WO2012147863A1 - ホットスタンプ部材用鋼板およびその製造方法 - Google Patents
ホットスタンプ部材用鋼板およびその製造方法 Download PDFInfo
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- WO2012147863A1 WO2012147863A1 PCT/JP2012/061238 JP2012061238W WO2012147863A1 WO 2012147863 A1 WO2012147863 A1 WO 2012147863A1 JP 2012061238 W JP2012061238 W JP 2012061238W WO 2012147863 A1 WO2012147863 A1 WO 2012147863A1
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- steel sheet
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- steel
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/02—Stamping using rigid devices or tools
- B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D37/00—Tools as parts of machines covered by this subclass
- B21D37/16—Heating or cooling
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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
- B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
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- 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
- 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
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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
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
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- 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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- 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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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- 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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- 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
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- C23C2/12—Aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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- C23C2/29—Cooling or quenching
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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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/62—Quenching devices
- C21D1/673—Quenching devices for die quenching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- the present invention relates to a steel sheet for a hot stamp member that can be suitably used for a hot stamp method, which is one of forming methods for obtaining a high-strength member, and a method for producing the same.
- a hot forming method called a hot stamp method is attracting attention.
- a steel sheet (work material) is heated to a predetermined temperature (generally a temperature at which it becomes an austenite phase) to reduce the strength (that is, to facilitate forming), and then the work material.
- the mold is formed at a low temperature (for example, room temperature).
- a quenching heat treatment quenching
- Patent Document 1 is excellent in impact characteristics and delayed fracture characteristics after hot forming (synonymous with hot stamping) by setting the amount of elements to be contained and the relationship between the amounts of elements within a predetermined range.
- a steel plate from which a member can be obtained is disclosed.
- Patent Document 2 as described above, high strength is achieved by setting the amount of elements to be contained and the relationship between the amounts of the elements within a predetermined range and performing heating before forming the steel sheet in a nitriding atmosphere or a carburizing atmosphere. A method of obtaining a part is disclosed.
- Patent Document 3 discloses a means for obtaining a hot press product with high productivity by defining chemical components and microstructure and limiting heating conditions and molding conditions.
- the present inventors have found that in the case of such a long part, the warp of the part, which was negligible in the case of the short part, occurs with a slight amount.
- the present inventors found that the fluctuation of the carbon concentration of the steel plate immediately before hot stamping (immediately before forming with a mold) is related to the occurrence of non-uniform strain. I got a feeling that it was. As a result of further research, it became clear that the melting behavior of iron carbide in the steel sheet in the heating process immediately before forming is the key to suppressing the occurrence of non-uniformity.
- a steel sheet for hot stamping has a microstructure composed of a ferrite phase as a main phase, a second phase such as pearlite, and iron carbide.
- carbon generated from the iron carbide in the heating step before forming is dissolved in the austenite phase, and the austenite phase is quenched and transformed into a martensite phase, whereby high strength can be obtained.
- the strength of the martensite phase produced depends strongly on the cooling conditions and the concentration of carbon dissolved in the austenite phase, so how to uniformly dissolve iron carbide in the heating process is a molded product obtained in the subsequent process. It can be easily guessed that it strongly affects the mechanical properties of
- Patent Documents 1 to 3 do not describe the distribution of carbide size. Patent Documents 1 and 2 do not disclose at all the conditions under which the cold-rolled steel sheet is annealed, and do not consider the control of carbides in the steel sheet. In Patent Document 3, there is no description regarding the heating history that is most important in controlling the state of carbides in the annealing of cold-rolled steel sheets, and the control of carbides is not studied.
- Patent Document 4 is a technique for obtaining a steel sheet having excellent local ductility and hardenability by setting the spheroidization rate and average particle size of carbide within a predetermined range. There is no description regarding the distribution of the thickness. Moreover, in order to obtain a predetermined metal structure, it is essential to carry out extremely special annealing, and since it is not premised on the production in general continuous annealing equipment or continuous hot dipping plating equipment, Patent Document 4 discloses annealing conditions. The distribution of the carbide size distribution is not controlled.
- Patent Document 5 is a technique for obtaining a steel sheet excellent in stability of strength against heat treatment conditions and delayed fracture resistance by setting the average particle size of iron carbide within a predetermined range. Does not describe the distribution of carbide size. Patent Document 5 does not disclose any heating history up to the maximum heating temperature, and does not control the distribution of carbide size.
- Patent Document 6 is a technique for obtaining a high-carbon steel sheet having excellent wear resistance by controlling the ratio of the average grain size of ferrite and the carbide of a predetermined size among the spherical carbides. There is no description regarding the distribution of carbide size. Moreover, in order to obtain a predetermined steel plate, it is indispensable to carry out long-time annealing in combination with a hot-rolled steel plate and a cold-rolled steel plate several times, and in general continuous annealing equipment and continuous hot dipping equipment. Since manufacturing is not premised, Patent Document 6 does not control the distribution of carbide size by devising annealing conditions.
- Patent Document 7 is a technique for obtaining a medium / high carbon high-strength steel sheet excellent in punchability by controlling the average particle diameter of ferrite and the average particle diameter of carbides. There is no description regarding the distribution of carbide size. Further, in addition to disclosing cold-rolled steel sheets that are cold-rolled and cold-rolled steel sheets that are annealed under low-temperature and long-term annealing conditions that are maintained at 350 to 700 ° C. for 10 to 40 hours, general continuous Since it is not premised on the production in annealing equipment or continuous hot dipping plating equipment, the distribution condition of the carbide size is not controlled by devising the annealing conditions.
- the present invention controls the distribution state of the size of the iron carbide contained in the steel sheet so that the warp that easily occurs when a long member is manufactured using the hot stamp method can be reduced.
- An object of the present invention is to provide a hot stamping steel plate and a method for producing the same.
- the present inventors have intensively studied to solve such problems. As a result, if the distribution of the diameter of the iron carbide contained from the surface of the steel plate to 1/4 position of the plate thickness is within a predetermined range, even if there is fluctuation in the cooling conditions at the time of molding, It was found that it is extremely effective in suppressing warpage. Moreover, it discovered that such a steel plate could be obtained by controlling the conditions at the time of recrystallization annealing of the cold-rolled steel plate, and also repeated trial and completed this invention. The summary is as follows.
- the steel sheet for a hot stamp member is C: 0.10 to 0.35%, Si: 0.01 to 1.0%, Mn: 0.3 to 2 in mass%. 0.3% and Al: 0.01 to 0.5%, P: 0.03% or less, S: 0.02% or less, and N: 0.1% or less, the balance being It has a chemical composition composed of Fe and inevitable impurities, and the standard deviation of the diameter of iron carbide contained from the surface to a position of 1/4 of the plate thickness is 0.8 ⁇ m or less.
- the chemical composition further includes, in mass%, Cr: 0.01 to 2.0%, Ti: 0.001 to 0.5%, Nb: 0.001 to 0.5%, B: 0.0005 to 0.01%, Mo: 0.01 to 1.0%, W: 0.01 to 0.5%, V: 0.01 to One or more selected from 0.5%, Cu: 0.01 to 1.0%, and Ni: 0.01 to 5.0% may be contained.
- the surface may have an Al plating layer with a plating thickness of 50 ⁇ m or less.
- the surface may have a Zn plating layer having a plating thickness of 30 ⁇ m or less.
- the surface may have a Zn—Fe alloy layer having a plating thickness of 45 ⁇ m or less.
