio.
- the oxidation furnace steel sheet temperature was measured with a radiation thermometer.
- reduction annealing is performed at 850 ° C. for 20 s, and after hot-dip plating is performed in a 460 ° C. galvanizing bath in which the Al addition amount is adjusted to 0.19%, the basis weight is about 50 g / m by gas wiping. Adjusted to 2 .
- the oxides of Si and Mn contained in the 5 ⁇ m steel sheet were quantified from the surface layer of the steel sheet below the plating layer, and the appearance and plating adhesion were evaluated. Furthermore, the tensile properties and fatigue resistance properties were investigated.
- the measurement method and the evaluation method are shown below. Quantitative determination of oxide of Si and oxide of Mn After dissolving the plated layer of the hot-dip galvanized steel sheet obtained above with hydrochloric acid containing an inhibitor, 5 ⁇ m was dissolved from the surface layer of the steel sheet in a non-aqueous solution by constant current electrolysis. . The obtained oxide residue was filtered with a Nuclepore filter having a diameter of 50 nm, and then the oxide trapped on the filter was subjected to ICP analysis after alkali melting to determine Si and Mn.
- Fatigue resistance test Stress ratio R Performed under the condition of 0.05, the fatigue limit (FL) was determined at 10 7 repetitions, the durability ratio (FL / TS) was determined, and a value of 0.60 or more was judged to be good fatigue resistance characteristics did.
- the stress ratio R is a value defined by (minimum repeated stress) / (maximum repeated stress).
- the hot-dip galvanized steel sheet (invention example) produced by the method of the present invention has excellent plating adhesion and good plating appearance despite being a high-strength steel containing Si, Mn and B. There is also good fatigue resistance.
- the hot-dip galvanized steel sheet (comparative example) manufactured outside the scope of the present invention is inferior in any one or more of plating adhesion and plating appearance.
- a slab obtained by melting steel having chemical components shown in Table 2 was hot-rolled, pickled, and then cold-rolled to obtain a cold-rolled steel sheet having a thickness of 1.2 mm.
- Example 2 Thereafter, oxidation treatment and reduction annealing were performed in the same manner as in Example 1. Furthermore, after hot-dip plating was performed in a 460 ° C. zinc plating bath in which the Al addition amount was adjusted to 0.13%, the basis weight was adjusted to about 50 g / m 2 by gas wiping, and at a predetermined temperature shown in Table 4 An alloying treatment was performed for 20 to 30 seconds.
- the Fe content in the plating layer was determined. Further, the oxides of Si and Mn contained in the 5 ⁇ m steel plate were quantified from the surface layer of the steel plate in and under the plating layer, and the appearance and plating adhesion were evaluated. Furthermore, the tensile properties and fatigue resistance properties were investigated.
- Fe content Dissolve the plating layer of the hot-dip galvanized steel sheet obtained above with hydrochloric acid containing an inhibitor, determine the amount of plating adhesion from the mass difference before and after dissolution, and further determine the Fe content in the plating layer from the amount of Fe contained in hydrochloric acid. Asked.
- the plating layer was dissolved in a non-aqueous solution by constant potential electrolysis, and then 5 ⁇ m from the steel sheet surface layer was dissolved in the non-aqueous solution by constant current electrolysis. After the oxide residue obtained in each dissolution step is filtered through a Nuclepore filter having a diameter of 50 nm, the oxide trapped on the filter is alkali-melted and then subjected to ICP analysis in the plating layer and below the plating layer. Quantification of Si and Mn in the oxide contained in a 5 ⁇ m steel plate from the steel plate surface layer was performed.
- the galvannealed steel sheet produced by the method of the present invention is excellent in plating adhesion despite being a high-strength steel containing Si, Mn and B.
- the plating appearance is also good and the fatigue resistance is also good.
- a hot-dip galvanized steel sheet (comparative example) manufactured outside the scope of the present invention is inferior in any one or more of plating adhesion, plating appearance, and fatigue resistance.
- the high-strength hot-dip galvanized steel sheet of the present invention is excellent in plating adhesion and fatigue resistance, and can be used as a surface-treated steel sheet for reducing the weight and strength of an automobile body itself.
