WO2017110030A1 - 高強度溶融めっき熱延鋼板およびその製造方法 - Google Patents

高強度溶融めっき熱延鋼板およびその製造方法 Download PDF

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Publication number
WO2017110030A1
WO2017110030A1 PCT/JP2016/004830 JP2016004830W WO2017110030A1 WO 2017110030 A1 WO2017110030 A1 WO 2017110030A1 JP 2016004830 W JP2016004830 W JP 2016004830W WO 2017110030 A1 WO2017110030 A1 WO 2017110030A1
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Prior art keywords
hot
steel sheet
less
dip
plating
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PCT/JP2016/004830
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English (en)
French (fr)
Inventor
正貴 木庭
善継 鈴木
弘之 増岡
Original Assignee
Ｊｆｅスチール株式会社
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Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to US16/065,419 priority Critical patent/US11066721B2/en
Priority to KR1020187017816A priority patent/KR102205787B1/ko
Priority to EP16877935.3A priority patent/EP3375902B1/en
Priority to MX2018007769A priority patent/MX2018007769A/es
Priority to CN201680076114.1A priority patent/CN108474092B/zh
Publication of WO2017110030A1 publication Critical patent/WO2017110030A1/ja

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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B15/012—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 aluminium or an aluminium alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
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    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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    • C—CHEMISTRY; METALLURGY
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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
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    • C—CHEMISTRY; METALLURGY
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    • 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
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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
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    • 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
    • C21D8/0421—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 characterised by the working steps
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    • C—CHEMISTRY; METALLURGY
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    • 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
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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
    • 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
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/1275—Next to Group VIII or IB metal-base component
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions

  • the present invention relates to a high-strength hot-dip hot-rolled steel sheet excellent in surface appearance and plating adhesion, which uses a high-strength hot-rolled steel sheet containing Si and Mn as a base material, and a method for producing the same.
  • a hot dip hot-rolled steel sheet is manufactured by using a steel sheet obtained by hot rolling a slab as a base material, recrystallizing the base steel sheet in a CGL annealing furnace, and then performing a hot dip coating process. Further, the alloyed hot-dip galvanized steel sheet is manufactured by further alloying after hot-dip plating.
  • hot-rolled steel sheet containing Si often has local scale residue or local smud generation due to per-acid washing on the surface after pickling, and further because the surface irregularities are rough, Defects such as non-plating and untreated alloy are likely to occur.
  • Non-plating is a phenomenon in which plating does not adhere to a part of the surface of the steel sheet in the hot dip treatment, and the surface of the steel sheet is exposed. Its size is usually in the order of mm, and its presence can be visually observed.
  • Patent Document 1 As a measure for preventing plating defects such as poor alloying when manufacturing an alloyed hot-dip galvanized steel sheet containing Si, Mn, and P as a base material, an acid of a hot-rolled steel sheet as a base material is disclosed. A method of performing shot blasting or brush grinding at the time of washing and descaling has been proposed.
  • Patent Document 2 proposes a method for improving the adhesion of a plating film in which the surface of a base material is ground, heated to 600 ° C. or higher in a reducing atmosphere, cooled, hot-dip plated, and then alloyed. .
  • Patent Document 3 proposes a manufacturing method in which a steel sheet is annealed in a non-oxidizing atmosphere and then rolled at a rolling reduction of 0.1 to 1.0% immediately before being immersed in a hot dip galvanizing bath.
  • Patent Document 4 a hot-rolled steel sheet or an annealed cold-rolled steel sheet is subjected to a light reduction with a rolling reduction of 1.0 to 20%, and a low-temperature heat treatment is performed at 520 to 650 ° C. for 5 seconds or more.
  • Patent Document 1 requires shot blasting or brush grinding on the base material before plating.
  • the method proposed in Patent Document 2 requires a grinding process.
  • both Patent Document 1 and Patent Document 2 require processing that is costly and troublesome, and thus there is a problem in that productivity is reduced.
  • Patent Document 3 is intended to prevent alloying delay, and a sufficient effect for improving the powdering resistance has not always been obtained.
  • Patent Document 4 does not provide a sufficiently high level of powdering resistance that can cope with the higher strength and workability required for current high-strength steel sheets.
  • Powdering is a phenomenon in which an alloy layer is crushed and peeled off inside a plating film that has undergone compression deformation, and the peeled plating film piece accumulates inside the mold, impairing the slidability of the plated steel sheet. This may cause defective forming of the plated steel sheet. In addition, peeling pieces accumulate and cause indentation flaws.
  • JP-A-6-158254 Japanese Patent Laid-Open No. 10-81948 JP 2012-97326 A JP 2002-317257 A
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a high-strength hot-dip hot-rolled steel sheet excellent in surface appearance and plating adhesion and a method for producing the same.
  • the present inventors diligently studied to solve the above problems. As a result, it was found that by controlling the surface roughness and residual stress of the steel sheet, a high-strength hot-dip hot-rolled steel sheet excellent in surface appearance and plating adhesion can be obtained.
  • the present invention is based on the above findings, and features are as follows.
  • component composition in mass%, C: 0.02% to 0.30%, Si: 0.01% to 1.0%, Mn: 0.3% to 2.5%, P: 0.08% or less, S: 0.02% or less, Al: 0.001% or more and 0.20% or less, with the balance being Fe and inevitable impurities, hot rolling, pickling Then, after rolling at a rolling reduction of 1% or more and 10% or less, a method for producing a high-strength hot-dip hot-rolled steel sheet, which is subjected to hot-dip plating.
  • Component composition is mass%, C: 0.02% to 0.30%, Si: 0.01% to 1.0%, Mn: 0.3% to 2.5%, P: 0.08% or less, S: 0.02% or less, Al: 0.001% or more and 0.20% or less, with the balance being Fe and unavoidable impurities, arithmetic mean roughness Ra of the steel sheet surface Is a high-strength hot-dip hot-rolled steel sheet having an average residual stress ⁇ of ⁇ -Fe (211) surface of the steel sheet surface of ⁇ 250 MPa ⁇ ⁇ ⁇ 30 MPa and a tensile strength of 590 MPa or more. .
  • the high-strength hot-plated hot-rolled steel sheet of the present invention has a tensile strength (TS) of 590 MPa or more, and uses a hot-rolled steel sheet as a base material and performs hot-dip plating, and further performs alloying after hot-dip plating. , Both are included.
  • the plating includes plating such as Zn plating, Zn—Al plating, and Al plating.
  • excellent surface appearance means having an appearance in which no plating or uneven alloying is observed.
