WO2011090184A1 - 加工性とスポット溶接性に優れた高強度溶融亜鉛めっき鋼板およびその製造方法 - Google Patents
加工性とスポット溶接性に優れた高強度溶融亜鉛めっき鋼板およびその製造方法 Download PDFInfo
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- WO2011090184A1 WO2011090184A1 PCT/JP2011/051159 JP2011051159W WO2011090184A1 WO 2011090184 A1 WO2011090184 A1 WO 2011090184A1 JP 2011051159 W JP2011051159 W JP 2011051159W WO 2011090184 A1 WO2011090184 A1 WO 2011090184A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0421—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
- C21D8/0426—Hot rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0421—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
- C21D8/0436—Cold rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/009—Pearlite
Definitions
- the present invention relates to a high-strength hot-dip galvanized steel sheet excellent in workability and spot weldability suitable as a member used in industrial fields such as automobiles and electricity, and a method for producing the same.
- Patent Document 1 proposes a steel sheet having excellent ductility by specifying chemical components, volume ratios of retained austenite and martensite, and manufacturing methods thereof.
- the steel plate excellent in ductility is proposed by prescribing
- Patent Document 3 proposes a steel sheet having excellent ductility by defining chemical components and defining volume fractions of ferrite, bainitic ferrite and retained austenite.
- Patent Documents 1 to 3 are mainly aimed at improving the ductility of high-strength thin steel sheets, the stretch flangeability (hole expansibility) is not sufficiently considered, so parts in press forming There is a problem that the application range of the shape is limited. Furthermore, in order to achieve the desired strength and workability, it is necessary to add a large amount of alloying elements. Hardening of the melted part of the spot welded part, softening of the heat affected zone (HAZ part), and solidification of the molten part There was a tendency for the weld strength to decrease due to the embrittlement of the steel.
- Patent Document 4 a high-strength cold-rolled steel sheet with improved spot weldability by microstructure control and a small amount of Mo is added.
- Patent Document 6 a steel sheet that has improved spot weldability is proposed in Patent Document 6 by reducing the amount of Si and P added to the composite structure steel sheet.
- Patent Document 4 it is proposed to suppress weld defects such as cracks and voids during spot welding by adding Mo, but only the tensile shear strength is examined, and cross tension is likely to cause problems with high-strength materials. It is hard to say that strength (ductility ratio) has been fully studied.
- Patent Document 5 it is proposed to ensure strength by precipitation strengthening of ferrite with charcoal and nitride, and to suppress the addition amount of C, Si, Mn so as not to cause cracks in the nugget at the check check. However, even if it can cope with the check at the time of welding, the practical spot weld strength is not considered.
- Patent Document 6 only the generation of dust and the fracture mode of the tensile test are examined, and not only the spot weld strength in practical use is taken into consideration, but also limited to manufacturing in the hot rolling process. Yes.
- the present invention has a high strength (tensile strength TS of 540 MPa or more), a high strength hot dip galvanized steel sheet excellent in workability (high ductility and high hole expansibility) and spot weldability, and It aims at providing the manufacturing method.
- C is 0.04 to 0.16%
- Si is 0.7 to 2.3%
- Mn is 1.5 to 1.6%
- P is 0.01 to 0.02%
- S is 0.
- the obtained steel was heated to 1200 ° C. and then hot-rolled to a thickness of 3.2 mm at a finishing temperature of 870 ° C. and held in a furnace at 520 ° C. for 1 hour. After that, the furnace was cooled. After pickling, the sheet thickness was cold-rolled to 1.4 mm to produce a cold-rolled steel sheet.
- an annealing treatment was performed at 825 ° C. for 120 seconds, and after cooling to 520 ° C., it was held as it was for 60 seconds.
- the obtained cold-rolled steel sheet was immersed in a hot-dip galvanizing bath and plated, and then alloyed at 550 ° C. for 15 seconds to produce a hot-dip galvanized steel sheet.
- the obtained steel sheet is subjected to spot welding of two layers under a welding condition where the cross-sectional nugget diameter is 5.0 mm, the shear tensile strength and the cross tensile strength are measured, and the ductility ratio (cross tensile strength / shear tensile strength) is evaluated. did.
- the spot welding was conducted and evaluated according to the Japan Welding Association (JWES) standard WES7301. As a result, as shown in FIG. 1, the product of C addition amount and Si addition amount showed a high ductility ratio in the range of 0.20 or less, and it was found that spot weldability was remarkably improved.
- JWES Japan Welding Association
- the present inventors further obtain a high-strength hot-dip galvanized steel sheet having high strength (tensile strength TS of 540 MPa or more) and excellent workability (high ductility and high hole expansibility) and spot weldability.
- high strength tensile strength TS of 540 MPa or more
- excellent workability high ductility and high hole expansibility
- the ferrite phase fraction (area ratio) and the structure of the second phase are appropriately adjusted, and the product of the addition amount of C and the addition amount of Si is further calculated.
