WO2020241864A1 - ホットスタンプ成形体 - Google Patents
ホットスタンプ成形体 Download PDFInfo
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- WO2020241864A1 WO2020241864A1 PCT/JP2020/021443 JP2020021443W WO2020241864A1 WO 2020241864 A1 WO2020241864 A1 WO 2020241864A1 JP 2020021443 W JP2020021443 W JP 2020021443W WO 2020241864 A1 WO2020241864 A1 WO 2020241864A1
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- plating layer
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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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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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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- 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
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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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
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- 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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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- 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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- C22C38/00—Ferrous alloys, e.g. steel alloys
- 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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- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- 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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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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
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- 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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- 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
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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- C25D3/00—Electroplating: Baths therefor
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
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- C25D3/00—Electroplating: Baths therefor
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- C25D3/00—Electroplating: Baths therefor
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
Definitions
- the present invention relates to a hot stamp molded article. More specifically, the present invention relates to a hot stamp molded article having improved coating film peeling resistance.
- the hot stamping method is often used for forming steel sheets used for automobile parts.
- the hot stamping method is a method in which a steel sheet is press-formed while being heated to a temperature in the austenite range, and then quenched (cooled) by a press die at the same time as the forming.
- a plating layer such as a Zn—Ni alloy plating layer may be provided on the surface of the steel sheet (for example, Patent Documents 1 to 3).
- a hot stamped molded product obtained by hot stamping a plated steel sheet having a plated layer on the steel sheet
- the purpose is to improve corrosion resistance, especially when used for automobile members.
- a coating film may be formed on a hot stamped molded product by subjecting it to a chemical conversion treatment to form a phosphate film and then performing electrodeposition coating. Therefore, it is important to prevent the coating film from easily peeling off from the molded product after forming such a coating film.
- a ZnO layer is provided on the outermost layer of the hot stamped molded product in order to improve the adhesion between the hot stamped molded product and the coating film.
- a Ni diffusion region exists on the surface layer of the steel plate constituting the member, and a metal corresponding to the ⁇ phase existing in the equilibrium state diagram of the Zn—Ni alloy in this order on the Ni diffusion region.
- Described is a hot press member having an intermetallic layer and a ZnO layer and having a natural immersion potential of -600 to -360 mV with respect to a standard hydrogen electrode in an air-saturated 0.5 MNaCl aqueous solution at 25 ° C. ⁇ 5 ° C. It is taught that the hot-pressed member has excellent coating adhesion to the chemical conversion-treated film by having a ZnO layer on the surface layer.
- Japanese Unexamined Patent Publication No. 2012-197505 Japanese Unexamined Patent Publication No. 2016-29214 Japanese Unexamined Patent Publication No. 2016-125101 Japanese Unexamined Patent Publication No. 2011-246801 Japanese Unexamined Patent Publication No. 2012-1816
- the hot press members described in Patent Documents 4 and 5 are intended to ensure the adhesion of the coating film to the chemical conversion treatment film coated on the surface due to the presence of the ZnO layer on the outermost layer.
- ZnO existing on the outermost surface layer of the hot press member has a sparse density and a relatively low strength, even if peeling at the interface between the ZnO layer and the coating film is suppressed, it is suppressed.
- the ZnO layer itself may be peeled off or broken. In other words, a part of the ZnO layer on which the coating film is formed may be peeled off or destroyed, and as a result, the coating film may be peeled off (removed) from the hot press member. Therefore, in the hot press members described in Patent Documents 4 and 5, there is room for improvement in preventing the coating film from peeling from the hot press member, that is, improving the coating film peeling resistance.
- an object of the present invention is to provide a hot stamped molded product having improved coating film peeling resistance by a novel configuration.
- the present inventors provide a ZnO region on the surface layer of the plating layer formed on the steel sheet to ensure the adhesion between the ZnO layer and the coating film, and to obtain the ZnO region.
- it is effective to improve the strength of the ZnO region on the surface layer of the plating layer by including not only oxygen and zinc but also elements other than zinc.
- the strength of the ZnO region is improved, peeling or breakage from the ZnO region is sufficiently prevented, and a hot stamp molded product having improved coating film peeling resistance can be obtained.
- the following is a hot stamped body.
- the hot stamp molded product according to (1) wherein in the Ni—Fe—Zn alloy region, the concentrations of Zn, O, Mn, and Si decrease from the surface side of the plating layer toward the steel plate side.
- the Ni—Fe—Zn alloy region is composed of a first region having an Fe concentration of less than 60% by mass and a second region having an Fe concentration of 60% by mass or more in order from the surface side of the plating layer.
- the Zn / Ni mass ratio in the first region is in the range of 2.0 or more and 15.0 or less, and the average Zn / Ni mass ratio in the second region is 0.5 or more and 2.0 or less.
- the present invention it is possible to provide a hot stamp molded product having improved strength of the ZnO region existing on the surface side of the plating layer, preventing peeling or breaking of ZnO itself, and having improved peeling resistance of the coating film. it can.