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Abstract
Description
[1]Si、MnおよびBを含有する鋼に対して、下式を満足する加熱到達温度T℃で酸化処理を行い、次いで、還元焼鈍、溶融亜鉛めっき処理を行う、高強度溶融亜鉛めっき鋼板の製造方法。
T≧58.65×[Si]+29440×[B]-13.59×[O2]+548.1
[Si]:鋼中のSi質量%
[B]:鋼中のB質量%
[O2]:酸化炉内雰囲気のO2体積%
[2]前記溶融亜鉛めっき処理後、更に460~600℃の温度で10~60秒間加熱する合金化処理を行う、前記[1]に記載の高強度溶融亜鉛めっき鋼板の製造方法。
[3]前記鋼の成分組成が、質量%で、C:0.01~0.20%、Si:0.1~2.0%、Mn:1.0~3.0%、B:0.0005~0.005%を含有し、残部がFeおよび不可避的不純物からなる、前記[1]または[2]に記載の高強度溶融亜鉛めっき鋼板の製造方法。
[4]前記[1]または[3]に記載の製造方法によって製造される合金化処理が行われない高強度溶融亜鉛めっき鋼板であり、めっき層下の鋼板表層から5μmの鋼板内に、Siの酸化物がSi量換算で0.05g/m2以上およびMnの酸化物がMn量換算で0.05g/m2以上含まれている、高強度溶融亜鉛めっき鋼板。
[5]前記[2]または[3]に記載の製造方法によって製造される合金化処理が行われる高強度溶融亜鉛めっき鋼板であり、めっき層中に、Siの酸化物がSi量換算で0.05g/m2以上およびMnの酸化物がMn量換算で0.05g/m2以上含まれ、さらに、めっき層下の鋼板表層から5μmの鋼板内にSiの酸化物がSi量換算で0.01g/m2以下およびMnの酸化物がMn量換算で0.01g/m2以下である、高強度溶融亜鉛めっき鋼板。
先ず、焼鈍工程前の酸化処理について説明する。鋼板を高強度化するためには、上述したように鋼にSi、Mnなどを添加することが有効である。しかし、これらの元素を添加した鋼板は、溶融亜鉛めっき処理を施す前に実施する焼鈍過程において、鋼板表面に、Si、Mnの酸化物が生成され、Si、Mnの酸化物が鋼板表面に存在するとめっき性を確保することが困難になる。
T≧58.65×[Si]+29440×[B]-13.59×[O2]+548.1 式(1)
但し、T:酸化処理における加熱到達温度℃、[Si]:鋼中のSi質量%、[B]:鋼中のB質量%、[O2]:酸化炉内雰囲気のO2体積%である。
C:0.01~0.20%
Cは、鋼組織として、マルテンサイトなどを形成させることで加工性を向上しやすくする。そのためには0.01%以上が好ましい。一方、0.20%を超えると溶接性が劣化する。したがって、C量は0.01%以上0.20%以下が好ましい。
Siは鋼を強化して良好な材質を得るのに有効な元素である。Siが0.1%未満では高強度を得るために高価な合金元素が必要になり、経済的に好ましくない。一方、2.0%を超えると上述した式(1)を満足する加熱到達温度が高温になるために操業上の問題が起きる場合がある。したがって、Si量は0.1%以上2.0%以下が好ましい。
Mnは鋼の高強度化に有効な元素である。機械特性や強度を確保するためは1.0%以上含有させることが好ましい。一方、3.0%を超えると溶接性や強度延性バランスの確保が困難になる場合がある。したがって、Mn量は1.0%以上3.0%以下が好ましい。
Bは鋼の焼入れ性を向上させるのに有効な元素である。0.0005%未満では焼き入れ効果が得られにくい。0.005%を超えると上述した式(1)を満足する酸化炉出側温度が高温になるために操業上の問題が起きる場合がある。したがって、B量は0.0005%以上0.005%以下が好ましい。
Alは熱力学的に最も酸化しやすいため、Si、Mnに先だって酸化し、Si、Mnの鋼板表面での酸化を抑制し、鋼板内部での酸化を促進する効果がある。この効果は0.01%以上で得られる。0.1%を超えるとコストアップになる。したがって、Al量は0.01%以上0.1%以下が好ましい。
通常、溶融亜鉛めっき鋼板は、母材鋼板を連続焼鈍設備において還元雰囲気中で焼鈍した後、亜鉛めっき浴に浸漬して亜鉛めっき処理を施し、亜鉛めっき浴から引き上げてガスワイピングノズルでめっき付着量を調整して製造される。また、更に、必要に応じて合金化加熱炉でめっき層の合金化処理を施して製造される。そして、溶融亜鉛めっき鋼板を高強度化するためには、上述したように鋼にSi、MnおよびBなどを添加することが有効であるが、焼鈍過程において、鋼板表面に、添加したSi、Mnが酸化物として生成し、良好なめっき密着性を確保することが困難になる。これに対し、本発明では、SiおよびB含有量に応じた酸化条件で還元焼鈍前に酸化処理を行うことで、SiおよびMnを鋼板内部で酸化させ、鋼板表面での酸化を防ぐ。その結果、めっき性が向上し、更にはめっきと鋼板の反応性を高めることができ、めっき密着性を改善させることが出来る。合金化処理を行わない溶融亜鉛めっき鋼板では、還元焼鈍時に形成したSiおよびMnの酸化物から成る内部酸化物はめっき層下の鋼板内に留まるが、合金化処理を施した溶融亜鉛めっき鋼板においては、めっき層と鋼板の界面からFe-Znの合金化反応が進行するために、内部酸化物は、めっき層中に分散する。よって、合金化処理を行わない溶融亜鉛めっき鋼板ではめっき層下の鋼板表層の内部酸化物量が、合金化処理を施した溶融亜鉛めっき鋼板ではめっき層中に含まれる内部酸化物量がめっき密着性に関係してくると考えられる。
