WO2022097733A1 - 合金化亜鉛めっき鋼板,電着塗装鋼板,自動車部品,電着塗装鋼板の製造方法,及び合金化亜鉛めっき鋼板の製造方法 - Google Patents
合金化亜鉛めっき鋼板,電着塗装鋼板,自動車部品,電着塗装鋼板の製造方法,及び合金化亜鉛めっき鋼板の製造方法 Download PDFInfo
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- WO2022097733A1 WO2022097733A1 PCT/JP2021/040870 JP2021040870W WO2022097733A1 WO 2022097733 A1 WO2022097733 A1 WO 2022097733A1 JP 2021040870 W JP2021040870 W JP 2021040870W WO 2022097733 A1 WO2022097733 A1 WO 2022097733A1
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- WIPO (PCT)
- Prior art keywords
- steel sheet
- less
- cold
- alloyed
- rolled steel
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- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 68
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K11/00—Resistance welding; Severing by resistance heating
- B23K11/10—Spot welding; Stitch welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K11/00—Resistance welding; Severing by resistance heating
- B23K11/16—Resistance welding; Severing by resistance heating taking account of the properties of the material to be welded
-
- 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
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
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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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- 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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- 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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- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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- Y10T428/12958—Next to Fe-base component
Definitions
- the present invention relates to a method for manufacturing an alloyed galvanized steel sheet, an electrodeposited coated steel sheet, an automobile part, an electrodeposited coated steel sheet having excellent resistance welding crack resistance, and a method for manufacturing an alloyed galvanized steel sheet.
- Patent Document 1 from the surface of the base material to a depth of 5.0 ⁇ m or more, at least a part of the crystal grain boundaries has an internal oxide layer coated with an oxide, and from the surface of the base material.
- a hot-dip galvanized steel sheet having a grain boundary coverage of 60% or more of the oxide in a region up to a depth of 5.0 ⁇ m is disclosed.
- Patent Document 2 the grain boundary oxidation is suppressed by controlling the hot rolling conditions, and further, Fe plating is performed after cold rolling to suppress the grain boundary oxidation during reduction annealing to reduce the grain boundary oxidation depth. By setting it to 0.0 ⁇ m or less, cracking of the welded portion under high current conditions such as scattering (spattering) is suppressed.
- the present inventors have newly found that the resistance welding crack resistance can be improved by forming the Fe-based electroplating layer on the surface of the steel sheet, but on the other hand, after forming the Fe-based electroplating layer, the steel sheet is tempered. It was found that the crystal orientation of the Fe-based electroplating layer and the cold-rolled steel sheet is integrated at a high ratio at the interface between the Fe-based electroplating layer and the cold-rolled steel sheet depending on the baking conditions. In the cold-rolled steel sheet in which the crystal orientations are integrated at a high ratio, the present inventors have found that zinc melted during resistance welding passes through the grain boundaries of the Fe-based electroplating layer and the crystal grains of the cold-rolled steel sheet. It was found that it became easier to invade the world. Furthermore, the present inventors have found that when the hot-dip galvanizing is alloyed, the surface layer of the Fe-based electroplating is consumed by the alloying, and this phenomenon becomes even more remarkable. In Patent Document 1, these phenomena have not been investigated at all.
- LME cracks are broadly classified into “cracks that occur on the surface in contact with electrodes (hereinafter, surface cracks)" and “cracks that occur near the corona bond between steel sheets (hereinafter, internal cracks)”. can do.
- the resistance welding crack resistance characteristic in the present specification refers to a characteristic that particularly prevents internal cracking.
- improvement of surface cracking is an issue, and there is no suggestion regarding internal cracking that may occur within an appropriate current range in which spatter does not occur.
- Fe-based electroplating aims to serve as a protective layer that functions as an effect of suppressing grain boundary oxidation during reduction quenching, and the effect of improving resistance-welded crack resistance by Fe-based electroplating itself has not been investigated at all. ..
- the present invention has resistance resistance in the welded portion even when the Fe-based electroplating layer and the cold-rolled steel sheet are integrated at a high ratio at the interface between the Fe-based electroplating layer and the cold-rolled steel sheet. It is an object of the present invention to provide an alloyed zinc-plated steel sheet having excellent weld cracking characteristics.
- the present inventors have conducted a cold-rolled steel sheet after cold rolling and before the baking process in order to satisfy the resistance-resistant weld cracking characteristics in the welded portion at a high level.
- a pre-welding Fe-based electroplating layer is formed as a pre-welding layer, and the Fe-based electroplating layer in the finally obtained alloyed zinc-plated steel sheet is attached to one side. : It was found that it is important to make it over 20.0 g / m 2 .
- the stress applied to the steel sheet surface during welding is alleviated, and the cold-rolled steel sheet is made of Si.
- the present invention was completed by finding that the Fe-based electroplating layer acts as a solid-dissolved Si-deficient layer to suppress a decrease in toughness due to Si solid-melting and improve resistance welding crack resistance in welds. I let you.
- the present invention has been made based on the above findings. That is, the gist structure of the present invention is as follows.
- a Si-containing cold-rolled steel sheet containing 0.1% by mass or more and 3.0% by mass or less of Si An Fe-based electroplating layer formed on at least one side of the Si-containing cold-rolled steel sheet and having an adhesion amount of more than 20.0 g / m 2 per side. It has an alloyed zinc plating layer formed on the Fe-based electroplating layer. Alloyed zinc in which the crystal orientation of the Fe-based electroplated layer and the Si-containing cold-rolled steel sheet is integrated at an interface between the Fe-based electroplated layer and the Si-containing cold-rolled steel sheet is more than 50%. Plated steel plate.
- the Si-containing cold-rolled steel sheet is, in addition to the Si, by mass%. C: 0.8% or less, Mn: 1.0% or more and 12.0% or less, P: 0.1% or less, S: 0.03% or less, Item 3.
- composition of the components is further increased.
- B 0.005% or less, Ti: 0.2% or less, Cr: 1.0% or less, Cu: 1.0% or less, Ni: 1.0% or less, Mo: 1.0% or less, Nb: 0.20% or less, V: 0.5% or less, Sb: 0.200% or less, Ta: 0.1% or less, W: 0.5% or less, Zr: 0.1% or less, Sn: 0.20% or less, Ca: 0.005% or less,
- the Fe-based electroplating layer is one or more selected from the group consisting of B, C, P, N, O, Ni, Mn, Mo, Zn, W, Pb, Sn, Cr, V and Co.
- the cold-rolled steel sheet is a test alloy in which a test piece cut out to a length of 50 ⁇ 150 mm in the direction perpendicular to the rolling direction and a hot-dip galvanized layer cut out to the same size has an adhesion amount of 50 g / m 2 per side. Stacked with hot-dip galvanized steel sheet to form a plate Next, using a servomotor pressure type single-phase AC (50 Hz) resistance welder, the plate assembly is performed on the plane perpendicular to the line connecting the central axes of the electrode pairs (tip diameter 6 mm) of the resistance welder.
- a servomotor pressure type single-phase AC (50 Hz) resistance welder the plate assembly is performed on the plane perpendicular to the line connecting the central axes of the electrode pairs (tip diameter 6 mm) of the resistance welder.
- the plate assembly was subjected to a pressing force of 3.5 kN, a hold time of 0.16 seconds, and a nugget diameter. Under the conditions of welding current and welding time, resistance welding is performed to form a plate assembly with welded parts.
- the cold-rolled steel sheet is subjected to the resistance welding under the condition that the hold time is 0.24 seconds to obtain the plate assembly with the welded portion, and the cross section of the welded portion is captured by the optical microscope (magnification 200).
- Manufacturing method of electrodeposited coated steel sheet including.
- Fe-based electroplating is applied to a cold-rolled steel sheet containing 0.1% by mass or more and 3.0% by mass or less of Si, and a pre-annealing Fe-based electroplating layer is formed on at least one side of the pre-annealing Fe-based electric sheet.
- the pre-annealed Fe-based electroplated steel sheet was annealed in an atmosphere with a dew point of -30 ° C or lower to obtain an Fe-based electroplated steel sheet.
- the Fe-based electroplated steel sheet was galvanized to obtain a galvanized steel sheet.
- the galvanized steel sheet is further alloyed to obtain an alloyed galvanized steel sheet having an Fe-based electroplating layer having an adhesion amount of more than 20.0 g / m 2 on one side. Manufacturing method.
- the cold-rolled steel sheet is subjected to Fe-based electroplating to obtain a pre-annealed Fe-based electroplated steel sheet in which a pre-annealed Fe-based electroplated layer is formed on at least one side.
- the pre-annealed Fe-based electroplated steel sheet was annealed in an atmosphere with a dew point of -30 ° C or lower to obtain an Fe-based electroplated steel sheet.
- the Fe-based electroplated steel sheet was galvanized to obtain a galvanized steel sheet.
- the galvanized steel sheet is further alloyed to obtain an alloyed galvanized steel sheet having an Fe-based electroplating layer having an adhesion amount of more than 20.0 g / m 2 on one side. Manufacturing method.
- the cold-rolled steel sheet is a test alloy in which a test piece cut out to a length of 50 ⁇ 150 mm in the direction perpendicular to the rolling direction and a hot-dip galvanized layer cut out to the same size has an adhesion amount of 50 g / m 2 per side. Stacked with hot-dip galvanized steel sheet to form a plate Next, using a servomotor pressure type single-phase AC (50 Hz) resistance welder, the plate assembly is performed on the plane perpendicular to the line connecting the central axes of the electrode pairs (tip diameter 6 mm) of the resistance welder.
- a servomotor pressure type single-phase AC (50 Hz) resistance welder the plate assembly is performed on the plane perpendicular to the line connecting the central axes of the electrode pairs (tip diameter 6 mm) of the resistance welder.
- the plate assembly was subjected to a pressing force of 3.5 kN, a hold time of 0.16 seconds, and a nugget diameter. Under the conditions of welding current and welding time, resistance welding is performed to form a plate assembly with welded parts.
- the cold-rolled steel sheet has a length of 0.1 mm or more when the cross section of the welded portion is observed with an optical microscope (magnification 200 times) under the condition that the hold time is 0.24 seconds.
- One or two or more elements selected from the group consisting of B, C, P, N, O, Ni, Mn, Mo, Zn, W, Pb, Sn, Cr, V and Co are subjected to the pre-electroplating Fe.
- the Fe-based electroplating is performed using the Fe-based electroplating bath containing the elements so that the total content of these elements is 10% by mass or less in the based electroplating layer, according to the above [12] to [17].
- the method for manufacturing an alloyed zinc-plated steel plate according to any one of the above items.
- the crystal orientation of the Fe-based electroplated layer and the Si-containing cold-rolled steel sheet is integrated at a high ratio at the interface between the Fe-based electroplated layer and the Si-containing cold-rolled steel sheet. It is possible to provide an alloyed zinc-plated steel sheet having excellent resistance welding crack resistance in a welded portion.
- FIG. 30 is a diagram showing an image in which a boundary line and a determination region are drawn after binarization processing of the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet.
- Invention Example No. It is a figure which shows the observation image of the interface of the Fe-based electroplating layer of 31 and the Si-containing cold-rolled steel sheet.
- FIG. 31 is a diagram showing an image in which a boundary line and a determination region are drawn after binarization processing of the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet.
- (A) is a diagram for explaining the evaluation method of resistance welding crack resistance in the welded part
- (b) the upper figure is the top view of the plate assembly after welding in the same evaluation
- the lower figure is the BB cross section of the upper figure. It is a figure.
- the unit of the content of each element in the component composition of the Si-containing cold-rolled steel sheet and the content of each element in the plating layer component composition is “mass%”, and unless otherwise specified, it is simply “. % ”.
- the numerical range represented by using "-” means a range including the numerical values before and after "-” as the lower limit value and the upper limit value.
- "high strength" of a steel sheet means that the tensile strength TS of the steel sheet measured in accordance with JIS Z 2241 (2011) is 590 MPa or more.
- LME cracks can be broadly classified into “cracks that occur on the surface in contact with the electrode (hereinafter, surface cracks)" and “cracks that occur near the corona bond between the steel plates (hereinafter, internal cracks)". It is known that surface cracking is likely to occur in resistance welding in a high current range where spatter occurs, and surface cracking can be suppressed by setting it within an appropriate current range where spatter does not occur. On the other hand, internal cracking occurs even if the current during resistance welding is within an appropriate range where spatter does not occur. Moreover, while surface cracks are easily found by visual inspection in the manufacturing process, internal cracks are hard to be found by visual inspection.
- internal cracking is a particularly big issue among LME cracking. If resistance welding is performed with the welding electrode at an angle to the steel sheet, residual stress may increase and internal cracks may occur. Since the residual stress is considered to increase as the strength of the steel sheet increases, there is concern about the occurrence of internal cracks as the strength of the steel sheet increases. In the present disclosure, among the resistance welding crack resistance characteristics, the characteristic of preventing this internal crack can be improved.
- FIG. 1 shows an outline of a cross section of the alloyed galvanized steel sheet 1 according to the present embodiment.
- the alloyed zinc-plated steel sheet 1 has a Fe-based electroplating layer 3 and an alloyed zinc-plated layer formed on the Fe-based electroplating layer on at least one side of the Si-containing cold-rolled steel sheet 2.
- Si 0.1% or more and 3.0% or less Si has a great effect of increasing the strength of steel by solid solution (solid solution strengthening ability) without significantly impairing workability, and thus achieves high strength of steel sheet. It is an effective element for. On the other hand, Si is also an element that adversely affects the resistance welding crack resistance in the weld. When Si is added to achieve high strength of the steel sheet, it is necessary to add 0.1% or more. When Si is less than 0.50%, there is no particular problem in the resistance welding crack resistance in the welded portion in the conventional welding with a hold time of about 0.24 seconds.
- the tact time during spot welding in the assembly process of automobile parts becomes an issue from the viewpoint of production cost, and if measures are taken by reducing the hold time, resistance welding crack resistance in the welded part even if the Si amount is less than 0.50%.
- the characteristics may be insufficient.
- Si content exceeds 3.0%, the hot rollability and the cold rollability are greatly deteriorated, which adversely affects the productivity and causes the ductility of the steel sheet itself to be lowered. Therefore, Si is added in the range of 0.1% or more and 3.0% or less.
- the amount of Si is preferably 0.50% or more, more preferably 0.7% or more, and more preferably 0.9% or more, which has a greater effect on the resistance welding crack resistance in the welded portion.
- the amount of Si is preferably 2.5% or less, more preferably 2.0% or less, still more preferably 1.7% or less.
- the Si-containing cold-rolled steel sheet according to the present embodiment requires that Si be contained in the above range, but other components may be allowed as long as the composition range of the ordinary cold-rolled steel sheet. Yes, and there are no particular restrictions. However, when the Si-containing cold-rolled steel sheet of the present embodiment has a high tensile strength (TS) of 590 MPa or more, it is preferable to have the following composition.