  • a high-strength hot-dip hot-rolled steel sheet excellent in surface appearance and plating adhesion can be obtained. Since it can withstand severe processing, it is extremely useful in terms of formability, and the industrial effect obtained by the present invention is great.
  • a hot-rolled hot-rolled steel sheet containing Si and Mn can be stably produced.
  • restrictions on the Si and Mn contents are relaxed, it is possible to use a base material containing a large amount of Si and Mn, and it is possible to obtain a great industrial effect such as easy design of steel components. be able to.
  • 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 component composition are “mass%”, and are simply “%” unless otherwise specified. Show.
  • the unit of hydrogen concentration is “vol%”, and is simply “%” unless otherwise specified.
  • the high-strength hot-dip hot-rolled steel sheet having excellent surface appearance and plating adhesion of the present invention is mass%, C: 0.02% or more and 0.30% or less, Si: 0.01% or more and 1.0% or less. Mn: 0.3% or more and 2.5% or less, P: 0.08% or less, S: 0.02% or less, Al: 0.001% or more and 0.20% or less, with the balance being Fe and It consists of inevitable impurities, the arithmetic mean roughness Ra of the steel sheet surface is 2.0 ⁇ m or less, the average residual stress ⁇ of the ⁇ -Fe (211) surface of the steel sheet surface satisfies ⁇ 250 MPa ⁇ ⁇ ⁇ 30 MPa, and It has a tensile strength of 590 MPa or more.
  • the present invention reduces the roughness of the steel sheet surface by applying a reduction to the steel sheet after hot rolling and pickling, and suppresses the adhesion amount and reaction unevenness of plating. Further, the present invention is characterized in that Fe—Al and Fe—Zn reactions are promoted by introducing residual stress on the surface of the steel sheet during rolling (rolling), thereby improving plating adhesion. As a result, a high-strength hot-dip hot-rolled steel sheet having excellent surface appearance and plating adhesion can be obtained.
  • the C content is 0.02% or more. Preferably it is 0.04% or more.
  • the C content is set to 0.30% or less. Preferably it is 0.20% or less.
  • Si 0.01% or more and 1.0% or less Si is effective as a solid solution strengthening element, and 0.01% or more is necessary to increase the strength of the steel sheet.
  • excessive Si content impairs wettability during hot dipping and impairs alloying reactivity, making it difficult to adjust the alloying and reducing plating appearance, plating adhesion, and powdering resistance.
  • the Si content is set to 0.01% to 1.0%.
  • Mn 0.3% to 2.5%
  • Mn is an element useful for increasing the strength of steel. In order to obtain this effect, it is necessary to contain 0.3% or more of Mn. However, if Mn is excessively contained, the wettability at the time of hot dipping is impaired and the alloying reactivity is impaired. Therefore, the adjustment of alloying becomes difficult and the plating appearance, plating adhesion, and powdering resistance are deteriorated. . From the above, the Mn content is set to 0.3% to 2.5%. Preferably it is 0.3% or more. Preferably it is 2.0% or less.
  • S 0.02% or less S needs to be 0.02% or less in order to reduce toughness when segregation or MnS is produced in large amounts at grain boundaries.
  • the lower limit of the S content is not particularly limited, and may be an impurity level.
  • Al 0.001% or more and 0.20% or less Al is added for the purpose of deoxidation of molten steel, but when the content is less than 0.001%, the purpose is not achieved. On the other hand, if the content exceeds 0.20%, a large amount of inclusions are generated, which causes wrinkling of the steel sheet. Therefore, the Al content is 0.001% or more and 0.20% or less.
  • the balance is Fe and inevitable impurities.
  • Ti 0.01% or more and 0.40% or less
  • Nb 0.001% or more and 0.200% or less
  • V 0.001% or more and 0.000% or more by mass%.
  • One or two or more of 500% or less, Mo: 0.01% or more and 0.50% or less, W: 0.001% or more and 0.200% or less can be contained.
  • Ti, Nb, V, Mo, and W are elements necessary for depositing precipitates (particularly carbides) in the base steel sheet, and one or more selected from the group consisting of these elements. It is preferable to contain. Usually, these elements are often contained in the form of precipitates containing these elements in the base steel sheet. Among these elements, Ti is particularly an element that has a high precipitation strengthening ability and is effective from the viewpoint of cost. However, if the content is less than 0.01%, the amount of precipitates in the base steel sheet necessary for containing precipitates (particularly carbides) in the alloyed hot-dip coating layer may be insufficient. If it exceeds 0.40%, the effect is saturated and the cost is increased.
  • the Ti content is 0.01% or more and 0.40% or less.
  • Nb, V, Mo, and W for the same reason regarding the upper limit and the lower limit of the Ti content range, when Nb is contained, the Nb content is 0.001% or more and 0.200% or less, and the V content is 0.00. 001% or more and 0.500% or less, Mo amount is 0.01% or more and 0.50% or less, and W amount is 0.001% or more and 0.200% or less.
  • the Fe—Al and Fe—Zn reactions on the steel sheet surface are made uniform to reduce unevenness of the coating amount.
  • the arithmetic average roughness (Ra) is used as the steel sheet surface roughness, and Ra is set to 2.0 ⁇ m or less in order to obtain the effect of improving the plating characteristics.
  • the surface roughness increases due to the scale wrinkles typified by the red scale, and the Si and Mn oxides formed during annealing. As a result, the alloying speed is delayed, and unevenness in alloying is easily realized.
  • Ra is 2.0 ⁇ m or less
  • the Fe—Al and Fe—Zn reactions on the steel sheet surface are made uniform, stress concentration during bending is prevented, surface appearance, plating adhesion, and powder resistance. Ring property does not deteriorate.
  • arithmetic mean roughness Ra can be measured by the method as described in the Example mentioned later. Further, by setting the rolling reduction after pickling to 1% or more and 10% or less, even when a base material containing a large amount of Si and Mn is used, the arithmetic average roughness Ra of the steel sheet surface is 2.0 ⁇ m or less. It can be.
  • the average residual stress ⁇ of the ⁇ -Fe (211) plane of the steel sheet surface satisfies ⁇ 250 MPa ⁇ ⁇ ⁇ ⁇ 30 MPa
  • compressive residual stress to the base material surface
  • restoration of the oxide film formed after pickling is accelerated
  • the residual stress is set to ⁇ 250 MPa ⁇ ⁇ ⁇ 30 MPa.
  • the pressure exceeds -30 MPa the introduction of compressive residual stress is insufficient, and the effect of improving the plating characteristics is hardly exhibited.
  • the average residual stress ⁇ of the ⁇ -Fe (211) plane on the steel sheet surface is set to ⁇ 250 MPa ⁇ ⁇ ⁇ ⁇ 30 MPa.