Siの酸化物およびMnの酸化物の定量
上記により得られた溶融亜鉛めっき鋼板のめっき層をインヒビターを含んだ塩酸によって溶解させた後に、非水溶液中で鋼板表層から5μmを定電流電解によって溶解した。得られた酸化物の残渣を50nmの径を有するニュークリポアフィルターでろ過した後に、フィルターに捕捉された酸化物をアルカリ融解後にICP分析し、SiおよびMnの定量を行った。
不めっきなどの外観不良が無い場合は外観良好(記号○)、ある場合は外観不良(記号×)と判定した。
ボールインパクト試験を行い、加工部をテープ剥離し、めっき層の剥離有無を目視判定した。
○:めっき層の剥離無し
×:めっき層が剥離
引張特性
圧延方向を引張方向としてJIS5号試験片を用いてJISZ2241に準拠した方法で行った。
応力比R:0.05の条件で行い、繰り返し数107で疲労限(FL)を求め、耐久比(FL/TS)を求め、0.60以上の値が良好な耐疲労特性と判断した。なお、応力比Rとは、(最少繰り返し応力)/(最大繰り返し応力)で定義されている値である。
Fe含有量(Fe含有率)
上記により得られた溶融亜鉛めっき鋼板のめっき層をインヒビターを含んだ塩酸によって溶解させ、溶解前後の質量差からめっき付着量を求め、さらに塩酸に含まれるFe量からめっき層中のFe含有率を求めた。
非水溶液中でめっき層を定電位電解によって溶解させ、更にその後、非水溶液中で鋼板表層から5μmを定電流電解によって溶解した。それぞれの溶解工程で得られた酸化物の残渣を50nmの径を有するニュークリポアフィルターでろ過した後に、フィルターに捕捉された酸化物をアルカリ融解後にICP分析によって、めっき層中、およびめっき層下の鋼板表層から5μmの鋼板内に含まれる酸化物中のSiおよびMnの定量を行った。
合金化処理後の外観を目視観察し、合金化ムラ、不めっきがないものを○、合金化ムラや不めっきがあるものは×とした。
めっき鋼板にセロテープ(登録商標)を貼りテープ面を90°曲げ曲げ戻しをしたときの単位長さ当たりの剥離量を蛍光X線によりZnカウント数を測定し、下記の基準に照らしてランク1~3のものを良好(○)、4以上のものを不良(×)と評価した。
蛍光X線カウント数 ランク
0-500未満 :1(良)
500-1000未満 :2
1000-2000未満:3
2000-3000未満:4
3000以上 :5(劣)
引張り特性および耐疲労特性は実施例1と同様な方法で評価した。
Claims (5)
- Si、MnおよびBを含有する鋼に対して、下式を満足する加熱到達温度T℃で酸化処理を行い、次いで、還元焼鈍、溶融亜鉛めっき処理を行う、高強度溶融亜鉛めっき鋼板の製造方法。
T≧58.65×[Si]+29440×[B]-13.59×[O2]+548.1
[Si]:鋼中のSi質量%
[B]:鋼中のB質量%
[O2]:酸化炉内雰囲気のO2体積% - 前記溶融亜鉛めっき処理後、更に460~600℃の温度で10~60秒間加熱する合金化処理を行う、請求項1に記載の高強度溶融亜鉛めっき鋼板の製造方法。
- 前記鋼の成分組成が、質量%で、C:0.01~0.20%、Si:0.1~2.0%、Mn:1.0~3.0%、B:0.0005~0.005%を含有し、残部がFeおよび不可避的不純物からなる、請求項1または2に記載の高強度溶融亜鉛めっき鋼板の製造方法。
- 請求項1または3に記載の製造方法によって製造される合金化処理が行われない高強度溶融亜鉛めっき鋼板であり、
めっき層下の鋼板表層から5μmの鋼板内に、Siの酸化物がSi量換算で0.05g/m2以上およびMnの酸化物がMn量換算で0.05g/m2以上含まれている、高強度溶融亜鉛めっき鋼板。 - 請求項2または3に記載の製造方法によって製造される合金化処理が行われる高強度溶融亜鉛めっき鋼板であり、
めっき層中に、Siの酸化物がSi量換算で0.05g/m2以上およびMnの酸化物がMn量換算で0.05g/m2以上含まれ、
さらに、めっき層下の鋼板表層から5μmの鋼板内に、Siの酸化物がSi量換算で0.01g/m2以下およびMnの酸化物がMn量換算で0.01g/m2以下である、高強度溶融亜鉛めっき鋼板。
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CN106191663B (zh) * | 2016-08-26 | 2018-05-01 | 武汉钢铁有限公司 | 一种屈服强度为280MPa级的铁-锌镀层钢板及生产方法 |
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CN106222541B (zh) * | 2016-08-26 | 2018-06-08 | 武汉钢铁有限公司 | 一种屈服强度为250MPa级的铁-锌镀层钢板及生产方法 |
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