WO2019026113A1 - 溶融亜鉛めっき鋼板 - Google Patents
溶融亜鉛めっき鋼板 Download PDFInfo
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- WO2019026113A1 WO2019026113A1 PCT/JP2017/027656 JP2017027656W WO2019026113A1 WO 2019026113 A1 WO2019026113 A1 WO 2019026113A1 JP 2017027656 W JP2017027656 W JP 2017027656W WO 2019026113 A1 WO2019026113 A1 WO 2019026113A1
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- layer
- steel sheet
- steel plate
- hot
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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
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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
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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
- B32B15/04—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
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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
- B32B15/04—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
- 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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- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/001—Heat treatment of ferrous alloys containing Ni
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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
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- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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- 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
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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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
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- 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
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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
- C23C28/028—Including graded layers in composition or in physical properties, e.g. density, porosity, grain size
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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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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- 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
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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
- 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
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- 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
- B32B15/012—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
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- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
- Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
Definitions
- the present invention relates to a high-strength galvanized steel sheet which is excellent in ductility, bendability, hole expansibility and plating adhesion at the time of bending deformation, and is excellent in continuous bending fatigue resistance.
- the plating layer does not peel off, the adhesion between the plating layer and the base steel plate is lost, and if there is a slight void in that portion, the outside air or moisture infiltrates the void, and plating is performed. The layer's corrosion protection function is lost. As a result, in the same manner as described above, the base steel plate may be corroded and rusted quickly. From these problems, as a high strength steel plate to be used after severe bending, etc., a plated steel plate provided with a hot-dip galvanized layer having excellent adhesion of the plating layer to the base steel plate is strongly desired. There is.
- Patent Document 4 the surface of the base steel plate is modified by adding a new annealing step and a pickling step before the general annealing step to improve adhesion of the plating layer, and plating is performed. Methods have been proposed to improve adhesion. However, the method described in Patent Document 4 has a problem in terms of cost because the number of steps is increased with respect to a general method of manufacturing a high strength plated steel plate.
- Patent Document 5 proposes a method of removing carbon from the surface layer portion of a base steel plate to enhance the adhesion of plating.
- the strength of the region from which carbon is removed is significantly reduced.
- the fatigue resistance which strongly depends on the characteristics of the surface layer is deteriorated and the fatigue strength is largely reduced.
- Patent Document 8 proposes a high-strength steel plate in which the microstructure of the steel plate is made of only ferrite.
- sufficiently high strength can not be obtained because the ferrite is only a soft ferrite.
- alloyed hot-dip galvanized steel sheets which have been subjected to an alloying treatment after hot-dip galvanizing treatment are widely used.
- the alloying treatment is a treatment in which the plating layer is heated to a temperature equal to or higher than the melting point of Zn, a large amount of Fe atoms is diffused from the base steel plate into the plating layer, and the plating layer is a layer mainly composed of Zn-Fe alloy.
- patent documents 9, 10, 11 propose alloyed hot-dip galvanized steel sheets excellent in plating adhesion.
- the present invention is excellent in the formability of a steel sheet represented by ductility, bendability and stretch flange formability, and the appearance uniformity of plating, fatigue resistance, weldability, corrosion resistance and plating adhesion It provides an excellent high strength galvanized steel sheet.
- the present inventors are to obtain a high-strength galvanized steel sheet excellent in formability of a steel sheet represented by ductility, bendability and stretch flange formability, fatigue resistance, weldability, corrosion resistance and plating adhesion. I made a careful study. As a result, the present inventors improved ductility and hole expandability (stretch flangeability) by controlling the microstructure of the steel sheet to a proper structure fraction. Moreover, the present inventors improved bendability and fatigue resistance by controlling the volume fraction of the hard phase on the base steel plate side from the boundary between the plated layer and the base steel plate.
- the inventors immediately under the Fe-Al alloy layer formed at the interface between the plating layer and the base steel plate. It has been found that the formation of a specific finely-divided layer consisting of extremely fine grains of a ferrite phase can suppress the occurrence of cracks and propagation during processing, and can suppress the peeling of plating that is the starting point. In addition, it has been found that by controlling the thicknesses of the finely-divided layer and the Fe-Al alloy layer in the width direction of the steel sheet within a specific range, it is possible to obtain a hot-dip galvanized steel sheet excellent in not only plating adhesion but also appearance uniformity.
- a hot-dip galvanized steel sheet having a hot-dip galvanized layer on at least one side of a base steel sheet The base steel plate is in mass%, C: 0.040% to 0.280%, Si: 0.05% to 2.00%, Mn: 0.50% to 3.50%, P: 0.0001% to 0.1000%, S: 0.0001% to 0.0100%, Al: 0.001% to 1.500%, N: 0.0001% to 0.0100%, O: 0.0001% to 0.0100%, Ti: 0% to 0.150%, Nb: 0% to 0.100%, V: 0% to 0.300%, Cr: 0% to 2.00%, Ni: 0% to 2.00%, Cu: 0% to 2.00%, Mo: 0% to 2.00%, B: 0% to 0.0100%, W: 0% to 2.00%, and Ca, Ce, Mg, Zr, La, and REM: 0% to 0.0100% in total Containing the chemical component of which the remainder is composed of Fe and impurities, With respect to the total thickness of
- the base steel plate has a finely divided layer in direct contact with the Fe-Al alloy layer, and the average thickness of the finely divided layer is 0.1 ⁇ m to 5.0 ⁇ m, and the average of the ferrite phase in the finely divided layer
- the grain size is 0.1 ⁇ m to 3.0 ⁇ m
- the refinement layer contains one or more oxides of Si and Mn
- the maximum diameter of the oxide is 0.01 ⁇ m to 0.4 ⁇ m
- a hot-dip galvanized steel sheet characterized in that the difference between the maximum thickness and the minimum thickness of the refined layer in the width direction of the steel sheet is within 2.0 ⁇ m.
- the hot-dip galvanized steel sheet according to (1) wherein the plating adhesion amount per one side of the hot-dip galvanized layer is 10 g / m 2 or more and 100 g / m 2 or less.
- the base steel plate is, in mass%, further, Ti: 0.001% to 0.150%, Nb: 0.001% to 0.100%, and V: 0.001% to 0.300%,
- the base steel plate is, in mass%, further, Cr: 0.01% to 2.00%, Ni: 0.01% to 2.00%, Cu: 0.01% to 2.00%, Mo: 0.01% to 2.00%, B: 0.0001% to 0.0100%, and W: 0.01% to 2.00%,
- the base steel plate is, further, at mass% Characterized in that it
- FIG. 1 is a view showing an example of a schematic view of a cross-sectional structure of a hot-dip galvanized steel sheet of the present invention.
- C 0.040% to 0.280%, Si: 0.01% to 2.00%, Mn: 0.50% to 3.% by mass. 50%, P: 0.0001% to 0.100%, S: 0.0001% to 0.0100%, Al: 0.001% to 1. 500%, O: 0.0001% to 0.0100% , N: 0.0001% to 0.0100%, and the rest is a galvannealed layer (hereinafter simply referred to as simply steel plate) on the surface of a base steel plate (hereinafter also simply referred to as a steel plate) having a chemical component consisting of Fe and impurities. It is also referred to as a plating layer).
- simply steel plate on the surface of a base steel plate (hereinafter also simply referred to as a steel plate) having a chemical component consisting of Fe and impurities. It is also referred to as a plating layer).
- board thickness of a base material steel plate is 0.6 mm or more and less than 5.0 mm. If the thickness of the base steel plate is less than 0.6 mm, it becomes difficult to keep the shape of the base steel plate flat, which is not appropriate. When the thickness of the base steel plate is 5.0 mm or more, the control of cooling in the manufacturing process becomes difficult, and the formability may be deteriorated without obtaining a predetermined microstructure.
- the plated layer has an Fe content of more than 0% and 3.0% or less, and an Al content of more than 0% and 1.0% or less.
- C 0.040% to 0.280%
- C is contained to increase the strength of the base steel plate.
- the C content exceeds 0.280%, the spot weldability deteriorates, so the C content is made 0.280% or less.
- the content of C is preferably 0.250% or less, and more preferably 0.220% or less.
- the C content is less than 0.040%, the strength decreases and it becomes difficult to secure a sufficient maximum tensile strength, so the C content is made 0.040% or more.
- the content of C is preferably 0.055% or more, and more preferably 0.070% or more.
- Si 0.05% to 2.00%
- Si is an element that suppresses the formation of iron-based carbides in the base steel sheet and enhances the strength and the formability.
- Si is also an element which embrittles steel materials, and when the content of Si exceeds 2.00%, problems such as cracking of a cast slab are likely to occur. Therefore, the content of Si is 2.00% or less.
- Si forms an oxide on the surface of the base steel plate in the annealing step, and significantly impairs the adhesion of the plating. From this viewpoint, the content of Si is preferably 1.500% or less, more preferably 1.200% or less.
- the content of Si is less than 0.05%, a large amount of coarse iron-based carbides are generated in the plating step of the hot-dip galvanized steel sheet, and the strength and the formability deteriorate. More than 05%.
- the content of Si is preferably 0.10% or more, and more preferably 0.25% or more.
- Mn 0.50% to 3.50%
- Mn is contained to enhance the strength by enhancing the hardenability of the base steel sheet.
- the content of Mn exceeds 3.50%, a coarse Mn-riched portion is formed at the center of the thickness of the base steel plate, which tends to cause embrittlement, and troubles such as cracking of the cast slab occur. It becomes easy to happen. Therefore, the content of Mn is set to 3.50% or less.
- the content of Mn is preferably 3.00% or less, and more preferably 2.80% or less.
- the content of Mn is less than 0.50%, a large amount of soft structure is formed during cooling after annealing, so it becomes difficult to secure a sufficiently high maximum tensile strength. Therefore, the content of Mn needs to be 0.50% or more.
- the content of Mn is preferably 0.80% or more, and more preferably 1.00% or more.
- P is an element that embrittles steel materials, and if the content of P exceeds 0.1000%, problems such as cracking of the cast slab or cracking of the slab during rolling tend to occur.
- the content of P is 0.1000% or less.
- P is also an element that embrittles the fusion zone generated by spot welding, and in order to obtain sufficient weld joint strength, the P content is preferably 0.0400% or less, and 0.0200% or less It is further preferable to On the other hand, making the content of P less than 0.0001% entails a significant increase in the manufacturing cost, so the content of P is made 0.0010% or more, with the lower limit of 0.0001%. Is preferred.
- S is an element that combines with Mn to form coarse MnS and reduces formability such as ductility, hole expansibility (stretch flangeability) and bendability, so the S content is made 0.0100% or less .
- S is also an element that degrades the spot weldability. Therefore, the content of S is preferably 0.0060% or less, more preferably 0.0035% or less.
- setting the content of S to less than 0.0001% entails a significant increase in manufacturing costs. Therefore, the lower limit value of the content of S is 0.0001%, preferably 0.0005% or more, and more preferably 0.0010% or more.
- Al 0.001% to 1.500%
- Al is an element that embrittles steel materials. If the content of Al exceeds 1.500%, troubles such as cracking of a cast slab are likely to occur, so the content of Al is set to 1.500% or less. In addition, since the spot weldability is deteriorated when the content of Al increases, the content of Al is more preferably 1.200% or less, and still more preferably 1.000% or less. On the other hand, the effect of the present embodiment can be exhibited without particularly setting the lower limit of the content of Al. However, Al is an impurity present in a small amount in the raw material, and a reduction in the content of less than 0.001% is accompanied by a significant increase in manufacturing cost. Therefore, the Al content is set to 0.001% or more. Al is also an element effective as a deoxidizing material, but in order to obtain the effect of deoxidation more sufficiently, the content of Al is more preferably 0.010% or more.
- N 0.0001% to 0.0100%
- N is an element which forms coarse nitrides and deteriorates formability such as ductility, hole expansibility (stretch flangeability) and bendability
- the content thereof needs to be suppressed. If the content of N exceeds 0.0100%, the deterioration of the formability becomes remarkable, so the upper limit of the N content is made 0.0100%.
- the excessive content of N causes the generation of blow holes at the time of welding, the smaller the content, the better. From these viewpoints, the N content is preferably 0.0070% or less, and more preferably 0.0050% or less.
- the lower limit of the content of N is not particularly limited, the effects of the present embodiment can be exhibited, but making the content of N less than 0.0001% causes a significant increase in manufacturing cost. From this, the lower limit of the N content is made 0.0001% or more.
- the N content is preferably 0.0003% or more, and more preferably 0.0005% or more.
- O 0.0001% to 0.0100% Since O forms an oxide and deteriorates the formability such as ductility, hole expandability (stretch flangeability) and bendability of a hot-dip galvanized steel sheet, it is necessary to suppress the content of O. When the content of O exceeds 0.0100%, the deterioration of the formability becomes remarkable, so the upper limit of the O content is made 0.0100%. Furthermore, the content of O is preferably 0.0050% or less, more preferably 0.0030% or less. Although the effect of the present embodiment is exhibited even if the lower limit of the content of O is not particularly defined, making the content of O less than 0.0001% entails a significant increase in the manufacturing cost. The lower limit is .0001%. The O content is preferably 0.0003% or more, more preferably 0.0005% or more.
- the following elements may be contained in the base material steel plate of the hot dip galvanized steel plate according to the present embodiment, as necessary.
- Ti 0.001% to 0.150%
- Nb 0.001% to 0.100%
- V 0.001% to 0.300. %
- And may contain one or more selected from the group consisting of
- Ti is an element that contributes to the increase in strength of a hot-dip galvanized steel sheet by precipitation strengthening, fine grain strengthening by suppressing the growth of ferrite crystal grains, and dislocation strengthening through suppression of recrystallization.
- the content of Ti exceeds 0.150%, precipitation of carbonitrides increases and the formability deteriorates, so the content of Ti is made 0.150% or less.
- the content of Ti is preferably 0.080% or less from the viewpoint of formability.
- the effect of the present embodiment is exhibited even if the lower limit of the content of Ti is not particularly defined, but the content of Ti is 0.001% or more in order to sufficiently obtain the strength increasing effect by Ti. Is preferred. It is more preferable that the content of Ti is 0.010% or more in order to further increase the strength of the hot-dip galvanized steel sheet.
- Nb is an element that contributes to the increase in strength of a hot-dip galvanized steel sheet by precipitation strengthening, fine grain strengthening by suppressing the growth of ferrite crystal grains, and dislocation strengthening through suppression of recrystallization.
- the content of Nb exceeds 0.100%, precipitation of carbonitrides increases and the formability of the hot-dip galvanized steel sheet deteriorates, so the content of Nb is made 0.100% or less. From the viewpoint of formability, the content of Nb is preferably 0.060% or less.
- the content of Nb should be 0.001% or more in order to sufficiently obtain the strength increase effect by Nb. Is preferred.
- the content of Nb is more preferably 0.005% or more.
- V is an element that contributes to the increase in strength of a hot-dip galvanized steel sheet by precipitation strengthening, fine grain strengthening by suppressing the growth of ferrite crystal grains, and dislocation strengthening through suppression of recrystallization.
- the content of V exceeds 0.300%, precipitation of carbonitrides increases and formability deteriorates. Therefore, the content of V is 0.300% or less.
- the content of V is preferably 0.200% or less.
- the content of V is preferably 0.001% or more, and more preferably 0.010% or more.
- Cr 0.01% to 2.00%
- Ni 0.01% to 2.00%
- Cu 0.01% to 2.00%
- Mo 0.01% to 2.00%
- B 0.0001% to 0.0100%
- W 0.01% to 2.00%, one or two selected from the group consisting of You may contain the above.
- Cr 0.01% to 2.00%
- Cr is an element that suppresses phase transformation at high temperature and is effective for increasing the strength of a hot-dip galvanized steel sheet, and may be contained instead of part of C and / or Mn.
- the content of Cr is set to 2.00% or less.
- the content of Cr is preferably 1.20% or less.
- the lower limit of the content of Cr is not particularly defined, the effect of the present embodiment is exhibited, but in order to sufficiently obtain the effect of strengthening by Cr, the content of Cr is 0.01% or more Is preferably 0.10% or more.
- Ni is an element which suppresses phase transformation at high temperature and is effective for strengthening the galvanized steel sheet, and may be contained in place of part of C and / or Mn. However, if the content of Ni exceeds 2.00%, the weldability is impaired, so the content of Ni is made 2.00% or less.
- the content of Ni is preferably 1.20% or less.
- the effect of the present embodiment is exhibited even if the lower limit of the content of Ni is not particularly defined, but the content of Ni is 0.01% or more in order to sufficiently obtain the effect of strengthening by Ni. Is preferably 0.10% or more.
- Cu is an element that enhances the strength of a hot-dip galvanized steel sheet by being present in the steel as fine particles, and can be contained instead of part of C and / or Mn. However, if the content of Cu exceeds 2.00%, the weldability is impaired, so the content of Cu is made 2.00% or less.
- the content of Cu is preferably 1.20% or less.