- the hot stamp molded product according to the present invention has a steel plate and a plating layer formed on at least one surface of the steel plate.
- the plating layers are formed on both sides of the steel sheet.
- the composition of the steel sheet in the present invention is not particularly limited, and may be determined in consideration of the strength of the hot stamped molded product after hot stamping and the hardenability at the time of hot stamping.
- the elements that can be contained in the steel sheet in the present invention will be described.
- "%" representing the content of each element in the component composition means mass% unless otherwise specified.
- the steel sheet in the present invention has C: 0.05% or more and 0.70% or less, Mn: 0.5% or more and 11.0% or less, Si: 0.05% or more and 2.50% in mass%.
- Al 0.001% or more and 1.500% or less
- P 0.100% or less
- S 0.100% or less
- N 0.010% or less
- O 0.010% or less
- C (C: 0.05% or more and 0.70% or less)
- C (carbon) is an element effective for improving the strength of the steel sheet.
- Automobile members may be required to have high strength of, for example, 980 MPa or more.
- the C content is preferably 0.05% or more.
- the C content is preferably 0.70% or less.
- the lower limit of the C content is preferably 0.10%, more preferably 0.12%, still more preferably 0.15%, and most preferably 0.20%.
- the upper limit of the C content is preferably 0.65%, more preferably 0.60%, still more preferably 0.55%, and most preferably 0.50%.
- Mn manganese
- Mn manganese
- Mn manganese
- the Mn content is preferably 11.0% or less.
- the lower limit of the Mn content is preferably 1.0%, more preferably 2.0%, still more preferably 2.5%, even more preferably 3.0%, and most preferably 3.5%.
- the upper limit of the Mn content is preferably 10.0%, more preferably 9.5%, still more preferably 9.0%, still more preferably 8.5%, and most preferably 8.0%.
- Si silicon
- Si silicon
- the Si content is preferably 0.05% or more.
- the Si content is preferably 2.50% or less.
- the lower limit of the Si content is preferably 0.10%, more preferably 0.15%, still more preferably 0.20%, and most preferably 0.30%.
- the upper limit of the Si content is preferably 2.00%, more preferably 1.80%, still more preferably 1.50%, and most preferably 1.20%.
- Al (Al: 0.001% or more and 1.500% or less)
- Al (aluminum) is an element that acts as a deoxidizing element.
- the Al content is preferably 0.001% or more.
- the Al content is preferably 1.500% or less.
- the lower limit of the Al content is preferably 0.010%, more preferably 0.020%, still more preferably 0.050%, and most preferably 0.100%.
- the upper limit of the Al content is preferably 1.000%, more preferably 0.800%, still more preferably 0.700%, and most preferably 0.500%.
- the lower limit of these elements is not particularly limited. However, the content of these elements may be more than 0.000% or 0.001% or more. On the other hand, if these elements are excessively contained, the toughness, ductility and / or processability may be deteriorated. Therefore, the upper limits of P and S are set to 0.100%, and the upper limits of N and O are set to 0.010%. Is preferable.
- the upper limit of P and S is preferably 0.080%, more preferably 0.050%.
- the upper limit of N and O is preferably 0.008%, more preferably 0.005%.
- the basic composition of the steel sheet in the present invention is as described above. Further, the steel sheet may contain at least one of the following optional elements in place of a part of the remaining Fe, if necessary.
- the steel sheet may contain B: 0% or more and 0.0040%.
- the steel sheet may contain Cr: 0% or more and 2.00% or less.
- the steel sheet is from Ti: 0% or more and 0.300% or less, Nb: 0% or more and 0.300% or less, V: 0% or more and 0.300% or less, and Zr: 0% or more and 0.300% or less. It may contain at least one selected from the group.
- the steel sheet contains at least one selected from the group consisting of Mo: 0% or more and 2.000% or less, Cu: 0% or more and 2.000% or less, and Ni: 0% or more and 2.000% or less. You may. Further, the steel sheet may contain Sb: 0% or more and 0.100% or less. Further, the steel sheet contains at least one selected from the group consisting of Ca: 0% or more and 0.0100% or less, Mg: 0% or more and 0.0100% or less, and REM: 0% or more and 0.1000% or less. You may. Hereinafter, these optional elements will be described in detail.
- B (B: 0.0040% or less)
- B (boron) is an element effective for improving hardenability during hot stamping.
- the B content may be 0%, but in order to surely obtain this effect, the B content is preferably 0.0005% or more.
- the B content is preferably 0.0040% or less.
- the lower limit of the B content is preferably 0.0008%, more preferably 0.0010%, and even more preferably 0.0015%.
- the upper limit of the B content is preferably 0.0035%, more preferably 0.0030%.
- Cr 0% or more and 2.00% or less
- Cr Cr (chromium) is an element effective for improving hardenability during hot stamping.
- the Cr content may be 0%, but in order to ensure this effect, the Cr content is preferably 0.01% or more.