- TS tensile strength
- C 0.8% or less (not including 0%) C improves workability by forming martensite or the like as a steel structure.
- the amount of C is preferably 0.8% or less, and more preferably 0.3% or less in order to obtain good weldability.
- the lower limit of C is not particularly limited, but in order to obtain good workability, the amount of C is preferably more than 0%, more preferably 0.03% or more, and containing 0.08% or more. Is even more preferable.
- Mn 1.0% or more and 12.0% or less Mn has the effect of solidifying and strengthening steel to increase its strength, as well as enhancing hardenability and promoting the formation of retained austenite, bainite, and martensite. It is an element. Such an effect is exhibited by adding 1.0% or more of Mn.
- the amount of Mn is preferably 1.0% or more, and preferably 12.0% or less.
- the amount of Mn is more preferably 1.3% or more, further preferably 1.5% or more, and most preferably 1.8% or more. Further, the amount of Mn is more preferably 3.5% or less, and further preferably 3.3% or less.
- P 0.1% or less (not including 0%) By suppressing the content of P, deterioration of weldability can be prevented. Further, it is possible to prevent P from segregating at the grain boundaries and prevent deterioration of ductility, bendability, and toughness. Further, when a large amount of P is added, the ferrite transformation is promoted and the crystal grain size becomes large. Therefore, the amount of P is preferably 0.1% or less.
- the lower limit of P is not particularly limited, and may be more than 0% and 0.001% or more due to restrictions in production technology.
- the amount of S is preferably 0.03% or less, and more preferably 0.02% or less.
- the amount of S is preferably 0.03% or less, and more preferably 0.02% or less.
- N 0.010% or less (not including 0%)
- the N content is preferably 0.010% or less.
- N forms coarse nitrides at high temperatures such as Ti, Nb, and V, and the effect of increasing the strength of the steel sheet by adding Ti, Nb, and V is impaired. Can be prevented.
- the content of N is preferably 0.005% or less, more preferably 0.003% or less, still more preferably 0.002% or less.
- the lower limit of the content of N is not particularly limited, and may be more than 0% and 0.0005% or more due to restrictions in production technology.
- Al 1.0% or less (not including 0%) Since Al is thermodynamically most easily oxidized, it has the effect of oxidizing Si and Mn prior to them, suppressing the oxidation of Si and Mn on the outermost layer of the steel sheet, and promoting the oxidation of Si and Mn inside the steel sheet. This effect is obtained when the amount of Al is 0.01% or more. On the other hand, if the amount of Al exceeds 1.0%, the cost will increase. Therefore, when added, the amount of Al is preferably 1.0% or less. The amount of Al is more preferably 0.1% or less. The lower limit of Al is not particularly limited, and may be more than 0% and may be 0.001% or more.
- composition of the components is further optional, B: 0.005% or less, Ti: 0.2% or less, Cr: 1.0% or less, Cu: 1.0% or less, Ni: 1.0% or less, Mo: 1.0% or less, Nb: 0.20% or less, V: 0.5% or less, Sb: 0.200% or less, Ta: 0.1% or less, W: 0.5% or less, Zr: 0. Contains one or more selected from the group consisting of 1% or less, Sn: 0.20% or less, Ca: 0.005% or less, Mg: 0.005% or less, and REM: 0.005% or less. obtain.
- B 0.005% or less
- B is an element effective for improving the hardenability of steel.
- the amount of B is preferably 0.0003% or more, and more preferably 0.0005% or more.
- the amount of B is preferably 0.005% or less.
- Ti 0.2% or less Ti is effective for strengthening precipitation of steel.
- the lower limit of Ti is not particularly limited, but it is preferably 0.005% or more in order to obtain the effect of strength adjustment.
- the Ti amount is preferably 0.2% or less, preferably 0.05% or less. Is more preferable.
- the amount of Cr is preferably 0.005% or more. By setting the amount of Cr to 0.005% or more, the hardenability can be improved and the balance between strength and ductility can be improved. When added, the amount of Cr is preferably 1.0% or less from the viewpoint of preventing cost increase.
- the amount of Cu is preferably 0.005% or more. By setting the amount of Cu to 0.005% or more, the formation of the residual ⁇ phase can be promoted. Further, when the amount of Cu is added, the amount of Cu is preferably 1.0% or less from the viewpoint of preventing cost increase.
- Ni 1.0% or less
- the amount of Ni is preferably 0.005% or more. By setting the amount of Ni to 0.005% or more, the formation of the residual ⁇ phase can be promoted. When Ni is added, the amount of Ni is preferably 1.0% or less from the viewpoint of preventing cost increase.
- the amount of Mo is preferably 0.005% or more. By setting the Mo amount to 0.005% or more, the effect of strength adjustment can be obtained. Further, when Mo is added, the amount of Mo is preferably 1.0% or less from the viewpoint of preventing cost increase.
- Nb 0.20% or less
- the amount of Nb is preferably 0.20% or less from the viewpoint of preventing cost increase.
- V 0.5% or less
- the amount of V is preferably 0.5% or less from the viewpoint of preventing cost increase.
- Sb 0.200% or less
- Sb can be contained from the viewpoint of suppressing decarburization of the steel sheet surface in a region of several tens of microns caused by nitriding, oxidation, or oxidation of the steel sheet surface.
- Sb suppresses nitriding and oxidation of the surface of the steel sheet, thereby preventing the amount of martensite produced on the surface of the steel sheet from decreasing, and improving the fatigue characteristics and surface quality of the steel sheet.
- the amount of Sb is preferably 0.001% or more.
- the amount of Sb is preferably 0.200% or less.
- Ta 0.1% or less Ta is 0.001% or more to obtain the effect of improving the strength.
- the amount of Ta is preferably 0.1% or less from the viewpoint of preventing cost increase.
- W 0.5% or less W is 0.005% or more, so that the effect of improving the strength can be obtained.
- the amount of W is preferably 0.5% or less from the viewpoint of preventing cost increase.
- Zr 0.1% or less
- the amount of Zr is preferably 0.1% or less from the viewpoint of preventing cost increase.
- Sn 0.20% or less
- Sn is an element that suppresses denitrification, deboronization, etc., and is effective in suppressing the decrease in strength of steel. In order to obtain such an effect, it is preferable that each is 0.002% or more. On the other hand, in order to obtain good impact resistance, the Sn amount is preferably 0.20% or less.
- Ca 0.005% or less Ca can control the morphology of sulfide and improve the ductility and toughness by containing 0.0005% or more. Further, from the viewpoint of obtaining good ductility, the amount of Ca is preferably 0.005% or less.
- Mg 0.005% or less
- the amount of Mg is preferably 0.005% or less from the viewpoint of preventing cost increase.
- REM 0.005% or less
- the amount of REM is preferably 0.005% or less from the viewpoint of obtaining good toughness.
- the balance other than the above components is Fe and unavoidable impurities.
- Fe-based electroplating layer 20.0 g / m 2
- the Fe-based electroplating layer is formed and then annealed.
- annealing After forming the Fe-based electroplating layer, it is possible to suppress the generation of flaws called pickups on the surface of the Fe-based plated steel sheet due to surface oxides such as Si and Mn formed during annealing, but Fe-based electricity.
- the crystal orientation of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet is integrated at a ratio of more than 50%. Therefore, the molten zinc easily invades the grain boundaries of the Si-containing cold-rolled steel sheet via the grain boundaries of the Fe-based electroplating layer.
- an Fe-based electroplating layer having an adhesion amount of more than 20.0 g / m 2 after the alloying treatment is formed.
- the Fe-based electroplating layer functions as a soft layer, which can relieve the stress applied to the surface of the steel plate during welding, and by reducing the residual stress in the resistance welded portion, the resistance weld crack resistance characteristics in the welded portion. (Stress relaxation effect). Further, when the amount of solid solution Si on the surface of the steel sheet is large, it is considered that the toughness of the welded portion is lowered and the resistance welding crack resistance property of the welded portion is deteriorated. On the other hand, when a certain amount or more of Fe-based electroplating layer is provided on the surface of the steel sheet, the Fe-based electroplating layer acts as a solid-dissolved Si-deficient layer, and the amount of Si solid-dissolved in the weld is reduced.
- the decrease in toughness of the welded portion due to melting can be suppressed and the resistance welding crack resistance in the welded portion can be improved (effect of suppressing the decrease in toughness).
- the contribution of the addition of these Fe-based electroplating layers to the resistance welding crack resistance effect of zinc plating in the grain boundary invasion suppression effect, stress relaxation effect, and toughness reduction suppression effect is complicated, but it is not quantitatively clear, but it is compounded. It is considered that it acts to improve the resistance welding crack resistance.
- the adhesion amount of the Fe-based electroplating layer per one side of the alloyed galvanized steel sheet should be more than 20.0 g / m 2 . is required.
- the upper limit of the adhesion amount per one side of the Fe-based electroplating layer is not particularly limited, but from the viewpoint of cost, the adhesion amount per one side of the Fe-based electroplating layer is preferably 60.0 g / m 2 .
- the adhesion amount of the Fe-based electroplating layer is preferably 25.0 g / m 2 or more, more preferably 30.0 g / m 2 or more, and further preferably 35.0 g / m 2 or more.
- the alloyed galvanized steel sheet preferably has Fe-based electroplated layers on both the front and back surfaces of the Si-containing cold-rolled steel sheet.
- the thickness of the Fe-based electroplating layer is measured as follows. A sample having a size of 10 ⁇ 15 mm is taken from an alloyed galvanized steel sheet and embedded in a resin to prepare a cross-section embedded sample. Observe any three places on the same cross section using a scanning electron microscope (SEM) at an acceleration voltage of 15 kV and a magnification of 2000 to 10000 times depending on the thickness of the Fe-based electroplating layer, and 3 fields of view. By multiplying the average value of the thickness of the above by the density of iron, it is converted into the amount of adhesion per one side of the Fe-based electroplating layer.
- SEM scanning electron microscope
- the Fe-based electroplating layer includes Fe-B alloys, Fe-C alloys, Fe-P alloys, Fe-N alloys, Fe-O alloys, Fe-Ni alloys, Fe-Mn alloys, and Fe-. Alloy plating layers such as Mo alloy and Fe-W alloy can be used.
- the component composition of the Fe-based electroplating layer is not particularly limited, but is selected from the group consisting of B, C, P, N, O, Ni, Mn, Mo, Zn, W, Pb, Sn, Cr, V and Co1. Alternatively, it is preferable that a total of 2 or more elements is contained in an amount of 10% by mass or less, and the balance is composed of Fe and unavoidable impurities.
- the C content is preferably 0.08% by mass or less.
- the ratio of the crystal orientation of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet integrated is over 50%.
- the ratio of the crystal orientation of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet exceeds 50%, the molten zinc is Fe-based. This is because it becomes easy to invade the crystal grain boundaries of the Si-containing cold-rolled steel sheet via the crystal grain boundaries of the electroplating layer, and the effect of providing the Fe-based electroplating layer according to the present embodiment becomes remarkable.
- the ratio of the crystal orientation of the Fe-based electroplated layer and the Si-containing cold-rolled steel sheet integrated at the interface between the Fe-based electroplated layer and the Si-containing cold-rolled steel sheet is , 70% or more, 75% or more.
- the upper limit of the ratio of the crystal orientation of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet is not particularly limited and is 100%. You may.
- the Si-containing cold-rolled steel sheet is subjected to Fe-based electroplating and then annealed, and as described later, the Si-containing cold-rolled steel sheet is annealed in an atmosphere of a low dew point.
- the ratio of crystal orientation with rolled steel sheet is high. Therefore, by forming an Fe-based electroplating layer having an adhesion amount of more than 20.0 g / m 2 , molten zinc passes through the grain boundaries of the Fe-based electroplating layer and crystal grains of the Si-containing cold-rolled steel sheet. It can be expected to delay the invasion of the field, and it can be expected that the resistance-resistant weld cracking characteristics in the welded portion will be further improved.
- the ratio at which the crystal orientations of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet are integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet is measured as follows.
- a sample having a size of 10 ⁇ 10 mm is taken from an alloyed galvanized steel sheet. Any part of the sample is processed with a focused ion beam (FIB) device, and the cross section is 45 ° with respect to the T cross section (cross section parallel to the rolling perpendicular direction of the steel plate and perpendicular to the surface of the steel plate).
- FIB focused ion beam
- FIG. 2 shows an outline of the observation sample.
- FIG. 2A is a perspective view of an observation sample.
- FIG. 2B is a cross-sectional view taken along the line AA of the observation sample shown in FIG. 2A.
- SIM scanning ion microscope
- Whether or not the crystal orientations of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet are integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet is determined by image processing.
- a method of evaluating the ratio of the crystal orientations being integrated will be described with reference to FIG.
- a boundary line B is used at the interface between the Fe-based electroplating layer 3 and the Si-containing cold-rolled steel sheet 2 of the above-mentioned SIM image using a scanning electron microscope. To draw.
- an image processed from the SIM image is created separately from the image on which the front boundary line is drawn.
- the crystal grain boundaries are emphasized by the Sobel filter for the imaged SIM image having a width of 1024 x a height of 943 pixels and 8 bits.
- the image in which the grain boundaries are emphasized is smoothed by a Gaussian filter (radius (R): 10 pixels).
- the image after the smoothing process is subjected to a binarization process (threshold value: 17).
- the boundary line B of the image on which the interface is drawn is transferred to the binarized image.
- a determination area having a width of 40 pixels centered on the boundary line B (a region surrounded by L 1 and L 2 in FIG.
- the total length in which the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet (the black-and-white boundary on the binarized image) does not exist in the determination region is calculated. It is regarded as the length of the part where the crystal orientation is integrated.
- the total length of the boundary line in which the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet does not exist in the determination region is calculated as follows. First, the entire judgment area is searched for a place where the judgment area can be divided into a substantially rectangular shape so that only one of black and white is included by the two normals of the boundary line B.
- FIG. 3 (c) shows an enlarged view of the part surrounded by the square in FIG. 3 (b).
- two black and white colors are included by two normals of the boundary line B (l 1 and l 2 , l 3 and l 4 in FIG. 3 (c)).
- the maximum distance between the intersections of the boundary line and the two normals at the location is totaled for the entire judgment area, and the Fe-based electroplating layer and Si-containing cold in the judgment area of the length of the boundary line are added.
- the total length at which the interface with the rolled steel plate exists. By subtracting the length, that is, the length of the portion where the crystal orientations are not integrated from the length of the interface in the observation field, the length of the portion where the crystal orientations are integrated can be obtained.
- FIG. 4 shows Comparative Example No. of Examples described later.
- the SIM image of the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet for No. 30 is shown.
- the image after the SIM image is image-processed and binarized as described above is shown in FIG. Comparative Example No.
- the ratio of the crystal orientations of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet was 97%.
- FIG. 6 the invention example No. of the examples described later is shown.