- high strength and workability ductility and hole expansibility
- the present invention has been made based on the above findings, and the gist thereof is as follows.
- Component composition is mass% C: 0.04% to 0.10%, Si: 0.7% to 2.3%, Mn: 0.8% to 2.0%, P : 0.03% or less, S: 0.003% or less, Al: 0.1% or less, N: 0.008% or less, and [C%] ⁇ [Si%] ⁇ 0.20 [C%] and [Si%] indicate the content of C and Si (mass%).
- the balance is composed of iron and inevitable impurities, and the structure has a ferrite phase of 75% or more in area ratio.
- a component composition it contains at least one element selected from Ti: 0.01% to 0.1% and Nb: 0.01% to 0.1% by mass%.
- a component composition it contains at least one element selected from Ta: 0.001% to 0.010% and Sn: 0.002% to 0.2% by mass%
- a steel slab having the composition described in any one of (1) to (5) is hot-rolled, pickled, and cold-rolled as necessary, and then up to a temperature range of 650 ° C. or higher.
- Heat at an average heating rate of °C / s or more hold for 15 to 600 s in the temperature range of 750 to 900 ° C, cool, hold for 10 to 200 s in the temperature range of 450 to 550 ° C, and then hot dip galvanizing After applying, in the temperature range of 500-600 °C 0.45 ⁇ exp [200 / (400 ⁇ T)] ⁇ ln (t) ⁇ 1.0
- T Average holding temperature (° C.)
- t Holding time (s)
- a method for producing a high-strength hot-dip galvanized steel sheet excellent in workability and spot weldability characterized by subjecting a galvanizing alloying treatment under conditions satisfying the above conditions.
- the present invention it becomes possible to produce a high-strength hot-dip galvanized steel sheet having high strength (tensile strength TS of 540 MPa or more) and excellent workability (high ductility and high hole expansibility) and spot weldability. .
- high-strength hot-dip galvanized steel sheet according to the present invention to, for example, automobile structural members, it is possible to further improve the safety of passengers and improve fuel efficiency by significantly reducing the weight of the vehicle body.
- Component composition C 0.04% or more and 0.10% or less C is an element important for strengthening steel, has high solid solution strengthening ability, and has an area ratio when utilizing structure strengthening. It is an indispensable element for adjusting hardness. If the amount of C is less than 0.04%, it will be difficult to obtain the necessary strengthening ability. On the other hand, if the amount of C exceeds 0.10%, weldability deteriorates and a low temperature transformation phase such as martensite is markedly cured, leading to a decrease in formability, particularly hole expansibility. Therefore, the C content is 0.04 to 0.10%.
- Si 0.7% or more and 2.3% or less Si promotes the formation of ferrite and improves the work hardening ability of the ferrite phase to improve ductility. In addition, it is an element effective for solid solution strengthening and effective for increasing strength. In order to obtain these effects, addition of 0.7% or more is necessary. However, excessive addition of Si exceeding 2.3% causes deterioration of surface properties and deterioration of plating adhesion. Therefore, Si is made 0.7% to 2.3%. Preferably, it is 1.2% or more and 1.8% or less.
- Mn 0.8% or more and 2.0% or less
- Mn is an element effective for strengthening steel.
- it is an element that stabilizes austenite, and is an element necessary for adjusting the fraction of the second phase. For this reason, it is necessary to add 0.8% or more of Mn.
- Mn is made 0.8% or more and 2.0% or less. Preferably they are 1.0% or more and 1.8% or less.
- P 0.03% or less
- P is an element effective for strengthening steel, but when added in excess of 0.03%, it causes embrittlement due to segregation at the grain boundary, and deteriorates impact resistance. It promotes solidification cracking during welding and reduces welding strength. Therefore, P is set to 0.03% or less. Preferably it is 0.02% or less, More preferably, it is 0.01% or less.
- S 0.003% or less S segregates at the grain boundary and embrittles the steel during hot working, and also exists as a sulfide to reduce local deformability. Furthermore, solidification cracking during welding is promoted and welding strength is reduced. Therefore, S is made 0.003% or less. Preferably it is 0.002% or less, More preferably, it is 0.001% or less.
- Al 0.1% or less Al is a ferrite-forming element and is an effective element for controlling the amount of ferrite produced during production. However, excessive addition of Al deteriorates slab quality during steelmaking. Therefore, Al is made 0.1% or less.
- N 0.008% or less
- N is an element that causes the most deterioration of the aging resistance of the steel, and it is preferably as small as possible. If it exceeds 0.008%, the deterioration of the aging resistance becomes significant. Therefore, N is set to 0.008% or less.
- the balance is Fe and inevitable impurities.
- at least one selected from the following elements can be added as necessary.