- the content of Cu is 0. It is preferably at least 01%, and more preferably at least 0.10%.
- Mo 0.01% to 2.00%
- Mo is an element that suppresses phase transformation at high temperature and is effective for increasing the strength of a hot-dip galvanized steel sheet, and may be contained instead of part of C and / or Mn.
- the content of Mo is preferably 1.20% or less.
- the lower limit of the content of Mo is not particularly limited, the effect of the present embodiment is exhibited, but in order to sufficiently obtain the effect of strengthening by Mo, the content of Mo is 0.01% or more Is preferably, and more preferably 0.05% or more.
- B is an element that suppresses phase transformation at high temperature and is effective for increasing the strength of a hot-dip galvanized steel sheet, and may be contained in place of part of C and / or Mn. However, if the content of B exceeds 0.0100%, the workability in hot is impaired and the productivity is reduced, so the content of B is made 0.0100% or less. From the viewpoint of productivity, the content of B is preferably 0.0050% or less. On the other hand, although the lower limit of the content of B is not particularly defined, the effect of the present embodiment is exhibited, but in order to sufficiently obtain the effect of increasing the strength by B, the content of B is made 0.0001% or more It is preferable to do. The content of B is more preferably 0.0005% or more in order to further increase the strength of the hot-dip galvanized steel sheet.
- W is an element that suppresses phase transformation at high temperature and is effective for increasing the strength of a hot-dip galvanized steel sheet, and may be contained instead of part of C and / or Mn. However, if the content of W exceeds 2.00%, the workability in hot is impaired and the productivity is reduced, so the content of W is made 2.00% or less.
- the content of W is preferably 1.20% or less.
- the lower limit of the content of W is not particularly limited, and the effect of the present embodiment is exhibited, but in order to sufficiently obtain the strengthening by W, the content of W is 0.01% or more Is preferably 0.10% or more.
- one or more selected from the group consisting of Ca, Ce, Mg, Zr, La, and REM as other elements are 0 in total. .0001% to 0.0100% may be contained.
- the reasons for containing these elements are as follows.
- REM is an abbreviation of Rare Earth Metal, and refers to an element belonging to the lanthanoid series.
- REM and Ce are often contained in misch metal, and in addition to La and Ce, they may contain elements of lanthanoid series in combination.
- the effect of the present embodiment can be exhibited even if the element contains lanthanoid elements other than La and Ce as impurities.
- the effects of the present embodiment can be exhibited even if metal La or Ce is contained.
- Ca, Ce, Mg, Zr, La, and REM are elements effective for improving the formability of the hot-dip galvanized steel sheet, and can contain one or more kinds. However, if the total content of one or more selected from the group consisting of Ca, Ce, Mg, Zr, La, and REM exceeds 0.0100%, the ductility may be impaired. The total content of the elements is 0.0100% or less. The total content of each of these elements is preferably 0.0070% or less.
- the lower limit of the content of one or more selected from the group consisting of Ca, Ce, Mg, Zr, La, and REM is not particularly limited, the effects of the present embodiment can be exhibited.
- the total content of these elements is preferably 0.0001% or more.
- the total content of one or more selected from the group consisting of Ca, Ce, Mg, Zr, La, and REM is more preferably 0.0010% or more.
- the balance of each element described above is Fe and impurities.
- Ti, Nb, V, Cr, Ni, Cu, Mo, B, and W it is accept
- Ca, Ce, Mg, Zr, La, and REM it is acceptable for Ca, Ce, Mg, Zr, La, and REM to contain a trace amount less than the lower limit value of the total amount as an impurity.
- the reason for defining the structure of the base steel plate of the hot-dip galvanized steel sheet according to the embodiment of the present invention is as follows.
- microstructure The microstructure of the base steel plate of the galvanized steel plate according to the embodiment of the present invention will be described. Although the characteristics of the steel material change with the microstructure, when quantifying the microstructure, it is not practical to quantify and define the microstructure over the entire area of the steel material. Therefore, in the present invention, the microstructure of 1/8 to 3/8 thickness centering on 1/4 thickness from the surface of the base steel plate, which shows a typical microstructure of the steel material, is quantified and specified. The central portion of the plate thickness can not be said to be representative of a steel plate because the microstructure changes due to strong solidification segregation.
- the portion near the surface layer of the steel sheet is not a microstructure representative of the steel sheet because the microstructure changes due to a local temperature change or reaction with the open air.
- the microstructure of the base steel plate of the hot-dip galvanized steel sheet according to the embodiment of the present invention is a ferrite phase (1 ⁇ 4 to 3 ⁇ 8 thickness centering on 1 ⁇ 4 thickness from the surface of the base steel plate)
- the volume fraction of ferrite is 40% or more and 97% or less
- the bainite phase hereinafter referred to as bainite
- bainitic ferrite phase hereinafter referred to as bainitic ferrite
- the fresh martensite phase hereinafter referred to as The total of hard structure consisting of one or more of fresh martensite and tempered martensite phase (hereinafter referred to as tempered martensite) is 3% or more in volume fraction
- retained austenite phase hereinafter referred to as retained austenite Is 0% to 8% (including 0%) in volume fraction
- “Ferrite” Ferrite is a structure with excellent ductility. However, since ferrite is soft and has low strength, a hot-dip galvanized steel sheet with a sufficient maximum tensile strength can not be obtained if the volume fraction of ferrite exceeds 97%. For this reason, the volume fraction of ferrite is 97% or less. In order to increase the tensile maximum strength of the hot-dip galvanized steel sheet, the volume fraction of ferrite is preferably 92% or less, and more preferably 85% or less. Furthermore, in order to obtain a hot-dip galvanized steel sheet having a maximum tensile strength exceeding 950 MPa, the volume fraction of ferrite is more preferably 80% or less, and further preferably 70% or less.
- volume fraction of ferrite is set to 50% or more.
- the volume fraction of ferrite is preferably 55% or more, more preferably 60% or more.
- Residual austenite is a structure that enhances the strength-ductility balance of hot-dip galvanized steel sheet.
- retained austenite is transformed to hard martensite with deformation and acts as a fracture origin, so stretch flangeability deteriorates, so the upper limit of the volume fraction of retained austenite is made 8%.
- the volume fraction of retained austenite is preferably small, preferably 5% or less, and more preferably 0% to 3% (including 0%).
- the volume fraction of retained austenite of the hot-dip galvanized steel sheet is preferably as small as possible, and may be 0%.
- Hard tissue In order to increase the maximum tensile strength of hot-dip galvanized steel sheet, it is necessary to make the volume fraction of hard structure consisting of at least one of bainite, bainitic ferrite, fresh martensite and tempered martensite 3% or more in total is there. In order to increase the tensile maximum strength of the hot-dip galvanized steel sheet, the volume fraction of hard structure is preferably 7% or more, and more preferably 15% or more. On the other hand, if the volume fraction of hard texture is excessively increased, the ductility of the hot-dip galvanized steel sheet is degraded, so the volume fraction of hard texture is limited to 60% or less. From this viewpoint, the volume fraction of hard tissue is preferably 55% or less, and more preferably 50% or less.
- Bainitic ferrite and bainite are structures excellent in the balance between strength and formability of hot-dip galvanized steel sheet, and bainitic ferrite and / or bainite having a volume fraction of 60% or less is contained in the steel sheet structure Is preferred. Further, bainitic ferrite and bainite are a microstructure having an intermediate strength between soft ferrite and hard martensite, tempered martensite and retained austenite, and it is more preferable that 5% or more is included from the viewpoint of stretch flangeability. Preferably, 10% or more is more preferable. On the other hand, when the volume fraction of bainitic ferrite and / or bainite exceeds 60%, the yield stress is excessively increased, and there is a concern that the shape freezing property is deteriorated, which is not preferable.
- the tempered martensite is a structure that greatly improves the tensile strength of the hot-dip galvanized steel sheet, and the steel sheet structure may contain 60% or less by volume fraction. From the viewpoint of tensile strength, the volume fraction of tempered martensite is preferably 5% or more. On the other hand, if the volume fraction of tempered martensite contained in the steel sheet structure exceeds 60%, the yield stress is excessively increased, and the shape freezing property may be deteriorated, which is not preferable.
- Fresh martensite greatly improves the tensile strength of the hot-dip galvanized steel sheet, but on the other hand it becomes a starting point of fracture and degrades stretch flangeability, so it is contained in the steel sheet structure in a volume fraction of 30% or less preferable.
- the volume fraction of fresh martensite is more preferably 20% or less, and still more preferably 10% or less.
- the steel sheet structure of the hot-dip galvanized steel sheet according to the embodiment of the present invention may include structures other than the above, such as pearlite and / or coarse cementite.
- structures other than the above such as pearlite and / or coarse cementite.
- ductility deteriorates. From this, the volume fraction of pearlite and / or coarse cementite contained in the steel sheet structure is 8% or less in total.
- the total volume fraction of pearlite and / or coarse cementite is preferably 5% or less in total.
- the steel sheet structure of the hot-dip galvanized steel sheet according to the embodiment of the present invention is a volume integral of retained austenite in the surface layer portion up to a depth of 20 ⁇ m in the steel sheet direction starting from the interface between the plating layer and the base steel sheet (base iron). Rate is limited to 3% or less, and the volume fraction "V1" of the hard texture in the surface layer portion is in the range of 1/8 thickness to 3/8 thickness centering on 1/4 thickness from the steel plate surface. It is in the range of not less than 0.10 times and not more than 0.90 times the volume fraction "V2" of the hard tissue.
- Retained austenite in the vicinity of the interface between the plating layer and the base iron Retained austenite in the vicinity of the interface between the plated layer of the hot-dip galvanized steel sheet and the base steel plate transforms into hard martensite with deformation, and fracture occurs during bending deformation where large strain is applied near the surface of the hot-dip galvanized steel sheet Since it acts as a starting point, it is a structure that contributes to the deterioration of bendability and fatigue resistance. From this point of view, the volume fraction of retained austenite is limited to 0% to 3% (including 0%) in the surface layer portion up to a depth of 20 ⁇ m in the steel plate direction starting from the interface between the plating layer and the base steel plate. There is a need.
- the volume fraction of retained austenite in the surface layer portion is preferably as low as possible, and may be 0%.
- the volume fraction of the hard structure in the surface layer portion starting from the interface between the plating layer and the base iron in the direction of the steel plate 20 ⁇ m is “V1”, 1 centered on 1/4 thickness from the surface of the steel plate Assuming that the total volume fraction in the range of 1/8 thickness to 3/8 thickness is "V2,” set the ratio V1 / V2 to not less than 0.10, and the strength in the surface layer of the galvanized steel sheet is sufficient.
- V1 / V2 is preferably 0.20 or more, more preferably 0.30 or more, and still more preferably 0.40 or more.
- the fraction of the hard structure in the surface layer part starting from the interface between the plating layer and the base iron to a depth of 20 ⁇ m is suppressed to some extent, and the strength in the vicinity of the hot-dip galvanized steel sheet surface is lowered to achieve local ductility. It is also possible to improve bendability by improving. From this viewpoint, in order to obtain good bendability, V1 / V2 is set to 0.90 or less, preferably 0.85 or less, and more preferably 0.80 or less.
- Si in BCC grain boundaries and / or grains of iron may have a fine oxide containing at least one of Mn.
- the volume fraction of each structure contained in the base steel plate of the galvanized steel sheet according to the embodiment of the present invention can be measured, for example, by the method described below.
- the volume fraction of ferrite, bainitic ferrite, bainite, tempered martensite, fresh martensite, pearlite and coarse cementite contained in the steel sheet structure of the galvanized steel sheet of the present invention can be measured by the following method. First, a sample is taken with a plate thickness section parallel to the rolling direction of the steel plate as an observation surface, and the observation surface is polished and nital etched.
- the volume fraction of retained austenite contained in the steel sheet structure of the hot-dip galvanized steel sheet of the present embodiment is evaluated by performing high-resolution crystal orientation analysis by EBSD (Electron Bach-Scattering Diffraction) method using FE-SEM.
- EBSD Electro Bach-Scattering Diffraction
- each measurement point is BCC (body-centered cubic structure) iron or FCC (face-centered cubic structure) iron, and the point determined as FCC iron is regarded as retained austenite, and the area of retained austenite
- the fraction can be measured and used as the volume fraction.
- the area fraction of retained austenite is integrated by measuring the crystal orientation in the area of 10000 ⁇ m 2 or more in total. It can be a rate.
- the hot-dip galvanized steel sheet of the present embodiment has an Fe—Al alloy layer 30 at the interface between the hot-dip galvanized layer 10 and the base steel plate 20. And a decarburized layer 50.
- the finer layer and the decarburized layer are layers formed by the progress of the decarburization reaction under the conditions controlled to a specific atmosphere in a specific temperature range in the annealing step as described later.
- the constituent phase in the finely divided layer and the decarburized layer is substantially a structure mainly composed of the ferrite phase 60 except for the oxide and inclusion particles.
- the volume fraction of the ferrite phase is 70% or more, and the remaining structure is a mixed structure occupied by one or more of the austenite phase, bainite phase, martensite phase, and pearlite phase. It refers to the layer.
- the definition of the finely divided layer is defined as the presence of the finely divided layer when the average particle diameter of the ferrite phase in the outermost part of the base steel plate is 1/2 or less of the average particle diameter of the ferrite phase in the decarburized layer .
- a boundary where the average particle diameter of the ferrite phase in the finely divided layer is more than 1/2 of the average particle diameter of the ferrite phase in the decarburized layer is defined as the boundary between the finely divided layer and the decarburized layer.
- the refinement layer is in direct contact with the Fe-Al alloy layer.
- the average thickness of the finely divided layer is 0.1 ⁇ m to 5.0 ⁇ m
- the average particle diameter of the ferrite phase in the finely divided layer is 0.1 ⁇ m to 3.0 ⁇ m
- one of Si and Mn in the finely divided layer is used.
- Or contains two or more oxides, and the maximum diameter of the oxide is 0.01 ⁇ m to 0.4 ⁇ m.
- the average thickness of the miniaturized layer is 0.1 ⁇ m to 5.0 ⁇ m. If the average thickness of the micronized layer is less than 0.1 ⁇ m, the effect of suppressing the occurrence of cracks and extension can not be obtained, and the effect of improving the plating adhesion can not be obtained. If it exceeds 5.0 ⁇ m, alloying of the plating layer (Zn-Fe alloy formation) proceeds, the Fe content in the plating layer increases, and the plating adhesion decreases.
- the average thickness of the preferred micronized layer is 0.2 ⁇ m to 4.0 ⁇ m, and more preferably 0.3 ⁇ m to 3.0 ⁇ m.
- the difference between the maximum thickness and the minimum thickness of the finely divided layer in the steel sheet width direction is within 2.0 ⁇ m.
- the maximum thickness and the minimum thickness of the above-mentioned refined layer in the width direction of the steel sheet are respectively measured at the positions of 50 mm from both edges and the thickness of the 8 refined layers obtained by equally dividing 7 Indicates the thickness and the minimum thickness.
- the alloying of the plating layer Zn-Fe alloy formation
- the difference between the maximum thickness and the minimum thickness of the finely divided layer in the steel sheet width direction is preferably 1.5 ⁇ m or less, and more preferably 1.0 ⁇ m or less preferable.
- the average particle size of the ferrite phase in the miniaturized layer is 0.1 ⁇ m to 3.0 ⁇ m. If the average grain size of the ferrite phase is less than 0.1 ⁇ m, the effect of suppressing the occurrence of cracks and the extension can not be obtained, and the effect of improving the plating adhesion can not be obtained. If the average grain size of the ferrite phase is more than 3.0 ⁇ m, the improvement effect of the plating adhesion can not be obtained.
- the average particle size of the preferred ferrite phase is 0.1 ⁇ m to 2.0 ⁇ m.
- the oxide of one or more of Si and Mn contained in the refinement layer is, for example, selected from SiO 2 , Mn 2 SiO 4 , MnSiO 3 , Fe 2 SiO 4 , FeSiO 3 and MnO. 1 type or 2 types or more are mentioned.
- the maximum diameter of one or more oxides of Si and Mn contained in the miniaturized layer is 0.01 ⁇ m to 0.4 ⁇ m. As described later, this oxide is formed inside the base steel plate in a specific temperature range at the time of annealing, and this oxide particle suppresses the growth of ferrite phase crystals on the surface of the base steel plate, and the refinement layer Is formed.
- the maximum diameter of the oxide is less than 0.01 ⁇ m, the formation of the micronized layer can not be sufficiently performed, and the plating adhesion is reduced.
- the maximum diameter of the oxide is more than 0.4 ⁇ m, the ferrite phase is coarsened, and the formation of the micronized layer is insufficient, and the oxide itself becomes a starting point of plating peeling, so that the plating adhesion is lowered.
- the preferred range of the maximum diameter of the oxide is 0.05 ⁇ m to 0.2 ⁇ m.