- the manufacturing method of the steel sheet for hot stamping members according to one aspect of the present invention is, in mass%, C: 0.10 to 0.35%, Si: 0.01 to 1.0%, Mn: 0.00. 3 to 2.3%, and Al: 0.01 to 0.5%, P: 0.03% or less, S: 0.02% or less, and N: 0.1% or less
- the change in the rate of increase in the steel sheet temperature from 300 ° C. to the maximum temperature S in units of ° C./s 2 in the cold rolled steel sheet having the chemical composition consisting of Fe and inevitable impurities as the balance d / dt ( ⁇ T / ⁇ t) Is recrystallized by heating so that the following formula 1 is satisfied and the maximum temperature S is 720 to 820 ° C.
- T is the steel sheet temperature in units of ° C.
- t is the time in units of s
- ⁇ T / ⁇ t is the time in the time ⁇ t seconds during heating of the recrystallization annealing in units of ° C / s. It refers to the rate of increase in steel sheet temperature.
- the chemical composition is further, in mass%, Cr: 0.01 to 2.0%, Ti: 0.001 to 0.00. 5%, Nb: 0.001 to 0.5%, B: 0.0005 to 0.01%, Mo: 0.01 to 1.0%, W: 0.01 to 0.5%, V: 0 One or more selected from 0.01 to 0.5%, Cu: 0.01 to 1.0%, and Ni: 0.01 to 5.0% may be contained.
- the d / dt ( ⁇ T / ⁇ t) is 10 seconds or less from the heating temperature history during the recrystallization annealing.
- coefficient of determination R 2 may be twice the coefficient of the variable of degree 2 at the time of determining the polynomial approximation curve of degree 2 such that 0.99 or more.
- the cold-rolled steel sheet is immersed in a Zn bath following the recrystallization annealing, and the cold-rolled steel sheet is used. After forming a Zn plating layer on the surface of the steel plate, the cold-rolled steel plate may be heated to 600 ° C. or less to form a Zn—Fe alloy layer on the surface of the cold-rolled steel plate.
- the steel sheet for a hot stamp member according to the above aspect of the present invention warpage generated in a long molded product obtained by molding with a widely used hot stamp facility is extremely small. Sometimes there is very little possibility of failure. For these reasons, the steel sheet for a hot stamp member according to the above aspect has an effect of expanding the application range (parts) of the hot stamp method.
- an Al plating layer, a Zn plating layer, and a Zn—Fe alloy layer with few defects such as galling, peeling and cracking after hot stamping. can be obtained. Therefore, in this case, the corrosion resistance and surface quality of the steel sheet for hot stamp members can be further improved.
- Example 1 It is a perspective view of the blank (steel plate) before shape
- Example 1 it is a graph which shows the relationship between the standard deviation of the magnitude
- Example 1 it is a graph which shows the relationship between the standard deviation of the magnitude
- Example 1 it is a graph which shows the relationship between d / dt ((DELTA) T / (DELTA) t) and the standard deviation of the magnitude
- Example 3, 4, and 5 it is a figure which shows the temperature history of the steel plate from a heating start to the maximum temperature.
- the present inventors produced a hot stamp member using a steel sheet containing C: 0.22%, Si: 0.3%, and Mn: 1.2% by mass%, and evaluated the characteristics. I did some research.
- the present inventors have examined in detail the actual state of warpage, particularly considering application to long parts. In the course of the study, it was found that even when a steel plate having almost the same chemical composition and tensile strength was hot stamped under the same conditions, there was a difference in the amount of warpage occurring in the molded product. Therefore, when the cause of the difference in warpage between steel plates was investigated in detail, the present inventors found that (i) there was a difference in hardness fluctuation near the surface of the molded product in comparison between steel plates.
- this difference is due to the iron carbide size distribution near the surface of the steel plate before hot stamping, and (iii) to obtain the desired iron carbide size distribution, It has been found that the conditions for recrystallization annealing of the rolled steel sheet may be controlled within a predetermined range.
- C is the most important element for increasing the strength of a steel sheet by the hot stamp method.
- 0.10% or more of C is contained in the steel.
- C is contained in the steel in an amount exceeding 0.35%, deterioration of toughness is a concern, so 0.35% is made the upper limit of the C amount.
- C amount is 0.32% or less, and it is more preferable that it is 0.30% or less.
- Si is a solid solution strengthening element, and 0.01 to 1.0% of Si can be effectively used as a solid solution strengthening element.
- 1.0% is made the upper limit of the Si amount.
- the lower limit of the amount of Si is a reference amount contained in steel due to deoxidation.
- Mn functions as a solid solution strengthening element like Si, and is a useful element that enhances the hardenability of the steel sheet.
- the amount of Mn in the steel is set to 0.3% or more. However, even if Mn is contained in the steel in excess of 2.3%, the effect is saturated, so 2.3% is made the upper limit of the Mn amount.
- the amount of Mn is preferably 0.5% or more, and more preferably 1.0% or more.
- Al is suitable as a deoxidizing element, 0.01% or more of Al may be contained in the steel. However, when a large amount of Al is contained in the steel, a coarse oxide is formed and the mechanical properties of the steel sheet are impaired. Therefore, the upper limit of the Al content is 0.5%.
- N is easily bonded to Ti and B, the N content is controlled to 0.1% or less so as not to reduce the intended effect of these elements.
- the N content is preferably as small as possible, so it is preferably 0.01% or less. If the amount of N is reduced more than necessary, a great load is applied to the steelmaking process, so 0.0010% may be used as a guideline for the lower limit of the amount of N.
- the above chemical elements are the basic components (basic elements) of the steel in the present embodiment, the basic elements are controlled (contained or restricted), and the chemical composition consisting of iron and unavoidable impurities as the balance is Basic composition.
- the following chemical elements may be further contained in the steel as necessary.
- the steel may contain one or more selective elements selected from Cr, Ti, Nb, B, Mo, W, V, Cu, and Ni. In order to reduce the alloy cost, it is not necessary to intentionally add these selective elements into the steel, and the lower limit of the amount of Cr, Ti, Nb, B, Mo, W, V, Cu, Ni is any 0%.
- Cr is an element having an effect of improving hardenability, it can be appropriately used. The effect becomes clear when the Cr content is 0.01% or more. On the other hand, even if Cr is added to the steel in excess of 2.0%, the effect is saturated, so 2.0% is made the upper limit of the Cr amount.
- Ti is an element that is desired to be used effectively because it functions to stably extract the effect of B described later through formation of nitride.
- the Ti content is preferably 0.001% or more.
- Ti is excessively added to the steel, nitride becomes excessive and the toughness and shear surface properties deteriorate, so 0.5% is made the upper limit of the Ti amount.
- Nb is an element to be used effectively because it forms carbonitride and increases the strength of steel.
- the Nb content in the steel may be 0.001% or more.
- Nb exceeds 0.5% in steel, the controllability of hot rolling may be impaired, so 0.5% is made the upper limit of the Nb amount.
- B is an element that enhances hardenability. If the steel contains B in an amount of 0.0005% or more, the effect of improving hardenability becomes clear. On the other hand, excessive addition of B leads to deterioration of hot workability and reduction of ductility, so 0.01% is made the upper limit of the B amount.
- the concentration at which the effect is saturated is preferably set as the upper limit.
- the upper limit of the Mo amount is preferably 1.0%, and the upper limits of the W amount and the V amount are preferably 0.5%.
- Cu has the effect of increasing the strength of the steel sheet by adding 0.01% or more of Cu to the steel.
- excessive Cu addition impairs the surface quality of the hot-rolled steel sheet, so 1.0% is made the upper limit of the Cu amount. Therefore, the amount of Cu may be 0.01 to 1.0%.