- Cr 0.05% to 1.0%, V: 0.005% to 0.5%, Mo: 0.005% to 0.5%, B: 0.0003% to 0.0050%
- Ni: 0.05% or more and 1.0% or less, Cu: 0.05% or more and 1.0% or less Cr, V, and Mo are added as necessary because they have an effect of improving the balance between strength and ductility. can do.
- the effect is obtained when Cr: 0.05% or more, V: 0.005% or more, and Mo: 0.005% or more.
- Cr is added in excess of 1.0%, V: 0.5%, and Mo: 0.5%
- the second phase fraction becomes excessive, and there is a concern that the strength is significantly increased.
- the cost increases. Therefore, when these elements are added, the amounts thereof are Cr: 0.05% to 1.0%, V: 0.005% to 0.5%, Mo: 0.005% to 0%, respectively. .5% or less.
- B has the effect of suppressing the formation and growth of ferrite from the austenite grain boundaries, and can be added as necessary.
- the effect is obtained at 0.0003% or more.
- it exceeds 0.0050% the workability deteriorates.
- the cost increases. Therefore, when adding B, it is made into 0.0003% or more and 0.0050% or less.
- Ni and Cu are effective elements for strengthening steel and can be used for strengthening steel as long as they are within the range specified in the present invention. It also promotes internal oxidation and improves plating adhesion. In order to obtain these effects, 0.05% or more is required. On the other hand, if both Ni and Cu are added in excess of 1.0%, the workability of the steel sheet is lowered. In addition, the cost increases. Therefore, when adding Ni and Cu, the addition amount is 0.05% or more and 1.0% or less, respectively.
- one or more elements can be contained from the following Ti and Nb.
- Nb 0.01% or more and 0.1% or less
- Ti 0.01% or more and 0.1% or less
- Nb 0.01% or more and 0.1% or less
- Ti is effective for precipitation strengthening of steel, and the effect is obtained at 0.01% or more, If it is within the range specified in the present invention, it may be used for strengthening steel. However, when each exceeds 0.1%, workability and shape freezing property will fall. In addition, the cost increases. Therefore, when adding Ti and Nb, the addition amount is set to 0.01% to 0.1% for Ti and 0.01% to 0.1% for Nb.
- one or more elements can be contained from the following Ta and Sn.
- Ta 0.001 to 0.010%
- Sn 0.002 to 0.2% Ta
- Ta forms alloy carbide and alloy carbonitride to contribute to high strength, and partly dissolves in Nb carbide and Nb carbonitride, and (Nb, Ta)
- the content is preferably 0.001% or more.
- Ta its content is preferably 0.010% or less.
- Sn can be added from the viewpoint of suppressing decarburization in the region of several tens of ⁇ m of the steel sheet surface layer caused by nitriding, oxidation, or oxidation of the steel sheet surface. By suppressing such nitriding and oxidation, the amount of martensite generated on the steel sheet surface is prevented from decreasing, and fatigue characteristics and aging resistance are improved. From the viewpoint of suppressing nitriding and oxidation, when adding Sn, its content is preferably 0.002% or more, and if it exceeds 0.2%, the toughness is reduced, so its content is reduced to 0. .2% or less is desirable.
- Sb 0.002 to 0.2%
- Sb can also be added from the viewpoint of suppressing decarburization in the region of several tens of ⁇ m of the steel sheet surface layer caused by nitridation, oxidation, or oxidation of the steel sheet surface, similarly to Sn. By suppressing such nitriding and oxidation, the amount of martensite generated on the steel sheet surface is prevented from decreasing, and fatigue characteristics and aging resistance are improved. From the viewpoint of suppressing nitriding and oxidation, when Sb is added, its content is preferably 0.002% or more, and if it exceeds 0.2%, the toughness is reduced, so the content is reduced to 0. .2% or less is desirable.
- Area ratio of ferrite phase 75% or more In order to ensure good ductility, the ferrite phase needs to have an area ratio of 75% or more.
- Area ratio of bainitic ferrite phase 1% or more In order to ensure good hole expansibility, that is, to reduce the hardness difference between soft ferrite and hard martensite, the area ratio of bainitic ferrite phase is 1 % Or more is necessary.
- Area ratio of pearlite phase 1% or more and 10% or less
- the area ratio of the pearlite phase needs to be 1% or more.
- the area ratio of the pearlite phase is set to 10% or less.
- Area ratio of martensite phase less than 5% In order to ensure good material stability, the area ratio of the martensite phase that greatly affects the tensile properties (TS, EL) needs to be less than 5%.
- reduce the amount of martensite that causes the material variation in the phase structure of the second phase and increase the amount of bainitic ferrite and pearlite that are softer than martensite. That is, it is necessary to satisfy the martensite area ratio / (bainitic ferrite area ratio + pearlite area ratio) ⁇ 0.6.
- carbides such as retained austenite, tempered martensite, and cementite may be produced. If the rate is satisfied, the object of the present invention can be achieved.