- the average thickness of the finely divided layer and the average particle diameter of the ferrite phase in the finely divided layer are measured by the methods described below. From the hot-dip galvanized steel sheet, a sample is taken with the thickness section parallel to the rolling direction of the base steel sheet as the observation surface. The observation surface of the sample is processed by a CP (Cross section polisher) apparatus, and the backscattered electron image with FE-SEM (Field Emission Scanning Electron Microscopy) is observed at 5000 ⁇ and measured.
- CP Cross section polisher
- the maximum diameter of one or more oxides of Si and Mn contained in the finely divided layer is measured by the method described below. From the hot-dip galvanized steel sheet, a sample is taken with the thickness section parallel to the rolling direction of the base steel sheet as the observation surface. The observation surface of the sample is processed by FIB (Focused Ion Beam) to prepare a thin film sample. After that, the thin film sample is observed at 30,000 ⁇ using FE-TEM (Field Emission Transmission Electron Microscopy). The thin film sample is observed in five fields of view, and the maximum value of the diameter of the oxide measured in the entire field of view is taken as the maximum diameter of the oxide in the thin film sample.
- FIB Fluorused Ion Beam
- the Fe—Al alloy layer is formed at the interface between the plating layer and the steel plate.
- the formation of the Fe—Al alloy layer can suppress the alloying (the formation of a Zn—Fe alloy) of the plating layer and can suppress the decrease in the plating adhesion.
- the occurrence of appearance unevenness due to alloying unevenness can also be suppressed.
- the appearance unevenness due to the alloying unevenness is more likely to occur in the galvanized steel sheet which is not subjected to the alloying treatment than the alloyed galvanized steel sheet which is subjected to the alloying treatment after the hot dip galvanizing treatment.
- the thickness of the Fe-Al alloy layer is 0.1 ⁇ m to 2.0 ⁇ m. If the thickness is less than 0.1 ⁇ m, the plating adhesion and the appearance may be reduced, and if the thickness is more than 2.0 ⁇ m, the plating adhesion may be reduced. Preferably, it is 0.1 ⁇ m to 1.0 ⁇ m.
- the difference between the maximum thickness and the minimum thickness of the Fe—Al alloy layer in the width direction of the steel sheet is within 0.5 ⁇ m.
- the maximum thickness and the minimum thickness of the Fe-Al alloy layer in the width direction of the steel plate are measured at positions of 50 mm from both edges and the thickness of eight Fe-Al alloy layers obtained by equally dividing 7 between them. The maximum thickness and the minimum thickness are shown.
- alloying of the plating layer Zn-Fe alloy formation
- the difference in thickness of the Fe-Al alloy layer in the steel plate width direction is large, it causes alloying unevenness. It may adversely affect the plating adhesion and the uniformity of the plating appearance.
- the difference between the maximum thickness and the minimum thickness of the Fe-Al alloy layer in the steel sheet width direction is preferably 0.4 ⁇ m or less, and 0.3 ⁇ m or less Is more preferred.
- the hot-dip galvanized layer has an Fe content of more than 0% and 3.0% or less, and an Al content of more than 0% and 1.0% or less. Furthermore, the hot-dip galvanized layer is made of Ag, B, Be, Bi, Ca, Cd, Co, Cr, Cs, Cu, Ge, Hf, I, K, La, Li, Mg, Mn, Mo, Na, Nb, Ni , Pb, Rb, Sb, Si, Sn, Sr, Ta, Ti, V, W, Zr, and REM may be contained or mixed.
- the hot-dip galvanized layer may contain columnar crystals composed of a copper phase (FeZn 13 ), but the coating ratio of the copper phase at the entire interface between the plated layer and the base steel plate is less than 20%. It is preferable from the viewpoint of plating adhesion. Furthermore, it is preferable that the adhesion amount of the hot dip galvanized layer in the single side
- Fe content in hot-dip galvanized layer more than 0% and 3.0% or less
- the Fe content in the hot-dip galvanized layer is more than 0% and not more than 3.0%.
- the Fe content of 0% is substantially difficult to produce.
- the plating adhesion decreases. If the Fe content is less than 0.3%, the plating adhesion may be lowered, so from the viewpoint of securing the plating adhesion, the preferable range of the Fe content is 0.3% to 2.5%, more preferably Is 0.5% to 2.0%.
- Al content in hot-dip galvanized layer more than 0% and less than 1.0%
- the Al content in the hot-dip galvanized layer is more than 0% and not more than 1.0%. If the plating bath does not contain Al, or if the content is extremely low, alloying of the plating layer proceeds and the plating adhesion decreases, so the Al content in the plating layer should be 0.1% or more Is preferred.
- the alloying of the plating layer indicates that Fe atoms diffuse into the plating layer to form a Zn—Fe alloy.
- the Al content exceeds 1.0%, the plating adhesion decreases. From the viewpoint of securing the plating adhesion, the preferred range of the Al content is 0.1% to 0.8%, and more preferably 0.2% to 0.5%.
- the adhesion amount of the plating layer to one surface of the base steel plate is preferably 10 g / m 2 or more. From the viewpoint of corrosion resistance, the adhesion amount is more preferably 20 g / m 2 or more, and still more preferably 30 g / m 2 or more.
- the adhesion amount of the plating layer is preferably 100 g / m 2 or less. From the viewpoint of continuous weldability, the adhesion amount is more preferably 93 g / m 2 or less, and still more preferably 85 g / m 2 or less.
- the slab having the above-mentioned chemical components is heated to 1080 ° C. or higher, and hot rolling is performed so that the rolling completion temperature is in the range of 850 ° C. to 980 ° C. It is a process of winding it as a steel plate and then winding it as a coil, and controlling the temperature of the hot rolled steel plate in the cooling process from 300 ° C.
- the cold rolling process of performing cold rolling with a total rolling reduction of 85% or less and the steel sheet after the cold rolling process have an average heating rate between 600 ° C and 750 ° C of 1.0 ° C / and the maximum heating temperature is (Ac1 + 25) ° C. or more and Ac3 ° C. or less and 750 ° C. or more, and then the average cooling rate between 760 ° C. and 700 ° C. is 0.1 ° C./s to 5.0 ° C.
- the plating bath temperature is 440 ° C to 470 ° C
- the steel sheet temperature at the entry into the plating bath is 430 ° C to 480 ° C, in the plating bath
- each manufacturing process will be described in detail.
- a base steel sheet is manufactured.
- the base steel plate is manufactured by casting a slab containing an alloying element according to the characteristics, subjecting it to hot rolling, and cold rolling.
- each manufacturing process will be described in detail.
- a slab to be subjected to hot rolling is cast. It is preferable that the chemical component (composition) of the slab is the above-mentioned component.
- the slab to be subjected to hot rolling one manufactured by a continuous cast slab or a thin slab caster can be used.
- the hot rolling process In the hot rolling step, it is preferable to set the heating temperature of the slab to 1080 ° C. or higher in order to suppress the anisotropy of the crystal orientation caused by casting.
- the heating temperature of the slab is more preferably 1150 ° C. or higher.
- the upper limit of the heating temperature of the slab is not particularly limited. Heating the slab above 1300 ° C. requires a large amount of energy input, leading to a significant increase in manufacturing costs. From this, it is preferable to set the heating temperature of the slab to 1300 ° C. or less.
- the completion temperature of the hot rolling is preferably 850 ° C. or more, and more preferably 870 ° C. or more.
- the completion temperature of hot rolling is set to 980 ° C. or less and to 950 ° C. or less.
- the hot rolled steel sheet after hot rolling is wound as a coil.
- the average cooling rate in the cooling process from hot rolling to winding is preferably 10 ° C./sec or more. This is to promote the transformation at a lower temperature to make the grain size of the hot rolled steel sheet finer and to make the effective crystal grain size of the base steel sheet after cold rolling and annealing fine.
- the winding temperature of the hot rolled steel sheet it is preferable to set the winding temperature of the hot rolled steel sheet to 450 ° C. or more and 650 ° C. or less. This is because the pearlite and / or coarse cementite having a major axis of 1 ⁇ m or more is dispersed in the microstructure of the hot-rolled steel sheet to be generated, and the strain introduced by cold rolling is localized. Thus, by performing reverse transformation to austenite of various crystal orientations in the annealing step, effective crystal grains of the base steel plate after annealing can be refined. If the coiling temperature is less than 450 ° C., pearlite and / or coarse cementite may not be formed, which is not preferable.
- the coiling temperature exceeds 650 ° C.
- pearlite and ferrite are respectively formed in a strip shape long in the rolling direction.
- the effective crystal grains of the base steel plate formed from the ferrite portion after cold rolling and annealing tend to be coarse with the rolling direction elongated, which is not preferable.
- the internal oxide layer may be formed unevenly under the scale layer (the center portion is thicker than the edge portion). This becomes noticeable when the coiling temperature exceeds 650 ° C.
- this internal oxide layer is not removed even in the subsequent steps (pickling and cold rolling) described later, it leads to non-uniform formation of the micronized layer and the Fe-Al alloy layer, which adversely affects the uniformity of plating adhesion and appearance. There is a possibility of Therefore, it is preferable to lower the winding temperature to 650 ° C. or less also from the viewpoint of plating adhesion and uniformity of appearance.
- the decarburizing behavior is controlled by controlling the cooling rate and controlling the steel sheet temperature in a section from finish rolling completion (hot rolling completion) to 300 ° C.
- the temperature control of the base material steel plate is performed within a range from the completion of finish rolling to 300 ° C., at a temperature Ae3 * ° C.
- the temperature range of the temperature control of the base steel plate in the section is the section up to 300 ° C.
- Ae3 * [° C.] can be determined using the following equation.
- C, Si, Mn, Al, Cr, Ni, Cu, and Mo are content [mass%] of each element.
- the decarburizing behavior of the steel plate is controlled separately in a first phase from completion of finish rolling to winding to a coil and a second phase from winding on a coil to reaching a room temperature. This is because decarburization proceeds in the first phase under the atmosphere, while in the second phase, the steel plates adhere to each other by winding them into a coil, and decarburization is performed under the condition that there is almost no infiltration of outside air. The progress of decarburization differs greatly between the two.
- the steel plate temperature is controlled to a range satisfying the following formula (1) in the cooling process from the completion of finish rolling to 300 ° C.
- Formula (1) is a formula related to the progress degree of decarburization behavior, and it shows that decarburization progresses, so that the value of Formula (1) is large.
- t [seconds] is an elapsed time from the completion of finish rolling
- t1 [seconds] is an elapsed time from the completion of finish rolling to the Ae3 * temperature
- t2 [seconds] ] Is an elapsed time from completion of finish rolling to winding into a coil
- t3 [seconds] is an elapsed time from completion of finish rolling to a steel sheet temperature of 300 ° C.
- T (t) [° C.] is a steel plate temperature
- W Si [mass%] and W Mn [mass%] are average contents of respective elements of Si and Mn in the entire steel sheet.
- each term of ⁇ , ⁇ , ⁇ and ⁇ is a constant term and is 8.35 ⁇ 10 8 , 2.20 ⁇ 10 4 , 1.73 ⁇ 10 10 and 2.64 ⁇ 10 4 , respectively.
- the first integral term in the parenthesis is a term related to the progress of decarburization during cooling of the first phase
- the second integral term is the progress of decarburization during cooling of the second phase It is a term related to the degree.
- decarburization proceeds as the base steel plate temperature increases and the dwell time increases.
- oxygen which is an element promoting decarburization, hardly exists in the atmosphere, and decarburization proceeds by oxygen attracted from Si and Mn in the steel from the surface scale layer, so the second integral
- the term includes the effects of the contents of Si and Mn, and the value of Formula (1) increases as the amount of Si and Mn in the steel increases, indicating that decarburization proceeds.
- the value of the above equation (1) is 0.8 or more Cool down to be From this viewpoint, it is preferable to perform cooling so that the value of the above formula (1) is 1.0 or more, and more preferably 1.3 or more.
- the steel sheet surface layer is decarburized excessively, V1 / V2 becomes less than 0.30, and the fatigue resistance of the steel plate is significantly degraded. Cooling is performed so that the value of (1) becomes 20.0 or less. From this viewpoint, it is preferable to perform cooling so that the value of the above formula (1) is 15.0 or less, and it is more preferable to set it to 10.0 or less.
- the hot-rolled steel plate manufactured in this way is pickled. Since pickling removes oxides on the surface of a hot rolled steel sheet, it is important for improving the plating property of the base steel sheet.
- the pickling may be performed once or in several times.
- the internal oxide layer formed under the scale layer is preferable from the viewpoint of enhancing pickling and removing it as much as possible from the viewpoint of uniform formation of the finely divided layer and the Fe-Al alloy layer and thereby uniform appearance.
- the pickling conditions are not particularly limited. For example, from the viewpoint of pickling efficiency and economy, the use of hydrochloric acid is preferred.
- the concentration of hydrochloric acid is 5% by mass or more as hydrogen chloride
- the pickling temperature is 80 ° C. or more
- the pickling time is 30 seconds or more as a recommended condition.
- Cold rolling process Next, the hot-rolled steel plate after pickling is cold-rolled to obtain a cold-rolled steel plate.
- the total rolling reduction is more preferably 75% or less, and still more preferably 70% or less.
- the lower limit of the total of the rolling reduction in the cold rolling process is not particularly limited. If the sum of the rolling reductions is less than 0.05%, the shape of the base steel plate becomes inhomogeneous, the plating does not adhere uniformly, and the appearance is impaired. Therefore, the content is preferably 0.05% or more, and more preferably 0.10% or more.
- cold rolling is preferably performed in a plurality of passes, the number of passes of cold rolling and the distribution of the rolling reduction to each pass does not matter.
- the total rolling reduction in cold rolling is in the range of more than 10% and less than 20%
- recrystallization does not proceed sufficiently in the subsequent annealing step, and coarse crystals containing a large amount of dislocations and losing malleability Grains may remain near the surface, which may degrade bendability and fatigue resistance.
- it is effective to reduce the sum of the rolling reduction and to minimize the accumulation of dislocations in the crystal grains to leave the malleability of the crystal grains.
- it is effective to increase the total rolling reduction, to allow recrystallization to proceed sufficiently in the annealing step, and to make the machined structure into recrystallized grains with little accumulation of dislocations inside.
- the total rolling reduction in the cold rolling step is preferably 10% or less, and more preferably 5.0% or less.
- the total rolling reduction is preferably 20% or more, and more preferably 30% or more.
- the cold rolled steel sheet is annealed.
- control of the atmosphere in the preheating zone, control of the heating system, and control of the atmosphere in the soaking zone are important in securing the plating adhesion and the appearance uniformity while appropriately and uniformly forming the finely divided layer and the Fe-Al alloy layer. It is.
- Log (P (H 2 O) / P (H 2 )), which is the Log value of the ratio of the water vapor partial pressure P (H 2 O) to the hydrogen partial pressure P (H 2 ), is ⁇ 1.
- the steel sheet is heated while passing to a temperature of 400 ° C to 800 ° C using a preheating burner with an air ratio of 0.7 to 1.0.
- adjusting the ratio of the water vapor partial pressure P (H 2 O) to the hydrogen partial pressure P (H 2 ) makes the Fe-Al alloy phase uniform in the width direction at the interface in the subsequent hot dip galvanization. It affects the precipitation and the surface properties of the steel plate before plating.
- the air ratio is preferably 1.0 or less, more preferably 0.9 or less.
- the air ratio is 0.7 or more, preferably 0.8 or more.
- the temperature of the steel sheet through which the preheating zone passes is less than 400 ° C., it is not possible to form a sufficient refined layer. Therefore, it is preferable to set the temperature of the steel sheet passing through the preheating zone to 400 ° C. or higher, and 600 ° C. or higher.
- the temperature of the steel sheet passing through the preheating zone exceeds 800 ° C., an oxide containing coarse Si and / or Mn is formed on the surface of the steel sheet, and the plating adhesion decreases. Therefore, it is preferable to set the temperature of the steel sheet passing through the preheating zone to 800 ° C. or less, and 750 ° C. or less.
- the heating rate in the preheating zone is slow, internal oxidation proceeds to form coarse oxides inside the steel sheet.
- the heating rate at 600 ° C. to 750 ° C. is important, and in order to avoid excessive decarburization of the surface layer of the steel plate and to suppress the formation of coarse oxides, the average heating rate during this period is 1.0 ° C./sec or more. You need to If the average heating rate during this period is less than 1.0 ° C./sec, coarse oxides are formed in the finely divided layer, and the plating adhesion and powdering properties are reduced.
- the average heating rate at 600 ° C. to 750 ° C. is preferably 50 ° C./sec or less while securing the processing time in the preheating zone. If the average heating rate is 50 ° C./sec or less, a uniform finely-divided layer can be easily obtained, and a plated layer excellent in plating adhesion and appearance uniformity can be obtained.