- Ni is an element that is desired to be effectively used since it has an effect of improving hardenability, and the effect becomes clear when the amount of Ni is 0.01% or more.
- the upper limit of the Ni amount is 5.0% at which the effect is saturated. Therefore, the Ni content may be 0.01 to 5.0%.
- Ni also has the function of suppressing the deterioration of the surface quality of the hot-rolled steel sheet due to the above-mentioned Cu, it is desirable to contain it simultaneously with Cu.
- components other than the above are Fe, but inevitable impurities mixed from melting raw materials such as scrap or refractories are allowed as other components.
- the steel sheet according to the present embodiment includes the above-described basic element, and the balance is at least one selected from the chemical composition consisting of Fe and inevitable impurities, or the above-described basic element and the above-described selective element. Seeds, the balance having a chemical composition consisting of Fe and inevitable impurities.
- the amount of warpage observed in the long member formed by the hot stamp method is the fluctuation of the hardness near the surface layer of the steel sheet, and the fluctuation of the carbon concentration before the hot stamping. It turned out to be strongly dependent on. Furthermore, it has been clarified that the fluctuation of the carbon concentration can be reduced if the size of the iron carbide is more uniform.
- the relationship between the magnitude of warpage and the fluctuation of hardness is not necessarily clear, but this relationship is probably related to the following mechanism. That is, among the factors governing the hardness of the martensite phase produced by quenching (degree of supersaturation of carbon, dislocation density, degree of refinement of structural units (such as laths and blocks), and the state of reprecipitated iron carbide) In particular, if there is a fluctuation in the dislocation density near the surface layer of the part, non-uniform residual stress is likely to be induced inside the part. In this case, warping may occur in an attempt to release non-uniform residual stress after the part is removed from the hot stamp mold.
- Warpage of a molded body molded by the hot stamp method is defined as follows.
- the blank 11 is formed into the shape steel 12 in the manner schematically shown in FIGS. 1A and 1B, and after the shape steel 12 is demolded, the shape steel 12 is left on the surface plate 21 as shown in FIG. did.
- the shape steel 12 is viewed from the width direction (when viewed from the side), the distance d (mm) between the line segment connecting both ends of the shape steel 12 in the longitudinal direction and the center in the longitudinal direction of the shape steel 12 is defined as the shape steel 12. It was defined as a warp.
- the width W was 170 mm and the length L was 1000 mm, and an equilateral steel 12 having a base of about 70 mm was obtained from the steel plate 11.
- curvature d was 5 mm or less, it evaluated that generation
- said molded object (section steel 12) is an example of the molded object produced in order to evaluate the curvature d at the time of shape
- the steel plate of this embodiment has various shapes. It can be applied to various molded products and various hot stamping conditions. The warpage generated in the formed body is reduced when the length of the formed body is shorter than 1000 mm or the width of the formed body is longer than 170 mm. However, the steel sheet of the present embodiment is changed to such a formed body. Even if applied, it is possible to obtain an effect of further suppressing the warpage d of the molded body.
- the standard deviation of the diameter of the iron carbide contained from the surface of the steel plate to the 1/4 position of the plate thickness is 0.8 ⁇ m or less.
- the standard deviation is more than 0.8 ⁇ m, the warp d of the molded body is more than 5 mm, and it is determined that the warp cannot be overlooked.
- the size distribution of iron carbide is measured as follows.
- a cross section parallel to the rolling direction of the steel sheet (cross section including the thickness direction) is polished and appropriately treated with a carbide appearing corrosive liquid (for example, a Picral corrosive liquid), and then subjected to a scanning electron microscope. Then, the cross-sectional area from the surface of the steel plate to the 1/4 position of the plate thickness is continuously observed at a magnification of 5000 times. The field of view is expanded until the number of measured iron carbides is at least 600. The size (diameter) of the iron carbide is the average of the longest side and the shortest side of the iron carbide. The standard deviation is calculated from the obtained iron carbide size data. A commercially available statistical software can be used for the calculation of the standard deviation.
- a carbide appearing corrosive liquid for example, a Picral corrosive liquid
- the average size of the iron carbide may be 0.5 ⁇ m or more or 1 ⁇ m or more. If the standard deviation of the diameter of the iron carbide is 0.8 ⁇ m or less, the average size of the iron carbide is not particularly limited, but may be, for example, 5 ⁇ m or less or 3 ⁇ m or less.
- the thickness of the Al plating layer, Zn plating layer, and Zn—Fe alloy layer does not affect the occurrence of warping of the part after hot stamping, but when these thicknesses are excessively large, There is a concern of affecting the moldability. As shown in the examples described later, galling was observed when the thickness of the Al plating layer was more than 50 ⁇ m, and when the thickness of the Zn plating layer was more than 30 ⁇ m, Zn was adhered to the mold. When the thickness of the Zn—Fe alloy layer exceeds 45 ⁇ m, cracks in the alloy layer are observed. Thus, productivity is impaired when the thickness of each layer is excessively large.
- the thickness of the Al plating layer may be limited to 50 ⁇ m or less
- the thickness of the Zn plating layer may be limited to 30 ⁇ m or less
- the thickness of the Zn—Fe alloy layer may be limited to 45 ⁇ m or less.
- the thickness of the Al plating layer is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more.
- the thickness of the Zn plating layer is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more.
- the thickness of the Zn—Fe alloy layer is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more.
- “Surface” is defined as follows in a steel sheet having any one of an Al plating layer, a Zn plating layer, and a Zn—Fe alloy layer on the surface.
- the Al plating layer of the steel plate of the present embodiment is composed of two layers of an outer layer mainly composed of Al and an inner layer (steel plate side) that is considered to be a layer formed by reaction of Al and Fe. It is configured.
- the boundary between this inner layer and the steel plate (plated steel plate) is defined as the surface of the steel plate.
- the Zn plating layer of the steel plate of the present embodiment includes an outer layer mainly composed of Zn, and an inner layer that is a layer formed by reaction of Al added in a trace amount in the Zn bath with Fe. It consists of two layers. The boundary between this inner layer and the steel plate (plated steel plate) is defined as the surface of the steel plate.
- the Zn—Fe alloy layer of the steel plate of the present embodiment is composed of a plurality of alloy layers containing Zn and Fe. Of these plural alloy layers, the boundary between the innermost (steel plate side) layer and the steel plate (plated steel plate) is defined as the surface.
- steelmaking, casting, hot rolling, and cold rolling are performed based on a conventional method to obtain a cold rolled steel sheet.
- the steel is made into a slab by continuous casting, and the obtained slab (steel) is, for example, 1300 ° C. or less.
- Hot rolling is started at a heating temperature (eg, 1000 to 1300 ° C.), and hot rolling is completed at around 900 ° C. (eg, 850 to 950 ° C.).
- a heating temperature eg, 1000 to 1300 ° C.
- hot rolling is completed at around 900 ° C. (eg, 850 to 950 ° C.).
- the hot rolling rate may be 60 to 90%.
- the hot-rolled steel sheet (steel) obtained after winding is cold-rolled through a pickling process.
- the cold rolling rate can be selected from 30 to 90%.
- Annealing for recrystallizing the cold-rolled steel sheet thus manufactured is extremely important.
- the change d / dt ( ⁇ T / ⁇ t) of the rise rate of the steel sheet temperature (sheet temperature) from 300 ° C. to the maximum temperature S (° C.) satisfies Equation 1, and S is 720 to 820.
- Annealing is performed so that it may become (degreeC).
- T is the steel plate temperature (° C.)