- the SIM image of the interface of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet with respect to 31 is shown.
- FIG. 7 The image after the SIM image is image-processed and binarized as described above is shown in FIG. 7.
- Invention Example No. In No. 31 the ratio of the crystal orientations of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet was 100%.
- the alloyed zinc plating layer formed on the Fe-based electroplating layer described above will be described.
- the "alloyed zinc-plated layer” means a zinc film formed on the surface of the steel sheet after the alloying treatment. Not limited to the method of forming a zinc film such as plating, spraying, and cold spraying, any zinc film formed on the surface of a steel sheet after alloying treatment is included in the "alloyed zinc plating layer".
- the alloyed zinc-plated layer may contain one or more selected from the group consisting of ⁇ phase, ⁇ 1 phase, ⁇ phase and ⁇ 1 phase.
- the surface of the cold-rolled steel plate after cold rolling and before the quenching process was pre-plated with an Fe-based electroplating layer before annealing before forming the zinc-plated layer, and alloyed after zinc-plating.
- the Fe-based electroplated layer in the alloyed zinc-plated steel plate with an adhesion amount of more than 20.0 g / m 2 per side, the resistance-resistant weld crack resistance in the welded portion of the alloyed zinc-plated steel plate is improved. Can be done.
- the composition of the alloyed zinc-plated layer is not particularly limited, but is composed of, for example, Al, Zn, Fe and unavoidable impurities.
- the Al content in the alloyed zinc-plated layer is not particularly specified, but in one example, the Al content is 0.05% by mass or more and 0.250% by mass or less.
- the Fe content in the alloyed zinc-plated layer is also not particularly limited, but in one example, the Fe content is 7.0% by mass or more and 15.0% by mass or less.
- the amount of adhesion per one side of the alloyed zinc-plated layer is not particularly limited, but may be 25 g / m 2 or more and 80 g / m 2 or less.
- the adhesion amount per one side of the alloyed zinc plating layer is 25 g / m 2 or more, the corrosion resistance can be further improved and the plating adhesion amount can be easily controlled. Further, when the adhesion amount per one side of the alloyed zinc plating layer is 80 g / m 2 or less, the plating adhesion is good.
- a high-strength alloyed galvanized steel sheet having a tensile strength TS of a steel sheet measured in accordance with JIS Z 2241 (2011) of 590 MPa or more.
- the strength of the alloyed galvanized steel sheet is more preferably 800 MPa or more.
- the plate thickness of the alloyed galvanized steel sheet according to the present embodiment is not particularly limited, but is usually 0.5 mm or more and may be 3.2 mm or less.
- a method for manufacturing an alloyed galvanized steel sheet will be described.
- a cold-rolled steel sheet containing 0.1% by mass or more and 3.0% by mass or less of Si is subjected to Fe-based electroplating, and a Fe-based electroplating layer before annealing is applied.
- a pre-rolled Fe-based electroplated steel sheet formed on at least one side.
- the pre-annealed Fe-based electroplated steel sheet was annealed in an atmosphere with a dew point of -30 ° C or lower to obtain an Fe-based electroplated steel sheet.
- the Fe-based electroplated steel sheet was galvanized to obtain a galvanized steel sheet.
- the galvanized steel sheet is further alloyed to obtain an alloyed galvanized steel sheet having an Fe-based electroplating layer having an adhesion amount of more than 20.0 g / m 2 on one side. It can be a manufacturing method of.
- a cold-rolled steel sheet containing 0.1% by mass or more and 3.0% by mass or less of Si is manufactured.
- the cold-rolled steel sheet may contain Si in an amount of 0.50% by mass or more and 3.0% by mass or less.
- the manufacturing method of the cold-rolled steel sheet can follow the usual manufacturing method of the cold-rolled steel sheet.
- a cold-rolled steel sheet is obtained by hot-rolling a steel slab having the above-mentioned composition to obtain a hot-rolled sheet, then pickling the hot-rolled sheet, and then cold-rolling the hot-rolled sheet. Manufactured by making cold-rolled steel sheets.
- the surface of the cold-rolled steel sheet is subjected to Fe-based electroplating treatment to obtain a pre-annealed Fe-based electroplated steel sheet in which a pre-annealed Fe-based electroplated layer is formed on at least one side.
- the Fe-based electroplating method is not particularly limited.
- a sulfuric acid bath, a hydrochloric acid bath, or a mixture of both can be applied as the Fe-based electroplating bath.
- the pre-annealed Fe-based electroplated steel sheet means that the Fe-based electroplated layer has not undergone the annealing process, and does not exclude the pre-annealed mode of the cold-rolled steel sheet before the Fe-based electroplating process. ..
- the amount of adhesion of the Fe-based electroplating layer before annealing is adjusted so that the amount of adhesion of the Fe-based electroplating layer on one side of the alloyed galvanized steel sheet obtained after the alloying treatment exceeds 20.0 g / m 2 .
- the amount of adhesion of the Fe-based electroplating layer before annealing can be adjusted by the energization time or the like.
- C. W. Fe0 (g / m 2 ) preferably satisfies the following equation (1).
- C.I. W. Zn Target value of adhesion amount per one side of alloyed zinc plating layer (g / m 2 )
- C.I. W. Zn Target value of adhesion amount per one side of alloyed zinc plating layer (g / m 2 )
- Mass% Fe Target value (mass%) of Fe content in the alloyed zinc-plated layer.
- a pre-quenched Fe-based electroplated layer having an amount exceeding the target value (g / m 2 ) + 20.0 (g / m 2 ) of the amount of Fe contained in the alloyed zinc-plated layer of the alloyed zinc-plated steel plate is formed.
- an Fe-based electrogalvanized layer of more than 20.0 g / m 2 can be obtained.
- the target value of the Fe content in the Zn and the alloyed zinc-plated layer is determined by the specifications predetermined for each application. Further, the amount of adhesion per surface of the Fe-based electroplating layer here can be calculated by the above-mentioned cross-sectional observation.
- the Fe ion content in the Fe-based electroplating bath before the start of energization is preferably 0.5 mol / L or more as Fe 2+ .
- the Fe ion content in the Fe-based electroplating bath before the start of energization is preferably 2.0 mol / L or less.
- Fe ions and at least selected from the group consisting of B, C, P, N, O, Ni, Mn, Mo, Zn, W, Pb, Sn, Cr, V and Co are selected. It can contain a kind of element.
- the total content of these elements in the Fe-based electroplating bath is preferably such that the total content of these elements in the pre-annealed Fe-based electroplating layer is 10% by mass or less.
- the metal element may be contained as a metal ion, and the non-metal element may be contained as a part of boric acid, phosphoric acid, nitric acid, organic acid and the like.
- the iron sulfate plating solution may contain a conductivity auxiliary agent such as sodium sulfate and potassium sulfate, a chelating agent, and a pH buffering agent.
- the other conditions of the Fe-based electroplating bath are not particularly limited.
- the temperature of the Fe-based electroplating solution is preferably 30 ° C. or higher, and preferably 85 ° C. or lower, in consideration of constant temperature retention.
- the pH of the Fe-based electroplating bath is not particularly specified, but it is preferably 1.0 or more from the viewpoint of preventing a decrease in current efficiency due to hydrogen generation, and considering the electric conductivity of the Fe-based electroplating bath, 3. 0 or less is preferable.
- the current density is preferably 10 A / dm 2 or more from the viewpoint of productivity, and is preferably 150 A / dm 2 or less from the viewpoint of facilitating the control of the adhesion amount of the Fe-based electroplating layer.
- the plate passing speed is preferably 5 mpm or more from the viewpoint of productivity, and is preferably 150 mmp or less from the viewpoint of stably controlling the adhesion amount.
- degreasing treatment and water washing for cleaning the surface of the cold-rolled steel sheet, and pickling treatment and water washing for activating the surface of the cold-rolled steel sheet are performed. Can be done. Following these pretreatments, Fe-based electroplating treatment is carried out.
- the method of degreasing treatment and washing with water is not particularly limited, and a usual method can be used.
- pickling treatment various acids such as sulfuric acid, hydrochloric acid, nitric acid, and mixtures thereof can be used. Of these, sulfuric acid, hydrochloric acid, or a mixture thereof is preferable.
- the acid concentration is not particularly specified, but is preferably about 1 to 20 mass% in consideration of the ability to remove the oxide film and the prevention of rough skin (surface defects) due to peracid washing.
- the pickling treatment liquid may contain a defoaming agent, a pickling accelerator, a pickling inhibitor and the like.
- the Fe-based electroplated steel sheet before annealing was subjected to a reducing atmosphere having a dew point of -30 ° C or lower and a hydrogen concentration of 1.0% by volume or more and 30.0% by volume or less.
- An Fe-based electroplated steel sheet is obtained by performing an annealing step of cooling after holding for 30 seconds or more and 600 seconds or less in a temperature range of 650 ° C. or higher and 900 ° C. or lower.
- the annealing step is performed to increase the strength of the steel sheet by removing the strain of the pre-annealed Fe-based electroplated steel sheet caused by the rolling process and recrystallizing the structure.
- the dew point of the annealing atmosphere in the annealing step is a low dew point of -30 ° C or less, which is a condition that does not require additional equipment such as humidification equipment.
- the dew point of ⁇ 30 ° C. or lower is preferably controlled in the temperature range of 650 ° C. or higher and 900 ° C. or lower.
- the present inventors have independently studied the ratio of the crystal orientation of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet, and the Fe-based method.
- the above oxides are difficult to form and the crystal grain size of the Fe-based electroplating layer becomes coarse. Therefore, when annealing is performed at a low dew point, it can be considered that the crystal orientation of the Fe-based electroplating layer is integrated with the crystal orientation of the Si-containing cold-rolled steel sheet at a high ratio.
- the dew point of the annealing atmosphere in the annealing process is -30 ° C or less due to the cost of the humidifying equipment of the annealing furnace, the Fe-based electroplating layer and Si at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet.
- the ratio of the crystal orientation integrated with the contained cold-rolled steel sheet increases.
- zinc melted during resistance welding easily invades the grain boundaries of the Si-containing cold-rolled steel sheet via the grain boundaries of the Fe-based electroplating layer.
- an Fe-based electroplating layer having a specific adhesion amount zinc melted during resistance welding passes through the crystal grain boundaries of the Fe-based electroplating layer to crystallize a Si-containing cold-rolled steel sheet. It delays the time to reach the grain boundary and improves the resistance welding crack resistance in the weld.
- the lower limit of the dew point in the annealed atmosphere is not particularly set, but it is preferably -80 ° C or higher because it is industrially difficult to realize it below -80 ° C.
- the dew point in the annealed atmosphere is more preferably ⁇ 55 ° C. or higher.
- Hydrogen concentration 1.0% by volume or more and 30.0% by volume or less
- the baking step is performed in a reducing atmosphere having a hydrogen concentration of 1.0% by volume or more and 30.0% by volume or less.
- Hydrogen plays a role of suppressing the oxidation of Fe on the surface of the pre-annealed Fe-based electroplated steel sheet during the annealing process and activating the surface of the steel sheet.
- the hydrogen concentration is 1.0% by volume or more, it is possible to avoid deterioration of the plating adhesion when the zinc plating layer is provided due to the oxidation of Fe on the surface of the steel sheet.
- the annealing step is preferably performed in a reducing atmosphere having a hydrogen concentration of 1.0% by volume or more, and more preferably performed in a reducing atmosphere having a hydrogen concentration of 2.0% by volume or more.
- the upper limit of the hydrogen concentration in the annealing step is not particularly limited, but from the viewpoint of cost, the hydrogen concentration is preferably 30.0% by volume or less, and more preferably 20.0% by volume or less.
- the rest of the annealing atmosphere other than hydrogen is preferably nitrogen.
- the holding time in the temperature range of 650 ° C or higher and 900 ° C or lower is preferably 30 seconds or longer and 600 seconds or lower. ..
- the holding time in the temperature range is preferably 30 seconds or more.
- the upper limit of the holding time in the temperature range is not particularly set, but from the viewpoint of productivity, the holding time in the temperature range is preferably 600 seconds or less.
- Maximum temperature reached by Fe-based electroplated steel sheet before annealing 650 ° C. or higher and 900 ° C. or lower
- the maximum temperature reached by Fe-based electroplated steel sheet before annealing is not particularly limited, but is preferably 650 ° C. or higher and 900 ° C. or lower.
- the natural oxide film of Fe formed on the surface of the Fe-based electroplating layer before annealing can be suitably reduced, and the plating adhesion when zinc plating is provided on the surface of the Fe-based electroplating steel sheet can be improved as described later. ..
- the maximum temperature reached of the Fe-based electroplated steel sheet is 900 ° C. or lower, it is possible to prevent the diffusion rate of Si and Mn in the steel from increasing too much and prevent the diffusion of Si and Mn on the surface of the steel sheet. Therefore, as will be described later, it is possible to improve the plating adhesion when zinc plating is provided on the surface of the Fe-based electroplated steel sheet. Further, if the maximum temperature reached is 900 ° C.
- the maximum temperature reached by the cold-rolled steel sheet is preferably 900 ° C. or lower. The maximum temperature reached is based on the temperature measured on the surface of the cold-rolled steel sheet.
- the Fe-based electroplated steel sheet is galvanized.
- the method of the zinc plating treatment is not particularly limited, and may be, for example, hot-dip plating, electroplating, cold spraying, plasma spraying, or the like.
- the Fe-based electroplated steel sheet may be cooled after the baking step and immersed in a hot-dip galvanizing bath to perform hot-dip galvanizing on the surface of the steel sheet.
- the hot dip galvanizing bath consists of Al, Zn and unavoidable impurities.
- the components of the hot-dip galvanized bath are not particularly specified, but the Al concentration in the bath is generally 0.05% by mass or more and 0.250% by mass or less.
- the Al concentration in the bath is 0.05% by mass or more, it is possible to prevent the occurrence of bottom dross and prevent the dross from adhering to the steel sheet and becoming defects.
- the Al concentration in the bath is 0.250% by mass or less, it is possible to prevent an increase in top dross, prevent the dross from adhering to the steel sheet and causing defects, and also lead to cost reduction.
- the bath temperature of the hot-dip galvanizing bath is usually in the range of 440 to 500 ° C
- the steel sheet is hot-dip galvanized at a plate temperature of 440 to 550 ° C. It is done by immersing it in it.
- the amount of adhesion per one side of the zinc-plated layer is preferably controlled to an amount such that the amount of adhesion per one side of the alloyed zinc-plated layer is 25 to 80 g / m 2 .
- the adhesion amount per one side of the alloyed zinc plating layer is 25 g / m 2 or more, the corrosion resistance can be further improved and the plating adhesion amount can be easily controlled. Further, when the adhesion amount per one side of the alloyed zinc plating layer is 80 g / m 2 or less, the plating adhesion is good.
- the amount of plating adhesion may be adjusted as appropriate.