- the Cr content may be 0.10% or more, 0.50% or more, or 0.70% or more.
- the Cr content is preferably 2.00% or less.
- the Cr content may be 1.50% or less, 1.20% or less, or 1.00% or less.
- Ti 0% or more and 0.300% or less
- Nb 0% or more and 0.300% or less
- V 0% or more and 0.300% or less
- Zr 0% or more and 0.300% or less
- Ti (titanium), Nb (niobium), V (vanadium) and Zr (zirconium) are elements that improve tensile strength through the miniaturization of metal structures.
- the content of these elements may be 0%, but in order to surely obtain this effect, the contents of Ti, Nb, V and Zr are preferably 0.001% or more, and 0.010. % Or more, 0.020% or more, or 0.030% or more.
- the Ti, Nb, V and Zr contents are preferably 0.300% or less, and may be 0.150% or less, 0.100% or less, or 0.060% or less.
- Mo molybdenum
- Cu 0% or more and 2.000% or less
- Ni 0% or more and 2.000% or less
- Mo (molybdenum), Cu (copper) and Ni (nickel) have the effect of increasing the tensile strength.
- the content of these elements may be 0%, but in order to surely obtain this effect, the contents of Mo, Cu and Ni are preferably 0.001% or more, and 0.010% or more. , 0.050% or more or 0.100% or more.
- the Mo, Cu and Ni contents are preferably 2.000% or less, and may be 1.500% or less, 1.000% or less, or 0.800% or less.
- Sb 0% or more and 0.100% or less
- Sb antimony
- the Sb content may be 0%, but in order to surely obtain this effect, the Sb content is preferably 0.001% or more.
- the Sb content may be 0.005% or more, 0.010% or more, or 0.020% or less.
- excessive content of Sb may cause a decrease in toughness. Therefore, the Sb content is preferably 0.100% or less.
- the Sb content may be 0.080% or less, 0.060% or less, or 0.050% or less.
- Ca 0% or more and 0.0100% or less
- Mg 0% or more and 0.0100% or less
- REM 0% or more and 0.1000% or less
- Ca (calcium), Mg (magnesium) and REM (rare earth metal) are elements that improve toughness after hot stamping by adjusting the shape of inclusions.
- the content of these elements may be 0%, but in order to surely obtain this effect, the Ca, Mg and REM contents are preferably 0.0001% or more, and 0.0010% or more. , 0.0020% or more or 0.0040% or more.
- Ca, Mg and REM are excessively contained, the effect is saturated and the production cost is increased.
- the Ca and Mg contents are preferably 0.0100% or less, and may be 0.0080% or less, 0.0060% or less, or 0.0050% or less.
- the REM content is preferably 0.1000% or less, and may be 0.0800% or less, 0.0500% or less, 0.0100% or less.
- the rest other than the above elements consists of iron and impurities.
- the "impurity” is a component mixed by various factors in the manufacturing process, including raw materials such as ore and scrap, when the base steel sheet is industrially manufactured, and the present invention is carried out. It includes components that are not intentionally added to the base steel sheet according to the form. Further, the impurities are elements other than the components described above, and are contained in the base steel sheet at a level at which the action and effect peculiar to the elements do not affect the characteristics of the hot stamped molded product according to the embodiment of the present invention. It also includes elements.
- the steel sheet in the present invention is not particularly limited, and general steel sheets such as hot-rolled steel sheets and cold-rolled steel sheets can be used. Further, the steel sheet in the present invention may have any thickness as long as a Zn—Ni plating layer described later can be formed on the steel sheet and hot stamping can be performed, for example, 0.1 to 3.2 mm. .. In order to obtain the hot stamped molded product according to the present invention, it is preferable that the surface roughness Ra of the steel sheet is 1.0 ⁇ m or more and 3.0 ⁇ m or less.
- the surface roughness of the steel sheet When the surface roughness of the steel sheet is set within such a range, a certain amount of contact area between the steel sheet and the plating layer such as the Zn—Ni plating layer formed on the surface of the steel sheet is secured, and the steel sheet is plated during hot stamping. The diffusion of the steel sheet component into the layer is likely to proceed. On the other hand, if the surface roughness is too high, the ZnO region of the surface layer of the plating layer may become excessively thick (for example, more than 5.0 ⁇ m).
- the plating layer in the present invention comprises a ZnO region and a Ni—Fe—Zn alloy region.
- the ZnO region is a region existing on the surface side of the plating layer and having an oxygen concentration of 10% by mass or more.
- the remaining region of the plating layer is a Ni—Fe—Zn alloy region, that is, the Ni—Fe—Zn alloy region is a region existing on the steel plate side of the plating layer and having an oxygen concentration of less than 10%. Therefore, the ZnO region and the Ni—Fe—Zn alloy region exist so as to be in contact with each other, and the plating layer is formed by these two regions.