- t is the time (s)
- ⁇ T / ⁇ t is the temperature change (° C./s) during the time ⁇ t (s) during the recrystallization annealing heating.
- D / dt ( ⁇ T / ⁇ t) indicates a change in plate temperature increasing rate from 300 ° C. to the maximum temperature S (° C./s 2 ).
- standard of 0 (zero) of t does not need to restrict
- the steel plate temperature at the time of annealing is measured using a radiation thermometer previously arranged in the annealing equipment or a thermocouple attached to the steel plate itself.
- the temperature history of the steel sheet thus obtained is expressed as a quadratic function of time, and d / dt ( ⁇ T / ⁇ t) is determined by using the second derivative of the quadratic function.
- a method for obtaining a quadratic function is to prepare a data set of (t, T) by reading the steel sheet temperature from the above temperature history at a short time interval (preferably 10 seconds or less or 5 seconds or less), and this data set is commercially available.
- a graph was created (again) using the spreadsheet software, and the graph was further approximated by a degree 2 polynomial approximation.
- the heating conditions from room temperature to 300 ° C. are not particularly limited.
- the steel plate After the steel plate temperature reaches the temperature S, the steel plate may be held at the temperature S for a short time, or may immediately shift to the cooling process.
- the holding time is desirably 180 s or less, and more desirably 120 s or less, from the viewpoint of suppressing the coarsening of the crystal grain size.
- the cooling rate from the temperature S is not particularly limited, but it is desirable to avoid rapid cooling with an average cooling rate of 30 ° C./s or more.
- Steel sheets for hot stamping are often processed into a predetermined shape by shearing and then used for hot stamping. Therefore, if rapid cooling is performed after annealing, the shear load increases and production efficiency decreases. Concerned.
- the steel sheet After annealing, the steel sheet may be cooled to room temperature, or may be immersed in a molten Al bath while cooling the steel sheet to form an Al plating layer on the surface of the steel sheet.
- the molten Al bath may contain 0.1 to 20% Si.
- Si contained in the Al plating layer affects the reaction between Al and Fe generated during heating before hot stamping. Excessive reaction may impair the press formability of the plating layer itself, while suppression of excessive reaction may cause Al to adhere to the press mold.
- the Si content in the Al plating layer is desirably 1 to 15%, more preferably 3 to 12%.
- the steel plate may be immersed in a molten Zn bath during cooling after annealing to form a Zn plating layer on the surface of the steel plate.
- the steel plate on which the Zn plating layer is formed is heated to 600 ° C. or lower to form a Zn—Fe alloy layer on the surface of the steel plate. It may be formed.
- the minimum of the temperature of alloying process is not restrict
- the molten Zn bath can contain 0.01 to 3% Al.
- Al in the molten Zn bath strongly affects the reaction between Zn and Fe.
- the reaction layer of Fe and Al becomes an obstacle, and mutual diffusion of Zn and Fe can be suppressed.
- Al is used to control the target layer to be the main layer among multiple layers with different workability and adhesion to the steel. it can.
- the thickness (plating thickness) of the Al plating layer, the Zn plating layer, and the Zn—Fe alloy layer may be controlled to a predetermined thickness or less. That is, the plating thickness is preferably 50 ⁇ m or less for the Al plating layer, the plating thickness is 30 ⁇ m or less for the Zn plating layer, and the plating thickness is 45 ⁇ m or less for the Zn—Fe alloy layer.
- the steel sheet for a hot stamp member according to the present invention has the effects of the present invention regardless of the plate thickness and strength after hot stamping, but hot rolling, cold rolling, annealing, and plating application (formation of a plating layer).
- the preferable thickness of the target steel plate is preferably about 0.5 to 3.5 mm.
- the preferable strength after hot stamping of the target steel sheet is preferably about 1200 to 2000 MPa in terms of tensile strength.
- Steel pieces (steel) having chemical components described in Table 1 were obtained by steelmaking and casting. These steels were heated to 1250 ° C., subjected to hot rolling at a finishing temperature of 910 ° C., and wound at a winding temperature of 620 ° C. to form a hot-rolled steel sheet having a thickness of 3.2 mm. These hot-rolled steel sheets were pickled and then cold-rolled to obtain 1.6 mm-thick cold-rolled steel sheets.
- the cold-rolled steel sheet was recrystallized and annealed under the conditions shown in Table 2 to obtain a hot stamping steel sheet.
- heating was performed at a constant heating rate of 10 ° C./s from 300 ° C. to 600 ° C., and then the cold-rolled steel sheet was heated at a constant heating rate of 2 ° C./s to 800 ° C.
- the change d / dt ( ⁇ T / ⁇ t) in the steel plate temperature increase rate was 0 (zero).
- Example 3 After polishing the cross section parallel to the rolling direction of the sample taken from this hot stamping steel plate, the microstructure of this cross section was revealed with a picral-based corrosive solution, and then the thickness of the cold rolled steel plate (sample) was reduced to 0. 0 in the thickness direction.
- a region up to a position (1/4 position of the plate thickness) separated by a distance of 4 mm was observed at a magnification of 5000 times with a scanning electron microscope, and the size of the iron carbide was measured. This observation was performed until the number of measured iron carbides reached 600 or more. Furthermore, the measured data was processed to determine the standard deviation.
- a 170 ⁇ 1000 mm blank was produced from the cold-rolled steel sheet, and this blank was formed into an equilateral steel having a base of about 70 mm by a hot stamp method, and the warpage d (mm) was made in the manner shown in FIG. It was measured.
- the heating conditions before hot stamping were a temperature of 900 ° C., a holding time of 1 minute, and 10 minutes. Further, a 210 ⁇ 300 mm blank 32 is produced from the cold-rolled steel sheet, and the blank 32 is formed by using the upper mold 31a and the lower mold 31b shown in FIG. Was subjected to hot stamping under the same conditions as above to obtain a material for measuring tensile strength. Two JIS No. 5 tensile test pieces were collected from these materials. Processing for sampling was performed by electric discharge machining. The obtained test piece was subjected to a tensile test to determine the tensile strength ⁇ B (average value of two pieces).
- Table 3 shows steel code, annealing conditions, change in steel plate temperature rise rate from 300 ° C. to maximum temperature S (° C.) d / dt ( ⁇ T / ⁇ t), average value and standard deviation of iron carbide size, ⁇ B (average value of two) and warpage d are shown.
- annealing conditions i, iii, iv, vi, viii, and ix that satisfy the conditions of the present invention (Nos. 1-8, 10, 11, 13, and 15-25)
- a tensile strength of 1200 to 1500 MPa was obtained, and the warpage was as small as 5 mm or less.
- warpage exceeding 5 mm was observed in the steel sheets (No. 9, 12, 14, 26, and 27) obtained by annealing under the annealing conditions that did not satisfy the conditions of the present invention.
- FIG. 4 when the heating condition before hot stamping is 900 ° C. and holding for 1 minute
- FIG. 5 when the heating condition before hot stamping is holding at 900 ° C. and holding for 10 minutes
- the standard deviation of the size of iron carbide from the surface of the steel plate before stamping to 1/4 position of the plate thickness It is clear that a long hot stamp member with a small warp can be obtained when the standard deviation of the thickness is 8 ⁇ m or less (No. 1 to 8, 10, 11, 13, and 15 to 25, indicated by open circle). became.
- this standard deviation exceeds 8 ⁇ m (No. 9, 12, 14, 26, and 27, indicated by solid circle or solid triangle), d is over 8 mm, and it has become clear that it cannot be overlooked.