- the method for adjusting the plating adhesion amount is not particularly limited, but in hot-dip galvanizing, for example, the plating adhesion amount is generally adjusted by gas wiping. In one example, the amount of plating adhered is adjusted by the gas pressure of gas wiping, the distance between the wiping nozzle and the steel plate, and the like.
- the galvanized layer is heat-alloyed by the alloying treatment.
- the alloying treatment is preferably performed at a temperature of 450 ° C. or higher and 600 ° C. or lower. By setting the alloying treatment to 450 ° C. or higher, it is possible to provide a steel sheet having excellent press formability without leaving the ⁇ phase. Further, by setting the alloying treatment to 600 ° C. or lower, the plating adhesion is good.
- the alloying time is preferably 5 s or more and 60 s or less.
- the Fe content (mass%) in the alloyed zinc-plated layer is measured in accordance with ISO 17925 (2004).
- the test solution after the plating peeling described above is analyzed by an inductive coupled plasma (ICP) emission analyzer, and the components such as Fe, Zn, and Al amounts constituting the alloyed zinc plating layer are contained in the test solution.
- the Fe content in the alloyed zinc-plated layer can be calculated by dividing the Fe content in the test solution by the total value and multiplying by 100. Here, the average value of the two locations is taken as the Fe content in the alloyed zinc-plated layer.
- a chemical conversion treatment film formed on the alloyed zinc-plated layer and an electrodeposition coating film formed on the chemical conversion film are further formed. It is also possible to provide an electrodeposited coated steel sheet having. Since the alloyed galvanized steel sheet according to the present embodiment has excellent resistance welding crack resistance in the welded portion, the electrodeposited coated steel sheet formed by using the alloyed galvanized steel sheet is particularly suitable for application to automobile parts. be.
- the types of the chemical conversion treatment film and the electrodeposition coating film are not particularly limited, and a known chemical conversion treatment film and an electrodeposition coating film can be used.
- the electrodeposition coating film is not particularly limited as long as it is an electrodeposition coating film for automobiles.
- the thickness of the electrodeposition coating film varies depending on the application, but it is preferably about 10 ⁇ m or more and 30 ⁇ m or less in the dry coating film. Further, according to the present embodiment, it is also possible to provide an alloyed galvanized steel sheet for electrodeposition coating for applying electrodeposition coating.
- the electrodeposition-coated steel sheet described above has a chemical conversion treatment step of subjecting an alloyed zinc-plated steel sheet to a chemical conversion treatment to obtain a chemical conversion-treated steel sheet having a chemical conversion-treated film formed on the alloyed zinc-plated layer, and the chemical conversion-treated steel sheet.
- the chemical conversion treatment and the electrodeposition coating treatment can be performed by a known method.
- a degreasing treatment for cleaning the surface of the alloyed galvanized steel sheet, a washing with water, and a surface adjustment treatment as necessary can be performed. Following these pretreatments, chemical conversion treatment is carried out.
- the method of degreasing treatment and washing with water is not particularly limited, and a usual method can be used.
- a surface conditioning agent having a Ti colloid or a zinc phosphate colloid can be used. When applying these surface conditioners, it is not necessary to provide a special process, and it may be carried out according to a conventional method.
- a desired surface conditioner is dissolved in a predetermined deionized water, and after sufficient stirring, a treatment liquid having a predetermined temperature (usually normal temperature, 25 to 30 ° C.) is used, and a steel sheet is placed in the treatment liquid for a predetermined time (usually, 25 to 30 ° C.). 20-30 seconds) Soak.
- the chemical conversion treatment in the next step is performed without continuing to dry.
- the chemical conversion treatment may also be carried out according to a conventional method.
- a desired chemical conversion treatment agent is dissolved in a predetermined deionized water, and after sufficient stirring, a treatment liquid having a predetermined temperature (usually 35 to 45 ° C.) is prepared, and a steel sheet is placed in the treatment liquid for a predetermined time (60 to 120 ° C.).
- a chemical conversion treatment agent for example, a zinc phosphate treatment agent for steel, a steel / aluminum combined type zinc phosphate treatment agent, a zirconium treatment agent, or the like can be used.
- electrodeposition coating is performed in the next process. Electrodeposition coating may also be performed according to a conventional method.
- the steel sheet After performing pretreatment such as water washing treatment as necessary, the steel sheet is immersed in the electrodeposited paint that has been sufficiently agitated, and the electrodeposition coating having a desired thickness is obtained by the electrodeposition treatment.
- the electrodeposition coating an anion type electrodeposition coating can be used in addition to the cationic electrodeposition coating. Further, depending on the intended use, a top coat may be applied after the electrodeposition coating.
- the present embodiment it is possible to provide an automobile part in which the above-mentioned electrodeposition-coated steel sheet is used for at least a part thereof. Since the alloyed galvanized steel sheet according to the present embodiment has excellent resistance welding crack resistance in the welded portion, the electrodeposited coated steel sheet using the alloyed galvanized steel sheet is particularly suitable for application to automobile parts.
- the automobile parts using the electrodeposition-coated steel sheet may contain a steel sheet other than the electrodeposition-coated steel sheet according to the present embodiment as a material. Since the electrodeposited coated steel sheet according to the present embodiment has excellent resistance welding crack resistance at the welded portion, LME cracking at the welded portion of an automobile part made of the alloyed galvanized steel sheet is preferably prevented.
- the type of the automobile part using the electrodeposited coated steel plate at least partially is not particularly limited, but may be, for example, a side sill part, a pillar part, an automobile body, or the like.
- the alloyed galvanized steel sheet according to this embodiment is Cold-rolled steel plate and An Fe-based electroplating layer formed on at least one side of the cold-rolled steel sheet and having an adhesion amount of more than 20.0 g / m 2 per side. It has an alloyed zinc plating layer formed on the Fe-based electroplating layer.
- the cold-rolled steel sheet is a test alloy in which a test piece cut out to a length of 50 ⁇ 150 mm in the direction perpendicular to the rolling direction and a hot-dip galvanized layer cut out to the same size has an adhesion amount of 50 g / m 2 per side. Stacked with hot-dip galvanized steel sheet to form a plate Next, using a servomotor pressure type single-phase AC (50 Hz) resistance welder, the plate assembly is performed on the plane perpendicular to the line connecting the central axes of the electrode pairs (tip diameter 6 mm) of the resistance welder.
- a servomotor pressure type single-phase AC (50 Hz) resistance welder the plate assembly is performed on the plane perpendicular to the line connecting the central axes of the electrode pairs (tip diameter 6 mm) of the resistance welder.
- the plate assembly was subjected to a pressing force of 3.5 kN, a hold time of 0.16 seconds, and a nugget diameter. Under the conditions of welding current and welding time, resistance welding is performed to form a plate assembly with welded parts.
- the cold-rolled steel sheet according to the present embodiment is not particularly limited as long as it is a steel sheet having inferior resistance weld cracking resistance in the welded portion when the sheet assembly partner is a galvanized steel sheet when evaluated by the following test.
- the composition of the cold-rolled steel sheet is also not particularly limited. The inventors have found that a cold-rolled steel sheet having a Si content of 0.1% by mass or more in steel is inferior in resistance welding crack resistance in a welded portion evaluated by the following test.
- the cold-rolled steel sheet is subjected to resistance welding under the condition that the hold time is 0.24 seconds to obtain a plate assembly with a welded portion, and when the cross section of the welded portion is observed with an optical microscope (magnification 200 times), it is 0. .
- It may be a cold-rolled steel sheet in which cracks having a length of 1 mm or more are observed. If the same cold-rolled steel sheet is used, the resistance welding crack resistance in the weld is generally inferior as the hold time is reduced. Therefore, when resistance welding is performed under the condition that the hold time is 0.24 seconds and the cross section of the weld is observed with an optical microscope (magnification 200 times), cracks with a length of 0.1 mm or more are generated.
- a method for evaluating resistance welding crack resistance in a welded portion will be described with reference to FIG.
- a test piece 6 cut out to a length of 50 ⁇ 150 mm with the rolling direction perpendicular (TD) as the longitudinal direction and the rolling direction as the short side is cut out to the same size, and the amount of adhesion per surface of the hot-dip galvanized layer is 50 g / m 2 . It is overlapped with the test alloyed hot-dip galvanized steel sheet 5 to form a plate assembly.
- the plate assembly is assembled so that the evaluation target surface (the surface on the Fe-based electroplating layer side) of the test piece 6 and the zinc plating layer of the test alloyed hot-dip galvanized steel sheet 5 face each other.
- the plate assembly is fixed to the fixing base 8 via a spacer 7 having a thickness of 2.0 mm.
- the spacer 7 is a pair of steel plates having a length direction of 50 mm, a length direction of 45 mm, and a thickness of 2.0 mm. Arrange so that they are aligned with both ends. Therefore, the distance between the pair of steel plates is 60 mm.
- the fixing base 8 is a single plate having a hole in the center.
- the plate assembly is pressurized with a pair of electrodes 9 (tip diameter: 6 mm) while the plate assembly is bent.
- a pair of electrodes 9 tip diameter: 6 mm
- resistance welding is performed at a welding current and welding time at which the nugget diameter r becomes 5.9 mm, and a plate assembly with a welded portion is formed. do.
- the pair of electrodes 9 pressurize the plate assembly from above and below in the vertical direction, and the lower electrode pressurizes the test piece 6 through the hole of the fixing base 8.
- the lower electrode and the fixing base 8 are fixed so that the lower electrode of the pair of electrodes 9 is in contact with the flat surface extending the surface where the spacer 7 and the fixing base 8 are in contact with each other. Make the electrodes movable. Further, the upper electrode is brought into contact with the central portion of the test alloyed hot-dip galvanized steel sheet 5. Further, in the plate assembly, the plate assembly is placed 5 on the longitudinal direction side of the plate assembly with respect to the vertical plane (horizontal direction in FIG. 8A) with respect to the line connecting the central axes of the electrode pairs of the resistance welder. ° Weld in a tilted state.
- the nugget diameter r means the distance between the ends of the nugget 10 in the longitudinal direction of the plate assembly.
- the plate assembly with the welded portion is cut along the line BB in the above figure of FIG. 8B so as to include the center of the welded portion including the nugget 10, and the cross section of the welded portion is optically measured. It was observed with a microscope (200x), and the resistance weld crack resistance in the weld was evaluated according to the following criteria. If it is ⁇ or ⁇ , it is judged that the resistance welding crack resistance in the welded part is excellent. If it is x, it is judged that the resistance welding crack resistance in the welded part is inferior.
- the resistance welding crack resistance property at the welded portion may be evaluated in the same manner according to the following criteria. ⁇ : No cracks with a length of 0.1 mm or more are observed with a hold time of 0.18 seconds ⁇ : Cracks with a length of 0.1 mm or more are observed with a hold time of 0.18 seconds, but the hold time is 0. .No cracks with a length of 0.1 mm or more are observed in 24 seconds ⁇ : Cracks with a length of 0.1 mm or more are observed with a hold time of 0.24 seconds.
- the Fe-based electroplating layer and the alloyed zinc-plated layer of the alloyed galvanized steel sheet according to the present embodiment are the same as those in the above-described first embodiment, the description thereof will be omitted here.
- the ratio of the crystal orientations of the Fe-based electroplating layer and the cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the cold-rolled steel sheet is more than 50% as in the above-described first embodiment.
- the details of the ratio of the crystal orientations of the Fe-based electroplating layer and the cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the cold-rolled steel sheet are the same as in the above-described first embodiment, and thus will be described here. Is omitted.
- the method for manufacturing an alloyed galvanized steel sheet according to an embodiment is as follows. Fe-based electroplating is applied to the cold-rolled steel sheet to obtain a pre-annealed Fe-based electroplated steel sheet in which a pre-annealed Fe-based electroplated layer is formed on at least one side. Next, the pre-annealed Fe-based electroplated steel sheet was annealed in an atmosphere with a dew point of -30 ° C or lower to obtain an Fe-based electroplated steel sheet. Next, the Fe-based electroplated steel sheet was galvanized to obtain a galvanized steel sheet.
- the galvanized steel sheet is further alloyed to obtain an alloyed galvanized steel sheet having an Fe-based electroplating layer having an adhesion amount of more than 20.0 g / m 2 on one side.
- the cold-rolled steel sheet is a test alloy in which a test piece cut out to a length of 50 ⁇ 150 mm in the direction perpendicular to the rolling direction and a hot-dip galvanized layer cut out to the same size has an adhesion amount of 50 g / m 2 per side.
- the plate assembly is performed on the plane perpendicular to the line connecting the central axes of the electrode pairs (tip diameter 6 mm) of the resistance welder. Is tilted 5 ° toward the longitudinal direction of the plate assembly, and a gap of 60 mm in the longitudinal direction of the plate assembly ⁇ 2.0 mm in the thickness direction of the plate assembly is provided between the lower electrode of the electrode pair and the test piece.
- a servomotor pressure type single-phase AC (50 Hz) resistance welder the plate assembly is performed on the plane perpendicular to the line connecting the central axes of the electrode pairs (tip diameter 6 mm) of the resistance welder. Is tilted 5 ° toward the longitudinal direction of the plate assembly, and a gap of 60 mm in the longitudinal direction of the plate assembly ⁇ 2.0 mm in the thickness direction of the plate assembly is provided between the lower electrode of the electrode pair and the test piece.
- the plate assembly With the lower electrode fixed to the plate assembly and the upper electrode of the electrode pair movable, the plate assembly was subjected to a pressing force of 3.5 kN, a hold time of 0.16 seconds, and a nugget diameter. Under the conditions of welding current and welding time, resistance welding is performed to form a plate assembly with welded parts. Next, when the plate assembly with the welded portion is cut in half along the longitudinal direction of the test piece so as to include the welded portion and the cross section of the welded portion is observed with an optical microscope (magnification 200 times), it is 0.1 mm. It is a cold-rolled steel sheet in which cracks of the above length are observed.
- the manufacturing method of the cold-rolled steel sheet can follow the usual manufacturing method of the cold-rolled steel sheet.
- a steel slab is hot-rolled to form a hot-rolled plate, then the hot-rolled plate is pickled, and then the hot-rolled plate is cold-rolled to produce a cold-rolled steel sheet.
- the cold-rolled steel sheet according to the present embodiment is not particularly limited as long as it is a steel sheet having inferior resistance welding crack resistance in the welded portion when the sheet assembly partner is a galvanized steel sheet when evaluated by the above-mentioned test.
- the composition of the cold-rolled steel sheet is also not particularly limited, and if the Si content in the steel is 0.1% by mass or more, the resistance-welded crack resistance in the welded portion evaluated by the following test is inferior. We have obtained the knowledge.