- the oxygen concentration is highest on the surface side of the plating layer, and the oxygen concentration decreases toward the steel plate side. Therefore, the ZnO region is from the surface of the hot stamped molded product to the position where the oxygen concentration is 10% by mass, and the remaining portion of the plating layer is the Ni—Fe—Zn alloy region.
- the plating layer of the hot stamped molded product according to the present invention is, for example, under an oxygen atmosphere (for example, an atmospheric atmosphere or a high-concentration oxygen atmosphere with an oxygen concentration of 25 to 30%) after forming a Zn—Ni alloy plating layer on a steel sheet. It can be obtained by hot stamping with. Alternatively, for example, it can be obtained by forming a Zn plating layer and a Ni plating layer on a steel sheet and then hot stamping in an oxygen atmosphere. Further, in order to efficiently diffuse the steel plate component such as Fe in the plating layer to obtain the hot stamped molded product according to the present invention, it is preferable to overheat the hot stamping.
- an oxygen atmosphere for example, an atmospheric atmosphere or a high-concentration oxygen atmosphere with an oxygen concentration of 25 to 30%
- “Overheat treatment” means heating for a short time (for example, about 3 to 10 seconds) at a temperature higher than the heating temperature of the hot stamp (for example, about + 50 ° C.) immediately before reaching the heating temperature (holding temperature) of the hot stamp. It means to perform processing.
- the overheat treatment By performing the overheat treatment, a large amount of the steel plate component can be diffused on the surface layer of the plating layer, and the hot stamped molded product according to the present invention can be reliably obtained. Therefore, the components that can be contained in the plating layer in the present invention include elements contained in the steel sheet (for example, Fe, Mn, Si, etc.) in addition to the elements (typically Zn and Ni) contained in the plating layer before hot stamping.
- impurity includes not only elements that are inevitably mixed in the manufacturing process, but also elements that are intentionally added to the extent that the coating film peeling resistance of the hot stamp molded product according to the present invention is not impaired. ..
- the concentration of each component in the plating layer in the present invention is measured by glow discharge analysis (GDS: Glow Discharge Spectroscopy) of quantitative analysis.
- GDS glow discharge analysis
- the concentration distribution of each component in the plate thickness direction is quantitatively specified. Therefore, the ZnO region and the Ni—Fe—Zn alloy region can be distinguished by measuring the oxygen concentration distribution of the plating layer by GDS and specifying the position where the oxygen concentration is 10% by mass.
- the GDS measurement conditions may be such that the measurement diameter is 4 mm ⁇ , the Ar gas pressure is 600 Pa, the power is 35 W, and the measurement time is 100 seconds.
- the device used may be GD-profiler2 manufactured by HORIBA, Ltd.
- the thickness of the plating layer in the present invention may be, for example, 3.0 ⁇ m or more and 20.0 ⁇ m or less per side.
- the ratio of the thickness occupied by the ZnO region in the plating layer is not particularly limited, but is preferably 3% or more and 30% or less from the viewpoint of ensuring adhesion to the coating film and corrosion resistance of the hot stamp molded product. More preferably, it is 5% or more and 20% or less.
- the ratio of the thickness occupied by the Ni—Fe—Zn region in the plating layer is preferably 70% or more and 97% or less, and 80% or more and 95% or less, from the viewpoint of ensuring the corrosion resistance of the flawed portion. preferable.
- the thickness of the plating layer can also be measured by, for example, specifying the region of the plating layer from the elemental analysis of the quantitative analysis GDS and converting the thickness. Alternatively, it can be measured by observing the cross section of the hot stamped article according to the present invention with an electron microscope.
- the plating layer has a ZnO region having an oxygen concentration of 10% by mass or more on the surface side of the plating layer.
- the ZnO region is typically formed by combining Zn in the plating layer formed before hot stamping with O in the atmosphere at the time of hot stamping, that is, by oxidizing Zn to ZnO. Area.
- the total average concentration of Fe, Mn and Si is 5% by mass or more and 30% by mass or less.
- the strength of the ZnO region is improved, the peeling or breaking of ZnO itself is suppressed, and the coating film peeling resistance of the hot stamped molded product is sufficiently obtained. be able to. If the total average concentration of Fe, Mn, and Si is less than 5% by mass, the ZnO region may not have sufficient strength and the coating film peeling resistance may decrease, and conversely, it exceeds 30% by mass.
- the total average concentration of Fe, Mn and Si in the ZnO region may be in the above range, and at least one of Fe, Mn and Si may be included, but Fe, Mn and Si are preferable. Everything is included. More preferably, Fe: 1% by mass or more and 10% by mass or less, Mn: 1% by mass or more and 10% by mass or less, and Si: 1% by mass or more and 10% by mass or less. Fe, Mn and Si contained in the ZnO region are of steel sheet origin.
- these elements contained in the steel sheet are diffused to the ZnO region of the plating layer during hot stamping.
- Mn and Si in the steel sheet which are relatively easily oxidized, can be more significantly diffused to the surface layer side in the plating layer when hot stamping is performed under oxygen atmosphere conditions.