- d / dt ( ⁇ T / ⁇ t) is less than ⁇ 0.2 or 0 or more, or S is less than 720 ° C., or S is more than 820 ° C. In any case, the standard deviation of the size of the iron carbide exceeds 0.8 ⁇ m.
- Steel pieces (steel) having chemical components shown in Table 4 were obtained by steelmaking and casting. These steels were made into hot-rolled steel sheets having a thickness of 3.0 mm under the same conditions as in Example 1. The hot-rolled steel sheets were pickled and cold-rolled to obtain 1.2-mm cold-rolled steel sheets.
- Example 1 Measure the size of iron carbide in the region from the surface of the obtained cold-rolled steel sheet to a position separated by a distance of 0.3 mm in the thickness direction (1/4 position of the plate thickness). Standard deviation was determined. Moreover, the cold-rolled steel sheet was hot stamped at 900 ° C. under two heating conditions of 1 minute and 5 minutes to obtain a shaped steel. Further, as in Example 1, the warpage d of the shape steel was measured, and a tensile test piece was taken from the shape steel, and the tensile strength ⁇ B was measured.
- Table 5 shows the results.
- the steel sheet for hot stamping which has been subjected to recrystallization annealing under the annealing conditions i and ix satisfying the conditions of the present invention, the steel sheet contains chemical components such as Mo, W, V, Cu, and Ni.
- the standard deviation of the size of the iron carbide from the surface of the steel plate to 1/4 position of the plate thickness was 0.8 ⁇ m or less.
- the warp of the long component (section steel) is 5 mm or less regardless of the heating conditions (holding time at 900 ° C.) before hot stamping, and it is clear that an excellent hot stamp member can be obtained. It became.
- the standard deviation of the size of the iron carbide from the steel sheet surface to the 1/4 position of the plate thickness was more than 0.8 ⁇ m.
- the warp of the hot stamp member obtained regardless of the heating conditions (holding time at 900 ° C.) before hot stamping is more than 5 mm, and it is clear that such a steel sheet is inferior in hot stamping formability. It became.
- Steel pieces (steel) having chemical components described in Table 6 were obtained by steelmaking and casting. These steels were made into a hot rolled steel sheet having a thickness of 2.5 mm under the same conditions as in Example 1. The hot rolled steel sheet was pickled and then cold rolled to obtain a 1.2 mm cold rolled steel sheet.
- d / dt ( ⁇ T / ⁇ t) used in the present invention is the temperature at a time interval of 10 seconds or less or 5 seconds or less (however, more than 0 seconds) from the heating temperature history during recrystallization annealing.
- the coefficient of t 2 (the coefficient of the variable of order 2) when the approximate curve (degree 2 polynomial approximation curve) is determined so that the determination coefficient R 2 is 0.99 or more.
- the size of the iron carbide in the region of the obtained steel plate from the boundary between the inner layer (Al and Fe reaction layer) of the Al plating layer and the steel plate to the position separated by 0.3 mm in the thickness direction The standard deviation of the size of the iron carbide was determined. Along with the measurement of iron carbide, the thickness of the Al plating layer (total of two layers) was also measured. Further, hot stamping was performed on the shape steel and the flat plate in the same manner as in Example 1, and the warpage d and the tensile strength ⁇ B were measured. However, the heating condition before hot stamping was held at 900 ° C. for 1 minute.
- the thickness of the Al plating layer exceeds 50 ⁇ m.
- galling occurred at a high frequency from the corner portion to the end portion of the shape steel.
- the upper limit of the thickness of Al plating is preferably 50 ⁇ m or less from the viewpoint of plating quality.
- the quality of the Al plating layer was evaluated as “A” when no galling occurred in the Al plating layer, and the quality of the Al plating layer as “B” when galling occurred in the Al plating layer. evaluated.
- Steel pieces (steel) having chemical components described in Table 6 were obtained by steelmaking and casting. These steels were made into a hot rolled steel sheet having a thickness of 2.5 mm under the same conditions as in Example 1. The hot rolled steel sheet was pickled and then cold rolled to obtain a 1.2 mm cold rolled steel sheet.
- the standard deviation of the size of the iron carbide was determined.
- the thickness of the Zn plating layer (total of two layers) was also measured.
- hot stamping was performed on the shape steel and the flat plate in the same manner as in Example 1, and the warpage d and the tensile strength ⁇ B were measured. However, there were two heating conditions before hot stamping: ⁇ 1> heated to 880 ° C. and held for 5 seconds, then air-cooled to 700 ° C. and ⁇ 2> held at 900 ° C. for 1 minute.
- the thickness of the Zn plating layer exceeds 30 ⁇ m.
- Zn was frequently adhered to the mold.
- the upper limit of the thickness of the Zn plating is preferably 30 ⁇ m or less from the viewpoint of plating quality.
- the quality of the Zn plating layer is evaluated as “A”, and when the Zn adheres to the mold, the quality of the Zn plating layer is evaluated as “B”. did.
- Steel pieces (steel) having chemical components described in Table 6 were obtained by steelmaking and casting. These steels were made into a hot rolled steel sheet having a thickness of 2.5 mm under the same conditions as in Example 1. The hot rolled steel sheet was pickled and then cold rolled to obtain a 1.2 mm cold rolled steel sheet.
- the size of the iron carbide in the region of the obtained steel plate from the boundary between the innermost layer (Zn and Fe reaction layer) of the Zn—Fe alloy layer and the steel plate to the position separated by 0.3 mm in the thickness direction. was measured, and the standard deviation of the size of the iron carbide was determined. Along with the measurement of iron carbide, the total thickness of the Zn—Fe alloy layer (consisting of 4 layers) was also measured. Further, hot stamping was performed on the shape steel and the flat plate in the same manner as in Example 1, and the warpage d and the tensile strength ⁇ B were measured. However, there were two heating conditions before hot stamping: ⁇ 1> heated to 880 ° C. and held for 5 seconds, then air-cooled to 700 ° C. and ⁇ 2> held at 900 ° C. for 1 minute.
- any of the examples Nos. 92 to 111
- hot stamp parts having a warp of 5 mm or less were obtained regardless of the heating conditions before hot stamping.
- the thickness of the Zn—Fe alloy layer exceeds 45 ⁇ m.
- fine cracks occurred in the alloy layer after hot stamping.
- the upper limit of the thickness of the Zn—Fe alloy layer is preferably 45 ⁇ m or less from the viewpoint of plating quality.
- the quality of the Zn—Fe alloy layer was evaluated as “A” when no fine cracks occurred in the Zn—Fe alloy layer, and the Zn when the fine cracks occurred in the Zn—Fe alloy layer.
- the quality of the —Fe alloy layer was evaluated as “B”.
- a steel plate capable of reducing warpage that is likely to occur when a long part is manufactured using a hot stamp method, and a manufacturing method thereof.