  • the average residual stress ⁇ can be set to ⁇ 250 MPa ⁇ ⁇ ⁇ ⁇ 30 MPa by setting the rolling reduction ratio after pickling to 1% to 10%.
  • the average residual stress ⁇ was measured using the parallel tilt method, and the residual stress ( ⁇ ) of the steel sheet was derived from an average of five analysis results from an arbitrary place and direction using an X-ray diffractometer. .
  • the gradient (R) is calculated according to the equation (1), and is combined with the Young's modulus (E) of the steel material.
  • the residual stress ( ⁇ ) can be obtained from the equation (2).
  • R ⁇ S / (sin 2 ⁇ ) (1)
  • ⁇ R ⁇ E (2)
  • the steel having the above component composition is hot-rolled, pickled, then rolled at a rolling reduction of 1% or more and 10% or less, and then subjected to hot-dipping treatment, whereby the high-strength hot-dip hot-rolled steel sheet of the present invention is obtained.
  • the furnace atmosphere is set to a hydrogen concentration of 2 vol% to 20 vol%, a dew point of -60 ° C to -10 ° C, and a steel sheet temperature (T) of 650 ° C to 750 ° C, T-50 ° C to T ° C. It is preferable to perform annealing that is held for 10 seconds or more and 500 seconds or less in the following temperature range. Further, an alloying treatment may be further performed after the hot dipping treatment.
  • Hot rolling hot rolling start temperature (slab heating temperature) In order to disperse fine precipitates such as Ti and Nb, Ti, Nb and the like need to be once dissolved in the steel plate before hot rolling. Therefore, the heating temperature (slab heating temperature) before hot rolling is preferably 1100 ° C. or higher. On the other hand, when it heats exceeding 1300 degreeC, internal oxidation in a steel surface layer is accelerated
  • the finish rolling temperature is preferably 800 ° C. or higher and 1000 ° C. or lower.
  • Hot-rolling temperature The steel sheet according to the present invention contains oxidizable elements such as Si, Mn, and Ti. Therefore, in order to suppress excessive oxidation of the steel sheet and ensure good surface properties, the hot rolling coiling temperature is preferably 600 ° C. or lower.
  • the hot rolling coiling temperature is 400 ° C. or lower, coil property defects due to uneven cooling are likely to occur, which may impair productivity. Therefore, the hot rolling coiling temperature is preferably 400 ° C. or higher and 600 ° C. or lower.
  • the hot-rolled steel sheet obtained by the pickling hot rolling process is descaled by pickling and then rolled.
  • Pickling is not particularly limited, and may be performed by a conventional method. At this time, rolling of 5% or less may be performed in the previous stage of the pickling process. By performing rolling at 5% or less, the descaling property is improved and the surface property is improved.
  • rolling is performed after hot rolling and pickling.
  • the rolling reduction during rolling is 1% or more and 10% or less.
  • the surface roughness is controlled and residual stress is introduced into the base metal surface.
  • the rolling reduction is 1% or more, the residual stress is sufficiently introduced, and the plateability of the steel sheet surface is improved.
  • the rolling reduction exceeds 10%, the effect of improving the plating characteristics is saturated, and a large amount of dislocations are introduced into the surface layer of the steel sheet, so that the surface layer structure becomes coarse during annealing before plating treatment, leading to a decrease in strength. .
  • Annealing can be performed before annealing hot dipping.
  • the conditions are not particularly limited, but it is preferable to maintain the steel sheet arrival temperature (T) in the temperature range of 650 ° C. to 750 ° C. and T-50 ° C. to T ° C. for 10 seconds to 500 seconds.
  • T steel sheet arrival temperature
  • the steel sheet arrival temperature is lower than 650 ° C., the oxide film after pickling is not completely reduced, and desired plating characteristics may not be obtained.
  • the surface of Si, Mn, etc. may be concentrated and the plating property may be deteriorated.
  • the holding time in the temperature range of T-50 ° C. or higher and T ° C.
  • the holding time is longer than 500 seconds in the temperature range of T-50 ° C. or higher and T ° C. or lower, the productivity of the hot-dip plated steel sheet may be hindered.
  • the furnace atmosphere is preferably a hydrogen concentration of 2% to 20% and a dew point of ⁇ 60 ° C. to ⁇ 10 ° C.
  • the atmosphere in the furnace may be any reducing property, and an atmosphere having a dew point of ⁇ 60 ° C. or more and ⁇ 10 ° C. or less, a hydrogen concentration of 2% or more and 20% or less and the balance of an inert gas is suitable.
  • the dew point is higher than ⁇ 10 ° C., the form of the Si oxide generated on the steel sheet surface tends to be a film.
  • a dew point lower than ⁇ 60 ° C. is difficult to realize industrially.
  • the hydrogen concentration is lower than 2%, the reducing property is weak. If it exceeds 20%, there is a concern of ignition on the inlet side of the annealing furnace where the atmosphere in the furnace comes into contact with the air, and stable operation becomes difficult. If it is 20% or less, sufficient reducing ability can be obtained.
  • Hot dipping treatment is carried out using a hot dipping bath after the steel sheet is subjected to reduction annealing in a continuous hot dipping plating line.
  • the composition of the hot dipping bath is, for example, in the case of hot dip galvanizing treatment, the Al concentration is in the range of 0.01% to 1.0%, and the balance is Zn and inevitable impurities.
  • the Al concentration is less than 0.01%, a Zn—Fe alloying reaction occurs during the plating treatment, a brittle alloy layer develops at the interface between the plating film and the steel plate (base material), and the plating adhesion deteriorates.
  • the Al concentration exceeds 1.0% the growth of the Fe—Al alloy layer becomes remarkable and the plating adhesion is hindered.
  • the plating bath temperature is not particularly limited, and may be 440 ° C. or higher and 480 ° C. or lower which is a normal operation range. Moreover, although there is no restriction
  • the alloying treatment temperature is preferably 550 ° C. or less. More preferably, it is 530 degrees C or less.
  • the alloying treatment time is preferably 10 seconds or more and 60 seconds or less from the viewpoint of cost and control. More preferably, it is within 40 seconds.
  • the heating method in the alloying treatment is not particularly limited, and any known method such as radiant heating, current heating, high frequency induction heating, or the like may be used. After alloying, cool to room temperature.
  • the post-treatment after plating is not particularly limited, and post-treatment that is usually performed such as adjustment of the material by temper rolling, adjustment of the flat shape by leveling or the like, and further chromate treatment may be performed as necessary.