- the total average concentration of these elements is preferably 7% by mass or more, more preferably 10% by mass or more or 15% by mass or more.
- the total average concentration of these elements is preferably 28% by mass or less, more preferably 25% by mass or less, or 20% by mass or less.
- ZnO near the surface of a hot stamped molded product obtained by hot stamping has a sparse density and relatively low strength, so that it is in a state where peeling or fracture is likely to occur. Then, even if a coating film is formed on the hot stamp molded body, a part of the ZnO region may be peeled off, and as a result, the coating film may be peeled off, so that sufficient coating film peeling resistance may not be guaranteed. ..
- the "coating film peeling resistance” means that the coating film does not peel off from the hot stamped molded product, that the coating film peels off from the interface between the coating film and the hot stamped molded product, and a part of the ZnO region (ZNO region).
- the strength of the ZnO region is improved by containing a predetermined amount of elements other than zinc: Fe, Mn and Si in the ZnO region of the surface layer of the hot stamped molded product.
- the ZnO region becomes hard, peeling (destruction) of ZnO itself is less likely to occur, and the coating film peeling resistance is improved as compared with the above-mentioned region containing only ZnO containing no element.
- total average concentration of Fe, Mn, and Si means that the region of oxygen concentration ⁇ 10% (that is, ZnO region) specified by the quantitative analysis GDS is divided into 10 divisions at equal intervals, and the center position of each division is defined. It is obtained by reading the Fe concentration, Mn concentration and Si concentration from the GDS result, obtaining the total concentration of these elements in each category, and averaging the total values of the obtained 10 Fe, Mn and Si. ..
- the ZnO region typically has a higher Zn concentration than the Ni concentration.
- the Zn / Ni mass ratio in the ZnO region is 5.0 or more.
- the mass ratio of Zn / Ni in the ZnO region is 5.0 or more means that the mass ratio of Zn / Ni is 5.0 or more at all positions in the ZnO region.
- ZnO is used. The region was divided into 10 divisions at equal intervals, the Zn concentration and Ni concentration at the center position of each division were read from the GDS result, and the Zn / Ni mass ratio of each division was obtained, and the obtained 10 Zn / Ni mass ratios were obtained. Can be judged by whether or not all of them are 5.0 or more.
- the Zn / Ni mass ratio in the ZnO region is preferably 5.5 or more, more preferably 6.0 or more, and even more preferably 7.0 or more.
- the upper limit of the region is not particularly limited, but may be, for example, 30.0 or 20.0.
- ZnO region of the hot stamped molded product The reason why more Zn is present in the ZnO region of the hot stamped molded product than in Ni is that when hot stamping is performed in an oxygen atmosphere, among Ni and Zn in the plating layer before hot stamping, compared to Ni. This is because Zn, which is easily oxidized, is oxidized by O in the hot stamping atmosphere to form ZnO.
- Zn / Ni mass ratio is 5.0 or more, a large amount of ZnO, which is an oxide, is present on the surface layer of the hot stamped body, so that the corrosion resistance of the surface layer of the hot stamped body is improved, and coating and hot stamping are performed. It also has excellent adhesion to the body. If the Zn / Ni mass ratio in the ZnO region is less than 5.0, ZnO is not sufficiently formed on the surface layer, so that the corrosion resistance and coating adhesion of the surface layer portion may be insufficient.
- the Zn / Ni mass ratio in the ZnO region is such that the steel sheet having the Zn—Ni alloy plating layer is hot under oxygen atmosphere conditions (atmospheric conditions or high concentration oxygen atmosphere conditions with an oxygen concentration of 25 to 30%). It can be obtained by stamping.
- oxygen atmosphere conditions atmospheric conditions or high concentration oxygen atmosphere conditions with an oxygen concentration of 25 to 30%.
- Zn which is easily oxidized, easily diffuses to the surface layer of the plating layer, and the Zn occupied volume increases by combining with oxygen to form ZnO.
- the Zn concentration in the ZnO region is increased. Can be made higher than the Ni concentration.
- the thickness of the ZnO region in the present invention is not particularly limited, but the lower limit is preferably 1.0 ⁇ m, more preferably 1.2 ⁇ m or 1.5 ⁇ m, still more preferably 1.8 ⁇ m or 2.0 ⁇ m, while The upper limit is preferably 5.0 ⁇ m, more preferably 4.8 ⁇ m or 4.5 ⁇ m, and even more preferably 4.3 ⁇ m or 4.0 ⁇ m.
- the thickness of the ZnO region is preferably 1.0 ⁇ m or more and 5.0 ⁇ m or less, and more preferably 2.0 ⁇ m or more and 5.0 ⁇ m or less. If the thickness of the ZnO region is less than 1.0 ⁇ m, the thickness of the ZnO region becomes insufficient, and the corrosion resistance may decrease. If the thickness of the ZnO region is more than 5.0 ⁇ m, the ZnO region becomes too thick, and there is a high possibility that peeling or breakage from the ZnO region will occur.