- Blank (steel plate) 12 Shape steel 21 Surface plate 31a Upper die 31b Lower die 32 Blank (steel plate) L Length W Width d Warp
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Abstract
Description
本願は、2011年4月27日に、日本に出願された特願2011-100019号に基づき優先権を主張し、その内容をここに援用する。
そこで、更に研究を進めたところ、成形直前の加熱工程における鋼板中の鉄炭化物の溶解挙動が不均一の発生を抑制する鍵を握っていることが明らかとなった。
特許文献1、2には、冷延鋼板をどのような条件で焼鈍したかについて全く開示されておらず、鋼板中の炭化物の制御について検討していない。
特許文献3には、冷延鋼板の焼鈍について、炭化物の状態を制御する上で最も重要である加熱履歴に関する記載はなく、炭化物の制御について検討していない。
また、所定の金属組織を得るために、極めて特殊な焼鈍を行うことが必須であり、一般的な連続焼鈍設備や連続溶融めっき設備での製造を前提としていないので、特許文献4では、焼鈍条件を工夫して炭化物の大きさの分布状態を制御していない。
特許文献5には、最高加熱温度までの加熱履歴について全く開示されておらず、炭化物の大きさの分布状態を制御していない。
また、所定の鋼板を得るために、熱延鋼板、および冷延鋼板に対して長時間焼鈍を複数回組み合わせて実施することが必須であり、一般的な連続焼鈍設備や連続溶融めっき設備での製造を前提としていないので、特許文献6では、焼鈍条件を工夫して炭化物の大きさの分布状態を制御していない。
特許文献7は、フェライトの平均粒径と炭化物の平均粒径を制御することで、打ち抜き性に優れた中・高炭素高強度鋼板を得るための技術であるが、この特許文献7には、炭化物の大きさの分布状態に関する記載はない。
また、冷延ままの冷延鋼板と、350~700℃に10~40時間保持する低温かつ長時間の焼鈍条件で焼鈍された冷延鋼板とが開示されていることに加え、一般的な連続焼鈍設備や連続溶融めっき設備での製造を前提としていないので、焼鈍条件を工夫して炭化物の大きさの分布状態を制御していない。
本発明者らの研究の結果、鉄炭化物の大きさの分布状態は、冷延鋼板の焼鈍時の、鋼板温度の上昇速度の変化と密接に関係していることも判明したが、以上のようにこうした視点に立ってホットスタンプ用の鋼板の製造方法について検討した例は見当たらない。
その要旨は、以下のとおりである。
-0.20≦d/dt(ΔT/Δt)<0 (式1)
ここで、Tは、℃の単位での前記鋼板温度、tは、sの単位での時間、ΔT/Δtは、℃/sの単位での前記再結晶焼鈍の加熱中の時間Δt秒間における前記鋼板温度の上昇速度を指す。
また、上記(3)~(5)の態様に係るホットスタンプ部材用鋼板では、ホットスタンプ後に、かじりや剥れ、割れ等の欠陥が少ないAlめっき層、Znめっき層、およびZn-Fe合金層を得ることができる。そのため、この場合には、ホットスタンプ部材用鋼板の耐食性及び表面品質をより高めることができる。
さらに、本発明の上記態様に係るホットスタンプ部材用鋼板の製造方法では、既設の製鉄設備を使用することができ、ホットスタンプ法により長尺の成形品を製造した場合であっても、反りを極めて低くすることができるホットスタンプ部材用鋼板を提供することができる。
加えて、上記(9)~(11)の態様に係るホットスタンプ部材用鋼板の製造方法では、ホットスタンプ部材用鋼板の耐食性及び表面品質をより高めることができる。
まず、鋼板の化学成分について説明する。以下では、各化学成分の「%」は、「質量%」を意味する。
Cは、ホットスタンプ法によって鋼板を高強度化する上で最も重要な元素である。ホットスタンプ後に少なくとも1200MPa程度の強度を得るには、鋼中にCを0.10%以上含有させる。その一方で、鋼中にCを0.35%を超えて含有させると、靭性の劣化が心配されるので、0.35%をC量の上限とする。靭性をより改善する場合には、C量が、0.32%以下であることが好ましく、0.30%以下であることがより好ましい。
Siは、固溶強化元素であり、0.01~1.0%のSiを固溶強化元素として有効に活用できる。しかしながら、1.0%を超えるSiを鋼中に含有させると、ホットスタンプ後に化成処理や塗装を行う際に不具合が生じることが懸念されるので、1.0%をSi量の上限とする。Si量の下限を特に限定することなく鉄炭化物を制御する効果を得ることができるが、必要以上にSi量を低減すると製鋼負荷が高まるため、Si量を0.01%以上とする。このSi量の下限は、脱酸に起因して鋼中に含有される目安量である。より安定した表面処理を行う場合には、Si量が、0.9%以下であることが好ましく、0.8%以下であることがより好ましい。
Mnは、Siと同様に固溶強化元素として機能する他に、鋼板の焼き入れ性を高める有用な元素である。このような強度及び焼入れ性向上の効果を明確に得るために、鋼中のMn量を0.3%以上とする。しかし、鋼中にMnを2.3%を超えて含有させてもその効果は飽和するので、2.3%をMn量の上限とする。より強度を高める場合には、Mn量が、0.5%以上であることが好ましく、1.0%以上であることがより好ましい。
両元素は、いずれも不純物であり、熱間加工性に影響を及ぼすため、P:0.03%以下、S:0.02%以下に制限する。
Alは、脱酸元素として好適であるので、鋼中にAlを0.01%以上含有させてよい。しかし、多量のAlを鋼中に含有させると、粗大な酸化物を形成して鋼板の機械的性質を損なう。そのため、Al量の上限を0.5%とする。
Nは、TiやBと容易に結合することからそれらの元素の目的とする効果を減じないようにN量を0.1%以下に制御する。靭性を高める場合には、N量は、少ない方がよいため、望ましくは0.01%以下である。必要以上にN量を低減すると製鋼工程に多大な負荷が掛かるので、0.0010%をN量の下限の目安としてもよい。
すなわち、必要に応じて、Cr、Ti、Nb、B、Mo、W、V、Cu、Niから選択される1種以上の選択元素を鋼中に含有させてもよい。合金コストの低減のためには、これら選択元素を意図的に鋼中に添加する必要はなく、Cr、Ti、Nb、B、Mo、W、V、Cu、Niの量の下限は、いずれも0%である。
Crは、焼き入れ性を高める効果を有する元素であるから適宜使用できる。その効果が明瞭となるのは、Cr量が0.01%以上である。一方で、Crを2.0%を超えて鋼中に添加してもその効果は飽和するので、2.0%をCr量の上限とする。
Tiは、窒化物の形成を通じて後述するBの効果を安定的に引き出す働きをするので有効に活用したい元素である。その働きを明確に得るためには、Ti量が0.001%以上であるとよい。一方で、鋼中にTiが過剰に添加されると、窒化物が過剰となり、靭性や剪断面性状が劣化するので、0.5%をTi量の上限とする。
Nbは、炭窒化物を形成し、鋼の強度を高めるので有効に活用したい元素である。このような強度向上の効果を明確に得るために、鋼中のNb量を0.001%以上としてもよい。しかしながら、鋼中にNbを0.5%を超えて含有させると、熱間圧延の制御性を損ねる恐れがあるので、0.5%をNb量の上限とする。
Bは焼入れ性を高める元素であり、鋼中に0.0005%以上のBを含むと、焼入れ性を高める効果が明瞭となる。一方、過剰なBの添加は熱間加工性の劣化と延性の低下につながるので、0.01%をB量の上限とする。
これらの元素は、いずれも焼き入れ性を高める効果を有する元素であるから適宜使用できる。その効果が明瞭となるのは、いずれの元素についても0.01%以上である。一方で、Mo、W、Vは、高価な元素であることから、効果が飽和する濃度を上限とすることが好ましい。Mo量の上限については1.0%、W量およびV量の上限については0.5%であるとよい。
Cuは、0.01%以上のCuを鋼中に添加することで鋼板の強度を高める効果を有する。一方で、過剰なCuの添加は熱間圧延鋼板の表面品位を損ねるので1.0%をCu量の上限とする。そのため、Cu量は、0.01~1.0%であってもよい。
Niは、焼入れ性を高める効果を有するので有効に活用したい元素であり、その効果は0.01%以上のNi量で明瞭となる。一方、Niは、高価な元素であるから、その効果が飽和する5.0%をNi量の上限とする。そのため、Ni量は、0.01~5.0%であってもよい。また、Niは、上記のCuによる熱間圧延鋼板の表面品位の低下を抑制する働きも有するので、Cuと同時に含有させることが望ましい。
鉄炭化物の大きさの分布状態は、本実施形態において最も重要な要件である。