- the maximum heating temperature in the annealing step is an important factor in order to control the fraction of the microstructure related to the formability of the steel sheet within a predetermined range. If the maximum heating temperature is low, coarse iron-based carbides remain unmelted in the steel and the formability deteriorates. If the maximum heating temperature is less than 750 ° C., coarse iron carbides in the hot-rolled steel sheet do not dissolve sufficiently, and may remain as a product sheet, which may significantly impair the ductility. In order to sufficiently dissolve iron-based carbides and enhance formability, the maximum heating temperature is preferably (Ac 1 point + 25) ° C. or more and 750 ° C. or more, and (Ac 1 point + 50) ° C. or more.
- the maximum heating temperature exceeds Ac3 point, the ferrite fraction in the steel decreases significantly, so the maximum heating temperature is set to Ac3 point or less. Further, from the viewpoint of plating adhesion, it is preferable to lower the maximum heating temperature in order to reduce the amount of oxides on the surface of the base iron. From this viewpoint, the maximum heating temperature is preferably 850 ° C. or less, more preferably 830 ° C. or less.
- the Ac1 point and Ac3 point of the steel plate are the starting point and the completion point of austenite reverse transformation, respectively, specifically, a small piece is cut out from the steel plate after hot rolling and heated to 1200 ° C. at 10 ° C./sec. It is obtained by measuring the volume expansion of
- the maximum heating temperature (750 ° C. or more) in the annealing step is reached in soaking zones.
- the atmosphere in this soaking zone controls Log (P (H 2 O) / P (H 2 )) to -1.7 to -0.2.
- Log (P (H 2 O) / P (H 2 )) is less than ⁇ 1.7, the micronized layer is not formed, and the plating adhesion is lowered.
- Log (P (H 2 O) / P (H 2 )) exceeds -0.2, decarburization proceeds excessively, and the hard phase on the surface of the base steel sheet is significantly reduced, and Coarse oxides are formed and the plating adhesion and powdering properties are reduced.
- the average thickness is 0.1 ⁇ m to 5.0 ⁇ m
- the average particle diameter of the ferrite phase is 0.1 ⁇ m to 3.0 ⁇ m
- the maximum diameter is 0.
- a finely divided layer is formed which contains oxides of Si and / or Mn which are between 01 ⁇ m and 0.4 ⁇ m.
- the predetermined microstructure can be obtained by controlling the temperature of the steel sheet in two stages of First, an average cooling rate between 760 ° C. and 700 ° C. is specified in order to sufficiently promote the formation of ferrite. If the average cooling rate from 760 ° C. to 700 ° C. exceeds 5.0 ° C./sec, the formation of ferrite may not proceed sufficiently, so the average cooling rate is set to 5.0 ° C./sec or less.
- the average cooling rate is preferably 3.5 ° C./second or less, more preferably 2.5 ° C./second or less.
- the average cooling rate from 760 ° C. to 700 ° C. is less than 0.3 ° C./sec, a large amount of pearlite may be generated, so the average cooling rate is 0.3 ° C./sec or more.
- the average cooling rate is preferably 0.5 ° C./sec or more, and more preferably 0.7 ° C./sec or more.
- a cooling rate from 650 ° C. to 500 ° C. is defined to avoid the formation of excessive pearlite and / or coarse cementite. If the average cooling rate from 650 ° C. to 500 ° C. is less than 1.0 ° C./sec, a large amount of pearlite and / or coarse cementite is generated, so the average cooling rate is set to 1.0 ° C./sec or more. Since it is preferable that pearlite and / or coarse cementite not be contained in the steel, the average cooling rate is preferably 2.0 ° C./s or more in order to sufficiently avoid the formation of these, and 3.0 It is more preferable to set it as ° C / sec or more.
- the upper limit of the average cooling rate in the temperature range of 650 ° C. to 500 ° C. is not particularly provided, but in order to obtain an excessively large average cooling rate, a refrigerant that does not interfere with special cooling equipment or plating step is preferable. Absent. From this viewpoint, the average cooling rate in the temperature range is preferably 100 ° C./second or less, and more preferably 70 ° C./second or less.
- the steel plate is allowed to rest for a predetermined time in a predetermined temperature range as martensitic transformation processing after the steel plate temperature reaches 500 ° C. until it reaches the plating bath. I don't care. It is more preferable to set the upper limit of the martensitic transformation processing temperature to a martensitic transformation start temperature Ms point and to set the upper limit to (Ms point-20) ° C.
- the lower limit of the martensitic transformation treatment is preferably 50 ° C, and more preferably 100 ° C.
- the martensitic transformation treatment time is preferably 1 second to 100 seconds, and more preferably 10 seconds to 60 seconds.
- the martensite obtained by the martensitic transformation process changes to tempered martensite by entering a high temperature plating bath in the plating step.
- Ms point [° C.] 541-474C / (1-VF) -15Si-35Mn-17Cr-17Ni + 19Al
- VF represents the volume fraction of ferrite
- C, Si, Mn, Cr, Ni, and Al represent the content [mass%] of each element.
- the steel plate may be kept in a predetermined temperature range for a certain period of time as bainite transformation treatment after the steel plate temperature reaches 500 ° C. and before reaching the plating bath.
- bainite transformation temperature exceeds 500 ° C., the formation of pearlite and / or coarse cementite proceeds, so the bainite transformation temperature is set to 500 ° C. or less.
- the bainite transformation treatment temperature is less than 350 ° C., the transformation does not proceed sufficiently, so the bainite transformation treatment temperature is set to 350 ° C. or more.
- the bainite transformation treatment time is set to 10 seconds or more in order to sufficiently promote transformation, and to 500 seconds or less in order to suppress the formation of pearlite and / or coarse cementite.
- the bainite transformation process and the martensitic transformation process are both performed after the pre-plating cooling step, the bainite transformation process and the martensitic transformation process are performed in order of implementation.
- the plating bath is mainly composed of zinc and has a composition in which the effective Al amount is 0.180% to 0.250%, which is a value obtained by subtracting the total Fe amount from the total Al amount in the plating bath. If the effective Al content in the plating bath is less than 0.180%, the formation of the Fe-Al alloy layer is not sufficient, the penetration of Fe into the plating layer proceeds, and the plating adhesion is impaired. It must be at least%. From this viewpoint, the effective Al amount in the plating bath is preferably 0.185% or more, and more preferably 0.190% or more.
- the effective Al amount in the plating bath exceeds 0.250%, the base steel plate and the Fe—Al alloy layer of the plating layer are excessively formed, and the plating adhesion is impaired.
- the effective Al amount in the plating bath needs to be 0.250% or less, preferably 0.240% or less, and more preferably 0.230% or less.
- the plating bath is Ag, B, Be, Bi, Ca, Cd, Co, Cr, Cs, Cu, Ge, Hf, I, K, La, Li, Mg, Mn, Mo, Na, Nb, Ni, Pb,
- Rb, Sb, Si, Sn, Sr, Ta, Ti, V, Zr, and REM may be mixed, depending on the content of each element, In some cases, the corrosion resistance and processability of the hot dip galvanized layer may be improved.
- the temperature of the plating bath is preferably 440 ° C. to 470 ° C. If the temperature of the plating bath is less than 440 ° C., the viscosity of the plating bath is excessively increased, which makes it difficult to control the thickness of the plating layer, and the appearance of the galvanized steel sheet is impaired. Therefore, the temperature of the plating bath is preferably 440 ° C. or higher, and more preferably 445 ° C. or higher. On the other hand, when the temperature of the plating bath exceeds 470 ° C., a large amount of fumes is generated, which makes it difficult to manufacture safely. Therefore, the temperature of the plating bath is preferably 470 ° C. or less, and more preferably 460 ° C. or less.
- the temperature when the base steel plate enters the plating bath is set to 430 ° C.
- the temperature of the base steel plate it is more preferable to limit the temperature of the base steel plate to the plating bath at 440 ° C. or more and 470 ° C. or less.
- the temperature of the plating bath is preferably stable at a temperature in the range of 440 ° C. to 470 ° C. If the temperature of the plating bath is unstable, the Fe content in the Fe—Al alloy layer and the plating layer becomes nonuniform, resulting in nonuniformity in the appearance and adhesion of the plating layer. In order to stabilize the temperature of the plating bath, it is preferable to substantially match the temperature of the steel plate at the time of entering the plating bath and the temperature of the plating bath.
- the temperature of the steel plate when entering the plating bath within ⁇ 10 ° C of the plating bath temperature, and within ⁇ 5 ° C of the plating bath temperature. More preferable.
- a high pressure gas mainly composed of nitrogen on the steel sheet surface to remove excess zinc in the surface layer. It is then cooled to room temperature. At that time, the diffusion of Fe atoms from the base steel plate to the plating layer hardly progresses, and the plating adhesion is secured by securing the cooling rate of 1 ° C / sec or more until the temperature of 350 ° C at which the formation of ⁇ phase almost stops. It is preferable from the viewpoint of
- cooling may be performed to 250 ° C. or less at an average cooling rate of 1.0 ° C./sec or more in order to obtain a hard structure.
- the average cooling rate is preferably 3.0 ° C./sec or more, more preferably 5.0 ° C./sec or more.
- reheating treatment may be performed to obtain tempered martensite.
- the treatment temperature and treatment time of the reheating treatment may be appropriately set according to the target characteristics. However, if the reheat treatment temperature is less than 250 ° C., a sufficient effect can not be obtained, while if it exceeds 350 ° C., the plating layer may be denatured and the plating adhesion may be deteriorated. It is preferable to set it as 250 degreeC or more and 350 degrees C or less. In addition, since the treatment effect is saturated when the reheat treatment time exceeds 1000 seconds, the treatment time is preferably set to 1000 seconds or less.
- a bainite transformation treatment may be performed in which a retention for 15 seconds to 500 seconds is performed in a temperature range of 250 ° C. to 350 ° C. in order to obtain retained austenite.
- the bainite transformation processing temperature is less than 250 ° C., martensite is formed and retained austenite is not sufficiently obtained. Therefore, the bainite transformation treatment temperature is preferably 250 ° C. or higher, and more preferably 300 ° C. or higher.
- the bainite transformation temperature is preferably 350 ° C.
- the bainite transformation treatment time is 15 seconds or more, the effect of the bainite transformation treatment can be sufficiently obtained.
- the bainite transformation treatment time is more preferably 25 seconds or more.
- a bainite transformation process can be efficiently performed as a bainite transformation process time is 500 second or less.
- the bainite transformation treatment time is more preferably 300 seconds or less.
- reheating treatment may be performed after cooling to 250 ° C. or less.
- the treatment temperature and treatment time of the reheating treatment may be appropriately set according to the target characteristics. However, if the reheat treatment temperature is less than 250 ° C., a sufficient effect can not be obtained. Therefore, the reheat treatment temperature is preferably 250 ° C. or more, and more preferably 280 ° C. or more.
- the reheat treatment temperature is preferably 350 ° C. or less, more preferably 330 ° C. or less.
- the treatment time is preferably set to 1000 seconds or less.
- the plated steel plate is subjected to bending and bending return deformation.
- the bending can be applied using rolls of 50 mm to 800 mm in diameter. If the roll diameter is less than 50 mm, a large amount of strain is introduced to the surface of the base steel plate by bending deformation, so the formability of the steel plate is impaired. Further, if the roll diameter is more than 800 mm, the amount of strain in the surface layer of the base steel plate is small, and the retained austenite is not sufficiently reduced.
- hot-dip galvanized steel sheet according to this embodiment can be manufactured by the manufacturing method described above, the present invention is not limited to the above-described embodiment.
- a film made of phosphorus oxide and / or a composite oxide containing phosphorus may be applied to the surface of the galvanized layer of the hot-dip galvanized steel sheet obtained by the method described above. Absent.
- a film made of a complex oxide containing phosphorus oxide and / or phosphorus can function as a lubricant when processing hot-dip galvanized steel sheet, and protect the galvanized layer formed on the surface of a base steel sheet Can.
- the hot-dip galvanized steel sheet cooled to room temperature may be cold-rolled at a rolling reduction of 3.00% or less for shape correction.
- the manufacturing method of the hot dip galvanized steel sheet concerning embodiment of this invention mentioned above is applied to manufacture of the hot dip galvanized steel sheet which is 0.6 mm or more and less than 5.0 mm in plate thickness of a base material steel plate. Is preferred. If the thickness of the base steel plate is less than 0.6 mm, it may be difficult to keep the shape of the base steel plate flat, which may not be appropriate. In addition, when the thickness of the base steel plate is 5.0 mm or more, control of cooling in the annealing step and the plating step may be difficult.
- the conditions in the present embodiment are an example of conditions adopted to confirm the practicability and effects of the present invention.
- the present invention is not limited to this one example of conditions.
- the present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the scope of the present invention.
- Example 1 A slab having the chemical components (compositions) A to BY shown in Tables 1 to 3 is cast and hot rolled under the hot rolling process conditions (slab heating temperature, rolling completion temperature) shown in Tables 4 to 7
- the steel sheet was cooled under the hot rolling process conditions (average cooling rate from completion of hot rolling to winding, winding temperature, formula (1)) shown in Table 4 to obtain a hot rolled steel sheet.
- the hot rolled steel sheet is subjected to pickling (immersed in 10% hydrochloric acid at 80 ° C., immersion time is shown in Tables 4 to 7), and the cold rolling process conditions (rolling reduction) shown in Tables 4 to 7 Cold rolling was performed to obtain a cold rolled steel sheet.
- heating process conditions air ratio in the preheating zone, Log (P (H 2 O) / P (H 2 ) in the preheating zone atmosphere
- annealing process shown in Tables 8 to 11 of the obtained cold rolled steel sheet Annealing was performed at Log (P (H 2 O) / P (H 2 )) in a soaking atmosphere, an average heating rate in a temperature range of 600 ° C. to 750 ° C., and a maximum heating temperature.
- the conditions shown in Tables 8 to 11 (cooling rate 1 (average cooling rate in a temperature range of 760 ° C. to 700 ° C.), cooling rate 2 (average cooling rate in a temperature range of 650 ° C.
- Cooling treatment was performed under martensitic transformation treatment conditions (treatment temperature, treatment time) and bainite transformation treatment 1 conditions (treatment temperature, treatment time) to obtain a base steel plate for plating treatment.
- it is immersed in a zinc plating bath under the conditions shown in Table 12 to Table 15 (effective Al amount, plating bath temperature, penetration temperature of steel plate), and under the conditions shown in Table 12 to Table 15 (cooling rate 3 (up to 350 ° C.) Cooling rate), cooling rate 4 (average cooling rate in the temperature range of 350 ° C. to 250 ° C.), bainite transformation treatment 2 conditions (treatment temperature, treatment time), reheat treatment conditions (treatment temperature, treatment time) After plating, cooling treatment was applied.
- the adhesion amount of the plating was determined by melting the plating layer using hydrochloric acid with an inhibitor, and comparing the weight before and after melting. At the same time, Fe concentration and Al concentration in the plating layer were measured by quantifying Fe and Al by ICP.
- the tensile test was made from a plated steel sheet, No. 5 test piece described in JIS Z 2201 was performed by the method described in JIS Z 2241, and yield strength YS, maximum tensile strength TS, and total elongation El were determined. The tensile properties were evaluated as good when the tensile maximum strength TS was 550 MPa or more.
- the hole expansion test was performed by the method described in JIS Z 2256. Among the formability, the ductility (total elongation) El and the hole expansibility ⁇ vary with the tensile maximum strength TS, but when the following formula (2) is satisfied, the strength, ductility and hole expansibility become good.
- a No. 5 test piece described in JIS Z 2201 was prepared from a hot-dip galvanized steel sheet, and a 90 ° V bending test was performed using the V block method described in JIS Z 2248.
- the radius at the bottom of the V block was changed from 1.0 mm to 6.0 mm in 0.5 mm steps, and the smallest radius at which no cracking occurred in the test piece was taken as the minimum bending radius r [mm].
- the bendability was evaluated by “r / t” in which the minimum bending radius r was normalized by the plate thickness t [mm], and the case where “r / t” was 2.0 or less was evaluated as good bendability.
- a No. 1 test piece described in JIS Z 2275 was prepared from a hot-dip galvanized steel sheet, and a one-sided plane bending fatigue test was performed in accordance with JIS Z 2273.
- the fatigue limit DL and the fatigue limit ratio DL / TS were evaluated by setting the maximum number of repetitions to 10,000,000 times, and a case where the fatigue limit ratio was 0.30 or more was regarded as a good fatigue resistance.
- the plating adhesion was subjected to a Dupont impact test on a plated steel plate which was given a uniaxial tensile strain of 5%.
- An adhesive tape is attached to the plated steel plate after impact test and then peeled off, and the case where the plating did not peel off is particularly good ( ⁇ ), and the case where the plating peeled off by 5% or more is regarded as defective (x).
- the case of less than 5% was regarded as good (o).
- the Dupont impact test was performed using a shooting die having a tip radius of 1/2 inch and dropping a 3 kg weight from a height of 1 m.
- Spot weldability was evaluated by performing a continuous point test. In the welding conditions in which the diameter of the fusion zone is 5.3 times to 5.7 times the square root of the plate thickness, 1000 spot weldings were continuously performed. Then, the diameter of the melted portion is compared between the first point d 1 and the 1000 point d 1000, and the case where d 1000 / d 1 is 0.90 or more is passed ( ⁇ ), the case less than 0.90 is not acceptable. Passed (x).