- the area ratio of ferrite, bainitic ferrite, pearlite, and martensite in the present invention is the area ratio of each phase in the observation area.
- the high-strength hot-dip galvanized steel sheet of the present invention is a steel slab having a component composition suitable for the above-described component composition range, hot-rolled, pickled, and cold-rolled as necessary, and a temperature range of 650 ° C. or higher. Is heated at an average heating rate of 5 ° C./s or more, held at a temperature range of 750 to 900 ° C. for 15 to 600 s, cooled, held at a temperature range of 450 to 550 ° C.
- the steel having the above component composition is melted by a generally known process, then formed into a slab through a lump or continuous casting, and then into a hot coil through hot rolling.
- hot rolling it is preferable to heat the slab to 1100 to 1300 ° C., perform hot rolling at a final finishing temperature of 850 ° C. or higher, and wind it on a steel strip at 400 to 650 ° C.
- the coiling temperature exceeds 650 ° C., the carbides in the hot-rolled sheet are coarsened, and such coarsened carbides cannot be melted during soaking at the time of annealing, so that the required strength may not be obtained. .
- cold rolling is performed as necessary.
- the annealing temperature exceeds 900 ° C.
- the austenite grains grow remarkably, and it becomes difficult to ensure the stability of bainitic ferrite due to the bainite transformation that occurs during holding after cooling, and the hole expansibility decreases.
- austenite coarsens it becomes difficult to ensure desired strength, and it may cause an increase in cost due to enormous energy consumption.
- the steel sheet is infiltrated into a normal bath temperature plating bath to perform hot dip galvanization, and the amount of adhesion is adjusted by gas wiping or the like. Furthermore, galvanization alloying treatment is performed under the following conditions.
- T average holding temperature (° C.)
- t holding time (s) is the following formula; 0.45 ⁇ exp [200 / (400 ⁇ T)] ⁇ ln (t) ⁇ 1.0
- An alloying treatment of galvanization is performed under conditions that satisfy the above conditions.
- the holding temperature does not have to be constant as long as it is within the above-described temperature range, and even if the heating rate changes during heating, it may be within the specified range. Thus, the gist of the present invention is not impaired. Further, as long as the thermal history is satisfied, the steel sheet may be heat-treated by any equipment. In addition, temper rolling of the steel sheet of the present invention for shape correction after heat treatment is also included in the scope of the present invention. In the present invention, it is assumed that the steel material is manufactured through normal steelmaking, casting, and hot rolling processes, but the manufacturing process is performed by omitting part or all of the hot rolling process by thin casting, for example. You may do it.
- the cold-rolled steel sheet or hot-rolled steel sheet (after pickling) obtained as described above is subjected to annealing, hot-dip galvanizing, and alloying treatment with a continuous hot-dip galvanizing line under the production conditions shown in Table 2, and hot-dip zinc A plated steel sheet was produced.
- the amount of plating adhesion was adjusted to be 35 to 45 g / m 2 per side.
- the area ratio of ferrite, bainitic ferrite, pearlite, and martensite in the obtained hot-dip galvanized steel sheet was corroded with 3% nital after polishing the plate thickness section parallel to the rolling direction of the steel sheet, and SEM (scanning type) Ten fields of view were observed at a magnification of 2000 using an electron microscope, and image processing was performed using Image-Pro of Media Cybernetics.
- the volume fraction of retained austenite is the same as that of the fcc iron with respect to the X-ray diffraction integrated intensity of the ⁇ 200 ⁇ , ⁇ 211 ⁇ , ⁇ 220 ⁇ planes of bcc iron on a 1/4 thickness plane using a Mo—K ⁇ radiation source. 200 ⁇ , ⁇ 220 ⁇ , and ⁇ 311 ⁇ plane X-ray diffraction integrated intensity ratio.
- the tensile test is conducted in accordance with Japanese Industrial Standard (JIS Z2241) using JIS No. 5 test piece with the tensile direction perpendicular to the rolling direction of the steel sheet, and TS (tensile strength) and EL (total elongation) are measured. did.
- JIS Z2241 Japanese Industrial Standard
- TS tensile strength
- EL total elongation
- the hole expansion test was performed in accordance with the Japan Iron and Steel Federation standard (JFST1001). After punching a hole with a diameter of 10 mm in a steel plate, a punch having a 60 ° cone was pushed into the hole in a state where the periphery was constrained, and the hole diameter at the crack initiation limit was measured. From the following formula, the hole expansion ratio ⁇ (%) was obtained, and the hole expandability (stretch flangeability) was evaluated.
- Limit hole expansion rate ⁇ (%) ⁇ (Df ⁇ D0) / D0 ⁇ ⁇ 100
- Df is the hole diameter at the time of crack occurrence (mm)
- D0 is the initial hole diameter (mm)
- ⁇ ⁇ 70 (%) is determined to be good.
- the spot welding and its evaluation were performed in accordance with the Japan Welding Association standard (WES7301).