成形体に発生する反りは、成形体の長さが1000mmよりも短くなったり、成形体の幅が170mmよりも長くなったりすると、小さくなるが、本実施形態の鋼板をこのような成形体に適用しても、成形体の反りdをさらに抑制する効果を得ることができる。
-0.2≦d/dt(ΔT/Δt)<0 ・・・ (式1)
ここで、Tは、鋼板温度(℃)を、tは、時間(s)を、ΔT/Δtは、再結晶焼鈍の加熱中の時間Δt(s)間における板温の温度変化(℃/s)を、d/dt(ΔT/Δt)は、300℃から最高温度Sまでの板温の上昇速度の変化(℃/s2)を指す。なお、tの0(零)の基準は、特に制限する必要はなく、例えば、再結晶焼鈍の加熱開始時間や再結晶焼鈍の加熱により300℃に達した時間であってもよい。
本発明に係るホットスタンプ部材用鋼板は、その板厚や、ホットスタンプ後の強度に関係なく本発明の効果を有するが、熱延、冷延、焼鈍、およびめっき付与(めっき層の形成)の各工程での高生産性確保の観点から、帯鋼として扱い得ることが望ましい。従って、対象とする鋼板の好ましい板厚は、概ね0.5~3.5mmであるとよい。また、部材の高強度化による軽量化をさらに進めるために、対象とする鋼板の好ましいホットスタンプ後の強度は、引張強さで、概ね1200~2000MPaであるとよい。
ここで、条件xでは、300℃から600℃まで一定の加熱速度10℃/sで加熱し、その後、800℃まで一定の加熱速度2℃/sで冷延鋼板を加熱した。この場合、300℃から600℃まで、および600℃から800℃までの両温度範囲について、鋼板温度の上昇速度の変化d/dt(ΔT/Δt)は各々0(零)であった。その他の条件では、300℃から温度Sまでの範囲において鋼板温度の上昇速度の変化d/dt(ΔT/Δt)が一定と見做せる加熱を行った。なお、このd/dt(ΔT/Δt)の求め方については実施例3にて詳しく述べる。
このホットスタンプ用鋼板から採取した試料の圧延方向と平行な断面を研磨し、ピクラール系腐食液でこの断面のミクロ組織を現出後、冷延鋼板(試料)の表面から厚さ方向に0.4mmの距離だけ離れた位置(板厚の1/4位置)までの領域を走査電子顕微鏡の倍率5000倍にて観察し、鉄炭化物の大きさを測定した。この観察を、鉄炭化物の測定数が600個以上となるまで行った。さらに、測定したデータを処理して標準偏差を求めた。
また、上記冷延鋼板から210×300mmのブランク32を作製し、図3に示す平板スタンプの上金型31aおよび下金型31bにてこのブランク32を形鋼12の成形条件(形状を除く)と同じ条件でホットスタンプし、引張強さの測定用素材を得た。これら素材からJIS5号引張試験片を2本採取した。採取のための加工を放電加工で行った。得られた試験片に対して引張試験を行い、引張強さσBを求めた(2本の平均値)。
一方、この標準偏差が8μm超の場合(No.9、12、14、26、および27、solid circleまたはsolid triangleで表示)にはdが8mm超となり、看過できないことが明らかとなった。
本発明の条件を満足する焼鈍条件i、およびixで再結晶焼鈍を行ったホットスタンプ用鋼板にあっては、Mo、W、V、Cu、およびNi等の化学成分を含有する鋼板であっても、鋼板の表面から板厚の1/4位置までの鉄炭化物の大きさの標準偏差が0.8μm以下であった。さらに、この場合には、ホットスタンプ前の加熱条件(900℃での保持時間)に依らず長尺部品(形鋼)の反りが5mm以下であり、優れたホットスタンプ部材が得られることが明らかとなった。
また、図7内に示すように、得られた近似式の決定係数(coefficient of determination)R2は、0.999であった。本発明で用いるd/dt(ΔT/Δt)は、この例のように、再結晶焼鈍時の加熱の温度履歴から10秒以下または5秒以下の時間間隔(但し、0秒超)で温度を読み取り、決定係数R2が0.99以上となるように近似曲線(次数2の多項式近似曲線)を決定した際のt2の係数(次数2の変数の係数)の2倍を用いるとよい。
得られた鋼板の、Alめっき層のうちの内側の層(AlとFeの反応層)と鋼板との境界から板厚方向に0.3mmの距離だけ離れた位置までの領域の鉄炭化物の大きさを測定し、鉄炭化物の大きさの標準偏差を求めた。鉄炭化物を測定するのに合わせて、Alめっき層(2層の合計)の厚さも測定した。更に、実施例1と同じ要領で形鋼及び平板へのホットスタンプを実行し、反りd及び引張強さσBの測定を行った。ただし、ホットスタンプ前の加熱条件は、900℃で1分間保持とした。
12 形鋼
21 定盤
31a 上金型
31b 下金型
32 ブランク(鋼板)
L 長さ
W 幅
d 反り
Claims (11)
- 質量%で、
C:0.10~0.35%、
Si:0.01~1.0%、
Mn:0.3~2.3%、および
Al:0.01~0.5%、
を含有し、
P:0.03%以下、
S:0.02%以下、および
N:0.1%以下
に制限し、
残部がFeおよび不可避的不純物からなる化学組成を有し、
表面から板厚の1/4の位置までに含まれる鉄炭化物の直径の標準偏差が0.8μm以下である
ことを特徴とするホットスタンプ部材用鋼板。 - 前記化学組成が、更に、質量%で、
Cr:0.01~2.0%、
Ti:0.001~0.5%、
Nb:0.001~0.5%、
B:0.0005~0.01%、
Mo:0.01~1.0%、
W:0.01~0.5%、
V:0.01~0.5%、
Cu:0.01~1.0%、および
Ni:0.01~5.0%
から選択される1種以上を含有することを特徴とする請求項1に記載のホットスタンプ部材用鋼板。 - 前記表面にめっき厚が50μm以下のAlめっき層を有することを特徴とする請求項1または2に記載のホットスタンプ部材用鋼板。
- 前記表面にめっき厚が30μm以下のZnめっき層を有することを特徴とする請求項1または2に記載のホットスタンプ部材用鋼板。
- 前記表面にめっき厚が45μm以下のZn-Fe合金層を有することを特徴とする請求項1または2に記載のホットスタンプ部材用鋼板。
- 質量%で、
C:0.10~0.35%、
Si:0.01~1.0%、
Mn:0.3~2.3%、および
Al:0.01~0.5%、
を含有し、
P:0.03%以下、
S:0.02%以下、および
N:0.1%以下
に制限し、
残部がFeおよび不可避的不純物からなる化学組成を有する冷延鋼板を、℃/s2の単位での300℃から最高温度Sまでの鋼板温度の上昇速度の変化d/dt(ΔT/Δt)が下記式1を満たし、かつ、前記最高温度Sが720~820℃となるように加熱して再結晶焼鈍を行う
ことを特徴とするホットスタンプ部材用鋼板の製造方法。
-0.20≦d/dt(ΔT/Δt)<0 (式1)
ここで、Tは、℃の単位での前記鋼板温度、tは、sの単位での時間、ΔT/Δtは、℃/sの単位での前記再結晶焼鈍の加熱中の時間Δt秒間における前記鋼板温度の上昇速度を指す。 - 前記化学組成が、更に、質量%で、
Cr:0.01~2.0%、
Ti:0.001~0.5%、
Nb:0.001~0.5%、
B:0.0005~0.01%、
Mo:0.01~1.0%、
W:0.01~0.5%、
V:0.01~0.5%、
Cu:0.01~1.0%、および
Ni:0.01~5.0%
から選択される1種以上を含有することを特徴とする請求項6に記載のホットスタンプ部材用鋼板の製造方法。 - 前記d/dt(ΔT/Δt)は、前記再結晶焼鈍時の加熱の温度履歴から10秒以下の時間間隔で温度を読み取り、決定係数R2が0.99以上となるように次数2の多項式近似曲線を決定した際の次数2の変数の係数の2倍であることを特徴とする請求項6または7に記載のホットスタンプ部材用鋼板の製造方法。
- 前記再結晶焼鈍に引き続き、前記冷延鋼板をAl浴に浸漬し、前記冷延鋼板の表面にめっき厚が50μm以下のAlめっき層を形成することを特徴とする請求項6または7に記載のホットスタンプ部材用鋼板の製造方法。
- 前記再結晶焼鈍に引き続き、前記冷延鋼板をZn浴に浸漬し、前記冷延鋼板の表面にめっき厚が30μm以下のZnめっき層を形成することを特徴とする請求項6または7に記載のホットスタンプ部材用鋼板の製造方法。
- 前記再結晶焼鈍に引き続き、前記冷延鋼板をZn浴に浸漬して前記冷延鋼板の表面にZnめっき層を形成した後、前記冷延鋼板を600℃以下に加熱して前記冷延鋼板の表面にめっき厚が45μm以下のZn-Fe合金層を形成することを特徴とする請求項6または7に記載のホットスタンプ部材用鋼板の製造方法。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES12776563.4T ES2683843T3 (es) | 2011-04-27 | 2012-04-26 | Lámina de acero para elementos de estampación en caliente y método de producción de la misma |