  • the galvanizing bath temperature was 460 ° C., and the amount of adhesion on one side was adjusted to 50 g / m 2 by wiping.
  • the alloying treatment was performed at an alloying temperature of 530 ° C.
  • Tensile test is JIS No. 5 test piece sampled so that the tensile direction is perpendicular to the rolling direction of the steel sheet, and No. JIS No. 5 sampled so that the tensile direction is parallel to the rolling direction of the steel sheet.
  • TS tensile strength
  • a sample collected so that the tensile direction is perpendicular to the rolling direction of the steel sheet and a sample collected so that the tensile direction is parallel to the rolling direction of the steel sheet are each subjected to a tensile test, and the average value is the tensile strength.
  • TS tensile strength
  • TS tensile strength
  • the plating adhesion of the hot-dip galvanized hot-rolled steel sheet was evaluated by a ball impact test. A ball impact test was performed under the conditions of a ball weight of 2.8 kg and a drop height of 1 m, the processed part was peeled off with tape, and the presence or absence of peeling of the plating layer was visually determined. ⁇ No plating layer peeling ⁇ Plating layer peeling Powdering resistance (after alloying) The hot-dip galvanized hot-rolled steel sheet was evaluated by testing the powdering resistance. A cellophane tape is applied to the galvannealed steel sheet, the tape surface is bent 90 degrees, bent back, and the tape is peeled off.
  • the amount of plating peeled per bent portion 10 mm ⁇ 40 mm was measured as a Zn count number by fluorescent X-rays and evaluated in accordance with the following criteria.
  • Table 2 The results obtained as described above are shown in Table 2 together with the production conditions.
  • the example of the present invention has good surface appearance, plating adhesion, and powdering resistance.
  • any one or more of surface appearance, plating adhesion, and powdering resistance is inferior.
  • the high-strength hot-dip hot-rolled steel sheet of the present invention is suitably used as an automobile part that has been rapidly strengthened and thinned in recent years.

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Abstract

表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板およびその製造方法を提供する。 成分組成として、質量％で、Ｃ：０．０２％以上０．３０％以下、Ｓｉ：０．０１％以上１．０％以下、Ｍｎ：０．３％以上２．５％以下、Ｐ：０．０８％以下、Ｓ：０．０２％以下、Ａｌ：０．００１％以上０．２０％以下を含有し、残部がＦｅおよび不可避的不純物からなる鋼を、熱間圧延、酸洗し、次いで、１％以上１０％以下の圧下率で圧延後、溶融めっき処理を行う。得られる鋼板は、鋼板表面の算術平均粗さＲａが２．０μｍ以下であり、鋼板表面のα-Ｆｅ（２１１）面の平均残留応力σが－２５０ＭＰａ≦σ≦－３０ＭＰａを満たし、かつ、５９０ＭＰａ以上の引張強度を有する。

Description

高強度溶融めっき熱延鋼板およびその製造方法
　本発明は、Ｓｉ、Ｍｎを含有する高強度熱延鋼板を母材とする、表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板およびその製造方法に関するものである。
　近年、自動車用鋼板の分野においては、燃費の向上や耐衝突特性の向上のため、５９０ＭＰａ以上の引張強度を有する高強度鋼板の適用が拡大しつつある。これらの高強度鋼板には、製造コストが安価な熱延鋼板が使用される場合があり、また、耐食性の向上等を目的として溶融めっきが施される場合がある。