- the cold-rolled steel sheet When the cold-rolled steel sheet is subjected to the above-mentioned resistance welding under the condition that the hold time is 0.24 seconds to obtain a plate assembly with a welded portion, and the cross section of the welded portion is observed with an optical microscope (magnification 200 times). , It may be a cold-rolled steel sheet in which cracks having a length of 0.1 mm or more are observed. If the same cold-rolled steel sheet is used, the resistance welding crack resistance in the weld is generally inferior as the hold time is reduced. Therefore, when resistance welding is performed under the condition that the hold time is 0.24 seconds and the cross section of the weld is observed with an optical microscope (magnification 200 times), cracks with a length of 0.1 mm or more are generated.
- the surface of the cold-rolled steel sheet is subjected to Fe-based electroplating treatment to obtain a pre-annealed Fe-based electroplated steel sheet. Since the details of the Fe-based electroplating process have been described above, the description thereof will be omitted here.
- the Fe-based electroplated steel sheet according to the present embodiment is galvanized to obtain a galvanized steel sheet. Since the details of the zinc plating treatment are the same as those in the first embodiment described above, the description thereof will be omitted here.
- the chemical conversion treatment film formed on the zinc plating layer and the electric voltage formed on the chemical conversion film on the alloyed zinc-plated steel sheet according to the present embodiment is also possible to provide an electrodeposition-coated steel sheet further having a coating film. Further, it is also possible to provide an alloyed galvanized steel sheet for electrodeposition coating for applying electrodeposition coating. Since the details of the method for manufacturing the electrodeposition-coated steel sheet and the electrodeposition-coated steel sheet are the same as those in the first embodiment described above, the description thereof will be omitted here.
- the slabs obtained by melting the steel with the chemical composition shown in Table 1 were hot-rolled, pickled, and cold-rolled to obtain a cold-rolled steel sheet with a plate thickness of 1.6 mm.
- the cold-rolled steel sheet is subjected to degreasing treatment with alkali, and then electrolytic treatment is performed using the steel sheet as a cathode under the conditions shown below.
- Manufactured plated steel sheets The amount of adhesion of the Fe-based electroplating layer before annealing was calculated by the above-mentioned cross-section observation method and controlled by the energization time. Subsequently, with respect to the pre-annealed Fe-based electroplated steel sheet, 15% H2 - N2 , an average tropical temperature of 800 ° C., and the dew point of the atmosphere were adjusted as shown in Tables 2-1 and 2-2 and Table 4 for reduction. Annealing was performed to obtain an Fe-based electroplated steel sheet.
- the Fe-based electroplated steel sheet was continuously subjected to an effective Al concentration in a bath of 0.132% by mass, and the balance was 460 ° C. consisting of Zn and unavoidable impurities.
- the tinting amount was adjusted to about 50 g / m 2 per side by gas wiping to obtain a galvanized steel sheet.
- the galvanized steel sheet was alloyed at 490 ° C. for different times to prepare samples of alloyed galvanized steel sheets having different Fe contents diffused into the alloyed galvanized layer.
- Fe-based electroplating bath Electrode containing 1.5 mol / L of Fe 2+ ions (anode): Iridium oxide electrode
- the adhesion amount per one side of the Fe-based electroplating layer, the adhesion amount of the alloyed zinc-plated layer, and the Fe content in the alloyed zinc-plated layer (Fe content in the alloyed zinc-plated layer) according to the above method. Mass%), and the ratio of the crystal orientation of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet was determined.
- the resistance weld crack resistance in the welded part of the alloyed galvanized steel sheet obtained as described above was investigated.
- the measurement method and evaluation method of resistance welding crack resistance in the welded part are shown below.
- the tensile strength of the sheet assembly partner is 980 MPa class with less than 0.5% Si, for which resistance welding crack resistance is not an issue at a hold time of 0.18 seconds.
- the resistance welding crack resistance property in the welded portion was evaluated in the case of a test alloyed hot-dip galvanized steel sheet (plate thickness 1.6 mm) having an adhesion amount of 50 g / m 2 per side.
- Welding time was 0.36 seconds
- hold time was 0.18 seconds and 0.24 seconds
- the nugget diameter was measured by changing the welding current each time, and evaluated by the welding current at which the nugget diameter was 5.9 mm.
- test alloyed hot-dip galvanized steel sheet which is the partner of the plate assembly, was used as the example data without cracks. This is because if cracks occur in the sheet assembly partner, the stress on the alloyed galvanized steel sheet to be evaluated will be dispersed and the evaluation will not be appropriate.
- the ratio of the crystal orientations of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet due to annealing at a high dew point is It was low and had good resistance welding crack resistance in the welded part.
- the pre-annealed Fe-based electroplated steel sheet is heated to an average tropical temperature of 800 ° C. with an average temperature rise rate of 10 ° C./sec or more in a temperature range of 400 ° C. or higher and 650 ° C. or lower, and reduction annealing is performed. Was given.
- the slab obtained by melting the steel having the chemical composition shown in Table 5 was hot-rolled, pickled, and cold-rolled to obtain a cold-rolled steel sheet having a plate thickness of 1.6 mm.
- the cold-rolled steel sheet is subjected to degreasing treatment with alkali, and then electrolytic treatment is performed using the steel sheet as a cathode under the conditions shown below.
- Manufactured plated steel sheets The amount of adhesion of the Fe-based electroplating layer before annealing was calculated by the above-mentioned cross-section observation method and controlled by the energization time.
- the Fe-based electroplated steel sheet before annealing was subjected to reduction annealing by adjusting the dew point of the atmosphere at 15% H2 - N2 , a soothing tropical temperature of 800 ° C. as shown in Table 6, and then subjected to reduction annealing.
- the Fe-based electroplated steel sheet was continuously subjected to an effective Al concentration in a bath of 0.132% by mass, and the balance was 460 ° C. consisting of Zn and unavoidable impurities.
- the tinting amount was adjusted to about 50 g / m 2 per side by gas wiping to obtain a galvanized steel sheet.
- the galvanized steel sheet was alloyed at 490 ° C. for different times to prepare samples of alloyed galvanized steel sheets having different Fe contents diffused into the alloyed galvanized layer.
- Fe-based electroplating bath Electrode containing 1.5 mol / L of Fe 2+ ions (anode): Iridium oxide electrode
- the adhesion amount per one side of the Fe-based electroplating layer, the adhesion amount of the alloyed zinc-plated layer, and the Fe content in the alloyed zinc-plated layer (Fe content in the alloyed zinc-plated layer) according to the above method. Mass%), and the ratio of the crystal orientation of the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet integrated at the interface between the Fe-based electroplating layer and the Si-containing cold-rolled steel sheet was determined.