- Two-layer spot welding of steel sheets was performed under welding conditions with a cross-sectional nugget diameter of 5.0 mm, shear tensile strength and cross tensile strength were measured, and ductility ratio (cross tensile strength / shear tensile strength) was evaluated. In the present invention, it was determined that the ductility ratio ⁇ 0.5 was good.
- the evaluation results are shown in Table 3.
- the high-strength hot-dip galvanized steel sheets of the examples of the present invention all have a TS of 540 MPa or more, exhibit excellent ductility and hole expansibility, and exhibit high spot weld strength.
- the high-strength hot-dip galvanized steel sheet of the comparative example is inferior in at least one characteristic of ductility, hole expansibility and spot welding strength.
- the present invention it is possible to produce a high-strength hot-dip galvanized steel sheet having high strength (tensile strength TS of 540 MPa or more) and excellent workability (high ductility and high hole expansibility) and spot weldability. It becomes.
- high-strength hot-dip galvanized steel sheet according to the present invention to, for example, automobile structural members, it is possible to further improve the safety of passengers and improve fuel efficiency by significantly reducing the weight of the vehicle body.
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Abstract
Description
0.45≦exp[200/(400−T)]×ln(t)≦1.0
T:平均保持温度(℃)、t:保持時間(s)
を満たす条件で亜鉛めっきの合金化処理を施すことを特徴とする加工性とスポット溶接性に優れた高強度溶融亜鉛めっき鋼板の製造方法。
C:0.04%以上0.10%以下
Cは、鋼を強化するにあたり重要な元素であり、高い固溶強化能を有するとともに、組織強化を利用する際に、その面積率や硬度を調整するために不可欠な元素である。C量が0.04%未満では、必要な強化能を得るのが困難になる。一方、C量が0.10%を超えると、溶接性が劣化するともに、マルテンサイトなどの低温変態相が著しく硬化して成形性、特に穴拡げ性の低下を招く。したがって、C量は0.04~0.10%とする。
Siはフェライト生成を促進するとともに、フェライト相の加工硬化能を高めて延性を向上する。また、固溶強化に有効な元素であり強度の上昇に有効である。これらの効果を得るためには0.7%以上の添加が必要である。しかしながら、2.3%を超えるSiの過剰な添加は、表面性状の劣化や、めっき密着性の低下を引き起こす。よって、Siは0.7%以上2.3%以下とする。好ましくは、1.2%以上1.8%以下である。
CとSiは、本発明においては複合的に添加量を制御することが極めて重要である。CとSiはいずれもスポット溶接時の溶融部の硬度を上昇して、溶融部と母材部間での応力集中を促進して溶接部強度を低下させる作用を有する。特に両方の元素を複合で添加させるとこの効果が相乗的に作用し、ある特定の値を超えると溶接部強度が極端に低下する。従って、C添加量(%)とSi添加量(%)の積を0.20以下とする。
Mnは、鋼の強化に有効な元素である。また、オーステナイトを安定化させる元素であり、第二相の分率調整に必要な元素である。このため、Mnは0.8%以上の添加が必要である。一方、2.0%を超えて過剰に添加すると、第二相中のマルテンサイト面積率が増加し、材質安定性の確保が困難となる。また、近年Mnの合金コストが高騰しているため、コストアップの要因にも繋がる。従って、Mnは0.8%以上2.0%以下とする。好ましくは1.0%以上1.8%以下である。
Pは、鋼の強化に有効な元素であるが、0.03%を超えて過剰に添加すると、粒界偏析により脆化を引き起こし、耐衝撃性を劣化させるとともに、溶接時の凝固割れを助長し溶接強度を低下させる。従って、Pは0.03%以下とする。好ましくは0.02%以下、より好ましくは0.01%以下である。
Sは、粒界に偏析して熱間加工時に鋼を脆化させるとともに、硫化物として存在して局部変形能を低下させる。さらに、溶接時の凝固割れを助長し溶接強度を低下させる。そのため、Sは0.003%以下とする。好ましくは0.002%以下、より好ましくは0.001%以下である。
Alは、フェライト生成元素であり、製造時におけるフェライト生成量をコントロールするのに有効な元素である。しかしながら、Alの過剰な添加は製鋼時におけるスラブ品質を劣化させる。そのため、Alは0.1%以下とする。
Nは、鋼の耐時効性を最も大きく劣化させる元素であり、少ないほど好ましく、0.008%を超えると耐時効性の劣化が顕著となる。従って、Nは0.008%以下とする。