- the test piece which cut out the plated steel plate in 150 mm x 70 mm was used for evaluation of corrosion resistance.
- the test piece was subjected to zinc phosphate-based dip-type chemical conversion treatment, then to cationic electrodeposition coating of 20 ⁇ m, and further to an intermediate coating of 35 ⁇ m and an upper coating of 35 ⁇ m, after which the back and end portions were sealed with an insulating tape.
- a CCT in which SST 6 hr ⁇ dry 4 hr ⁇ wet 4 hr ⁇ freeze 4 hr is one cycle was used.
- the evaluation of post-paint corrosion resistance was carried out by cross-cutting the coated surface to the base steel plate with a cutter, and measuring the blister width after the CCT 60 cycle. The case where the blister width was 3.0 mm or less was taken as pass ( ⁇ ), and the case where it was over 3.0 mm was taken as fail ( ⁇ ).
- the chipping property was evaluated using the test piece which cut out the plated steel plate to 70 mm x 150 mm. First, each of the steps of automobile degreasing, formation of a chemical conversion film, and 3-coat coating was performed on a test piece. Next, while the test piece was cooled to ⁇ 20 ° C., 10 pieces of crushed stone (0.3 g to 0.5 g) were vertically irradiated at an air pressure of 2 kgf / cm 2 . Irradiation of crushed stone was repeated five times for each test piece. Thereafter, for each test piece, a total of 50 chipping marks were observed, and the position of the peeling interface was evaluated according to the following criteria. Those with a peeling interface above the plating layer (plating layer-conversion film interface or electrodeposition coating / intermediate coating interface) are accepted ( ⁇ ), and there is even one interface peeling in the plating layer-base iron The thing was rejected (x).
- Powdering property was evaluated using V bending (JIS Z 2248) in order to evaluate the processability of a plating layer.
- the plated steel sheet was cut into 50 ⁇ 90 mm, and a molded body was formed by a 1R-90 ° V-shaped die press to obtain a test body. Tape peeling was performed at the valleys of each test body. Specifically, a cellophane tape having a width of 24 mm was pressed onto the bent portion of the test body and pulled apart, and a portion of 90 mm in length of the cellophane tape was visually judged. Evaluation criteria were as follows. When the peeling of the plating layer was less than 5% with respect to the area of the processed portion, it was accepted ( ⁇ ), and when the peeling of the plating layer was more than 5% with respect to the area of the processed portion, it was rejected ( ⁇ ).
- Appearance uniformity evaluation measures the lightness (L * value) of a total of 8 places which divided the position 50 mm from both edges in the steel plate width direction and 7 between them, and the difference of the maximum value minus the minimum value is less than 5
- the thing was made uniform ((circle)), a thing 5 or more and less than 10 a little non-uniform
- Experimental Example 187 is an example in which the content of C is small, the volume fraction of the hard phase is small, and sufficient strength, ductility, and hole expandability can not be obtained.
- Experimental Example 188 is an example in which the content of C is large and the spot weldability is deteriorated. In addition, the fraction of martensite was large, and the fatigue resistance, ductility, hole expandability and bendability were inferior.
- Experimental Example 189 is an example in which the content of Si is small, a large amount of pearlite and coarse cementite are formed in the annealing step and the plating step, and the formability of the steel sheet is not sufficiently obtained.
- Experimental Example 190 is an example in which the experiment was interrupted because the content of Si was large and the slab was broken during heating in the hot rolling process.
- Experimental Example 191 is an example in which the content of Mn is small, a large amount of pearlite and coarse cementite are formed in the annealing step and the plating step, and the formability of the steel sheet is not sufficiently obtained.
- Experimental Example 192 is an example in which the experiment was interrupted because the content of Mn was large and the slab was broken during heating in the hot rolling process.
- Experimental Example 193 is an example in which the experiment was interrupted because cracking occurred when the slab was rolled in the hot rolling process because the content of P is large.
- Experimental Example 194 is an example in which ductility, hole expansibility, bendability, spot weldability, and fatigue resistance are deteriorated because the content of S is large and a large amount of coarse sulfide is formed.
- Experimental Example 195 is an example in which the experiment was interrupted because the content of Al was large and the slab was broken during transportation in the hot rolling process.
- Experimental Example 196 is an example in which the ductility, the hole expansibility, the bendability, the spot weldability, and the fatigue resistance are deteriorated because the content of N is large and a large amount of coarse nitride is generated.
- Experimental Example 197 is an example in which ductility, hole expansibility, bendability, spot weldability, and fatigue resistance are deteriorated because a large amount of coarse oxide is generated and a large content of O is generated.
- Example 28 131, and 155 in the hot rolling step, the value of the formula (1) is small, the fraction (V1 / V2) of the hard phase in the surface layer is large, and sufficient bendability can not be obtained. It is.
- the value of Formula (1) in Examples 51, 114, and 165, in the hot rolling step, the value of Formula (1) is large, decarburization in the surface layer proceeds excessively, and the fraction (V1 / V2) of the hard phase becomes small, and sufficient resistance This is an example in which fatigue characteristics can not be obtained.
- the difference between the maximum value and the minimum value of the thickness of the refined layer in the steel sheet width direction was 2
- the difference between the maximum value and the minimum value of the thickness of the Fe—Al alloy layer in the width direction of the steel sheet was more than 0.5 ⁇ m. Therefore, the plating appearance was somewhat nonuniform.
- Experimental Example 67 is an example in which, in the annealing step, the maximum heating temperature (TM) is higher than the Ac3 temperature, the volume fraction of the ferrite phase at a 1 ⁇ 4 thickness decreases, and the ductility and bendability deteriorate.
- Experimental Example 183 is an example in which the maximum heating temperature (TM) is lower than (Ac1 + 20) ° C. in the annealing step, coarse iron-based carbides remain unmelted, and the ductility and hole expansibility deteriorate.
- Experimental Example 46 is an example in which the air ratio of the preheating zone is small and the plating adhesion is deteriorated in the heating step of the annealing step.
- Experimental Example 181 is an example in which the plating adhesion is deteriorated because Log (P (H 2 O) / P (H 2 )) in the preheating zone is small and the surface layer is not refined in the heating step of the annealing step.
- the average particle diameter of ferrite on the surface was 3.2 ⁇ m, and the maximum diameter of the oxide inside the steel plate in the range of 0.5 ⁇ m from the surface was less than 0.01 ⁇ m.
- the appearance defect by non-plating also generate
- Example 198 in the heating step of the annealing step, Log (P (H 2 O) / P (H 2 )) in the preheating zone is large, and the finely divided layer in the surface layer becomes excessively thick, and the plating layer is alloyed (
- the plating adhesion deteriorates because the formation of a Zn--Fe alloy excessively progresses and the Fe content in the plating layer increases.
- the difference between the maximum value and the minimum value of the thickness of the Fe—Al alloy layer in the width direction of the steel plate was more than 0.5 ⁇ m, and the plating appearance was uneven.
- Experimental Example 22 is an example in which in the cooling step of the annealing step, the average cooling rate (cooling rate 1) between 760 ° C. and 700 ° C. is small, a large amount of pearlite is generated, and the ductility and hole expansibility deteriorate.
- the average cooling rate (cooling rate 1) between 760 ° C. and 700 ° C. is large, the volume fraction of ferrite phase at 1/4 thickness is small, and sufficient ductility is obtained.
- Experimental Example 137 is an example in which in the cooling step of the annealing step, the average cooling rate (cooling rate 2) between 650 ° C. and 500 ° C. is small, a large amount of pearlite is generated, and the ductility and hole expansibility deteriorate.
- the effective Al concentration in the plating bath is low, and a sufficient thickness of the Fe-Al alloy layer is not formed, the Fe content in the plating layer becomes large, and the plating adhesion and chipping This is an example in which the properties of powder, powdering and appearance of plating can not be obtained.
- the effective Al concentration in the plating bath is extremely low, the Fe-Al alloy layer is not formed, and the Fe content in the plating layer is excessively increased, and sufficient plating adhesion, chipping This is an example in which the properties, powdering properties, and plating appearance uniformity can not be obtained.
- Experimental Example 148 is an example in which the effective Al concentration in the plating bath is high in the plating step, the Al content in the plating layer is excessively increased, and sufficient plating adhesion and spot weldability can not be obtained.
- Experimental Example 180 is an example in which the cooling rate after plating is small in the plating step, the Fe content in the plating layer is excessively increased, and sufficient plating adhesion, chipping property, and powdering property can not be obtained.
- Experimental Examples 8, 17, 31, 81, and 179 are examples in which martensitic transformation treatment is performed in the cooling step of the annealing step, and are high in formability, plating adhesion, weldability, corrosion resistance, and fatigue resistance.
- a hot-dip galvanized steel sheet was obtained.
- Experimental Examples 37, 45, 66, 89, 102, 104, 108, 142, 149, and 162 are examples in which bainite transformation treatment 1 is performed in the cooling step of the annealing step, and the formability, plating adhesion, and weldability are obtained.
- a high strength galvanized steel sheet excellent in corrosion resistance and fatigue resistance was obtained.
- Experimental Example 43 is an example in which bainite transformation treatment 1 was performed in the cooling step of the annealing step.
- Experimental Example 174 is an example in which bainite transformation treatment 1 was performed in the cooling step of the annealing step, but since the treatment time was long, pearlite and coarse cementite were formed, and the ductility and hole expansibility deteriorated.
- Experimental Examples 25, 41, 55, 90, 113, 135, 152, 170, 184 are examples in which the bainite transformation process 2 is applied in the post-plating cooling step, and the formability, plating adhesion, weldability, corrosion resistance and A high strength galvanized steel sheet excellent in fatigue resistance was obtained.
- Experimental Example 163 is an example in which the bainite transformation process 2 is performed in the post-plating cooling step, but is an example in which a large amount of retained austenite is generated and the bendability is impaired because the process temperature is high.
- Experimental Examples 5, 20, 48, 53, 62, 73, 76, 87, 94, 112, 129, and 186 are examples in which reheating treatment is performed in the post-plating cooling step, and the formability, plating adhesion, A high strength galvanized steel sheet excellent in weldability, corrosion resistance and fatigue resistance was obtained.
- Experimental Example 18 is an example in which martensitic transformation treatment and bainite transformation treatment 1 were performed in the cooling step of the annealing step, and high strength molten zinc excellent in formability, plating adhesion, weldability, corrosion resistance and fatigue resistance. A plated steel plate was obtained.
- Experimental Examples 9, 110, 132, 138, 154, and 169 are examples in which bainite transformation treatment 1 is applied in the cooling step of the annealing step, and then bainite transformation treatment 2 is applied in the post-plating cooling step. A high strength galvanized steel sheet excellent in plating adhesion, weldability, corrosion resistance and fatigue resistance was obtained.
- Experimental Examples 24, 34 and 96 are examples in which reheating treatment is performed in the post-plating cooling step after the bainite transformation treatment 1 is performed in the cooling step of the annealing step, and the formability, plating adhesion, and weldability are obtained.
- a high strength galvanized steel sheet excellent in corrosion resistance and fatigue resistance was obtained.
- Experimental Example 11 is an example in which bainite transformation 2 and reheating are applied in the post-plating cooling step, and a high-strength galvanized steel sheet excellent in formability, plating adhesion, weldability, corrosion resistance and fatigue resistance. However, as described later, the plating appearance was somewhat nonuniform.
- Experimental Example 172 is an example in which after bainite transformation treatment 1 is performed in the cooling step of the annealing step, bainite transformation treatment 2 and reheating treatment are performed in the post-plating cooling step. High strength hot-dip galvanized steel sheet excellent in corrosion resistance, corrosion resistance and fatigue resistance was obtained.
- Experimental example 79 is an example in which the diameter of the roll used for processing was small in the bending-bending-back processing step of the processing step, and excessive strain was introduced into the surface layer portion of the steel plate, and therefore the ductility was deteriorated.
- the diameter of the roll used for processing was large in the bending-bending-back processing step of the processing step and sufficient strain was not introduced in the surface layer portion of the steel plate, a large amount of retained austenite exists in the surface portion of the steel plate , Is an example where the bendability is deteriorated.
- the coiling temperature in the hot rolling step is 650 ° C. or more, and the difference between the maximum value and the minimum value of the thickness of the finely divided layer in the steel sheet width direction is more than 2.0 ⁇ m, and Since the difference between the maximum value and the minimum value of the thickness of the Fe—Al alloy layer in the width direction was more than 0.5 ⁇ m, the plating appearance was somewhat nonuniform.
- the coiling temperature in the hot rolling step was 650 ° C. or more in the same manner as described above in Experimental Examples 4 and 12, the thickness of the refined layer in the steel plate width direction was increased by prolonging the pickling time in the pickling step.
- the difference between the maximum value and the minimum value improves within 2.0 ⁇ m, and the difference between the maximum value and the minimum value of the thickness of the Fe-Al alloy layer in the steel sheet width direction improves within 0.5 ⁇ m, and a good plating appearance Uniformity was obtained.
- Example 200 although the coiling temperature was less than 650 ° C., since the pickling time was as short as 15 seconds, the non-uniformly formed internal oxide layer could not be completely removed, and the steel sheet in the width direction
- the difference between the maximum value and the minimum value of the thickness of the refined layer was more than 2.0 ⁇ m, and the difference between the maximum value and the minimum value of the thickness of the Fe-Al alloy layer in the steel sheet width direction was more than 0.5 ⁇ m
- the plating appearance was somewhat nonuniform.
- the present invention is a technology effective for a high-strength galvanized steel sheet excellent in plating appearance uniformity, formability, fatigue resistance characteristics, weldability, corrosion resistance and plating adhesion and a method for producing the same. And according to the embodiment of the present invention, it is excellent in ductility, hole expansibility and bendability, further excellent in plating adhesion after molding, having high fatigue limit, and high with excellent spot weldability and corrosion resistance. It is possible to provide a high strength galvanized steel sheet and a method of manufacturing the same.