- the resistance weld crack resistance in the welded part of the alloyed galvanized steel sheet obtained as described above was investigated.
- the measurement method and evaluation method of resistance welding crack resistance in the welded part are shown below.
- the tensile strength of the sheet assembly partner is 590 MPa class with less than 0.1% Si, for which resistance welding crack resistance is not an issue at a hold time of 0.14 seconds.
- the resistance welding crack resistance property in the welded portion was evaluated in the case of a test alloyed hot-dip galvanized steel sheet (plate thickness 1.6 mm) having an adhesion amount of 50 g / m 2 per side.
- Welding time was 0.36 seconds
- hold time was 0.14 seconds and 0.16 seconds
- the nugget diameter was measured by changing the welding current each time, and evaluated by the welding current at which the nugget diameter was 5.9 mm.
- test alloyed hot-dip galvanized steel sheet which is the partner of the plate assembly, was used as the example data without cracks. This is because if cracks occur in the sheet assembly partner, the stress on the alloyed galvanized steel sheet to be evaluated will be dispersed and the evaluation will not be appropriate.
- the alloyed galvanized steel sheet manufactured by the present invention not only has excellent resistance welding crack resistance in welds, but also has high strength and excellent workability, so it can only be used as a material for automobile parts. However, it can also be suitably used as a material for applications that require similar characteristics in the fields of home appliances and building materials.
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Abstract
Description
前記Si含有冷延鋼板の少なくとも片面に形成された,片面あたりの付着量が20.0g/m2超であるFe系電気めっき層と,
前記Fe系電気めっき層上に形成された合金化亜鉛めっき層とを有し,
前記Fe系電気めっき層と前記Si含有冷延鋼板との界面において前記Fe系電気めっき層と前記Si含有冷延鋼板との結晶方位が一体化している割合が50%超である,合金化亜鉛めっき鋼板。
C:0.8%以下,
Mn:1.0%以上12.0%以下,
P:0.1%以下,
S:0.03%以下,
N:0.010%以下及び
Al:1.0%以下を含有し,残部がFe及び不可避的不純物からなる成分組成を有する,前記[1]から[3]のいずれか1項に記載の合金化亜鉛めっき鋼板。
B:0.005%以下,
Ti:0.2%以下,
Cr:1.0%以下,
Cu:1.0%以下,
Ni:1.0%以下,
Mo:1.0%以下,
Nb:0.20%以下,
V:0.5%以下,
Sb:0.200%以下,
Ta:0.1%以下,
W:0.5%以下,
Zr:0.1%以下,
Sn:0.20%以下,
Ca:0.005%以下,
Mg:0.005%以下及び
REM:0.005%以下
からなる群から選ばれる1種または2種以上を含有する,前記[4]に記載の合金化亜鉛めっき鋼板。
前記冷延鋼板の少なくとも片面に形成された,片面あたりの付着量が20.0g/m2超であるFe系電気めっき層と,
前記Fe系電気めっき層上に形成された合金化亜鉛めっき層とを有し,
前記Fe系電気めっき層と前記冷延鋼板との界面において前記Fe系電気めっき層と前記冷延鋼板との結晶方位が一体化している割合が50%超である,合金化亜鉛めっき鋼板。
ここで,前記冷延鋼板は,圧延直角方向を長手として50×150mmに切り出した試験片を,同サイズに切り出した溶融亜鉛めっき層の片面あたりの付着量が50g/m2である試験用合金化溶融亜鉛めっき鋼板と重ねて板組とし,
次いで,サーボモータ加圧式で単相交流(50Hz)の抵抗溶接機を用いて,該抵抗溶接機の電極対(先端径6mm)の中心軸同士を結んだ線に対する垂直面に対して前記板組を該板組の長手方向側に5°傾け,前記電極対の下側電極と前記試験片との間に前記板組の長手方向60mm×前記板組の厚さ方向2.0mmの空隙を設けて前記下側電極と前記板組とを固定し,前記電極対の上側電極を可動にした状態で,前記板組に,加圧力:3.5kN,ホールドタイム:0.16秒,並びにナゲット径が5.9mmになる溶接電流及び溶接時間の条件にて抵抗溶接を施して溶接部付き板組とし,
次いで,前記溶接部付き板組を溶接部を含むように前記試験片の長手方向に沿って半切して,該溶接部の断面を光学顕微鏡(倍率200倍)で観察した場合に,0.1mm以上の長さのき裂が認められる冷延鋼板である。
前記化成処理鋼板に電着塗装処理を施して,前記化成処理皮膜上に電着塗装皮膜が形成された電着塗装鋼板を得る,電着塗装工程と,
を含む,電着塗装鋼板の製造方法。
次いで,前記焼鈍前Fe系電気めっき鋼板を露点-30℃以下の雰囲気下で焼鈍して,Fe系電気めっき鋼板とし,
次いで,前記Fe系電気めっき鋼板に亜鉛めっきを施して,亜鉛めっき鋼板とし,
次いで,前記亜鉛めっき鋼板に,合金化処理をさらに施して,片面あたりの付着量が20.0g/m2超のFe系電気めっき層を有する合金化亜鉛めっき鋼板を得る,合金化亜鉛めっき鋼板の製造方法。
(C.W.Fe0)>20.0+(C.W.Zn)×[mass%Fe]/100・・・(1)
ここで,C.W.Zn:合金化亜鉛めっき層の片面あたりの付着量の目標値(g/m2)
ただし,25.0g/m2≦C.W.Zn≦80.0g/m2
[mass%Fe]:前記合金化亜鉛めっき層中のFe含有量の目標値(質量%)
次いで,前記焼鈍前Fe系電気めっき鋼板を露点-30℃以下の雰囲気下で焼鈍して,Fe系電気めっき鋼板とし,
次いで,前記Fe系電気めっき鋼板に亜鉛めっきを施して,亜鉛めっき鋼板とし,
次いで,前記亜鉛めっき鋼板に,合金化処理をさらに施して,片面あたりの付着量が20.0g/m2超のFe系電気めっき層を有する合金化亜鉛めっき鋼板を得る,合金化亜鉛めっき鋼板の製造方法。
ここで,前記冷延鋼板は,圧延直角方向を長手として50×150mmに切り出した試験片を,同サイズに切り出した溶融亜鉛めっき層の片面あたりの付着量が50g/m2である試験用合金化溶融亜鉛めっき鋼板と重ねて板組とし,
次いで,サーボモータ加圧式で単相交流(50Hz)の抵抗溶接機を用いて,該抵抗溶接機の電極対(先端径6mm)の中心軸同士を結んだ線に対する垂直面に対して前記板組を該板組の長手方向側に5°傾け,前記電極対の下側電極と前記試験片との間に前記板組の長手方向60mm×前記板組の厚さ方向2.0mmの空隙を設けて前記下側電極と前記板組とを固定し,前記電極対の上側電極を可動にした状態で,前記板組に,加圧力:3.5kN,ホールドタイム:0.16秒,並びにナゲット径が5.9mmになる溶接電流及び溶接時間の条件にて抵抗溶接を施して溶接部付き板組とし,
次いで,前記溶接部付き板組を溶接部を含むように前記試験片の長手方向に沿って半切して,該溶接部の断面を光学顕微鏡(倍率200倍)で観察した場合に,0.1mm以上の長さのき裂が認められる冷延鋼板である。
(C.W.Fe0)>20.0+(C.W.Zn)×[mass%Fe]/100・・・(1)
ここで,C.W.Zn:合金化亜鉛めっき層の片面あたりの付着量の目標値(g/m2)
ただし,25.0g/m2≦C.W.Zn≦80.0g/m2
[mass%Fe]:前記合金化亜鉛めっき層中のFe含有量の目標値(質量%)
なお,以下の説明において,Si含有冷延鋼板の成分組成の各元素の含有量,めっき層成分組成の各元素の含有量の単位はいずれも「質量%」であり,特に断らない限り単に「%」で示す。また,本明細書中において,「~」を用いて表される数値範囲は,「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。また,本明細書において,鋼板が「高強度」であるとは,JIS Z 2241(2011)に準拠して測定した鋼板の引張強さTSが590MPa以上であることを意味する。
図1に,本実施形態に係る合金化亜鉛めっき鋼板1の断面の概要を示す。図1に示すように,合金化亜鉛めっき鋼板1は,Si含有冷延鋼板2の少なくとも片面に,Fe系電気めっき層3と,該Fe系電気めっき層上に形成された合金化亜鉛めっき層4とを有する。まず,Si含有冷延鋼板の成分組成について説明する。
Siは,加工性を大きく損なうことなく,固溶により鋼の強度を高める効果(固溶強化能)が大きいため,鋼板の高強度化を達成するのに有効な元素である。一方で,Siは溶接部における耐抵抗溶接割れ特性に悪影響を及ぼす元素でもある。Siを鋼板の高強度化を達成するために添加する場合には,0.1%以上の添加が必要である。Siが0.50%未満では,従来の0.24秒程度のホールドタイムによる溶接では,溶接部における耐抵抗溶接割れ特性に特に問題は生じない。しかしながら,自動車部品の組み立て工程におけるスポット溶接時のタクトタイムが生産コストの観点で課題となり,ホールドタイム低減による対策が取られた場合,Si量が0.50%未満でも溶接部における耐抵抗溶接割れ特性が不十分となる場合がある。一方,Siの含有量が3.0%を超えると,熱間圧延性及び冷間圧延性が大きく低下し,生産性に悪影響を及ぼしたり,鋼板自体の延性の低下を招いたりする。よって,Siは0.1%以上3.0%以下の範囲で添加する。Si量は,好ましくは0.50%以上,より好ましくは0.7%以上,さらに好ましくは溶接部における耐抵抗溶接割れ特性への影響がより大きい0.9%以上とする。また,Si量は,好ましくは2.5%以下,より好ましくは2.0%以下,さらに好ましくは1.7%以下とする。
Cは,鋼組織としてマルテンサイトなどを形成させることで加工性を向上する。Cを含有させる場合,良好な溶接性を得るため,C量は0.8%以下とすることが好ましく,0.3%以下とすることがより好ましい。Cの下限は特に限定されないが,良好な加工性を得るためにはC量は0%超であることが好ましく,0.03%以上とすることがより好ましく,0.08%以上含有させることがさらに好ましい。
Mnは,鋼を固溶強化して高強度化するとともに,焼入性を高め,残留オーステナイト,ベイナイト,及びマルテンサイトの生成を促進する作用を有する元素である。このような効果は,Mnを1.0%以上添加することで発現する。一方,Mn量が12.0%以下であれば,コストの上昇を招かずに上記効果が得られる。よって,Mn量は1.0%以上とすることが好ましく,12.0%以下とすることが好ましい。Mn量は1.3%以上とすることがより好ましく,1.5%以上とすることがさらに好ましく,1.8%以上とすることが最も好ましい。また,Mn量は3.5%以下とすることがより好ましく,3.3%以下とすることがさらに好ましい。
Pの含有量を抑制することで,溶接性の低下を防ぐことができる。さらにPが粒界に偏析することを防いで,延性,曲げ性,及び靭性が劣化することを防ぐことができる。また,Pを多量に添加すると,フェライト変態を促進することで結晶粒径も大きくなってしまう。そのため,P量は0.1%以下とすることが好ましい。Pの下限は特に限定されず,生産技術上の制約から0%超であり得,0.001%以上であり得る。
S量は0.03%以下とすることが好ましく,0.02%以下とすることがより好ましい。S量を抑制することで,溶接性の低下を防ぐとともに,熱間時の延性の低下を防いで,熱間割れを抑制し,表面性状を著しく向上することができる。さらに,S量を抑制することで,不純物元素として粗大な硫化物を形成することにより,鋼板の延性,曲げ性,伸びフランジ性の低下を防ぐことができる。これらの問題はS量が0.03%を超えると顕著となり,Sの含有量は極力低減することが好ましい。Sの下限は特に限定されず,生産技術上の制約から0%超であり得,0.0001%以上であり得る。
Nの含有量は0.010%以下とすることが好ましい。Nの含有量を0.010%以下とすることで,NがTi,Nb,Vと高温で粗大な窒化物を形成することでTi,Nb,V添加による鋼板の高強度化の効果が損なわれることを防ぐことができる。また,Nの含有量を0.010%以下とすることで靭性の低下も防ぐことができる。さらに,Nの含有量を0.010%以下とすることで,熱間圧延中にスラブ割れ,表面疵が発生することを防ぐことができる。Nの含有量は,好ましくは0.005%以下であり,より好ましくは0.003%以下であり,さらに好ましくは0.002%以下である。Nの含有量の下限は特に限定されず,生産技術上の制約から0%超であり得,0.0005%以上であり得る。
Alは熱力学的に最も酸化しやすいため,Si及びMnに先だって酸化し,Si及びMnの鋼板最表層での酸化を抑制し,Si及びMnの鋼板内部での酸化を促進する効果がある。この効果はAl量が0.01%以上で得られる。一方,Al量が1.0%を超えるとコストアップになる。したがって,添加する場合,Al量は1.0%以下とすることが好ましい。Al量は0.1%以下とすることがより好ましい。Alの下限は特に限定されず,0%超であり得,0.001%以上であり得る。
Bは鋼の焼入れ性を向上させるのに有効な元素である。焼入れ性を向上するためには,B量は0.0003%以上とすることが好ましく,0.0005%以上とすることがより好ましい。しかし,Bを過度に添加すると成形性が低下するため,B量は0.005%以下とすることが好ましい。
Tiは鋼の析出強化に有効である。Tiの下限は特に限定されないが,強度調整の効果を得るためには,0.005%以上とすることが好ましい。しかし,Tiを過度に添加すると,硬質相が過大となり,成形性が低下するため,Tiを添加する場合,Ti量は0.2%以下とすることが好ましく,0.05%以下とすることがより好ましい。
Cr量は0.005%以上とすることが好ましい。Cr量を0.005%以上とすることで,焼き入れ性を向上し,強度と延性とのバランスを向上することができる。添加する場合,コストアップを防ぐ観点から,Cr量は1.0%以下とすることが好ましい。
Cu量は0.005%以上とすることが好ましい。Cu量を0.005%以上とすることで,残留γ相の形成を促進することができる。また,Cu量を添加する場合,コストアップを防ぐ観点から,Cu量は1.0%以下とすることが好ましい。
Ni量は0.005%以上とすることが好ましい。Ni量を0.005%以上とすることで,残留γ相の形成を促進することができる。また,Niを添加する場合,コストアップを防ぐ観点から,Ni量は1.0%以下とすることが好ましい。
Mo量は0.005%以上とすることが好ましい。Mo量を0.005%以上とすることで,強度調整の効果を得ることができる。また,Moを添加する場合,コストアップを防ぐ観点から,Mo量は1.0%以下が好ましい。
Nbは,0.005%以上含有することで強度向上の効果が得られる。また,Nbを含有する場合,コストアップを防ぐ観点から,Nb量は0.20%以下とすることが好ましい。
Vは,0.005%以上含有することで強度向上の効果が得られる。また,Vを含有する場合,コストアップを防ぐ観点から,V量は0.5%以下とすることが好ましい。
Sbは鋼板表面の窒化,酸化,あるいは酸化により生じる鋼板表面の数十ミクロン領域の脱炭を抑制する観点から含有することができる。Sbは,鋼板表面の窒化及び酸化を抑制することで,鋼板表面においてマルテンサイトの生成量が減少するのを防止し,鋼板の疲労特性及び表面品質を改善する。このような効果を得るために,Sb量は0.001%以上とすることが好ましい。一方,良好な靭性を得るためには,Sb量は0.200%以下とすることが好ましい。