- the concentration of each component contained in the ZnO region in the present invention is determined by the quantitative analysis GDS as described above. Under the same conditions as the GDS conditions described above, at least Zn, Ni, O, Fe, Si and Mn are designated as target elements for measurement. Further, the thickness of the ZnO region can be determined by specifying a range of oxygen concentration ⁇ 10% by mass by quantitative analysis GDS and measuring the depth thereof.
- the hot stamped compact according to the present invention has a Ni—Fe—Zn alloy region on the steel plate side of the plating layer, which is in contact with the above-mentioned ZnO region and has an oxygen concentration of less than 10% by mass.
- Zn, Ni, O, Fe, Mn and Si are present in the alloy region.
- the Ni—Fe—Zn alloy region typically contains Zn and Ni contained in the plating layer before hot stamping and in the steel sheet by diffusing Fe in the steel sheet into the plating layer during heating of the hot stamping. This is a region where Fe diffused from is alloyed. Further, Mn and Si in the steel sheet are also diffused in the Ni—Fe—Zn alloy region at the same time as Fe to be alloyed.
- the concentrations of Zn, O, Mn and Si decrease from the surface side of the plating layer toward the steel plate side.
- the Fe concentration increases from the surface side of the plating layer toward the steel plate side.
- the concentrations of Zn, O, Mn, and Si decrease from the surface side of the plating layer toward the steel plate side means that in the Ni—Fe—Zn alloy region, these concentrations are decreased from the surface side of the plating layer toward the steel plate side.
- the concentration of the element is monotonically decreasing, that is, when the concentration of any of the listed elements is measured by GDS or the like at any two positions, the plating layer of the two positions It means that the position closer to the surface side has a higher concentration than the other position. It is sufficient that the concentration of each element decreases monotonically, and its linearity does not matter.
- sufficient Fe, Mn and Si are diffused in the ZnO region on the surface side of the plating layer, and the Ni—Fe—Zn alloy region is ensured while ensuring the coating film peeling resistance and the flawed corrosion resistance.
- Ni and Zn of the plating layer before hot stamping and Fe in the steel plate can be alloyed.
- the Ni—Fe—Zn alloy region is composed of a first region having an Fe concentration of less than 60% by mass and a second region having an Fe concentration of 60% by mass or more in order from the surface side of the plating layer. May be.
- the distinction between the first region and the second region in the Ni—Fe—Zn alloy region can be made by measuring the Fe concentration by the quantitative analysis GDS.
- the Ni—Fe—Zn alloy region is a region on the steel sheet side of the plating layer, and typically, during hot stamping, Zn contained in the plating layer before hot stamping is diffused into the steel sheet. This diffusion occurs more remarkably closer to the steel sheet. Therefore, in the alloy region, the Zn concentration decreases from the surface side of the plating layer toward the steel plate side. Further, since O is typically contained in the atmosphere at the time of hot stamping, the concentration of O decreases as it progresses from the surface side of the plating layer to the steel plate side in the plating layer.
- Mn and Si are elements existing in the steel sheet before hot stamping, but by hot stamping in an oxygen atmosphere, the surface of the plating layer is given priority over Fe because of its easiness of oxidation. Can spread to the side. Therefore, in the alloy region, the concentrations of Mn and Si decrease from the surface side of the plating layer toward the steel plate side.
- the Zn / Ni mass ratio in the first region of the Ni—Fe—Zn alloy region is preferably in the range of 2.0 or more and 15.0 or less. More preferably, in the first region, the Zn / Ni mass ratio changes continuously in the range of 2.0 or more and 15.0 or less from the surface side of the plating layer toward the steel plate side. "The Zn / Ni mass ratio in the first region is in the range of 2.0 or more and 15.0 or less" means that the mass ratio of Zn / Ni is 2.0 or more and 15 or more at all positions in the first region.
- the first region is divided into 10 divisions at equal intervals, and the Zn concentration and Ni concentration at the center position of each division are read from the GDS result and each is The Zn / Ni mass ratio of the classification can be obtained, and it can be determined whether or not all the obtained 10 Zn / Ni mass ratios are 2.0 or more and 15.0 or less.
- the Zn / Ni mass ratio in the first region is in the above range, a sufficient amount of Zn can be secured in the region, and the amount of Zn in the other regions can also be made sufficient.
- Zn existing in the region is oxidized to ZnO to form an oxide film (referred to as "sacrificial anticorrosion action"), whereby the flaw is formed. Corrosion of the portion can be suppressed, and the corrosion resistance of the flawed portion of the hot stamped molded product can be improved. If the Zn / Ni mass ratio in the first region is less than 2.0, the sacrificial anticorrosion action of Zn cannot be sufficiently exerted, and the corrosion resistance of the flawed portion may be insufficient. On the other hand, if it exceeds 15.0, Zn in other regions may be insufficient, so that the corrosion resistance of the entire hot stamped molded product may be insufficient.