　一般的に、溶融めっき熱延鋼板は、スラブを熱間圧延した鋼板を母材として用い、母材鋼板をＣＧＬの焼鈍炉で再結晶焼鈍し、その後、溶融めっき処理を行い製造される。また、合金化溶融めっき鋼板は、溶融めっき後、さらに合金化処理を行い製造される。
　上記のような用途に使用される溶融めっき鋼板は、表面外観や、めっき付着性がよいことが重要である。しかしながら、Ｓｉを含有する溶融めっき熱延鋼板は、酸洗後の表面に局所的なスケール残りや過酸洗による局所的なスマッド生成がある場合が多く、さらには表面の凹凸が粗いために、不めっきや合金化未処理などの欠陥が生じやすい。不めっきは、溶融めっき処理でめっきが鋼板表面の一部に付着せず、鋼板表面が露出する現象であり、そのサイズは通常ｍｍオーダーのため、その存在を目視することができる。
　上記問題を解決するためにいくつかの提案がなされている。例えば、特許文献１には、母材がＳi 、Ｍn 、Ｐなどを含有する合金化溶融亜めっき鋼板を製造する際の合金化不良などのめっき欠陥防止対策として、母材の熱延鋼板の酸洗脱スケールに際してショットブラスト処理やブラシ研削を施す方法が提案されている。 
　特許文献２には、母材表面を研削した後に還元性雰囲気中で６００℃以上に加熱し、冷却して溶融めっき処理し、次いで合金化処理するめっき皮膜の密着性改善方法が提案されている。 
　特許文献３には、鋼板を非酸化性雰囲気で焼鈍後、溶融亜鉛めっき浴に浸漬直前に、圧下率０．１～１．０％の圧延を施す製造方法が提案されている。 
　特許文献４には、熱間鋼板または焼鈍済みの冷延鋼板に、圧下率が１．０～２０％の軽圧下を施し、５２０～６５０℃で５秒以上保持する低温加熱処理を施し、質量％でＡｌ：０．０１～０．１８％を含有する溶融亜鉛めっき浴に浸漬し、次いで合金化処理する合金化溶融亜鉛めっき鋼板の製造方法が提案されている。
　しかしながら、特許文献１で提案されている方法は、めっき前の母材に対してショットブラストやブラシ研削を必要とする。特許文献２で提案されている方法は研削処理を必要とする。このように、特許文献１、特許文献２のいずれもコストと手間がかかる処理を必要とするため、生産性の低下を招くという問題があった。 
　特許文献３は、合金化遅れの防止を目的としたものであり、耐パウダリング性の改善に関して必ずしも十分な効果が得られるものではなかった。
　また、特許文献４で提案されている方法では、現在の高強度鋼板において要求される更に高い強度、加工性に対応できる、十分に高いレベルの耐パウダリング性は得られていない。
　溶融めっき皮膜を合金化するとめっき皮膜が硬質になるため、成形時にめっき皮膜の損傷（パウダリングなど）が生じやすい。パウダリングは、圧縮変形を受けためっき皮膜内部で合金層が粉状に砕かれて剥離する現象であり、剥離しためっき皮膜片が金型内部に堆積し、めっき鋼板の摺動性を阻害し、めっき鋼板の成形不良が生じる原因になる。また、剥離片が堆積して押し込み疵の原因にもなる。
特開平６－１５８２５４号公報 特開平１０－８１９４８号公報 特開２０１２－９７３２６号公報 特開２００２－３１７２５７号公報
　本発明は、かかる事情に鑑みてなされたものであって、表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板およびその製造方法を提供することを目的とする。
　本発明者らは、上記の課題を解決すべく、鋭意検討した。その結果、鋼板表面の粗さや残留応力を制御することにより、表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板が得られることを見出した。
　本発明は上記知見に基づくものであり、特徴は以下の通りである。
［１］成分組成として、質量％で、Ｃ：０．０２％以上０．３０％以下、Ｓｉ：０．０１％以上１．０％以下、Ｍｎ：０．３％以上２．５％以下、Ｐ：０．０８％以下、Ｓ：０．０２％以下、Ａｌ：０．００１％以上０．２０％以下を含有し、残部がＦｅおよび不可避的不純物からなる鋼を、熱間圧延、酸洗し、次いで、１％以上１０％以下の圧下率で圧延後、溶融めっき処理を行う高強度溶融めっき熱延鋼板の製造方法。
［２］成分組成として、さらに、質量％で、Ｔｉ：０．０１％以上０．４０％以下、Ｎｂ：０．００１％以上０．２００％以下、Ｖ：０．００１％以上０．５００％以下、Ｍｏ：０．０１％以上０．５０％以下、Ｗ：０．００１％以上０．２００％以下のうち１種または２種以上を含有する前記［１］に記載の高強度溶融めっき熱延鋼板の製造方法。
［３］前記圧延後、前記溶融めっき処理前に、炉内雰囲気を水素濃度２ｖｏｌ％以上２０ｖｏｌ％以下かつ露点－６０℃以上－１０℃以下とし、鋼板到達温度（Ｔ）が６５０℃以上７５０℃以下、Ｔ－５０℃以上Ｔ℃以下の温度域で１０秒以上５００秒以下保持する焼鈍を行う前記［１］または［２］に記載の高強度溶融めっき熱延鋼板の製造方法。
［４］前記溶融めっき処理後、さらに、合金化処理を行う前記［１］～［３］のいずれかに記載の高強度溶融めっき熱延鋼板の製造方法。
[５]成分組成は、質量％で、Ｃ：０．０２％以上０．３０％以下、Ｓｉ：０．０１％以上１．０％以下、Ｍｎ：０．３％以上２．５％以下、Ｐ：０．０８％以下、Ｓ：０．０２％以下、Ａｌ：０．００１％以上０．２０％以下を含有し、残部がＦｅおよび不可避的不純物からなり、鋼板表面の算術平均粗さＲａが２．０μｍ以下であり、鋼板表面のα-Ｆｅ（２１１）面の平均残留応力σが－２５０ＭＰａ≦σ≦－３０ＭＰａを満たし、かつ、５９０ＭＰａ以上の引張強度を有する高強度溶融めっき熱延鋼板。
［６］成分組成として、さらに、質量％で、Ｔｉ：０．０１％以上０．４０％以下、Ｎｂ：０．００１％以上０．２００％以下、Ｖ：０．００１％以上０．５００％以下、Ｍｏ：０．０１％以上０．５０％以下、Ｗ：０．００１％以上０．２００％以下のうち１種または２種以上を含有する前記［５］に記載の高強度溶融めっき熱延鋼板。
　なお、本発明の高強度溶融めっき熱延鋼板は、引張強度（TS）５９０ＭPa以上であり、熱延鋼板を母材とし、溶融めっき処理を行うもの、溶融めっき処理後さらに合金化処理を行うもの、いずれも含むものである。また、めっきとしては、Ｚｎめっき、Ｚｎ－Ａｌめっき、Ａｌめっきなどのめっきを対象とする。
　また、表面外観に優れるとは、不めっきや合金化ムラが認められない外観を有することをいう。
　本発明によれば、表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板が得られる。厳しい加工にも耐えられることから成形性の面で極めて有用であり、本発明により得られる工業上の効果は大きい。