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Abstract
Description
また、自動車用鋼板については、一般に屋外で使用されるため、優れた耐食性が要求されるのが通常である。
これらのような問題から、苛酷な曲げ加工などを施して使用される高強度鋼板としては、母材鋼板に対するめっき層の密着性が優れた溶融亜鉛めっき層を備えためっき鋼板が強く望まれている。
前記母材鋼板は、質量%で、
C:0.040%~0.280%、
Si:0.05%~2.00%、
Mn:0.50%~3.50%、
P:0.0001%~0.1000%、
S:0.0001%~0.0100%、
Al:0.001%~1.500%、
N:0.0001%~0.0100%、
O:0.0001%~0.0100%、
Ti:0%~0.150%、
Nb:0%~0.100%、
V:0%~0.300%、
Cr:0%~2.00%、
Ni:0%~2.00%、
Cu:0%~2.00%、
Mo:0%~2.00%、
B:0%~0.0100%、
W:0%~2.00%、および
Ca、Ce、Mg、Zr、La、およびREM:合計で0%~0.0100%
を含み
残部がFeおよび不純物からなる化学成分を有し、
前記母材鋼板の全厚に対して、前記母材鋼板の表面から1/4厚を中心とした1/8厚~3/8厚の範囲において、
フェライト相が体積分率で50%以上97%以下、
ベイナイト相とベイニティックフェライト相とフレッシュマルテンサイト相と焼戻しマルテンサイト相とのうち1種以上からなる硬質組織の合計が体積分率で3%以上、
残留オーステナイト相が体積分率で0%~8%、
パーライト相と粗大セメンタイト相との合計が体積分率で0%~8%であり、
前記溶融亜鉛めっき層と母材鋼板との界面から鋼板方向深さ20μmまでの表層部において、
残留オーステナイトが体積分率で0%~3%であり、
前記表層部における前記硬質組織の体積分率V1と、鋼板表面から1/4厚を中心とした1/8厚~3/8厚の範囲における前記硬質組織の体積分率V2との比であるV1/V2を0.10以上0.90以下の範囲としたミクロ組織を有し、
前記溶融亜鉛めっき層におけるFe含有量が0%超3.0%以下であり、Al含有量が0%超1.0%以下であり、
前記溶融亜鉛めっき層と前記母材鋼板との界面に、平均厚さが0.1μm~2.0μmであり、鋼板幅方向における最大厚さと最小厚さとの差が0.5μm以内であるFe-Al合金層を有し、
前記母材鋼板内に、前記Fe-Al合金層に直接接する微細化層を有し、前記微細化層の平均厚さが0.1μm~5.0μm、前記微細化層内におけるフェライト相の平均粒径が0.1μm~3.0μmであり、前記微細化層中にSiおよびMnの1種または2種以上の酸化物を含有し、前記酸化物の最大径が0.01μm~0.4μmであり、鋼板幅方向における前記微細化層の最大厚さと最小厚さとの差が2.0μm以内であることを特徴とする、溶融亜鉛めっき鋼板。
(2)前記溶融亜鉛めっき層の片面当たりのめっき付着量が10g/m2以上、100g/m2以下であることを特徴とする、(1)に記載の溶融亜鉛めっき鋼板。
(3)前記母材鋼板が、質量%で、さらに、
Ti:0.001%~0.150%、
Nb:0.001%~0.100%、および
V:0.001%~0.300%、
からなる群から選ばれた1種または2種以上を含有することを特徴とする、(1)または(2)に記載の溶融亜鉛めっき鋼板。
(4)前記母材鋼板が、質量%で、さらに、
Cr:0.01%~2.00%、
Ni:0.01%~2.00%、
Cu:0.01%~2.00%、
Mo:0.01%~2.00%、
B:0.0001%~0.0100%、および
W:0.01%~2.00%、
からなる群から選ばれた1種または2種以上を含有することを特徴とする、(1)~(3)のいずれか1つに記載の溶融亜鉛めっき鋼板。
(5)前記母材鋼板が、質量%で、さらに、
Ca、Ce、Mg、Zr、La、およびREMからなる群から選ばれた1種または2種以上を合計で0.0001%~0.0100%含有することを特徴とする、(1)~(4)のいずれか1つに記載の溶融亜鉛めっき鋼板。
なお、母材鋼板の板厚は0.6mm以上、5.0mm未満であることが適切である。母材鋼板の板厚が0.6mm未満であると、母材鋼板の形状を平坦に保つことが困難となり、適当ではない。また、母材鋼板の板厚が5.0mm以上であると、製造過程における冷却の制御が困難となり、所定のミクロ組織が得られずに成形性が劣化することがある。
めっき層は、Fe含有量が0%超3.0%以下であり、Al含有量が0%超1.0%以下である。
Cは、母材鋼板の強度を高めるために含有される。しかしながら、Cの含有量が0.280%を超えると、スポット溶接性が劣化するため、C含有量は0.280%以下とする。なお、スポット溶接性の観点から、Cの含有量は0.250%以下であることが好ましく、0.220%以下であることがより好ましい。一方、Cの含有量が0.040%未満であると、強度が低下し、十分な引張最大強度を確保することが困難となるため、C含有量は0.040%以上とする。なお、強度をより一層高めるためには、Cの含有量は0.055%以上であることが好ましく、0.070%以上であることがより好ましい。
Siは、母材鋼板における鉄系炭化物の生成を抑制し、強度と成形性を高める元素である。しかしながら、Siは鋼材を脆化させる元素でもあり、Siの含有量が2.00%を超えると、鋳造したスラブが割れるなどのトラブルが起こりやすくなる。このため、Siの含有量は2.00%以下とする。さらに、Siは焼鈍工程において母材鋼板の表面に酸化物を形成し、めっきの密着性を著しく損なう。この観点から、Siの含有量は1.500%以下であることが好ましく、1.200%以下であることがより好ましい。一方、Siの含有量が0.05%未満では、溶融亜鉛めっき鋼板のめっき工程において、粗大な鉄系炭化物が多量に生成され、強度および成形性が劣化するため、Siの含有量は0.05%以上とする。なお、鉄系炭化物の生成を抑制する観点から、Siの含有量は0.10%以上であることが好ましく、0.25%以上がより好ましい。
Mnは、母材鋼板の焼入れ性を高めることで強度を高めるために含有されている。しかしながら、Mnの含有量が3.50%を超えると、母材鋼板の板厚中央部に粗大なMn濃化部が生じて、脆化が起こりやすくなり、鋳造したスラブが割れるなどのトラブルが起こりやすくなる。そのため、Mnの含有量は3.50%以下とする。また、Mnの含有量が増大すると溶融亜鉛めっき鋼板のスポット溶接性も劣化する。このことから、Mnの含有量は3.00%以下であることが好ましく、2.80%以下であることがより好ましい。一方、Mnの含有量が0.50%未満であると、焼鈍後の冷却中に軟質な組織が多量に形成されるため、充分に高い引張最大強度を確保することが難しくなる。したがって、Mnの含有量は0.50%以上とする必要がある。溶融亜鉛めっき鋼板の強度をより高めるためには、Mnの含有量は0.80%以上であることが好ましく、1.00%以上であることがより好ましい。
Pは、鋼材を脆化させる元素であり、さらにPの含有量が0.1000%を超えると、鋳造したスラブが割れたり、圧延中にスラブが割れたりするなどのトラブルが起こりやすくなるため、Pの含有量は0.1000%以下とする。また、Pはスポット溶接によって生じる溶融部を脆化させる元素でもあり、充分な溶接継手強度を得るためには、Pの含有量は0.0400%以下とすることが好ましく、0.0200%以下とすることが更に好ましい。一方、Pの含有量を0.0001%未満とすることは、製造コストの大幅な増加を伴うことから、Pの含有量は、0.0001%を下限値とし、0.0010%以上とすることが好ましい。
Sは、Mnと結びついて粗大なMnSを形成し、延性、穴拡げ性(伸びフランジ性)および曲げ性といった成形性を低下させる元素であるため、Sの含有量を0.0100%以下とする。またSは、スポット溶接性を劣化させる元素でもある。このため、Sの含有量は0.0060%以下とすることが好ましく、0.0035%以下とすることがより好ましい。一方、Sの含有量を0.0001%未満とすることは、製造コストの大幅な増加を伴う。このため、Sの含有量は、0.0001%を下限値とし、0.0005%以上とすることが好ましく、0.0010%以上とすることがより好ましい。
Alは、鋼材を脆化させる元素である。Alの含有量が1.500%を超えると、鋳造したスラブが割れるなどのトラブルが起こりやすくなるため、Alの含有量は1.500%以下とする。また、Alの含有量が増えるとスポット溶接性が悪化するため、Alの含有量は1.200%以下とすることがより好ましく、1.000%以下とすることがさらに好ましい。一方、Alの含有量の下限は特に定めずとも本実施形態の効果は発揮される。ところが、Alは原料中に微量に存在する不純物であり、その含有量を0.001%未満とするには製造コストの大幅な増加が伴う。このため、Al含有量は0.001%以上とする。またAlは脱酸材としても有効な元素であるが、脱酸の効果を、より十分に得るためには、Alの含有量は0.010%以上とすることがより好ましい。
Nは、粗大な窒化物を形成し、延性、穴拡げ性(伸びフランジ性)および曲げ性といった成形性を劣化させる元素であることから、その含有量を抑える必要がある。Nの含有量が0.0100%を超えると、成形性の劣化が顕著となることから、N含有量の上限を0.0100%とする。またNの過剰な含有は、溶接時のブローホール発生の原因になることから、含有量は少ない方が良い。これらの観点から、N含有量は0.0070%以下であることが好ましく、0.0050%以下であることがより好ましい。一方、Nの含有量の下限は、特に定めなくても本実施形態の効果は発揮されるが、Nの含有量を0.0001%未満にすることは、製造コストの大幅な増加を招く。このことから、N含有量の下限は0.0001%以上とする。N含有量は0.0003%以上であることが好ましく、0.0005%以上であることがより好ましい。
Oは、酸化物を形成し、溶融亜鉛めっき鋼板の延性、穴拡げ性(伸びフランジ性)および曲げ性といった成形性を劣化させることから、Oの含有量を抑える必要がある。Oの含有量が0.0100%を超えると、成形性の劣化が顕著となることから、O含有量の上限を0.0100%とした。さらにOの含有量は0.0050%以下であることが好ましく、0.0030%以下であることがより好ましい。Oの含有量の下限は、特に定めなくても本実施形態の効果は発揮されるが、Oの含有量を0.0001%未満とすることは、製造コストの大幅な増加を伴うため、0.0001%を下限とする。O含有量は0.0003%以上であることが好ましく、0.0005%以上であることがより好ましい。
Tiは、析出物強化、フェライト結晶粒の成長抑制による細粒強化、および再結晶の抑制を通じた転位強化によって、溶融亜鉛めっき鋼板の強度上昇に寄与する元素である。しかし、Tiの含有量が0.150%を超えると、炭窒化物の析出が多くなって成形性が劣化するため、Tiの含有量は0.150%以下とする。また、成形性の観点から、Tiの含有量は0.080%以下であることが好ましい。一方、Tiの含有量の下限は特に定めなくても本実施形態の効果は発揮されるが、Tiによる強度上昇効果を十分に得るためには、Tiの含有量は0.001%以上であることが好ましい。溶融亜鉛めっき鋼板のより一層の高強度化のためには、Tiの含有量は0.010%以上であることがより好ましい。
Nbは、析出物強化、フェライト結晶粒の成長抑制による細粒強化および再結晶の抑制を通じた転位強化により、溶融亜鉛めっき鋼板の強度上昇に寄与する元素である。しかし、Nbの含有量が0.100%を超えると、炭窒化物の析出が多くなって溶融亜鉛めっき鋼板の成形性が劣化するため、Nbの含有量は0.100%以下とする。成形性の観点から、Nbの含有量は0.060%以下であることが好ましい。一方、Nbの含有量の下限は特に定めなくても本実施形態の効果は発揮されるが、Nbによる強度上昇効果を十分に得るには、Nbの含有量は0.001%以上であることが好ましい。溶融亜鉛めっき鋼板のより一層の高強度化のためには、Nbの含有量は0.005%以上であることがより好ましい。
Vは、析出物強化、フェライト結晶粒の成長抑制による細粒強化および再結晶の抑制を通じた転位強化により、溶融亜鉛めっき鋼板の強度上昇に寄与する元素である。しかし、Vの含有量が0.300%を超えると、炭窒化物の析出が多くなって成形性が劣化する。このため、Vの含有量は0.300%以下とする。Vの含有量は0.200%以下であることが好ましい。一方、Vの含有量の下限は特に定めなくても本実施形態の効果は発揮される。Vによる強度上昇効果を十分に得るためには、Vの含有量は0.001%以上であることが好ましく、0.010%以上であることがさらに好ましい。
Crは、高温での相変態を抑制し、溶融亜鉛めっき鋼板の高強度化に有効な元素であり、Cおよび/又はMnの一部に代えて含有してもよい。しかし、Crの含有量が2.00%を超えると、熱間での加工性が損なわれて生産性が低下することから、Crの含有量は2.00%以下とする。Crの含有量は1.20%以下であることが好ましい。一方、Crの含有量の下限は特に定めなくても本実施形態の効果は発揮されるが、Crによる高強度化の効果を十分に得るためには、Crの含有量は0.01%以上であることが好ましく、0.10%以上であることがさらに好ましい。
Niは、高温での相変態を抑制し、溶融亜鉛めっき鋼板の高強度化に有効な元素であり、Cおよび/又はMnの一部に代えて含有してもよい。しかし、Niの含有量が2.00%を超えると、溶接性が損なわれることから、Niの含有量は2.00%以下とする。Niの含有量は1.20%以下であることが好ましい。一方、Niの含有量の下限は特に定めなくても本実施形態の効果は発揮されるが、Niによる高強度化の効果を十分に得るには、Niの含有量は0.01%以上であることが好ましく、0.10%以上であることがさらに好ましい。
Cuは、微細な粒子として鋼中に存在することにより溶融亜鉛めっき鋼板の強度を高める元素であり、Cおよび/又はMnの一部に代えて含有することができる。しかし、Cuの含有量が2.00%を超えると、溶接性が損なわれることから、Cuの含有量は2.00%以下とする。Cuの含有量は1.20%以下であることが好ましい。一方、Cuの含有量の下限は特に定めなくても本実施形態の効果は発揮されるが、Cuによる溶融亜鉛めっき鋼板高強度化の効果を十分に得るには、Cuの含有量は0.01%以上であることが好ましく、0.10%以上であることがさらに好ましい。
Moは、高温での相変態を抑制し、溶融亜鉛めっき鋼板の高強度化に有効な元素であり、Cおよび/又はMnの一部に代えて含有してもよい。しかし、Moの含有量が2.00%を超えれば、熱間での加工性が損なわれて生産性が低下することから、Moの含有量は2.00%以下とする。Moの含有量は1.20%以下であることが好ましい。一方、Moの含有量の下限は特に定めなくても本実施形態の効果は発揮されるが、Moによる高強度化の効果を十分に得るためには、Moの含有量は0.01%以上であることが好ましく、0.05%以上であることがさらに好ましい。
Bは、高温での相変態を抑制し、溶融亜鉛めっき鋼板の高強度化に有効な元素であり、Cおよび/又はMnの一部に代えて含有してもよい。しかし、Bの含有量が0.0100%を超えると、熱間での加工性が損なわれて生産性が低下することから、Bの含有量は0.0100%以下とする。生産性の観点からは、Bの含有量は0.0050%以下であることが好ましい。一方、Bの含有量の下限は特に定めなくても本実施形態の効果は発揮されるが、Bによる高強度化の効果を十分に得るには、Bの含有量を0.0001%以上とすることが好ましい。さらなる溶融亜鉛めっき鋼板の高強度化のためには、Bの含有量が0.0005%以上であることがより好ましい。
Wは、高温での相変態を抑制し、溶融亜鉛めっき鋼板の高強度化に有効な元素であり、Cおよび/又はMnの一部に代えて含有してもよい。しかし、Wの含有量が2.00%を超えると、熱間での加工性が損なわれて生産性が低下することから、Wの含有量は2.00%以下とする。Wの含有量は1.20%以下であることが好ましい。一方、Wの含有量の下限は、特に定めることなく本実施形態の効果は発揮されるが、Wによる高強度化を十分に得るためには、Wの含有量は0.01%以上であることが好ましく、0.10%以上であることがさらに好ましい。
本発明の実施形態に係る溶融亜鉛めっき鋼板の母材鋼板のミクロ組織について説明する。鋼材の特性はミクロ組織によって変化するが、ミクロ組織を定量化する場合、鋼材の全領域に亘ってミクロ組織を定量化し、規定することは現実的でない。このため、本発明では鋼材の代表的なミクロ組織を示す、母材鋼板の表面から1/4厚を中心とした1/8厚~3/8厚におけるミクロ組織を定量化し、規定する。板厚中央部は、強い凝固偏析によりミクロ組織が変化するため、鋼板を代表するミクロ組織とは言えない。鋼板の表層に近い部位は、局所的な温度変化又は外気との反応によりミクロ組織が変化するため、鋼板を代表するミクロ組織とは言えない。
本発明の実施形態にかかる溶融亜鉛めっき鋼板の母材鋼板におけるミクロ組織は、母材鋼板の表面から1/4厚を中心とした1/8厚~3/8厚の範囲において、フェライト相(以下、フェライトという)が体積分率で40%以上、97%以下であり、ベイナイト相(以下、ベイナイトという)とベイニティックフェライト相(以下、ベイニティックフェライトという)とフレッシュマルテンサイト相(以下、フレッシュマルテンサイトという)と焼戻しマルテンサイト相(以下、焼戻しマルテンサイトという)のうち1種以上からなる硬質組織の合計が体積分率で3%以上であり、残留オーステナイト相(以下、残留オーステナイトという)が体積分率で0%~8%(0%を含む)であり、パーライト相(以下、パーライトという)と粗大セメンタイト相(以下、セメンタイトという)との合計が体積分率で0%~8%(0%を含む)であるものである。