- the lower limit of the Zn / Ni mass ratio in the first region is preferably 2.5, more preferably 3.0, and the upper limit is preferably 14.0, more preferably 13.0, still more preferably 12. It is 0.
- the average Zn / Ni mass ratio in the second region of the Ni—Fe—Zn alloy region is preferably 0.5 or more and 2.0 or less.
- Zn in the plating layer formed before hot stamping diffuses on the surface side of the plating layer and in the steel sheet during hot stamping, but in the hot stamping molded product according to the present invention, Ni ⁇ which is in contact with the steel sheet.
- a predetermined amount of Zn remains even in the second region of the Fe—Zn alloy region. If Zn remains in the second region in the above range, even if the plating layer or the underlying steel plate is flawed, the sacrificial anticorrosion effect of Zn can be exhibited, so that the corrosion resistance of the flawed portion is improved. Can be made to.
- the sacrificial anticorrosion action of Zn may not be sufficiently exhibited, and the corrosion resistance of the flawed portion may be insufficient.
- Zn may not be sufficiently diffused in the surface layer portion of the plating layer or Zn may be insufficient in the first region, and the corrosion resistance of the entire hot stamped molded product is poor. May be sufficient. Due to the insufficient corrosion resistance of the hot stamped molded product as a whole, the peeling resistance of the coating film may be somewhat reduced, or the corrosion resistance of the flawed portion may be reduced.
- the average Zn / Ni mass ratio in the second region is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more.
- the average Zn / Ni mass ratio in the second region is preferably 1.9 or less or 1.8 or less, more preferably 1.7 or less or 1.5 or less, and further preferably 1.2 or less. Therefore, most preferably, the average Zn / Ni mass ratio in the second region is 0.8 or more and 1.2 or less.
- the "average Zn / Ni mass ratio in the second region” means that the region (second region) in which the Fe concentration ⁇ 60% in the Ni—Fe—Zn alloy region is divided into 10 divisions at equal intervals, and each division It can be obtained by reading the Zn concentration and Ni concentration at the center position of the above from the GDS result, obtaining the Zn / Ni mass ratio of each category, and averaging the 10 obtained Zn / Ni mass ratios.
- the thickness of the Ni—Fe—Zn alloy region can be determined by specifying the range of oxygen concentration ⁇ 10% by mass by quantitative analysis GDS and measuring the depth thereof. Similarly, the thickness of the first region (Fe concentration ⁇ 60% by mass) and the second region (Fe concentration ⁇ 60% by mass) of the Ni—Fe—Zn alloy region is determined from the Fe concentration obtained by GDS. Can be decided.
- the thickness of the ZnO region and the Zn / Ni mass ratio of the first region and the second region in the Ni—Fe—Zn alloy region are appropriately controlled, for example, the ZnO region.
- the thickness of is 1.0 ⁇ m or more and 5.0 ⁇ m or less
- the Zn / Ni mass ratio in the first region is 2.0 or more and 15.0 or less, preferably 2.5 or more and 15.0 or less, and in the second region.
- the hot stamp molded product according to the present invention can be suitably used for automobile members.
- the hot stamp molded body is subjected to chemical conversion treatment with a chemical conversion treatment liquid (for example, PB-SX35 manufactured by Nippon Parkerizing Co., Ltd.) and then electrodeposited paint (for example, Nippon Paint (for example, Nippon Paint)).
- a coating film can be formed by painting Powernics 110) manufactured by Co., Ltd. and baking it at a temperature of 120 to 250 ° C.
- the film thickness of the coating film may be, for example, 5 to 30 ⁇ m.
- a Zn—Ni plated layer is formed on at least one side, preferably both sides of the steel sheet, for example, by electroplating, and then the obtained plated steel sheet is hot stamped under predetermined conditions. Obtainable. It is also possible to form a Zn plating layer and a Ni plating layer instead of the Zn—Ni plating layer. The case of forming the Zn—Ni plating layer will be described below.
- the method for producing a steel sheet used for producing the hot stamped molded product according to the present invention is not particularly limited.
- a steel sheet can be obtained by adjusting the composition of molten steel to a desired range, hot rolling, winding, and cold rolling.
- the thickness of the steel plate in the present invention may be, for example, 0.1 mm to 3.2 mm.
- the steel sheet in the present invention has a surface roughness Ra of 1.0 ⁇ m or more in order to obtain a hot stamped molded product according to the present invention by diffusing a steel sheet component such as Fe into the plating layer. It is preferably set to 0 ⁇ m or less.
- the method for obtaining such surface roughness is not particularly limited, and a method known to those skilled in the art can be used.
- composition of the steel sheet used is not particularly limited, but as described above, in terms of mass%, C: 0.05% or more and 0.70% or less, Mn: 0.5% or more and 11.0% or less, Si: 0. 0.05% or more and 2.50% or less, Al: 0.001% or more and 1.500% or less, P: 0.100% or less, S: 0.100% or less, N: 0.010% or less, O: 0 It is preferable that the content is 010% or less and B: 0.0005% or more and 0.0040% or less, and the balance is composed of iron and impurities.