Ｓｉ、Ｍｎを含有する溶融めっき熱延鋼板を安定して製造することができる。かつ、Ｓｉ、Ｍｎ含有量の制限が緩和されるので、Ｓi 、Ｍnを大量に含有する母材を使用することが可能となり、鋼成分の設計が容易になるなど、工業的に大きな効果を得ることができる。
　以下、本発明について具体的に説明する。
なお、以下の説明において、鋼成分組成の各元素の含有量の単位およびめっきの成分組成の各元素の含有量の単位はいずれも「質量％」であり、特に断らない限り単に「％」で示す。また、水素濃度の単位はいずれも「ｖｏｌ％」であり、特に断らない限り単に「％」で示す。
　本発明の表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板は、質量％で、Ｃ：０．０２％以上０．３０％以下、Ｓｉ：０．０１％以上１．０％以下、Ｍｎ：０．３％以上２．５％以下、Ｐ：０．０８％以下、Ｓ：０．０２％以下、Ａｌ：０．００１％以上０．２０％以下を含有し、残部がＦｅおよび不可避的不純物からなり、鋼板表面の算術平均粗さＲａが２．０μｍ以下であり、鋼板表面のα-Ｆｅ（２１１）面の平均残留応力σが－２５０ＭＰａ≦σ≦－３０ＭＰａを満たし、かつ、５９０ＭＰａ以上の引張強度を有することを特徴とする。すなわち、本発明は、熱間圧延、酸洗後の鋼板に圧下を加えることで鋼板表面の粗さを低減し、めっきの付着量、反応ムラを抑制する。さらに、圧下（圧延）時に鋼板表面に残留応力を導入することによってＦｅ－Ａｌ、Ｆｅ－Ｚｎ反応を促進し、めっき密着性を向上させることを特徴とする。以上の結果、表面外観及びめっき密着性に優れる高強度溶融めっき熱延鋼板が得られることになる。
　まず、本発明の対象とする表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の鋼成分組成の限定理由について説明する。
　Ｃ：０．０２％以上０．３０％以下
Ｃは少ないほど母材の成形性が良好となるが、Ｃを含有させることで鋼板の強度を安価に高めることができる。従って、Ｃ含有量は０．０２％以上とする。好ましくは０．０４％以上である。一方、Ｃを過剰に含有させると鋼板の靱性や溶接性が低下するので、Ｃ含有量は０．３０％以下とする。好ましくは０．２０％以下である。
　Ｓi：０．０１％以上１．０％以下
Ｓi は固溶強化元素として有効であり、鋼板の強度を高めるためにも０．０１％以上が必要である。しかしながら、Ｓi を過度に含有させると溶融めっき時の濡れ性を損ない、合金化反応性を損なうために、合金化の調整が困難となってめっき外観やめっき密着性、耐パウダリング性の低下を招く。以上より、Ｓｉ含有量は０．０１％以上１．０％以下とする。
　Ｍn：０．３％以上２．５％以下
Ｍn は鋼の強度を高めるのに有用な元素である。この効果を得るには、Ｍn を０．３％以上含有させる必要がある。しかしながら、Ｍnを過度に含有させると溶融めっき時の濡れ性を損ない、合金化反応性を損なうため、合金化の調整が困難となってめっき外観やめっき密着性、耐パウダリング性の低下を招く。以上より、Ｍn含有量は０．３％以上２．５％以下とする。好ましくは０．３％以上である。好ましくは２．０％以下である。
　Ｐ：０．０８％以下
Ｐが０．０８％を超えて含有すると溶接性が劣化すると共に、表面品質が劣化する。また、合金化処理時には合金化処理温度をより高くしないと所望の合金化度とすることができないが、合金化処理温度を上昇させると母材鋼板の延性が劣化すると同時に合金化溶融めっき層の密着性が劣化する。そのため、Ｐ含有量は０．０８％以下である。
　Ｓ：０．０２％以下
Ｓは粒界に偏析またはＭｎＳが多量に生成した場合、靭性を低下させるため、含有量を０．０２％以下とする必要がある。Ｓ含有量の下限は特に限定されず、不純物程度であってもよい。
　Ａｌ：０．００１％以上０．２０％以下
Ａｌは溶鋼の脱酸を目的に添加されるが、その含有量が０．００１％未満の場合、その目的が達成されない。一方、０．２０％を超えて含有すると、介在物が多量に発生し、鋼板の疵の原因となる。そのため、Ａｌ含有量は０．００１％以上０．２０％以下である。
　残部はＦe および不可避的不純物である。
　本発明では、下記を目的として、さらに、質量％で、Ｔｉ：０．０１％以上０．４０％以下、Ｎｂ：０．００１％以上０．２００％以下、Ｖ：０．００１％以上０．５００％以下、Ｍｏ：０．０１％以上０．５０％以下、Ｗ：０．００１％以上０．２００％以下のうち１種または２種以上を含有することができる。
　Ｔｉ、Ｎｂ、Ｖ、ＭｏおよびＷは、母材鋼板中に析出物（特に、炭化物）を析出させるために必要な元素であり、これらの元素からなる群から選ばれる１種または２種以上を含有することが好ましい。通常、これらの元素は、母材鋼板中でこれらの元素を含む析出物の形で含有される場合が多い。
これらの元素のなかで、特にＴｉは析出強化能が高く、コストの観点からも有効な元素である。しかしながら、含有量が０．０１％未満では合金化溶融めっき層中に析出物（特に、炭化物）を含有させるために必要な母材鋼板中の析出物量が不十分な場合がある。０．４０％を超えるとその効果は飽和し、コストアップとなる。そのため、Ｔｉを含有する場合は、Ｔｉ含有量は、０．０１％以上０．４０％以下である。
なお、Ｎｂ、Ｖ、Ｍｏ、Ｗについても上記Ｔｉの含有範囲の上限および下限に関する同様の理由から、含有する場合は、Ｎｂ量は０．００１％以上０．２００％以下、Ｖ量は０．００１％以上０．５００％以下、Ｍｏ量は０．０１％以上０．５０％以下、Ｗ量は０．００１％以上０．２００％以下である。
　鋼板表面の算術平均粗さＲａが２．０μｍ以下
本発明では、鋼板の表面粗さを制御することで、鋼板表面のＦｅ－Ａｌ及びＦｅ－Ｚｎ反応を均一化し、めっき付着量ムラを軽減させる。鋼板表面粗さとして算術平均粗さ（Ｒａ）を使用し、めっき特性の改善効果を得るためにＲａを２．０μｍ以下とする。特にＳi 、Ｍnを多量に含有する母材を使用した場合には、赤スケールを代表としたスケール疵に起因して表面粗さが増大することに加え、焼鈍時に形成されるＳi 、Ｍn酸化物によって合金化速度が遅延し、合金化ムラが顕在化しやすくなる。これに対して、Ｒａが２．０μｍ以下であれば、鋼板表面でのＦｅ－Ａｌ及びＦｅ－Ｚｎ反応を均一化させ、曲げ加工時の応力集中を防ぎ、表面外観、めっき密着性および耐パウダリング性が劣化することがない。なお、算術平均粗さＲａは後述する実施例に記載の方法にて測定することができる。また、酸洗後の圧延の圧下率を１％以上１０％以下とすることで、Ｓi 、Ｍnを大量に含有する母材を使用した場合でも鋼板表面の算術平均粗さＲａを２．０μｍ以下とすることができる。