フェライトは優れた延性を有する組織である。しかし、フェライトは軟質であることから低強度であるため、フェライトの体積分率を97%超とすると十分な引張最大強度の溶融亜鉛めっき鋼板を得られない。このため、フェライトの体積分率は97%以下とする。溶融亜鉛めっき鋼板の引張最大強度を高めるため、フェライトの体積分率は92%以下とすることが好ましく、85%以下とすることがより好ましい。さらに、引張最大強度が950MPaを超える溶融亜鉛めっき鋼板を得るには、フェライトの体積分率を80%以下とすることがさらに好ましく、さらには70%以下とすることが好ましい。一方、フェライトの体積分率が50%未満では十分な延性が得られないため、フェライトの体積分率を50%以上とする。フェライトの体積分率を55%以上とすることが好ましく、60%以上であることがさらに好ましい。
残留オーステナイトは溶融亜鉛めっき鋼板の強度-延性バランスを高める組織である。一方、残留オーステナイトは変形に伴って硬質なマルテンサイトに変態し、破壊の起点として働くため、伸びフランジ性が劣化することから、残留オーステナイトの体積分率の上限を8%とする。溶融亜鉛めっき鋼板の成形性の観点から、残留オーステナイトの体積分率は小さいことが好ましく、5%以下とすることが好ましく、0%~3%(0%を含む)とすることが更に好ましい。溶融亜鉛めっき鋼板の残留オーステナイトの体積分率は小さいほど好ましく、0%でも構わない。
溶融亜鉛めっき鋼板の引張最大強度を高めるため、ベイナイトとベイニティックフェライトとフレッシュマルテンサイトと焼戻しマルテンサイトとのうち1種以上からなる硬質組織の体積分率を合計で3%以上とする必要がある。溶融亜鉛めっき鋼板の引張最大強度を高めるため、硬質組織の体積分率は7%以上とすることが好ましく、15%以上とすることがさらに好ましい。一方、硬質組織の体積分率を過度に高めると溶融亜鉛めっき鋼板の延性が劣化することから、硬質組織の体積分率を60%以下に制限する。この観点から、硬質組織の体積分率は55%以下とすることが好ましく、50%以下であることが更に好ましい。
ベイニティックフェライトおよびベイナイトは、溶融亜鉛めっき鋼板の強度と成形性のバランスに優れた組織であり、体積分率で60%以下のベイニティックフェライトおよび/またはベイナイトが鋼板組織に含まれていることが好ましい。また、ベイニティックフェライトおよびベイナイトは、軟質なフェライトと硬質なマルテンサイト、焼戻しマルテンサイトおよび残留オーステナイトの中間の強度を有するミクロ組織であり、伸びフランジ性の観点から5%以上含まれることがより好ましく、10%以上含まれることがさらに好ましい。一方、ベイニティックフェライトおよび/またはベイナイトの体積分率が60%を超えると、降伏応力が過度に高まり、形状凍結性が劣化することが懸念されるため好ましくない。
焼戻しマルテンサイトは、溶融亜鉛めっき鋼板の引張強度を大きく向上させる組織であり、鋼板組織に体積分率で60%以下含まれていてもよい。引張強度の観点から、焼戻しマルテンサイトの体積分率は5%以上とすることが好ましい。一方、鋼板組織に含まれる焼戻しマルテンサイトの体積分率が60%を超えると、降伏応力が過度に高まり、形状凍結性が劣化することが懸念されるため好ましくない。
フレッシュマルテンサイトは、溶融亜鉛めっき鋼板の引張強度を大きく向上させるが、一方で破壊の起点となって伸びフランジ性を劣化させるため、鋼板組織に体積分率で30%以下含まれていることが好ましい。特に穴拡げ性を高めるにはフレッシュマルテンサイトの体積分率を20%以下とすることがより好ましく、10%以下とすることが更に好ましい。
本発明の実施形態にかかる溶融亜鉛めっき鋼板の鋼板組織には、パーライトおよび/または粗大なセメンタイトなど上記以外の組織が含まれていてもよい。しかし、溶融亜鉛鋼板の鋼板組織中にパーライトおよび/または粗大なセメンタイトが多くなると、延性が劣化する。このことから、鋼板組織に含まれるパーライトおよび/または粗大なセメンタイトの体積分率は、合計で8%以下する。なお、パーライトおよび/または粗大なセメンタイトの体積分率は合計で5%以下であることが好ましい。
溶融亜鉛めっき鋼板のめっき層と母材鋼板との界面近傍にある残留オーステナイトは、変形に伴い硬質なマルテンサイトへと変態し、溶融亜鉛めっき鋼板の表面近傍に大きなひずみが加わる曲げ変形に際して破壊の起点として働くことから、曲げ性および耐疲労特性の劣化に寄与する組織である。この観点から、めっき層と母材鋼板との界面を起点とする鋼板方向深さ20μmまでの表層部においては、残留オーステナイトの体積分率を0%~3%(0%を含む)と制限する必要がある。なお、当該表層部における残留オーステナイトの体積分率は低いほど好ましく、0%でも構わない。
溶融亜鉛めっき鋼板のめっき層と母材鋼板(地鉄)との界面近傍にある硬質組織は、溶融亜鉛めっき鋼板の表層部における強度を高め、疲労限強度を大きく向上させ、耐疲労特性の改善に寄与する組織である。この観点から、めっき層と地鉄との界面を起点とする鋼板方向深さ20μmまでの表層部における硬質組織の体積分率を「V1」、鋼板の表面から1/4厚を中心とした1/8厚~3/8厚の範囲における合計体積分率を「V2」とした場合、これらの比であるV1/V2を0.10以上として、溶融亜鉛めっき鋼板の表層部における強度を十分に高める必要がある。なお、耐疲労特性を十分に向上するには、V1/V2は0.20以上であることが好ましく、0.30以上であることがより好ましく、0.40以上であることがさらに好ましい。一方、めっき層と地鉄との界面を起点とする鋼板方向深さ20μmまでの表層部における硬質組織の分率をある程度抑制し、溶融亜鉛めっき鋼板表面近傍の強度を下げて局所的な延性を向上することにより、曲げ性を改善されることも可能である。この観点から、良好な曲げ性を得るため、V1/V2は0.90以下とし、0.85以下とすることが好ましく、0.80以下とすることがより好ましい。
微細化層及び脱炭層は後述するように焼鈍工程において特定の温度域で特定の雰囲気に制御した条件で脱炭反応が進行することで生成する層である。このため、微細化層及び脱炭層内の構成相は酸化物および介在物粒子を除いては、実質的にフェライト相60が主体の組織である。具体的には、フェライト相の体積分率が70%以上であり、残部組織をオーステナイト相、ベイナイト相、マルテンサイト相、パーライト相のうちの1種または2種以上が占める混合組織になっている層のことを指す。
微細化層の定義は、母材鋼板の最表部におけるフェライト相の平均粒径が、脱炭層におけるフェライト相の平均粒径の1/2以下である場合に、微細化層が存在すると定義する。微細化層におけるフェライト相の平均粒径が、脱炭層におけるフェライト相の平均粒径の1/2超となる境界を、微細化層と脱炭層との境界と定義する。
微細化層中に含有するSiおよびMnの1種または2種以上の酸化物の最大径は0.01μm~0.4μmである。この酸化物は、後述するように、焼鈍時に特定の温度域で母材鋼板内部に形成されるもので、この酸化物粒子によって母材鋼板表層のフェライト相結晶の成長が抑制され、微細化層が形成される。酸化物の最大径が0.01μm未満であると微細化層の形成が十分にできず、めっき密着性が低下する。酸化物の最大径が0.4μm超であるとフェライト相が粗大化し、微細化層の形成が不十分であるとともに、その酸化物自体がめっき剥離の起点となるためめっき密着性が低下する。酸化物の最大径の好ましい範囲は0.05μm~0.2μmである。
本発明の実施形態においては、めっき層と鋼板との界面にはFe-Al合金層が形成されている。Fe-Al合金層の形成により、めっき層が合金化(Zn-Fe合金生成)するのを抑制し、めっき密着性低下を抑制することができる。加えて、合金化むらによる外観むらの発生も抑制することができる。合金化むらによる外観むらは、溶融亜鉛めっき処理後に合金化処理を施した合金化溶融亜鉛めっき鋼板よりも、合金化処理をしない溶融亜鉛めっき鋼板の方が生じやすい。Fe-Al合金層の厚みは0.1μm~2.0μmとする。0.1μm未満であるとめっき密着性および外観が低下する場合があり、2.0μm超であるとめっき密着性が低下する場合がある。好ましくは0.1μm~1.0μmである。
本発明の実施形態においては、溶融亜鉛めっき層は、Fe含有量が0%超3.0%以下であり、Al含有量が0%超1.0%以下である。さらに、溶融亜鉛めっき層はAg、B、Be、Bi、Ca、Cd、Co、Cr、Cs、Cu、Ge、Hf、I、K、La、Li、Mg、Mn、Mo、Na、Nb、Ni、Pb、Rb、Sb、Si、Sn、Sr、Ta、Ti、V、W、Zr、REMの1種または2種以上を含有、あるいは混入するものであってもよい。このように、溶融亜鉛めっき層が、上記の元素の1種または2種以上を含有、あるいは混入するものであっても、本発明の効果は損なわれず、その含有量によっては耐食性および加工性が改善される等好ましい場合もある。
また、本実施形態においては、溶融亜鉛めっき層はζ相(FeZn13)からなる柱状晶を含んでもよいが、めっき層と母材鋼板との全界面のζ相の被覆割合は20%未満であることがめっき密着性の観点から好ましい。
さらに、母材鋼板の片面における溶融亜鉛めっき層の付着量は10g/m2以上、100g/m2以下であることが好ましい。
溶融亜鉛めっき層におけるFe含有量は0%超3.0%以下である。Fe含有量0%は実質的に製造困難である。Fe含有量が3.0%を超えるとめっき密着性が低下する。Fe含有量が0.3%未満では、めっき密着性が低下する場合があるため、めっき密着性確保の観点からFe含有量の好ましい範囲は0.3%~2.5%であり、更に好ましくは0.5%~2.0%である。
溶融亜鉛めっき層におけるAl含有量は0%超1.0%以下である。めっき浴中にAlを含まない場合、もしくは極端に含有量が少ない場合はめっき層の合金化が進み、めっき密着性が低下するため、めっき層中のAl含有量は0.1%以上とすることが好ましい。ここでめっき層の合金化とはFe原子がめっき層中に拡散し、Zn-Fe合金が生成することを指す。Al含有量が1.0%を超えるとめっき密着性が低下する。めっき密着性確保の観点からAl含有量の好ましい範囲は0.1%~0.8%であり、更に好ましくは0.2%~0.5%である。
溶融亜鉛めっき層の母材鋼板片面への付着量が少ないと十分な耐食性が得られないおそれがある。このことから、めっき層の母材鋼板片面への付着量は10g/m2以上とすることが好ましい。耐食性の観点から、付着量は20g/m2以上がより好ましく、30g/m2以上がさらに好ましい。一方、めっき層の付着量が多いと、スポット溶接を行った際の電極損耗が激しくなり、連続して溶接を行った際に溶融ナゲット径の減少および溶接継手強度の劣化が起こるおそれがある。このため、めっき層の付着量を100g/m2以下とすることが好ましい。連続溶接性の観点から、付着量は93g/m2以下であることがより好ましく、85g/m2以下であることがさらに好ましい。
次に、本発明の実施形態にかかる溶融亜鉛めっき鋼板を製造する方法について詳細に説明する。
以下、各製造工程について詳細に説明する。
母材鋼板は、特性に応じた合金元素を含有したスラブを鋳造し、熱間圧延を施し、冷間圧延を施すことで製造される。
以下、各製造工程について詳細に説明する。
まず、熱間圧延に供するスラブを鋳造する。スラブの化学成分(組成)は上述の成分であることが好ましい。熱間圧延に供するスラブは、連続鋳造スラブや薄スラブキャスターなどで製造したものを用いることができる。
熱延工程においては、鋳造に起因する結晶方位の異方性を抑制するため、スラブの加熱温度を1080℃以上とすることが好ましい。スラブの加熱温度は、より好ましくは、1150℃以上とする。一方、スラブの加熱温度の上限は、特に定めない。1300℃を超えてスラブを加熱するには、多量のエネルギーを投入する必要があり、製造コストの大幅な増加を招く。このことから、スラブの加熱温度は1300℃以下とすることが好ましい。
また、熱延鋼板を巻き取った後、スケール層の下に内部酸化層が不均一に(エッジ部より中央部の方が厚く)形成される場合がある。巻取り温度が650℃を超えるとそれが顕著になる。この内部酸化層が後述する後工程(酸洗、冷延)でも除去されない場合には、微細化層およびFe-Al合金層の不均一な形成につながり、めっき密着性および外観の均一性に悪影響を及ぼす可能性がある。したがって、めっき密着性および外観の均一性の観点からも巻取り温度は650℃以下に下げることが好ましい。
母材鋼板の温度制御は、仕上げ圧延完了から300℃に至るまでの区間のうち、母材鋼板表面において鉄のBCC相が安定となる温度Ae3*℃以下となる範囲において行う。これは、鉄のBCC相からの脱炭が、高温における安定相であるFCC相からの脱炭に比べて早く進むためである。なお本実施形態においては、母材鋼板温度が300℃よりも低い温度範囲では、酸素の拡散速度が十分に遅く、脱炭の進行速度についても脱炭挙動に影響しないと見なせるため、熱延工程における母材鋼板の温度制御の温度範囲は300℃に至るまでの区間とする。
なお、Ae3*[℃]は次の式を用いて求めることができる。
なお、式(1)における各項について、t[秒]は仕上げ圧延完了からの経過時間であり、t1[秒]は仕上げ圧延完了からAe3*温度に至るまでの経過時間であり、t2[秒]は仕上げ圧延完了からコイルに巻取るまでの経過時間であり、t3[秒]は仕上げ圧延完了から鋼板温度が300℃に至るまでの経過時間である。また、T(t)[℃]は鋼板温度であり、WSi[質量%]およびWMn[質量%]はそれぞれ鋼板全体におけるSi、Mnの各元素の平均含有量である。さらに、α、β、γ、δの各項は定数項であり、それぞれ8.35×108、2.20×104、1.73×1010、2.64×104である。
次に、酸洗後の熱延鋼板に冷間圧延を行って冷延鋼板を得る。
冷間圧延では、圧下率の合計が85%を超えると、鋼板の延性が失われ、冷間圧延中に鋼板が破断する危険性が高まる。このため、圧下率の合計を85%以下とすることが好ましい。この観点から、圧下率の合計は75%以下とすることがより好ましく、70%以下とすることが更に好ましい。冷間圧延工程における圧下率の合計の下限は特に定めない。圧下率の合計が0.05%未満では、母材鋼板の形状が不均質となり、めっきが均一に付着せず、外観が損なわれる。このため、0.05%以上とすることが好ましく、0.10%以上とすることが更に好ましい。なお、冷間圧延は複数のパスで行うことが好ましいが、冷間圧延のパス数および各パスへの圧下率の配分は問わない。
本発明の実施形態においては、冷延鋼板に焼鈍を施す。本発明の実施形態においては、予熱帯と均熱帯とめっき帯とを有する連続焼鈍めっきラインを用いることが好ましい。そして、焼鈍工程を行いながら予熱帯と均熱帯とを通過させ、めっき帯に到着するまでに焼鈍工程を終了し、めっき帯においてめっき工程を行うことが好ましい。
特に、予熱帯における雰囲気、加熱方式の制御、均熱帯における雰囲気の制御が微細化層およびFe-Al合金層を適切で均一に生成させながら、めっき密着性および外観均一性を確保する上で重要である。
予熱帯において、水蒸気分圧P(H2O)と水素分圧P(H2)との比を調整することは、後続の溶融亜鉛めっきにおいて界面にFe-Al合金相を幅方向に均一に析出させること及びめっき前の鋼板の表面性状に影響を及ぼす。
これは、予熱帯においては空気比を調整することで、Si等の強脱酸元素の酸化膜の鋼板表面への生成を抑制する。これと共に、水蒸気分圧P(H2O)と水素分圧P(H2)との比を調整することで、鋼板表面での過剰な脱炭素を抑制する。このことで、後続のめっき工程において、鋼板表面の粒界における過剰なFe-Zn合金反応を抑制して、Fe-Al合金反応が選択的に起きる様にする。Fe-Al合金反応が選択的に起きることで、均一なFe-Al合金層の形成を促し、優れためっき密着性、外観均一化を得ることができる。Log(P(H2O)/P(H2))が-0.2を超えるとFe-Zn合金化が後続のめっき工程で起こり易くなり、めっき中のFe濃度が高くなる。それにより、めっき密着性が低下し、外観むらも生じやすくなる。一方、Log(P(H2O)/P(H2))が-1.7未満であると、鋼板表面に炭素濃度が高い部分が出来、表面に微細化層が形成しないため、めっき密着性が低下する。
「空気比」とは、単位体積の混合ガスに含まれる空気の体積と、単位体積の混合ガスに含まれる燃料ガスを完全燃焼させるために理論上必要となる空気の体積との比であり、下記の式で示される。
空気比=[単位体積の混合ガスに含まれる空気の体積(m3)]/[単位体積の混合ガスに含まれる燃料ガスを完全燃焼させるために理論上必要となる空気の体積(m3)]
また、予熱帯を通板させる鋼板温度が400℃未満だと、十分な微細化層を形成することができない。したがって、予熱帯を通板させる鋼板温度は400℃以上とし、600℃以上とすることが好ましい。一方、予熱帯を通板させる鋼板温度が800℃を超える高温では、粗大なSiおよび/またはMnを含む酸化物が鋼板表面に生成し、めっき密着性が低下する。したがって、予熱帯を通板させる鋼板温度は800℃以下とし、750℃以下とすることが好ましい。
予熱帯における加熱速度が遅いと内部酸化が進行し、鋼板内部に粗大な酸化物が生成する。特に、600℃~750℃における加熱速度は重要であり、鋼板表層部の過度の脱炭を避け、粗大な酸化物の生成を抑制するためにこの間の平均加熱速度を1.0℃/秒以上とする必要がある。この間の平均加熱速度が1.0℃/秒未満の場合、微細化層中に粗大な酸化物が形成し、めっき密着性およびパウダリング性が低下する。鋼板表層部の過度の脱炭、及び粗大な酸化物の生成を避けるため、600℃~750℃間の平均加熱速度は1.5℃/秒以上とすることが好ましく、2.0℃/秒以上とすることがより好ましい。600℃~750℃における平均加熱速度は、予熱帯における処理時間を確保して、50℃/秒以下とすることが好ましい。平均加熱速度が50℃/秒以下であると、均一な微細化層が得られやすく、めっき密着性および外観の均一性に優れためっき層が得られる。