Taは,0.001%以上含有することで強度向上の効果が得られる。また,Taを含有する場合,コストアップを防ぐ観点から,Ta量は0.1%以下とすることが好ましい。
Wは,0.005%以上含有することで強度向上の効果が得られる。また,Wを含有する場合,コストアップを防ぐ観点から,W量は0.5%以下とすることが好ましい。
Zrは,0.0005%以上含有することで強度向上の効果が得られる。また,Zrを含有する場合,コストアップを防ぐ観点から,Zr量は0.1%以下とすることが好ましい。
Snは脱窒,脱硼等を抑制して,鋼の強度低下抑制に有効な元素である。こうした効果を得るにはそれぞれ0.002%以上とすることが好ましい。一方,良好な耐衝撃性を得るために,Sn量は0.20%以下とすることが好ましい。
Caは,0.0005%以上含有することで硫化物の形態を制御し,延性,靭性を向上させることができる。また,良好な延性を得る観点から,Ca量は0.005%以下とすることが好ましい。
Mgは,0.0005%以上含有することで硫化物の形態を制御し,延性,靭性を向上させることができる。また,Mgを含有する場合,コストアップを防ぐ観点から,Mg量は0.005%以下とすることが好ましい。
REMは,0.0005%以上含有することで硫化物の形態を制御し,延性,靭性を向上させることができる。また,REMを含有する場合,良好な靭性を得る観点から,REM量は0.005%以下とすることが好ましい。
Fe系電気めっき層:20.0g/m2超
合金化処理後の片面あたりの付着量が20.0g/m2超のFe系電気めっき層を有することで溶接部における耐抵抗溶接割れ特性が向上するメカニズムは明らかではないが,本発明者らは以下の通り考えている。本実施形態においては,後述するように,Fe系電気めっき層を形成後に焼鈍を施す。Fe系電気めっき層を形成後に焼鈍を施すことにより,焼鈍時に形成するSi及びMn等の表面酸化物によりピックアップと呼ばれる押疵がFe系めっき鋼板表面に発生することを抑制できる反面,Fe系電気めっき層とSi含有冷延鋼板との界面においてFe系電気めっき層とSi含有冷延鋼板との結晶方位が50%超の割合で一体化する。そのため,溶融した亜鉛がFe系電気めっき層の結晶粒界を経由してSi含有冷延鋼板の結晶粒界に侵入しやすくなる。さらに,亜鉛めっき層に合金化処理を施す場合,Fe系電気めっき層の表層が合金化により消費されるため,合金化しない亜鉛めっき鋼板に比べ,溶接部における耐抵抗溶接割れ特性を向上することが難しくなる。したがって,本実施形態においては,合金化処理後の付着量が20.0g/m2超のFe系電気めっき層を形成させる。20.0g/m2超の付着量を有するFe系電気めっき層を形成させることにより,抵抗溶接時に溶融した亜鉛がSi含有冷延鋼板の結晶粒界に到達する時間を遅延させ,溶接部における耐抵抗溶接割れ特性を改善することができると考えられる(亜鉛の粒界侵入抑制効果)。また,Fe系電気めっき層が軟質層として機能し,溶接時に鋼板表面に付与される応力を緩和することができ,抵抗溶接部の残留応力を低減することにより,溶接部における耐抵抗溶接割れ特性を向上させ得ると考えられる(応力緩和効果)。さらに,鋼板表面における固溶Si量が多い場合には溶接部で靭性が低下して溶接部における耐抵抗溶接割れ特性が劣化するものと考えられる。これに対し,一定量以上のFe系電気めっき層を鋼板表面に有する場合,該Fe系電気めっき層が固溶Si欠乏層として働き,溶接部に固溶するSi量が減少するため,Si固溶による溶接部の靭性の低下が抑制されて溶接部における耐抵抗溶接割れ特性が改善し得ると考えられる(靭性低下抑制効果)。これらFe系電気めっき層付与による亜鉛めっきの粒界侵入抑制効果,応力緩和効果,及び靭性低下抑制効果の耐抵抗溶接割れ特性への寄与は複雑ゆえ定量的には明らかではないが,複合的に作用して耐抵抗溶接割れ特性を改善しているものと考えられる。溶接部における耐抵抗溶接割れ特性を向上させる効果を生じさせるためには,合金化後の亜鉛めっき鋼板において,Fe系電気めっき層の片面あたりの付着量を20.0g/m2超とすることが必要である。Fe系電気めっき層の片面あたりの付着量の上限は特に限定されないが,コストの観点から,Fe系電気めっき層の片面あたりの付着量を60.0g/m2以下とすることが好ましい。Fe系電気めっき層の付着量は,好ましくは25.0g/m2以上,より好ましくは30.0g/m2以上,さらに好ましくは35.0g/m2以上とする。合金化亜鉛めっき鋼板は,好ましくはSi含有冷延鋼板の表裏両面にFe系電気めっき層を有する。Fe系電気めっき層の付着量を25.0g/m2以上とすることで,溶接部における耐抵抗溶接割れ特性が特に良好となる。
(Fe系電気めっき層とSi含有冷延鋼板との界面においてFe系電気めっき層とSi含有冷延鋼板との結晶方位が一体化している割合)=(Fe系電気めっき層とSi含有冷延鋼板との界面のうち,Fe系電気めっき層とSi含有冷延鋼板との結晶方位が一体化している箇所の長さ)÷(観察視野での界面の長さ)×100・・・(2)
次に,合金化亜鉛めっき鋼板の製造方法について説明する。
一実施形態に係る合金化亜鉛めっき鋼板の製造方法は,Siを0.1質量%以上3.0質量%以下含有する冷延鋼板にFe系電気めっきを施して,焼鈍前Fe系電気めっき層が少なくとも片面に形成された焼鈍前Fe系電気めっき鋼板とし,
次いで,前記焼鈍前Fe系電気めっき鋼板を露点-30℃以下の雰囲気下で焼鈍して,Fe系電気めっき鋼板とし,
次いで,前記Fe系電気めっき鋼板に亜鉛めっきを施して,亜鉛めっき鋼板とし,
次いで,前記亜鉛めっき鋼板に,合金化処理をさらに施して,片面あたりの付着量が20.0g/m2超のFe系電気めっき層を有する合金化亜鉛めっき鋼板を得る,合金化亜鉛めっき鋼板の製造方法であり得る。
(C.W.Fe0)>20.0+(C.W.Zn)×[mass%Fe]/100・・・(1)
ここで,C.W.Zn:合金化亜鉛めっき層の片面あたりの付着量の目標値(g/m2)
ただし,25.0g/m2≦C.W.Zn≦80.0g/m2
[mass%Fe]:前記合金化亜鉛めっき層中のFe含有量の目標値(質量%)
つまり,合金化亜鉛めっき鋼板の合金化亜鉛めっき層中に含まれるFe量の目標値(g/m2)+20.0(g/m2)超の量の焼鈍前Fe系電気めっき層を形成すれば,最終的に20.0g/m2超のFe系電気めっき層を得ることができる。
本実施形態において,焼鈍工程における焼鈍雰囲気の露点は,加湿設備等の追加設備が不要な条件となる-30℃以下の低露点とする。露点-30℃以下の制御は650℃以上900℃以下の温度域にて行なうことが好ましい。本発明者らは独自の検討によって,Fe系電気めっき層とSi含有冷延鋼板との界面においてFe系電気めっき層とSi含有冷延鋼板との結晶方位が一体化している割合と,Fe系電気めっき層形成後の焼鈍工程における焼鈍雰囲気の露点との間に相関関係があることを見出した。すなわち,Fe系電気めっき層形成後の焼鈍前Fe系電気めっき鋼板に焼鈍を施す際に,焼鈍雰囲気の露点が低いほど,焼鈍後に得られるFe系電気めっき鋼板のFe系電気めっき層とSi含有冷延鋼板との結晶方位が一体化している割合が高く,逆に焼鈍雰囲気の露点が高いほどFe系電気めっき層とSi含有冷延鋼板との結晶方位が一体化している割合が低いことが分かった。このように,Fe系電気めっき層とSi含有冷延鋼板との結晶方位が一体化している割合と,露点との間に相関関係が見いだせる理由は明らかではないが,以下のように推測することができる。一定以上の高露点で制御した場合,焼鈍時に鋼板からFe系電気めっき層へ拡散する元素がFe系電気めっき層の内部で酸化物として形成し,この酸化物がFe系電気めっき層の結晶粒の成長を阻害し,細粒化させる。一方で,Fe系電気めっき層を形成後に低露点の雰囲気下にて焼鈍を施した場合,上記のような酸化物は形成されにくく,Fe系電気めっき層の結晶粒径が粗大化する。そのため,低露点で焼鈍を施した際にはFe系電気めっき層の結晶方位がSi含有冷延鋼板との結晶方位と高い割合で一体化すると考えることができる。焼鈍炉の加湿設備のコストなどを理由に,焼鈍工程における焼鈍雰囲気の露点を-30℃以下とした場合,Fe系電気めっき層とSi含有冷延鋼板との界面においてFe系電気めっき層とSi含有冷延鋼板との結晶方位が一体化している割合が高まる。その結果,合金化亜鉛めっき鋼板とした場合,抵抗溶接時に溶融した亜鉛がFe系電気めっき層の結晶粒界を経由してSi含有冷延鋼板の結晶粒界に侵入しやすくなる。本実施形態においては,特定の付着量を有するFe系電気めっき層を形成させることにより,抵抗溶接時に溶融した亜鉛がFe系電気めっき層の結晶粒界を経由してSi含有冷延鋼板の結晶粒界に到達する時間を遅延させ,溶接部における耐抵抗溶接割れ特性を改善する。焼鈍雰囲気の露点の下限は特に定めないが,-80℃未満は工業的に実現が困難であるため,-80℃以上とすることが好ましい。焼鈍雰囲気の露点はより好ましくは-55℃以上である。
焼鈍工程は,水素濃度が1.0体積%以上30.0体積%以下の還元性雰囲気中で行う。水素は,焼鈍工程中の焼鈍前Fe系電気めっき鋼板表面のFeの酸化を抑制し,鋼板表面を活性化する役割を果たす。水素濃度が1.0体積%以上であれば,鋼板表面のFeが酸化することにより,後述するように亜鉛めっき層を設ける際にめっき密着性が劣化することを回避することができる。よって,焼鈍工程は水素濃度1.0体積%以上の還元性雰囲気にて行うことが好ましく,2.0体積%以上の還元性雰囲気にて行うことがより好ましい。焼鈍工程における水素濃度の上限は特に限定されないが,コストの観点から,水素濃度は30.0体積%以下とすることが好ましく,20.0体積%以下とすることがより好ましい。焼鈍雰囲気の水素以外の残部は,窒素とすることが好ましい。
焼鈍工程において,650℃以上900℃以下の温度域での保持時間を,30秒以上600秒以下とすることが好ましい。当該温度域での保持時間を30秒以上とすることで,焼鈍前Fe系電気めっき層表面に形成したFeの自然酸化膜を好適に除去し,後述するようにFe系電気めっき鋼板表面に亜鉛めっき層を設ける際のめっき密着性を向上することができる。よって,当該温度域での保持時間は30秒以上とすることが好ましい。当該温度域での保持時間の上限は特に定めないが,生産性の観点から,当該温度域での保持時間は600秒以下とすることが好ましい。
焼鈍前Fe系電気めっき鋼板の最高到達温度は特に限定されないが,650℃以上900℃以下とすることが好ましい。焼鈍前Fe系電気めっき鋼板の最高到達温度を650℃以上とすることで,鋼板組織の再結晶が好適に進み,所望の強度を得ることができる。また,焼鈍前Fe系電気めっき層表面に形成したFeの自然酸化膜を好適に還元させ,後述するようにFe系電気めっき鋼板表面に亜鉛めっきを設ける際のめっき密着性を向上することができる。また,Fe系電気めっき鋼板の最高到達温度が900℃以下であれば,鋼中のSi及びMnの拡散速度が増加しすぎることを防ぎ,鋼板表面へのSi及びMnの拡散を防ぐことができるため,後述するようにFe系電気めっき鋼板表面に亜鉛めっきを設ける際のめっき密着性を向上することができる。また,最高到達温度が900℃以下であれば,熱処理炉の炉体ダメージを防ぐことができ,コストダウンすることもできる。よって,冷延鋼板の最高到達温度は900℃以下とすることが好ましい。なお,上記最高到達温度は,冷延鋼板の表面にて測定された温度を基準とする。
前記焼鈍工程後に,Fe系電気めっき鋼板に亜鉛めっきを施す。亜鉛めっき処理の方法は特に限定されないが,例えば溶融めっき,電気めっき,コールドスプレー,及びプラズマ溶射等であり得る。溶融亜鉛めっきを施す場合,一例においては,焼鈍工程後にFe系電気めっき鋼板を冷却し,溶融亜鉛めっき浴中に浸漬して,鋼板表面に溶融亜鉛めっきを施せばよい。溶融亜鉛めっき浴はAl,Zn及び不可避的不純物からなる。溶融亜鉛めっき浴の成分は特に規定しないが,一般的に浴中Al濃度が0.05質量%以上0.250質量%以下である。浴中Al濃度を0.05質量%以上とすれば,ボトムドロスの発生を防ぎ,ドロスが鋼板に付着して欠陥になることを防ぐことができる。また,浴中Al濃度を0.250質量%以下とすることで,トップドロスの増加を防ぎ,ドロスが鋼板に付着して欠陥になることを防ぐとともに,コストダウンにもつながる。溶融亜鉛めっき処理のその他の条件は制限されるものではないが,例えば,溶融亜鉛めっき浴の浴温度は通常の440~500℃の範囲で,板温440~550℃で鋼板を溶融亜鉛めっき浴中に浸漬させて行う。
まず,合金化亜鉛めっき鋼板から20×25mmサイズのサンプルを2か所採取する。それぞれの重量を測定した後,JIS H 0401(2013)またはISO 17925(2004)に規定された試験液を用いてFe系電気めっき層を有する片側の合金化亜鉛めっき層の剥離を行い,再び重量測定を行う。めっき剥離前の重量からめっき剥離後の重量を差し引き,めっき剥離部分の表面積で除することにより,合金化亜鉛めっき層の片面あたりの付着量を算出することができる。ここでは,2か所の平均値を合金化亜鉛めっき層の片面あたりの付着量とする。
また,本実施形態によれば,上述した合金化亜鉛めっき鋼板上に,前記合金化亜鉛めっき層上に形成された化成処理皮膜と,該化成皮膜上に形成された電着塗装皮膜とをさらに有する電着塗装鋼板を提供することもできる。本実施形態に係る合金化亜鉛めっき鋼板は,溶接部における耐抵抗溶接割れ特性に優れるため,該合金化亜鉛めっき鋼板を用いて形成した電着塗装鋼板は,自動車部品への適用に特に好適である。化成処理皮膜,及び電着塗装皮膜の種類は特に限定されず,公知の化成処理皮膜,及び電着塗装皮膜とすることができる。化成処理皮膜としては,リン酸亜鉛皮膜,ジルコニウム皮膜等が使用できる。電着塗装皮膜としては,自動車用の電着塗装皮膜であれば特に限定されない。電着塗装皮膜の厚みは,用途により異なるが,乾燥状態の塗膜で10μm以上30μm以下程度とすることが好ましい。また,本実施形態によれば,電着塗装を施すための電着塗装用合金化亜鉛めっき鋼板を提供することもできる。
次いで,上述した電着塗装鋼板の製造方法について説明する。上述した電着塗装鋼板は,合金化亜鉛めっき鋼板に化成処理を施して,前記合金化亜鉛めっき層上に化成処理皮膜が形成された化成処理鋼板を得る,化成処理工程と,前記化成処理鋼板に電着塗装処理を施して,前記化成処理皮膜上に電着塗装皮膜が形成された電着塗装鋼板を得る,電着塗装工程と,を含む,電着塗装鋼板の製造方法によって製造することができる。化成処理,及び電着塗装処理は,公知の方法によることができる。なお,化成処理を施す前の処理として,合金化亜鉛めっき鋼板表面を清浄化するための脱脂処理,水洗及び必要に応じて表面調整処理を施すことができる。これらの前処理に引き続いて化成処理を実施する。脱脂処理及び水洗の方法は特に限定されず,通常の方法を用いることができる。表面調整処理においては,Tiコロイド,あるいはリン酸亜鉛コロイドを有する表面調整剤等を使用できる。これらの表面調整剤を施すに際して,特別な工程を設ける必要はなく,常法に従い実施すればよい。例えば,所望の表面調整剤を所定の脱イオン水に溶解させ,十分攪拌したのち,既定の温度(通常は常温,25~30℃)の処理液とし,該処理液中に鋼板を所定時間(20~30秒)浸漬させる。引き続き乾燥させることなく,次工程の化成処理を行う。化成処理においても,常法に従い実施すればよい。例えば,所望の化成処理剤を所定の脱イオン水に溶解させ,十分攪拌したのち,所定の温度(通常35~45℃)の処理液とし,該処理液中に鋼板を所定時間(60~120秒)浸漬させる。化成処理剤としては,例えば鋼用のリン酸亜鉛処理剤,鋼・アルミニウム併用型のリン酸亜鉛処理剤,及びジルコニウム処理剤等を使用できる。引き続き,次工程の電着塗装を行う。電着塗装も,常法に従い実施すればよい。必要に応じて水洗処理等の前処理を施したのち,十分攪拌された電着塗料に鋼板を浸漬し,電着処理によって所望の厚みの電着塗装を得る。電着塗装としては,カチオン型の電着塗装の他,アニオン型電着塗装を使用できる。さらに,用途に応じて電着塗装後に上塗り塗装などを施してもよい。
また,本実施形態によれば,上述した電着塗装鋼板を少なくとも一部に用いてなる自動車部品を提供することができる。本実施形態に係る合金化亜鉛めっき鋼板は,溶接部における耐抵抗溶接割れ特性に優れるため,該合金化亜鉛めっき鋼板を用いた電着塗装鋼板は,自動車部品への適用に特に好適である。電着塗装鋼板を用いてなる自動車部品は,本実施形態に係る電着塗装鋼板以外の鋼板を,素材として含んでいてもよい。本実施形態に係る電着塗装鋼板は溶接部における耐抵抗溶接割れ特性に優れるため,該合金化亜鉛めっき鋼板を用いてなる自動車部品の溶接部におけるLME割れが好適に防がれる。電着塗装鋼板を少なくとも一部に用いてなる自動車部品の種類は特に限定されないが,例えば,サイドシル部品,ピラー部品,及び自動車車体等であり得る。
次に,本発明の実施形態2に係る合金化亜鉛めっき鋼板について説明する。
本実施形態に係る合金化亜鉛めっき鋼板は,
冷延鋼板と,
前記冷延鋼板の少なくとも片面に形成された,片面あたりの付着量が20.0g/m2超であるFe系電気めっき層と,
前記Fe系電気めっき層上に形成された合金化亜鉛めっき層とを有し,
前記Fe系電気めっき層と前記冷延鋼板との界面において前記Fe系電気めっき層と前記冷延鋼板との結晶方位が一体化している割合が50%超である,合金化亜鉛めっき鋼板であり得る。