　鋼板表面のα-Ｆｅ（２１１）面の平均残留応力σが－２５０ＭＰａ≦σ≦－３０ＭＰａを満たす
本発明では、母材表面に圧縮残留応力を導入することで、Ｆｅ－Ａｌ反応性、Ｆｅ－Ｚｎ合金化反応性を向上させる。また、酸洗後に形成される酸化被膜の還元を促進する。このようなめっき特性の改善効果を得るために、上記残留応力を－２５０ＭＰａ≦σ≦－３０ＭＰａとする。－３０ＭＰａ超えの場合は、圧縮残留応力の導入が不十分となり、めっき特性の改善効果が発現しにくい。－２５０ＭＰａ未満の場合はめっき性特性の改善効果が飽和することに加え、鋼板表層に多量の転位が導入されることでめっき処理前の焼鈍中に表層組織が粗大化し、強度の低下につながる。よって、鋼板表面のα-Ｆｅ（２１１）面の平均残留応力σは、－２５０ＭＰａ≦σ≦－３０ＭＰａとする。なお、平均残留応力σは、酸洗後の圧延の圧下率を１％以上１０％以下とすることで－２５０ＭＰａ≦σ≦－３０ＭＰａとすることができる。
　また、平均残留応力σの測定には並傾法を使用し、鋼板の残留応力（σ）は、Ｘ線回折装置を用いて、任意の場所・方向からの分析結果５点の平均により導出した。α-Ｆｅ（２１１）面ピーク強度（Ｓ）の変位値（ΔＳ）と傾斜角度ψの関係から、式（１）に従って勾配（Ｒ）を算出し、鋼材のヤング率（Ｅ）と合わせ、以下の式（２）により残留応力（σ）を求めることができる。
Ｒ＝ΔＳ／（ｓｉｎ２ψ）　　（１）
σ＝Ｒ×Ｅ　（２）
　次に、表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の製造方法について、説明する。
　上記成分組成を有する鋼を、熱間圧延、酸洗し、次いで、１％以上１０％以下の圧下率で圧延後、溶融めっき処理を行うことで、本発明の高強度溶融めっき熱延鋼板が製造される。さらに、圧延後、炉内雰囲気を水素濃度２ｖｏｌ％以上２０ｖｏｌ％以下かつ露点－６０℃以上－１０℃以下とし、鋼板到達温度（Ｔ）が６５０℃以上７５０℃以下、Ｔ－５０℃以上Ｔ℃以下の温度域で１０秒以上５００秒以下保持する焼鈍を行うことが好ましい。また、溶融めっき処理後、さらに、合金化処理を行ってもよい。
　熱間圧延
熱間圧延開始温度（スラブ加熱温度）
ＴｉやＮｂ等の微細析出の分散を行うためには、熱間圧延を行う前にＴｉやＮｂ等を一旦鋼板中に溶解させる必要がある。そのため、熱間圧延する前の加熱温度（スラブ加熱温度）は１１００℃以上が好ましい。一方で、１３００℃を超えて加熱した場合には、鋼表層での内部酸化が促進され、表面性状が劣化する恐れがある。よって、熱間圧延前のスラブ加熱温度は１１００℃以上１３００℃以下が好ましい。
仕上げ圧延温度
熱間圧延時の変形抵抗を小さくし、操業を容易にするために、仕上げ圧延温度を８００℃以上とすることが好ましい。一方、１０００℃を超えて仕上げ圧延した場合には、スケール疵が発生しやすくなり、表面性状が劣化する場合がある。よって、仕上げ圧延温度は８００℃以上１０００℃以下とすることが好ましい。
熱延巻取り温度
本発明にかかる鋼板は、ＳｉやＭｎ、Ｔｉを初めとした易酸化性元素を含有する。そのため、鋼板の過度な酸化を抑制し、良好な表面性状を確保するためには、熱延巻取り温度は６００℃以下であることが好ましい。一方、熱延巻取り温度が４００℃以下の場合には、冷却ムラに起因したコイル性状不良が生じやすくなるために、生産性を損なう恐れがある。よって、熱延巻取り温度は４００℃以上６００℃以下が好ましい。
　酸洗
熱間圧延工程によって得られた熱延鋼板は、酸洗によって脱スケールを施し、その後に圧延を実施する。酸洗は特に限定せず、常法でよい。この時、酸洗工程の前段階で５％以下の圧延を施しても良い。５％以下の圧延を施すことで、脱スケール性が向上し、表面性状の改善に繋がる。
　１％以上１０％以下の圧下率で圧延
鋼板表面のめっき性を改善するために、熱延、酸洗後に圧延を実施する。圧延の際の圧下率は、１％以上１０％以下とする。圧下を加えることで表面粗さの制御と母材表面に残留応力の導入を行う。圧下率を１％以上とすることで残留応力の導入が充分となり、鋼板表面のめっき性が改善される。圧下率が１０％超えでは、めっき特性の改善効果が飽和することに加え、鋼板表層に多量の転位が導入されることでめっき処理前の焼鈍中に表層組織が粗大化し、強度の低下につながる。
　焼鈍
溶融めっき処理前に焼鈍を行うことができる。条件は特に限定しないが、鋼板到達温度（Ｔ）が６５０℃以上７５０℃以下、Ｔ－５０℃以上Ｔ℃以下の温度域で１０秒以上５００秒以下保持することが好ましい。鋼板到達温度が６５０℃より低い温度の場合、酸洗後の酸化皮膜が完全には還元されず、所望するめっき特性を得ることができない場合がある。また、７５０℃より高い温度では、Ｓｉ、Ｍｎなどが表面濃化してめっき性が劣化する恐れがある。また、Ｔ－５０℃以上Ｔ℃以下の温度域での保持時間が１０秒より短い場合、酸洗後の酸化皮膜が完全には還元されず、溶融めっき外観とめっき特性が低下する場合がある。一方、Ｔ－５０℃以上Ｔ℃以下の温度域で保持時間が５００秒より長くなると、溶融めっき鋼板の生産性に支障をきたす場合がある。
　また、炉内雰囲気は水素濃度２％以上２０％以下かつ露点－６０℃以上－１０℃以下とすることが好ましい。炉内雰囲気は還元性であれば良く、露点－６０℃以上－１０℃以下、水素濃度：２％以上２０％以下で残部が不活性ガスからなる雰囲気が好適である。露点が－１０℃より高いと、鋼板表面に生成するＳｉ酸化物の形態が膜状となり易い。一方、－６０℃より低い露点は工業的に実現が困難である。水素濃度が２％より低い場合は還元性が弱い。２０％を超えると炉内雰囲気と大気が接触する焼鈍炉入側で発火する懸念があり、安定操業が困難になる。２０％以下であれば十分な還元能力が得られる。
　溶融めっき処理
溶融めっき処理は連続溶融めっきラインにて、前記鋼板を還元焼鈍したのち、溶融めっき浴を用いて実施する。
溶融めっき浴の組成は、例えば、溶融亜鉛めっき処理の場合は、Ａｌ濃度０．０１％以上１．０％以下の範囲とし、残部をＺｎおよび不可避的不純物とする。Ａｌ濃度が０．０１％未満の場合、めっき処理時にＺｎ－Ｆｅ合金化反応が起こり、めっき皮膜と鋼板（母材）の界面に脆い合金層が発達し、めっき密着性が劣化する。Ａｌ濃度が１．０％を超えるとＦｅ－Ａｌ合金層の成長が顕著となり、めっき密着性を阻害する。めっき浴温度は特に限定する必要はなく、通常の操業範囲である４４０℃以上４８０℃以下でよい。また、めっき目付量については特に制約はないが、耐食性の観点３０ｇ／ｍ２以上、加工性の観点１５０ｇ/ｍ２以下であることが好ましい。