Cr、V、Moは強度と延性のバランスを向上させる作用を有するので必要に応じて添加することができる。その効果は、Cr:0.05%以上、V:0.005%以上、Mo:0.005%以上で得られる。しかしながら、それぞれCr:1.0%、V:0.5%、Mo:0.5%を超えて過剰に添加すると、第二相分率が過大となり著しい強度上昇等の懸念が生じる。また、コストアップの要因にもなる。従って、これらの元素を添加する場合には、その量をそれぞれCr:0.05%以上1.0%以下、V:0.005%以上0.5%以下、Mo:0.005%以上0.5%以下とする。
Ti、Nbは鋼の析出強化に有効で、その効果はそれぞれ0.01%以上で得られ、本発明で規定した範囲内であれば鋼の強化に使用して差し支えない。しかし、それぞれが0.1%を超えると加工性および形状凍結性が低下する。また、コストアップの要因にもなる。従って、Ti、Nbを添加する場合には,その添加量をTiは0.01%以上0.1%以下、Nbは0.01%以上0.1%以下とする。
Taは、TiやNbと同様、合金炭化物や合金炭窒化物を形成して高強度化に寄与するのみならず、Nb炭化物やNb炭窒化物に一部固溶し、(Nb,Ta)(C,N)のような複合析出物を形成することで、析出物の粗大化を著しく抑制して、析出強化による強度への寄与を安定化させる効果があると考えられる。そのため、Taを添加する場合は、その含有量を0.001%以上とすることが望ましい。しかし、過剰に添加した場合、上記の析出物安定化効果が飽和するのみならず、合金コストが上昇するため、Taを添加する場合は、その含有量を0.010%以下とすることが望ましい。
SbもSnと同様に鋼板表面の窒化、酸化、あるいは酸化により生じる鋼板表層の数10μm領域の脱炭を抑制する観点から添加することができる。このような窒化や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、疲労特性や耐時効性を改善させる。窒化や酸化を抑制する観点から、Sbを添加する場合は、その含有量は0.002%以上とすることが望ましく、0.2%を超えると靭性の低下を招くため、その含有量を0.2%以下とすることが望ましい。
良好な延性を確保するためには、フェライト相は面積率で75%以上必要である。
良好な穴拡げ性の確保のため、即ち軟質なフェライトと硬質なマルテンサイトの硬度差を緩和させるために、ベイニティックフェライト相の面積率は1%以上必要である。
良好な穴拡げ性の確保のため、パーライト相の面積率が1%以上必要である。強度−延性バランス向上の観点から、パーライト相の面積率を10%以下とする。
良好な材質安定性を確保するために、引張特性(TS、EL)に大きく影響を及ぼすマルテンサイト相の面積率は5%未満である必要がある。
良好な材質安定性を確保するために、第二相の相構成を、材質バラツキの要因となるマルテンサイトの量を低減し、マルテンサイトより軟質なベイニティックフェライトやパーライトの量を多くすること、つまり、マルテンサイト面積率/(ベイニティックフェライト面積率+パーライト面積率)≦0.6を満たす必要がある。
0.45≦exp[200/(400−T)]×ln(t)≦1.0
T:平均保持温度(℃)、t:保持時間(s)
(ここで、exp(X)、ln(X)はそれぞれXの指数関数、自然対数を示す)
を満たす条件で亜鉛めっきの合金化処理を施す方法によって製造できる。以下、詳細に説明する。
650℃以上の温度域までの平均加熱速度が5℃/s未満の場合、焼鈍中に微細で均一に分散したオーステナイト相が生成されず、最終組織において第二相が局所的に集中して存在する組織が形成され、良好な穴拡げ性の確保が困難である。また、通常よりも長い炉が必要となり、多大なエネルギー消費にともなうコスト増と生産効率の悪化を引き起こす。加熱炉としてDFF(Direct Fired Furnace)を用いることが好ましい。これは、DFFによる急速加熱により、内部酸化層を形成させ、Si、Mn等の酸化物の鋼板最表層への濃化を防ぎ、良好なめっき性を確保するためである。
750~900℃の温度域にて、具体的には、オーステナイト単相域、もしくはオーステナイトとフェライトの2相域で、15~600s間焼鈍(保持)する。焼鈍温度が750℃未満の場合や、保持(焼鈍)時間が15s未満の場合には、鋼板中の硬質なセメンタイトが十分に溶解しない場合や、フェライトの再結晶が完了しない場合があり、延性や穴拡げ性が低下する。一方、焼鈍温度が900℃を超える場合には、オーステナイト粒の成長が著しく、冷却後の保持中に生じるベイナイト変態によるベイニティックフェライトの安定確保が困難となり、穴拡げ性が低下する。また、保持(焼鈍)時間が600sを超える場合は、オーステナイトが粗大化し、所望の強度確保が困難となり、また、多大なエネルギー消費にともなうコスト増を引き起こす場合がある。
保持温度が550℃を超える場合、または保持時間が10s未満の場合は、ベイナイト変態が促進せず、ベイニティックフェライトが殆ど得られないため、所望の穴拡げ性を得られない。また、保持温度が450℃未満もしくは保持時間が200sを超える場合、第二相の大半がベイナイト変態促進により生成した固溶炭素量の多いオーステナイトとベイニティックフェライトになり、所望のパーライト面積率が得られず、かつ、硬質なマルテンサイト面積率が増加し、良好な穴拡げ性と材質安定性が得られない。
0.45≦exp[200/(400−T)]×ln(t)≦1.0
を満たす条件で亜鉛めっきの合金化処理を行う。
限界穴拡げ率λ(%)={(Df−D0)/D0}×100
Dfは亀裂発生時の穴径(mm)、D0は初期穴径(mm)
本発明では、λ≧70(%)の場合を良好と判定した。
Claims (6)
- 成分組成は、質量%でC:0.04%以上0.10%以下、Si:0.7%以上2.3%以下、Mn:0.8%以上2.0%以下、P:0.03%以下、S:0.003%以下、Al:0.1%以下、N:0.008%以下を含有し、かつ、〔C%〕×〔Si%〕≦0.20(〔C%〕、〔Si%〕はC、Siの含有量(質量%)を示す。)を満たし、残部が鉄および不可避的不純物からなり、組織は、面積率で、75%以上のフェライト相と1%以上のベイニティックフェライト相と1%以上10%以下のパーライト相を有し、さらに、マルテンサイト相の面積率が5%未満であり、かつ、マルテンサイト面積率/(ベイニティックフェライト面積率+パーライト面積率)≦0.6を満たすことを特徴とする加工性とスポット溶接性に優れた高強度溶融亜鉛めっき鋼板。