ここで,前記冷延鋼板は,圧延直角方向を長手として50×150mmに切り出した試験片を,同サイズに切り出した溶融亜鉛めっき層の片面あたりの付着量が50g/m2である試験用合金化溶融亜鉛めっき鋼板と重ねて板組とし,
次いで,サーボモータ加圧式で単相交流(50Hz)の抵抗溶接機を用いて,該抵抗溶接機の電極対(先端径6mm)の中心軸同士を結んだ線に対する垂直面に対して前記板組を該板組の長手方向側に5°傾け,前記電極対の下側電極と前記試験片との間に前記板組の長手方向60mm×前記板組の厚さ方向2.0mmの空隙を設けて前記下側電極と前記板組とを固定し,前記電極対の上側電極を可動にした状態で,前記板組に,加圧力:3.5kN,ホールドタイム:0.16秒,並びにナゲット径が5.9mmになる溶接電流及び溶接時間の条件にて抵抗溶接を施して溶接部付き板組とし,
次いで,前記溶接部付き板組を溶接部を含むように前記試験片の長手方向に沿って半切して,該溶接部の断面を光学顕微鏡(倍率200倍)で観察した場合に,0.1mm以上の長さのき裂が認められる冷延鋼板である。
図8を用いて,溶接部における耐抵抗溶接割れ特性の評価方法について説明する。圧延直角方向(TD)を長手とし,圧延方向を短手として50×150mmに切り出した試験片6を,同サイズに切り出した,溶融亜鉛めっき層の片面あたりの付着量が50g/m2である試験用合金化溶融亜鉛めっき鋼板5と重ねて板組とする。板組は,試験片6の評価対象面(Fe系電気めっき層側の面)と,試験用合金化溶融亜鉛めっき鋼板5の亜鉛めっき層とが向かい合うように組み立てる。当該板組を,厚さ2.0mmのスペーサー7を介して,固定台8に固定する。スペーサー7は,長手方向50mm×短手方向45mm×厚さ2.0mmの一対の鋼板であり,図8(a)に示すように,一対の鋼板各々の長手方向端面が,板組短手方向両端面とそろうように配置する。よって,一対の鋼板間の距離は60mmとなる。固定台8は,中央部に穴が開いた一枚の板である。
◎ : ホールドタイム0.14秒で0.1mm以上の長さのき裂が認められない
○ : ホールドタイム0.14秒で0.1mm以上の長さのき裂が認められるが,ホールドタイム0.16秒で0.1mm以上の長さのき裂が認められない
× : ホールドタイム0.16秒で0.1mm以上の長さのき裂が認められる
◎ : ホールドタイム0.18秒で0.1mm以上の長さのき裂が認められない
○ : ホールドタイム0.18秒で0.1mm以上の長さのき裂が認められるが,ホールドタイム0.24秒で0.1mm以上の長さのき裂が認められない
× : ホールドタイム0.24秒で0.1mm以上の長さのき裂が認められる
一実施形態に係る合金化亜鉛めっき鋼板の製造方法は,
冷延鋼板にFe系電気めっきを施して,焼鈍前Fe系電気めっき層が少なくとも片面に形成された焼鈍前Fe系電気めっき鋼板とし,
次いで,前記焼鈍前Fe系電気めっき鋼板を露点-30℃以下の雰囲気下で焼鈍して,Fe系電気めっき鋼板とし,
次いで,前記Fe系電気めっき鋼板に亜鉛めっきを施して,亜鉛めっき鋼板とし,
次いで,前記亜鉛めっき鋼板に,合金化処理をさらに施して,片面あたりの付着量が20.0g/m2超のFe系電気めっき層を有する合金化亜鉛めっき鋼板を得る,合金化亜鉛めっき鋼板の製造方法であり得る。
ここで,前記冷延鋼板は,圧延直角方向を長手として50×150mmに切り出した試験片を,同サイズに切り出した溶融亜鉛めっき層の片面あたりの付着量が50g/m2である試験用合金化溶融亜鉛めっき鋼板と重ねて板組とし,
次いで,サーボモータ加圧式で単相交流(50Hz)の抵抗溶接機を用いて,該抵抗溶接機の電極対(先端径6mm)の中心軸同士を結んだ線に対する垂直面に対して前記板組を該板組の長手方向側に5°傾け,前記電極対の下側電極と前記試験片との間に前記板組の長手方向60mm×前記板組の厚さ方向2.0mmの空隙を設けて前記下側電極と前記板組とを固定し,前記電極対の上側電極を可動にした状態で,前記板組に,加圧力:3.5kN,ホールドタイム:0.16秒,並びにナゲット径が5.9mmになる溶接電流及び溶接時間の条件にて抵抗溶接を施して溶接部付き板組とし,
次いで,前記溶接部付き板組を溶接部を含むように前記試験片の長手方向に沿って半切して,該溶接部の断面を光学顕微鏡(倍率200倍)で観察した場合に,0.1mm以上の長さのき裂が認められる冷延鋼板である。
〔電解条件〕
浴温:50℃
pH:2.0
電流密度:45A/dm2
Fe系電気めっき浴:Fe2+イオンを1.5mol/L含む
電極(陽極):酸化イリジウム電極
合金化亜鉛めっき鋼板について,上述した方法に従って,板組相手が,0.18秒のホールドタイムにおいて耐抵抗溶接割れ特性が課題とならないSiが0.5%未満の引張強さが980MPa級,及び片面あたりの付着量が50g/m2の試験用合金化溶融亜鉛めっき鋼板(板厚1.6mm)である場合の溶接部における耐抵抗溶接割れ特性を評価した。溶接時間は0.36秒,ホールドタイムは0.18秒及び0.24秒とし,実施例No.毎に溶接電流を変化させてナゲット径を測定し,ナゲット径が5.9mmとなる溶接電流にて評価した。また,板組相手である試験用合金化溶融亜鉛めっき鋼板に割れが発生していないものを実施例データとして採用した。板組相手に割れが発生した場合,評価対象の合金化亜鉛めっき鋼板への応力が分散し,適切な評価とならないためである。
〔電解条件〕
浴温:50℃
pH:2.0
電流密度:45A/dm2
Fe系電気めっき浴:Fe2+イオンを1.5mol/L含む
電極(陽極):酸化イリジウム電極
合金化亜鉛めっき鋼板について,上述した方法に従って,板組相手が,0.14秒のホールドタイムにおいて耐抵抗溶接割れ特性が課題とならないSiが0.1%未満の引張強さが590MPa級,及び片面あたりの付着量が50g/m2の試験用合金化溶融亜鉛めっき鋼板(板厚1.6mm)である場合の溶接部における耐抵抗溶接割れ特性を評価した。溶接時間は0.36秒,ホールドタイムは0.14秒及び0.16秒とし,実施例No.毎に溶接電流を変化させてナゲット径を測定し,ナゲット径が5.9mmとなる溶接電流にて評価した。また,板組相手である試験用合金化溶融亜鉛めっき鋼板に割れが発生していないものを実施例データとして採用した。板組相手に割れが発生した場合,評価対象の合金化亜鉛めっき鋼板への応力が分散し,適切な評価とならないためである。
2 Si含有冷延鋼板
3 Fe系電気めっき層
4 合金化亜鉛めっき層
5 試験用合金化溶融亜鉛めっき鋼板
6 試験片
7 スペーサー
8 固定台
9 電極
10 ナゲット
11 き裂
Claims (18)
- Siを0.1質量%以上3.0質量%以下含有するSi含有冷延鋼板と,
前記Si含有冷延鋼板の少なくとも片面に形成された,片面あたりの付着量が20.0g/m2超であるFe系電気めっき層と,
前記Fe系電気めっき層上に形成された合金化亜鉛めっき層とを有し,
前記Fe系電気めっき層と前記Si含有冷延鋼板との界面において前記Fe系電気めっき層と前記Si含有冷延鋼板との結晶方位が一体化している割合が50%超である,合金化亜鉛めっき鋼板。 - 前記Si含有冷延鋼板は,Siを0.50質量%以上3.0質量%以下含有する,請求項1に記載の合金化亜鉛めっき鋼板。
- 前記Fe系電気めっき層の片面あたりの付着量が,25.0g/m2以上である,請求項1または2に記載の合金化亜鉛めっき鋼板。
- 前記Si含有冷延鋼板は,前記Siに加えて,質量%で,
C:0.8%以下,
Mn:1.0%以上12.0%以下,
P:0.1%以下,
S:0.03%以下,
N:0.010%以下及び
Al:1.0%以下を含有し,残部がFe及び不可避的不純物からなる成分組成を有する,請求項1から3のいずれか1項に記載の合金化亜鉛めっき鋼板。 - 前記成分組成がさらに,
B:0.005%以下,
Ti:0.2%以下,
Cr:1.0%以下,
Cu:1.0%以下,
Ni:1.0%以下,
Mo:1.0%以下,
Nb:0.20%以下,
V:0.5%以下,
Sb:0.200%以下,
Ta:0.1%以下,
W:0.5%以下,
Zr:0.1%以下,
Sn:0.20%以下,
Ca:0.005%以下,
Mg:0.005%以下及び
REM:0.005%以下
からなる群から選ばれる1種または2種以上を含有する,請求項4に記載の合金化亜鉛めっき鋼板。 - 前記Fe系電気めっき層は,B,C,P,N,O,Ni,Mn,Mo,Zn,W,Pb,Sn,Cr,V及びCoからなる群から選ばれる1または2以上の元素を合計で10質量%以下含み,残部はFe及び不可避的不純物からなる成分組成を有する,請求項1から5のいずれか1項に記載の合金化亜鉛めっき鋼板。
- 冷延鋼板と,
前記冷延鋼板の少なくとも片面に形成された,片面あたりの付着量が20.0g/m2超であるFe系電気めっき層と,
前記Fe系電気めっき層上に形成された合金化亜鉛めっき層とを有し,
前記Fe系電気めっき層と前記冷延鋼板との界面において前記Fe系電気めっき層と前記冷延鋼板との結晶方位が一体化している割合が50%超である,合金化亜鉛めっき鋼板。
ここで,前記冷延鋼板は,圧延直角方向を長手として50×150mmに切り出した試験片を,同サイズに切り出した溶融亜鉛めっき層の片面あたりの付着量が50g/m2である試験用合金化溶融亜鉛めっき鋼板と重ねて板組とし,
次いで,サーボモータ加圧式で単相交流(50Hz)の抵抗溶接機を用いて,該抵抗溶接機の電極対(先端径6mm)の中心軸同士を結んだ線に対する垂直面に対して前記板組を該板組の長手方向側に5°傾け,前記電極対の下側電極と前記試験片との間に前記板組の長手方向60mm×前記板組の厚さ方向2.0mmの空隙を設けて前記下側電極と前記板組とを固定し,前記電極対の上側電極を可動にした状態で,前記板組に,加圧力:3.5kN,ホールドタイム:0.16秒,並びにナゲット径が5.9mmになる溶接電流及び溶接時間の条件にて抵抗溶接を施して溶接部付き板組とし,
次いで,前記溶接部付き板組を溶接部を含むように前記試験片の長手方向に沿って半切して,該溶接部の断面を光学顕微鏡(倍率200倍)で観察した場合に,0.1mm以上の長さのき裂が認められる冷延鋼板である。 - 前記冷延鋼板は,前記ホールドタイムを0.24秒とした条件にて,前記抵抗溶接を施して前記溶接部付き板組を得,前記溶接部の断面を前記光学顕微鏡(倍率200倍)で観察した場合に,0.1mm以上の長さのき裂が認められる冷延鋼板である,請求項7に記載の合金化亜鉛めっき鋼板。
- 請求項1から8のいずれか1項に記載の合金化亜鉛めっき鋼板上に,化成処理皮膜と,該化成処理皮膜上に形成された電着塗装皮膜とをさらに有する,電着塗装鋼板。
- 請求項9に記載の電着塗装鋼板を少なくとも一部に用いてなる,自動車部品。
- 請求項1から8のいずれか1項に記載の合金化亜鉛めっき鋼板に化成処理を施して,前記合金化亜鉛めっき層上に化成処理皮膜が形成された化成処理鋼板を得る,化成処理工程と,
前記化成処理鋼板に電着塗装処理を施して,前記化成処理皮膜上に電着塗装皮膜が形成された電着塗装鋼板を得る,電着塗装工程と,
を含む,電着塗装鋼板の製造方法。 - Siを0.1質量%以上3.0質量%以下含有する冷延鋼板にFe系電気めっきを施して,焼鈍前Fe系電気めっき層が少なくとも片面に形成された焼鈍前Fe系電気めっき鋼板とし,
次いで,前記焼鈍前Fe系電気めっき鋼板を露点-30℃以下の雰囲気下で焼鈍して,Fe系電気めっき鋼板とし,
次いで,前記Fe系電気めっき鋼板に亜鉛めっきを施して,亜鉛めっき鋼板とし,
次いで,前記亜鉛めっき鋼板に,合金化処理をさらに施して,片面あたりの付着量が20.0g/m2超のFe系電気めっき層を有する合金化亜鉛めっき鋼板を得る,合金化亜鉛めっき鋼板の製造方法。 - 前記冷延鋼板は,Siを0.5質量%以上3.0質量%以下含有する,請求項12に記載の合金化亜鉛めっき鋼板の製造方法。
- 前記焼鈍前Fe系電気めっき層の片面あたりの付着量C.W.Fe0(g/m2)が下式(1)を満足する,請求項12または13に記載の合金化亜鉛めっき鋼板の製造方法。
(C.W.Fe0)>20.0+(C.W.Zn)×[mass%Fe]/100・・・(1)
ここで,C.W.Zn:合金化亜鉛めっき層の片面あたりの付着量の目標値(g/m2)
ただし,25.0g/m2≦C.W.Zn≦80.0g/m2
[mass%Fe]:前記合金化亜鉛めっき層中のFe含有量の目標値(質量%) - 冷延鋼板にFe系電気めっきを施して,焼鈍前Fe系電気めっき層が少なくとも片面に形成された焼鈍前Fe系電気めっき鋼板とし,
次いで,前記焼鈍前Fe系電気めっき鋼板を露点-30℃以下の雰囲気下で焼鈍して,Fe系電気めっき鋼板とし,
次いで,前記Fe系電気めっき鋼板に亜鉛めっきを施して,亜鉛めっき鋼板とし,
次いで,前記亜鉛めっき鋼板に,合金化処理をさらに施して,片面あたりの付着量が20.0g/m2超のFe系電気めっき層を有する合金化亜鉛めっき鋼板を得る,合金化亜鉛めっき鋼板の製造方法。
ここで,前記冷延鋼板は,圧延直角方向を長手として50×150mmに切り出した試験片を,同サイズに切り出した溶融亜鉛めっき層の片面あたりの付着量が50g/m2である試験用合金化溶融亜鉛めっき鋼板と重ねて板組とし,
次いで,サーボモータ加圧式で単相交流(50Hz)の抵抗溶接機を用いて,該抵抗溶接機の電極対(先端径6mm)の中心軸同士を結んだ線に対する垂直面に対して前記板組を該板組の長手方向側に5°傾け,前記電極対の下側電極と前記試験片との間に前記板組の長手方向60mm×前記板組の厚さ方向2.0mmの空隙を設けて前記下側電極と前記板組とを固定し,前記電極対の上側電極を可動にした状態で,前記板組に,加圧力:3.5kN,ホールドタイム:0.16秒,並びにナゲット径が5.9mmになる溶接電流及び溶接時間の条件にて抵抗溶接を施して溶接部付き板組とし,
次いで,前記溶接部付き板組を溶接部を含むように前記試験片の長手方向に沿って半切して,該溶接部の断面を光学顕微鏡(倍率200倍)で観察した場合に,0.1mm以上の長さのき裂が認められる冷延鋼板である。 - 前記冷延鋼板は,前記ホールドタイムを0.24秒とした条件にて,前記溶接部の断面を光学顕微鏡(倍率200倍)で観察した場合に,0.1mm以上の長さのき裂が認められる冷延鋼板である,請求項15に記載の合金化亜鉛めっき鋼板の製造方法。
- 前記焼鈍前Fe系電気めっき層の片面あたりの付着量C.W.Fe0(g/m2)が下式(1)を満足する,請求項15または16に記載の合金化亜鉛めっき鋼板の製造方法。
(C.W.Fe0)>20.0+(C.W.Zn)×[mass%Fe]/100・・・(1)
ここで,C.W.Zn:合金化亜鉛めっき層の片面あたりの付着量の目標値(g/m2)
ただし,25.0g/m2≦C.W.Zn≦80.0g/m2
[mass%Fe]:前記合金化亜鉛めっき層中のFe含有量の目標値(質量%) - B,C,P,N,O,Ni,Mn,Mo,Zn,W,Pb,Sn,Cr,V及びCoからなる群から選ばれる1または2以上の元素を,前記焼鈍前Fe系電気めっき層中でこれらの元素の合計含有量が10質量%以下となるように含有するFe系電気めっき浴を用いて,前記Fe系電気めっきを施す,請求項12から17のいずれか1項に記載の合金化亜鉛めっき鋼板の製造方法。
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JP2022520146A JP7323063B2 (ja) | 2020-11-06 | 2021-11-05 | 合金化亜鉛めっき鋼板,電着塗装鋼板,自動車部品,電着塗装鋼板の製造方法,及び合金化亜鉛めっき鋼板の製造方法 |
US18/251,269 US20230407485A1 (en) | 2020-11-06 | 2021-11-05 | Alloyed galvanized steel sheet, electrodeposition-coated steel sheet, automotive part, method of producing electrodeposition-coated steel sheet, and method of producing alloyed galvanized steel sheet |
KR1020237018523A KR20230098325A (ko) | 2020-11-06 | 2021-11-05 | 합금화 아연 도금 강판, 전착 도장 강판, 자동차 부품, 전착 도장 강판의 제조 방법 및, 합금화 아연 도금 강판의 제조 방법 |
MX2023005275A MX2023005275A (es) | 2020-11-06 | 2021-11-05 | Lámina de acero galvanizado por aleación, lámina de acero recubierta por electrodeposición, pieza automotriz, método de producción de lámina de acero recubierta por electrodeposición, y método de producción de lámina de acero galvanizado por aleación. |
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CN116568869A (zh) | 2023-08-08 |
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