| JP2013512435A JP5472531B2 (ja) | 2011-04-27 | 2012-04-26 | ホットスタンプ部材用鋼板およびその製造方法 |
| PL12776563T PL2703511T3 (pl) | 2011-04-27 | 2012-04-26 | Blacha stalowa cienka na elementy wytłaczane na gorąco i sposób jej wytwarzania |
| CN201280019667.5A CN103492600B (zh) | 2011-04-27 | 2012-04-26 | 热冲压部件用钢板及其制造方法 |
| CA2832894A CA2832894C (en) | 2011-04-27 | 2012-04-26 | Steel sheet for hot stamping member and method of producing same |
| KR1020137028414A KR101617505B1 (ko) | 2011-04-27 | 2012-04-26 | 핫 스탬프 부재용 강판 및 그 제조 방법 |
| RU2013148558/02A RU2552817C1 (ru) | 2011-04-27 | 2012-04-26 | Стальной лист для горячештампованного изделия и способ его изготовления |
| EP12776563.4A EP2703511B1 (en) | 2011-04-27 | 2012-04-26 | Steel sheet for hot stamping members and method for producing same |
| MX2013012422A MX351086B (es) | 2011-04-27 | 2012-04-26 | Lámina de acero para miembro de estampado en caliente y método para producir la misma. |
| US14/112,414 US9617624B2 (en) | 2011-04-27 | 2012-04-26 | Steel sheet for hot stamping member and method of producing same |
| BR112013027213-9A BR112013027213B1 (pt) | 2011-04-27 | 2012-04-26 | Chapa de aço para elemento de estampagem a quente e método para produção da mesma |
| ZA2013/07763A ZA201307763B (en) | 2011-04-27 | 2013-10-17 | Steel sheet for hot stamping member and method of producing same |
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| JP2011-100019 | 2011-04-27 |
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| EP (1) | EP2703511B1 (ja) |
| JP (1) | JP5472531B2 (ja) |
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| CN (1) | CN103492600B (ja) |
| BR (1) | BR112013027213B1 (ja) |
| CA (1) | CA2832894C (ja) |
| ES (1) | ES2683843T3 (ja) |
| MX (1) | MX351086B (ja) |
| PL (1) | PL2703511T3 (ja) |
| RU (1) | RU2552817C1 (ja) |
| TW (1) | TWI454584B (ja) |
| WO (1) | WO2012147863A1 (ja) |
| ZA (1) | ZA201307763B (ja) |
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| JP2015131995A (ja) * | 2014-01-14 | 2015-07-23 | 新日鐵住金株式会社 | ホットスタンプ用鋼板およびその製造方法 |
| JP2015199995A (ja) * | 2014-04-09 | 2015-11-12 | 新日鐵住金株式会社 | 自動車部材の製造方法 |
| JP2017524804A (ja) * | 2014-05-12 | 2017-08-31 | ティッセンクルップ スチール ヨーロッパ アクチェンゲゼルシャフトThyssenKrupp Steel Europe AG | 腐食耐性金属コーティングが提供された鋼部材を製造するための方法ならびに鋼部材 |
| JP2017529457A (ja) * | 2014-12-24 | 2017-10-05 | ポスコPosco | 曲げ性に優れたhpf成形部材及びその製造方法 |
| US10533237B2 (en) | 2014-12-24 | 2020-01-14 | Posco | Hot press forming parts having excellent bending properties and method for manufacturing the same |
| US10151013B2 (en) | 2014-12-24 | 2018-12-11 | Posco | Hot press forming parts having excellent bending properties and method for manufacturing the same |
| JP2023538796A (ja) * | 2021-07-30 | 2023-09-12 | ヒュンダイ スチール カンパニー | 熱間プレス用鋼板及びそれを用いて製造されたアルミニウム系メッキブランク |
| JP2024546126A (ja) * | 2021-12-10 | 2024-12-17 | ヒュンダイ スチール カンパニー | ホットスタンピング用素材 |
| JP2024546125A (ja) * | 2021-12-10 | 2024-12-17 | ヒュンダイ スチール カンパニー | ホットスタンピング用素材 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20140044987A1 (en) | 2014-02-13 |
| JP5472531B2 (ja) | 2014-04-16 |
| TW201300550A (zh) | 2013-01-01 |
| ES2683843T3 (es) | 2018-09-28 |
| KR101617505B1 (ko) | 2016-05-02 |
| EP2703511A1 (en) | 2014-03-05 |
| CN103492600B (zh) | 2015-12-02 |
| CA2832894A1 (en) | 2012-11-01 |
| EP2703511A4 (en) | 2015-09-30 |
| MX351086B (es) | 2017-09-29 |
| RU2552817C1 (ru) | 2015-06-10 |
| PL2703511T3 (pl) | 2018-10-31 |
| TWI454584B (zh) | 2014-10-01 |
| ZA201307763B (en) | 2014-06-25 |
| MX2013012422A (es) | 2013-12-06 |
| US9617624B2 (en) | 2017-04-11 |
| EP2703511B1 (en) | 2018-05-30 |
| BR112013027213B1 (pt) | 2019-04-02 |
| JPWO2012147863A1 (ja) | 2014-07-28 |
| CN103492600A (zh) | 2014-01-01 |
| KR20130136565A (ko) | 2013-12-12 |
| CA2832894C (en) | 2017-07-11 |
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