Ms点[℃]=541-474C/(1-VF)-15Si-35Mn-17Cr-17Ni+19Al
なお、製造中にフェライトの体積分率を直接測定することは困難である。このため、本発明においてMs点を決定するにあたっては、連続焼鈍ラインに通板させる前の冷延鋼板の小片を切り出し、その小片を連続焼鈍ラインに通板させた場合と同じ温度履歴で焼鈍して、小片のフェライトの体積の変化を測定し、その結果を用いて算出した数値をフェライトの体積分率VFとしている。
次に、このようにして得られた母材鋼板をめっき浴に浸漬する。
めっき浴は、亜鉛を主体とし、めっき浴中の全Al量から全Fe量を引いた値である有効Al量が0.180%~0.250%である組成を有する。めっき浴中の有効Al量が0.180%を下回ると、Fe-Al合金層の形成が十分ではなく、めっき層中へのFeの侵入が進み、めっき密着性が損なわれるため、0.180%以上とする必要がある。この観点から、めっき浴中の有効Al量は0.185%以上であることが好ましく、0.190%以上であることが更に好ましい。一方、めっき浴中の有効Al量が0.250%を超えると、母材鋼板とめっき層のFe-Al合金層が過度に生成し、めっき密着性が損なわれる。この観点から、めっき浴中の有効Al量は0.250%以下とする必要があり、0.240%以下とすることが好ましく、0.230%以下とすることが更に好ましい。
ベイナイト変態処理時間が15秒以上であると、ベイナイト変態処理を行うことの効果が十分に得られる。ベイナイト変態処理時間は25秒以上であることがより好ましい。ベイナイト変態処理時間が500秒以下であると、ベイナイト変態処理を効率よく行うことができる。ベイナイト変態処理時間は300秒以下であることがより好ましい。
また、再加熱処理時間が1000秒を超えると処理効果が飽和するため、処理時間は1000秒以下とすることが好ましい。
次に、鋼板温度を100℃以下まで冷却した後、母材鋼板表層の残留オーステナイトを減少させるため、めっき鋼板に曲げ-曲げ戻し変形を施す。曲げは直径が50mm~800mmのロールを用いて施すことができる。ロール径が50mm未満では、曲げ変形によって母材鋼板表層に多量のひずみが導入されるため、鋼板の成形性が損なわれる。また、ロール径が800mm超では母材鋼板表層におけるひずみ量が小さく、残留オーステナイトが十分に減少しない。曲げ-曲げ戻し変形は、母材鋼板の表裏各面における残留オーステナイトを減少させるため、表裏各面を曲げ外側とする変形を、それぞれ1回以上施す必要があるため、合計で2回以上の曲げ-曲げ戻し変形を施す必要がある。これによって、母材鋼板の表裏両面における残留オーステナイトを所定の範囲に収めることができる。
リン酸化物および/またはリンを含む複合酸化物からなる皮膜は、溶融亜鉛めっき鋼板を加工する際に潤滑剤として機能させることができ、母材鋼板の表面に形成した亜鉛めっき層を保護することができる。
表1~表3に示すA~BYの化学成分(組成)を有するスラブを鋳造し、表4~表7に示す熱延工程条件(スラブ加熱温度、圧延完了温度)で熱間圧延し、表4~表7に示す熱延工程条件(熱延完了から巻取りまでの平均冷却速度、巻取温度、式(1))で冷却し、熱延鋼板を得た。
その後、熱延鋼板に酸洗(80℃の10%塩酸に浸漬、浸漬時間は表4~表7に示す)を施して、表4~表7に示す冷延工程条件(圧下率)の冷間圧延を施し、冷延鋼板を得た。
次に、表12~表15に示す条件(有効Al量、めっき浴温度、鋼板の侵入温度)で亜鉛めっき浴に浸漬し、表12~表15に示す条件で(冷却速度3(350℃までの平均冷却速度)、冷却速度4(350℃~250℃の温度域での平均冷却速度)、ベイナイト変態処理2の条件(処理温度、処理時間)、再加熱処理条件(処理温度、処理時間))でめっき後冷却処理を施した。次に、表12~表15に示す条件(ロール径、加工回数)で曲げ-曲げ戻し加工を施し、さらに、表12~表15に示す条件(圧下率)で冷間圧延を施し、実験例1~202の溶融亜鉛めっき鋼板を得た(ただし、一部の実験例においては、実験を中断したものもある)。
穴拡げ試験は、JIS Z 2256に記載の方法で行った。成形性のうち、延性(全伸び)Elおよび穴拡げ性λは、引張最大強度TSに伴って変化するが、下記式(2)を満たす場合に強度、延性および穴拡げ性を良好とする。
TS1.5×El×λ0.5 ≧ 2.0×106 ・・・式(2)
実験例188はCの含有量が大きく、スポット溶接性が劣化した例である。また、マルテンサイトの分率が大きくなり、耐疲労特性、延性、穴拡げ性および曲げ性が劣位であった。
実験例190はSiの含有量が大きく、熱延工程において、スラブが加熱中に割れたため、実験を中断した例である。
実験例192はMnの含有量が大きく、熱延工程において、スラブが加熱中に割れたため、実験を中断した例である。
実験例194はSの含有量が大きく、多量の粗大硫化物が生成したため、延性、穴拡げ性、曲げ性、スポット溶接性および耐疲労特性が劣化した例である。
実験例195はAlの含有量が大きく、熱延工程において、スラブが搬送中に割れたため、実験を中断した例である。
実験例197はOの含有量が大きく、多量の粗大酸化物が生成したため、延性、穴拡げ性、曲げ性、スポット溶接性および耐疲労特性が劣化した例である。
実験例51、114、165は、熱間圧延工程において、式(1)の値が大きく、表層における脱炭が過度に進み、硬質相の分率(V1/V2)が小さくなり、十分な耐疲労特性が得られなかった例である。
実験例202は、焼鈍工程において、600℃~750℃の間の温度域での平均加熱速度が大きすぎたことから、鋼板幅方向における微細化層の厚みの最大値と最小値の差が2.0μm超であり、さらに、鋼板幅方向におけるFe-Al合金層の厚みの最大値と最小値の差が0.5μm超であった。そのため、めっき外観がやや不均一であった。
実験例183は、焼鈍工程において、最高加熱温度(TM)が(Ac1+20)℃よりも低く、粗大な鉄系炭化物が溶け残り、延性および穴拡げ性が劣化した例である。
実験例46は、焼鈍工程の加熱工程において、予熱帯の空気比が小さく、めっき密着性が劣化した例である。なお、めっき密着性の劣化により、曲げ変形時にめっき剥離が生じたため、パウダリング性も劣化した。また、不めっきによる外観不良も発生した。
実験例168は、焼鈍工程の加熱工程において、均熱帯におけるLog(P(H2O)/P(H2))が小さく、母材鋼板表層の粒径が微細化せず、めっき密着性が劣化した例である。なお、母材鋼板表面におけるフェライトの平均粒径は3.4μmであり、表面から0.5μmの範囲における鋼板内部の酸化物の最大径は0.01μm未満であった。
実験例75は、焼鈍工程の加熱工程において、均熱帯におけるLog(P(H2O)/P(H2))が特に大きく、表層における脱炭が過度に進行したため、硬質相の分率(V1/V2)が小さくなり、耐疲労特性が劣化した例である。加えて、母材鋼板の表層の微細化層が過度に厚くなり、めっき層の合金化(Zn-Fe合金の生成)が過度に進行し、めっき層中のFe含有量が増加したため、めっき密着性、チッピング性、パウダリング性が劣化した例である。
実験例49は、焼鈍工程の冷却工程において、760℃~700℃間の平均冷却速度(冷却速度1)が大きく、1/4厚におけるフェライト相の体積分率が小さくなり、十分な延性が得られなかった例である。
実験例137は、焼鈍工程の冷却工程において、650℃~500℃間の平均冷却速度(冷却速度2)が小さく、多量のパーライトが生成し、延性および穴拡げ性が劣化した例である。
実験例14は、めっき工程において、めっき浴中の有効Al濃度が極めて低く、Fe-Al合金層が形成されず、且つめっき層中のFe含有量が過度に高まり、十分なめっき密着性、チッピング性、パウダリング性、めっき外観均一性が得られなかった例である。
実験例148は、めっき工程において、めっき浴中の有効Al濃度が高く、めっき層中のAl含有量が過度に高まり、十分なめっき密着性、スポット溶接性が得られなかった例である。
実験例180は、めっき工程において、めっき後冷却速度が小さく、めっき層中のFe含有量が過度に高まり、十分なめっき密着性、チッピング性、パウダリング性が得られなかった例である。
実験例37、45、66、89、102、104、108、142、149、162は、焼鈍工程の冷却工程において、ベイナイト変態処理1を施した例であり、成形性、めっき密着性、溶接性、耐食性および耐疲労特性に優れた高強度溶融亜鉛めっき鋼板が得られた。
実験例43は、焼鈍工程の冷却工程において、ベイナイト変態処理1を施した例であるが、処理温度が高かったため、パーライトおよび粗大セメンタイトが生成し、延性および穴拡げ性が劣化した。
実験例174は、焼鈍工程の冷却工程において、ベイナイト変態処理1を施した例であるが、処理時間が長かったため、パーライトおよび粗大セメンタイトが生成し、延性および穴拡げ性が劣化した。
実験例163は、めっき後冷却工程において、ベイナイト変態処理2を施した例であるが、処理温度が高かったため、多量の残留オーステナイトが生成し、曲げ性が損なわれた例である。
実験例5、20、48、53、62、73、76、87、94、112、129、186は、めっき後冷却工程において、再加熱処理を施した例であり、成形性、めっき密着性、溶接性、耐食性および耐疲労特性に優れた高強度溶融亜鉛めっき鋼板が得られた。
実験例9、110、132、138、154、169は、焼鈍工程の冷却工程において、ベイナイト変態処理1を施した後、めっき後冷却工程において、ベイナイト変態処理2を施した例であり、成形性、めっき密着性、溶接性、耐食性および耐疲労特性に優れた高強度溶融亜鉛めっき鋼板が得られた。
実験例24、34、96は、焼鈍工程の冷却工程において、ベイナイト変態処理1を施した後、めっき後冷却工程において、再加熱処理を施した例であり、成形性、めっき密着性、溶接性、耐食性および耐疲労特性に優れた高強度溶融亜鉛めっき鋼板が得られた。
実験例59は、加工工程の曲げ-曲げ戻し加工工程において、加工に用いたロールの直径が大きく、鋼板表層部に十分にひずみが導入されなかったため、鋼板表層部に多量の残留オーステナイトが存在し、曲げ性が劣化した例である。
一方、実験例4、12は上記同様に、熱延工程における巻取温度が650℃以上であったが、酸洗工程における酸洗時間を長くすることで、鋼板幅方向における微細化層の厚みの最大値と最小値の差が2.0μm以内に好転するとともに、鋼板幅方向におけるFe-Al合金層の厚みの最大値と最小値の差が0.5μm以内に好転し、良好なめっき外観均一性が得られた。
実施例200では、巻取温度が650℃未満であったが、酸洗時間が15秒と短かったため、不均一に生成した内部酸化層を完全に除去することができず、鋼板の幅方向における微細化層の厚さの最大値と最小値の差が2.0μm超となり、さらに、鋼板幅方向におけるFe-Al合金層の厚みの最大値と最小値の差が0.5μm超であったことから、めっき外観がやや不均一であった。
Claims (5)
- 母材鋼板の少なくとも一方の側に溶融亜鉛めっき層を有する溶融亜鉛めっき鋼板であって、
前記母材鋼板は、質量%で、
C:0.040%~0.280%、
Si:0.05%~2.00%、
Mn:0.50%~3.50%、
P:0.0001%~0.1000%、
S:0.0001%~0.0100%、
Al:0.001%~1.500%、
N:0.0001%~0.0100%、
O:0.0001%~0.0100%、
Ti:0%~0.150%、
Nb:0%~0.100%、
V:0%~0.300%、
Cr:0%~2.00%、
Ni:0%~2.00%、
Cu:0%~2.00%、
Mo:0%~2.00%、
B:0%~0.0100%、
W:0%~2.00%、および
Ca、Ce、Mg、Zr、La、およびREM:合計で0%~0.0100%
を含み
残部がFeおよび不純物からなる化学成分を有し、
前記母材鋼板の全厚に対して、前記母材鋼板の表面から1/4厚を中心とした1/8厚~3/8厚の範囲において、
フェライト相が体積分率で50%以上97%以下、
ベイナイト相とベイニティックフェライト相とフレッシュマルテンサイト相と焼戻しマルテンサイト相とのうち1種以上からなる硬質組織の合計が体積分率で3%以上、
残留オーステナイト相が体積分率で0%~8%、
パーライト相と粗大セメンタイト相との合計が体積分率で0%~8%であり、
前記溶融亜鉛めっき層と母材鋼板との界面から鋼板方向深さ20μmまでの表層部において、
残留オーステナイトが体積分率で0~3%であり、
前記表層部における前記硬質組織の体積分率V1と、鋼板表面から1/4厚を中心とした1/8厚~3/8厚の範囲における前記硬質組織の体積分率V2との比であるV1/V2を0.10以上0.90以下の範囲としたミクロ組織を有し、
前記溶融亜鉛めっき層におけるFe含有量が0%超3.0%以下であり、Al含有量が0%超1.0%以下であり、
前記溶融亜鉛めっき層と前記母材鋼板との界面に、平均厚さが0.1μm~2.0μmであり、鋼板幅方向における最大厚さと最小厚さとの差が0.5μm以内であるFe-Al合金層を有し、
前記母材鋼板内に、前記Fe-Al合金層に直接接する微細化層を有し、前記微細化層の平均厚さが0.1μm~5.0μm、前記微細化層内におけるフェライト相の平均粒径が0.1μm~3.0μmであり、前記微細化層中にSiおよびMnの1種または2種以上の酸化物を含有し、前記酸化物の最大径が0.01μm~0.4μmであり、鋼板幅方向における前記微細化層の最大厚さと最小厚さとの差が2.0μm以内であることを特徴とする、溶融亜鉛めっき鋼板。 - 前記溶融亜鉛めっき層の片面当たりのめっき付着量が10g/m2以上、100g/m2以下であることを特徴とする、請求項1に記載の溶融亜鉛めっき鋼板。
- 前記母材鋼板が、質量%で、さらに、
Ti:0.001%~0.150%、
Nb:0.001%~0.100%、および
V:0.001%~0.300%、
からなる群から選ばれた1種または2種以上を含有することを特徴とする、請求項1または2に記載の溶融亜鉛めっき鋼板。 - 前記母材鋼板が、質量%で、さらに、
Cr:0.01%~2.00%、
Ni:0.01%~2.00%、
Cu:0.01%~2.00%、
Mo:0.01%~2.00%、
B:0.0001%~0.0100%、および
W:0.01%~2.00%、
からなる群から選ばれた1種または2種以上を含有することを特徴とする、請求項1~3のいずれか1項に記載の溶融亜鉛めっき鋼板。 - 前記母材鋼板が、質量%で、さらに、
Ca、Ce、Mg、Zr、La、およびREMからなる群から選ばれた1種または2種以上を合計で0.0001%~0.0100%含有することを特徴とする、請求項1~4のいずれか1項に記載の溶融亜鉛めっき鋼板。
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| PCT/JP2017/027656 WO2019026113A1 (ja) | 2017-07-31 | 2017-07-31 | 溶融亜鉛めっき鋼板 |
| US16/635,511 US10953631B2 (en) | 2017-07-31 | 2017-07-31 | Hot-dip galvanized steel sheet |
| JP2017558512A JP6315154B1 (ja) | 2017-07-31 | 2017-07-31 | 溶融亜鉛めっき鋼板 |
| CN201780093473.2A CN110959048B (zh) | 2017-07-31 | 2017-07-31 | 热浸镀锌钢板 |
| BR112020001163-0A BR112020001163A2 (pt) | 2017-07-31 | 2017-07-31 | chapa de aço galvanizada por imersão a quente |
| KR1020207001778A KR102345533B1 (ko) | 2017-07-31 | 2017-07-31 | 용융 아연 도금 강판 |
| EP17920192.6A EP3663425B1 (en) | 2017-07-31 | 2017-07-31 | Hot-dip galvanized steel sheet |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20200156349A1 (en) | 2020-05-21 |
| US10953631B2 (en) | 2021-03-23 |
| JP6315154B1 (ja) | 2018-04-25 |
| CN110959048B (zh) | 2022-01-04 |
| EP3663425A1 (en) | 2020-06-10 |
| CN110959048A (zh) | 2020-04-03 |
| EP3663425A4 (en) | 2020-11-25 |
| JPWO2019026113A1 (ja) | 2019-08-08 |
| KR102345533B1 (ko) | 2021-12-31 |
| EP3663425B1 (en) | 2024-03-06 |
| BR112020001163A2 (pt) | 2020-07-21 |
| KR20200020854A (ko) | 2020-02-26 |
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