- さらに、成分組成として、質量%で、Cr:0.05%以上1.0%以下、V:0.005%以上0.5%以下、Mo:0.005%以上0.5%以下、B:0.0003%以上0.0050%以下、Ni:0.05%以上1.0%以下、Cu:0.05%以上1.0%以下から選ばれる少なくとも1種の元素を含有することを特徴とする請求項1に記載の加工性とスポット溶接性に優れた高強度溶融亜鉛めっき鋼板。
- さらに、成分組成として、質量%で、Ti:0.01%以上0.1%以下、Nb:0.01%以上0.1%以下から選ばれる少なくとも1種の元素を含有することを特徴とする請求項1または2に記載の加工性とスポット溶接性に優れた高強度溶融亜鉛めっき鋼板。
- さらに、成分組成として、質量%で、Ta:0.001%以上0.010%以下、Sn:0.002%以上0.2%以下のうちから選ばれる少なくとも1種の元素を含有することを特徴とする請求項1~3のいずれかに記載の加工性とスポット溶接性に優れた高強度溶融亜鉛めっき鋼板。
- さらに、成分組成として、質量%で、Sb:0.002%以上0.2%以下を含有することを特徴とする請求項1~4のいずれかに記載の加工性とスポット溶接性に優れた高強度溶融亜鉛めっき鋼板。
- 請求項1~5のいずれかに記載の成分組成を有する鋼スラブを、熱間圧延、酸洗し、必要に応じて冷間圧延した後、650℃以上の温度域まで5℃/s以上の平均加熱速度で加熱し、750~900℃の温度域で15~600s保持し、冷却した後、450~550℃の温度域にて10~200s保持し、次いで、溶融亜鉛めっきを施した後、500~600℃の温度域において、
0.45≦exp[200/(400−T)]×ln(t)≦1.0
T:平均保持温度(℃)、t:保持時間(s)
を満たす条件で亜鉛めっきの合金化処理を施すことを特徴とする加工性とスポット溶接性に優れた高強度溶融亜鉛めっき鋼板の製造方法。
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| MX2012008274A MX2012008274A (es) | 2010-01-22 | 2011-01-18 | Hoja de acero galvanizado de alta resistencia sumergido en caliente que tiene capacidad de formacion y capacidad de soldarse por puntos excelentes y metodo para su fabricacion. |
| CN201180006873.8A CN102712978B (zh) | 2010-01-22 | 2011-01-18 | 加工性和点焊性优良的高强度热镀锌钢板及其制造方法 |
| EP11734790.6A EP2527484B1 (en) | 2010-01-22 | 2011-01-18 | Method for manufacturing a high-strength galvanized steel sheet having excellent formability and spot weldability |
| KR1020127020267A KR101445465B1 (ko) | 2010-01-22 | 2011-01-18 | 가공성과 스폿 용접성이 우수한 고강도 용융 아연 도금 강판 및 그 제조 방법 |
| US13/522,050 US20130048155A1 (en) | 2010-01-22 | 2011-01-18 | High-strength galvanized steel sheet having excellent formability and spot weldability and method for manufacturing the same |
| CA2786381A CA2786381C (en) | 2010-01-22 | 2011-01-18 | High-strength galvanized steel sheet having excellent formability and spot weldability and method for manufacturing the same |
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| US20130000796A1 (en) * | 2010-03-31 | 2013-01-03 | Nippon Steel Corporation | High strength, hot dipped galvanized steel sheet excellent in shapeability and method of production of same |
| EP2781614A4 (en) * | 2011-11-17 | 2015-07-15 | Jfe Steel Corp | HOT-ROLLED STEEL SHEET FOR HIGH-STRENGTH HOT-DIP GALVANIZED STEEL SHEET OR HIGH-STRENGTH HOT-DIP GALVANIZED STEEL SHEET, AND PROCESS FOR PRODUCTION THEREOF |
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| JP5786317B2 (ja) * | 2010-01-22 | 2015-09-30 | Jfeスチール株式会社 | 材質安定性と加工性に優れた高強度溶融亜鉛めっき鋼板およびその製造方法 |
| IN2014DN08847A (ja) * | 2012-04-25 | 2015-05-22 | Nippon Steel & Sumitomo Metal Corp | |
| JP5633594B2 (ja) * | 2013-04-02 | 2014-12-03 | Jfeスチール株式会社 | 打ち抜き性および耐熱ひずみ特性に優れた冷延鋼板およびその製造方法 |