　合金化処理
合金化処理温度が５５０℃を超えると、合金化処理時に、鋼板（母材）とめっき皮膜の界面に硬質で脆いΓ相の生成が著しく、表面粗さが大きくなると共に耐パウダリング性が劣化する。よって、合金化処理温度は５５０℃以下が好ましい。さらに好ましくは５３０℃以下である。 
合金化処理時間は、コストや制御上の問題点から、１０秒以上６０秒以下とするのが好ましい。より好ましくは４０秒以内である。
合金化処理における加熱方法は特に限定する必要がなく、輻射加熱、通電加熱、高周波誘導加熱など、公知のいずれの方法でもよい。合金化処理を施した後は常温まで冷却する。めっき後の後処理は特に限定する必要はなく、調質圧延による材質の調整やレベリング等による平坦形状の調整、さらには必要に応じてクロメート処理等通常行われる後処理を施しても構わない。
　以下、本発明を実施例に基づいて具体的に説明するが、本発明は本実施例に限定されるものではない。
表１に示す成分を有するスラブを用い、通常の鋳造、熱延、酸洗後に、表２に示すような条件で圧延、焼鈍、溶融亜鉛めっき処理、さらに一部については合金化処理を行った。
熱延酸洗後の鋼板表面の残留応力（σ）は、Ｘ線回折装置を用いて、任意の場所・方向からの分析結果１０点の平均により導出した。
鋼板表面の算術平均粗さＲａは、圧延方向及び圧延方向と直行する方向について算術平均粗さを測定し、それぞれの方向に対して３回測定を行い、得られた結果の平均値とした。
　溶融亜鉛めっき処理を施すに際し、亜鉛めっき浴温度は４６０℃で行い、ワイピングで片面辺りの付着量を５０ｇ／ｍ2に調整した。合金化処理は、合金化温度５３０℃で実施した。
　以上により得られた溶融亜鉛めっき熱延鋼板について、下記に示す試験を行い、引張特性、めっき表面外観性及びめっき密着性（耐パウダリング性）を評価した。測定方法および評価基準を下記に示す。
　引張特性
引張試験は、引張方向が鋼板の圧延方向と直角方向となるようにサンプルを採取したＪＩＳ５号試験片、および、引張方向が鋼板の圧延方向と平行となるようにサンプルを採取したＪＩＳ５号試験片を用いて、ＪＩＳ Ｚ ２２４１（２０１１年）に準拠して行い、ＴＳ（引張強度）を測定した。引張方向が鋼板の圧延方向と直角方向となるように採取したサンプルと引張方向が鋼板の圧延方向と平行となるように採取したサンプル、それぞれで各５本引張試験を行い、平均値を引張強度（ＴＳ）とし、引張強度（ＴＳ）が５９０ＭＰａ以上を良好と判断した。
　めっき表面外観性
溶融めっき後及び合金化処理後の外観を目視観察し、不めっき、合金ムラがないものを○、不めっきや合金ムラがあるものは×とした。
　めっき密着性
溶融亜鉛めっき熱延鋼板のめっき密着性は、ボールインパクト試験で評価した。ボール重量２．８ｋｇ、落下高さ１ｍの条件で、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。
○　めっき層の剥離なし
×　めっき層が剥離
　耐パウダリング性
（合金化処理後の）溶融亜鉛めっき熱延鋼板のめっき密着性は、耐パウダリング性を試験することで評価した。合金化溶融めっき鋼板にセロハンテープを貼り、テープ面に９０度曲げ、曲げ戻しを施し、テープを剥がす。剥がしたテープに付着した鋼板から、曲げ戻し部１０ｍｍ×４０ｍｍ当たりの剥離しためっきの量を、蛍光Ｘ線によるＺｎカウント数として測定し、下記基準に照らして評価した。
蛍光Ｘ線カウント数　　 　　　ランク
１５００未満 ：　　　　　　　◎（良）
１５００以上３０００未満 ：　○
３０００以上５０００未満 ：　△
５０００以上 　　　　　　：　×（劣）
　以上により得られた結果を製造条件と併せて表２に示す。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
 　表２より、本発明例は、表面外観、めっき密着性、耐パウダリング性のいずれも良好である。一方、比較例では、表面外観、めっき密着性、耐パウダリング性のいずれか一つ以上が劣る。
　本発明の高強度溶融めっき熱延鋼板は、近年急速に高強度化・薄肉化が進んできている自動車部品として好適に用いられる。

Claims (6)

  1. 　成分組成として、質量％で、Ｃ：０．０２％以上０．３０％以下、Ｓｉ：０．０１％以上１．０％以下、Ｍｎ：０．３％以上２．５％以下、Ｐ：０．０８％以下、Ｓ：０．０２％以下、Ａｌ：０．００１％以上０．２０％以下を含有し、残部がＦｅおよび不可避的不純物からなる鋼を、熱間圧延、酸洗し、次いで、１％以上１０％以下の圧下率で圧延後、溶融めっき処理を行う高強度溶融めっき熱延鋼板の製造方法。
  2. 　成分組成として、さらに、質量％で、Ｔｉ：０．０１％以上０．４０％以下、Ｎｂ：０．００１％以上０．２００％以下、Ｖ：０．００１％以上０．５００％以下、Ｍｏ：０．０１％以上０．５０％以下、Ｗ：０．００１％以上０．２００％以下のうち１種または２種以上を含有する請求項１に記載の高強度溶融めっき熱延鋼板の製造方法。
  3. 　前記圧延後、前記溶融めっき処理前に、炉内雰囲気を水素濃度２ｖｏｌ％以上２０ｖｏｌ％以下かつ露点－６０℃以上－１０℃以下とし、鋼板到達温度（Ｔ）が６５０℃以上７５０℃以下、Ｔ－５０℃以上Ｔ℃以下の温度域で１０秒以上５００秒以下保持する焼鈍を行う請求項１または２に記載の高強度溶融めっき熱延鋼板の製造方法。
  4. 　前記溶融めっき処理後、さらに、合金化処理を行う請求項１～３のいずれか一項に記載の高強度溶融めっき熱延鋼板の製造方法。
  5. 　成分組成は、質量％で、Ｃ：０．０２％以上０．３０％以下、Ｓｉ：０．０１％以上１．０％以下、Ｍｎ：０．３％以上２．５％以下、Ｐ：０．０８％以下、Ｓ：０．０２％以下、Ａｌ：０．００１％以上０．２０％以下を含有し、残部がＦｅおよび不可避的不純物からなり、
    鋼板表面の算術平均粗さＲａが２．０μｍ以下であり、鋼板表面のα-Ｆｅ（２１１）面の平均残留応力σが－２５０ＭＰａ≦σ≦－３０ＭＰａを満たし、かつ、５９０ＭＰａ以上の引張強度を有する高強度溶融めっき熱延鋼板。
  6. 　成分組成として、さらに、質量％で、Ｔｉ：０．０１％以上０．４０％以下、Ｎｂ：０．００１％以上０．２００％以下、Ｖ：０．００１％以上０．５００％以下、Ｍｏ：０．０１％以上０．５０％以下、Ｗ：０．００１％以上０．２００％以下のうち１種または２種以上を含有する請求項５に記載の高強度溶融めっき熱延鋼板。
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