| BR112017021206A2 (ja) * | 2015-04-15 | 2018-07-03 | Nippon Steel & Sumitomo Metal Corporation | A hot-rolled steel product and a manufacturing method for the same |
| CN109695006A (zh) * | 2017-10-20 | 2019-04-30 | 鞍钢股份有限公司 | 一种耐腐蚀链板用钢及其制造方法 |
| JP6828855B1 (ja) | 2019-03-29 | 2021-02-10 | Jfeスチール株式会社 | 鋼板およびその製造方法 |
| KR102245228B1 (ko) * | 2019-09-20 | 2021-04-28 | 주식회사 포스코 | 균일연신율 및 가공경화율이 우수한 강판 및 이의 제조방법 |
| CN118703903A (zh) * | 2023-03-27 | 2024-09-27 | 宝山钢铁股份有限公司 | 一种点焊性能优异的带镀层超高强钢及其制造方法 |
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- 2011-01-18 WO PCT/JP2011/051159 patent/WO2011090184A1/ja not_active Ceased
- 2011-01-18 EP EP11734790.6A patent/EP2527484B1/en active Active
- 2011-01-18 CA CA2786381A patent/CA2786381C/en not_active Expired - Fee Related
- 2011-01-18 US US13/522,050 patent/US20130048155A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130000796A1 (en) * | 2010-03-31 | 2013-01-03 | Nippon Steel Corporation | High strength, hot dipped galvanized steel sheet excellent in shapeability and method of production of same |
| US9228244B2 (en) * | 2010-03-31 | 2016-01-05 | Nippon Steel & Sumitomo Metal Corporation | High strength, hot dipped galvanized steel sheet excellent in shapeability and method of production of same |
| US10113220B2 (en) | 2010-03-31 | 2018-10-30 | Nippon Steel & Sumitomo Metal Corporation | High strength, hot dipped galvanized steel sheet excellent in shapeability and method of production of same |
| EP2781614A4 (en) * | 2011-11-17 | 2015-07-15 | Jfe Steel Corp | HOT-ROLLED STEEL SHEET FOR HIGH-STRENGTH HOT-DIP GALVANIZED STEEL SHEET OR HIGH-STRENGTH HOT-DIP GALVANIZED STEEL SHEET, AND PROCESS FOR PRODUCTION THEREOF |
| US9758847B2 (en) | 2011-11-17 | 2017-09-12 | Jfe Steel Corporation | Hot-rolled steel sheet for high-strength galvanized steel sheet or high-strength galvannealed steel sheet and method for manufacturing the same (as amended) |
| EP2792762A4 (en) * | 2011-12-12 | 2015-07-29 | Jfe Steel Corp | HIGH STRENGTH COLD LAMINATED STEEL SHEET AND HIGH ELASTICITY RATIO AND PROCESS FOR PRODUCING THE SAME |
| US9994941B2 (en) | 2011-12-12 | 2018-06-12 | Jfe Steel Corporation | High strength cold rolled steel sheet with high yield ratio and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011168879A (ja) | 2011-09-01 |
| KR20120099517A (ko) | 2012-09-10 |
| KR101445465B1 (ko) | 2014-09-26 |
| EP2527484B1 (en) | 2019-03-13 |
| CA2786381C (en) | 2017-07-04 |
| TW201137171A (en) | 2011-11-01 |
| MX2012008274A (es) | 2012-08-03 |
| EP2527484A4 (en) | 2016-02-17 |
| CA2786381A1 (en) | 2011-07-28 |
| CN102712978B (zh) | 2014-07-30 |
| TWI433960B (zh) | 2014-04-11 |
| EP2527484A1 (en) | 2012-11-28 |
| CN102712978A (zh) | 2012-10-03 |
| JP4883216B2 (ja) | 2012-02-22 |
| US20130048155A1 (en) | 2013-02-28 |
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