- the method for forming the Zn—Ni plating layer is not particularly limited, but it is preferably formed by electroplating. Further, Ni or the like may be plated as pre-plating before the formation of this plating. The case where the Zn—Ni plating layer is formed by electroplating will be described below.
- the plating adhesion amount is preferably 25 g / m 2 or more and 90 g / m 2 or less per side, and 30 g / m 2 or more and 50 g / m 2 or less. Is more preferable.
- the Zn / Ni ratio of the plating layer may be, for example, 3.0 or more and 20.0 or less, and preferably 4.0 or more and 10.0 or less.
- the composition of the bath used for forming the Zn—Ni plating layer is, for example, nickel sulfate hexahydrate: 25 to 350 g / L, zinc sulfate heptahydrate: 10 to 150 g / L, and sodium sulfate: 25 to. It may be 75 g / L.
- the current density may be 10 to 150 A / dm 2 .
- the bath composition and the current density can be appropriately adjusted so as to obtain a desired plating adhesion amount and Zn / Ni ratio.
- the bath temperature and the bath pH may be appropriately adjusted so as not to cause plating burn, and may be, for example, 40 to 70 ° C. and 1.0 to 3.0, respectively.
- the plating adhesion amount and the Zn / Ni ratio of the formed Zn—Ni plating layer can be measured by inductively coupled plasma (ICP) emission spectroscopy.
- ICP inductively coupled plasma
- the steel sheet on which the Zn—Ni plating layer is formed is hot stamped.
- the heating temperature of the hot stamp may be such that the steel sheet can be heated to a temperature in the austenite region, for example, in the range of 800 ° C. or higher and 1000 ° C. or lower.
- the rate of temperature rise is preferably 2 to 10 ° C./sec, and more preferably 3 to 5 ° C./sec. If the heating rate is too slow, Fe is excessively diffused on the surface, and the total average concentration of Fe, Mn, and Si in the finally obtained ZnO region exceeds 30% by mass and / or the ZnO region becomes thick. It may be too much.
- the holding time after heating can be appropriately set to 0.5 minutes or more and 5.0 minutes or less. It is more preferably 1.0 minute or more and 4.0 minutes or less, and most preferably 2.0 minutes or more and 4.0 minutes or less. If the holding time is too short, the desired amount of diffusion may not occur, and if it is too long, the ZnO region may become too thick.
- the heating temperature, the rate of temperature rise, and the holding time are interrelated with respect to the diffusion of the steel sheet component from the steel sheet to the plating layer and the formation of the ZnO region.
- the holding time after heating may be relatively short, but when the heating rate is relatively fast or when overheating is not performed.
- the holding time after heating needs to be relatively long.
- the specific values of the heating temperature, the rate of temperature rise, and the holding time are also affected by the composition and adhesion amount of the plating, the thickness of the steel sheet, the presence or absence of overheating treatment, and the like.
- the hot stamping may be performed at a relatively high temperature immediately after the steel sheet is taken out from the heating furnace, or the hot stamping may be performed after allowing the steel sheet to cool to a predetermined temperature.
- the characteristics of the resulting plating layer can vary. Therefore, even if the heating temperature, temperature rise rate, and holding time are the same, the plating layer can be subjected to the plating composition and adhesion amount, the thickness of the steel sheet, the presence or absence of overheating treatment, the temperature at which hot stamping is actually performed, and the like.
- Features can change.
- heating temperature temperature rising rate
- holding time are based on conditions such as plating composition and adhesion amount, steel plate thickness, presence / absence of overheat treatment, and temperature at which hot stamping is actually performed. It is preferable to make an appropriate selection in consideration.
- overheating treatment can be performed during this hot stamping treatment.
- the overheat treatment makes it possible to efficiently diffuse the steel sheet component such as Fe into the plating layer.
- the product of the difference between the overheat treatment temperature and the heating temperature of the hot stamp hereinafter referred to as “excess temperature”
- the overheat time is 150 or more and 300 or less.
- the excess temperature is 25 ° C. or higher and 150 ° C. or lower, and the overheat time is 3 seconds or longer.
- the atmosphere at the time of hot stamping is preferably performed in an oxygen atmosphere of 10 to 30%, and for example, it can be performed in an air atmosphere or a high concentration oxygen atmosphere having an oxygen concentration of 25 to 30%.
- a high dew point atmosphere such as an oxygen atmosphere
- Zn in the plating layer and Fe, Si and Mn in the steel sheet, particularly easily oxidizable Zn, Si and Mn, are positively added to the surface side of the plating layer. It can be diffused so that a desired amount of each element is present on the surface side of the plating layer.
- a ZnO region and a Ni—Fe—Zn alloy region in the present invention are formed by performing a hot stamping treatment including an overheating treatment particularly in an oxygen atmosphere, and Fe, in a desired amount, is formed in the ZnO region. Si and Mn are diffused. Further, after the heat treatment, cooling (quenching) can be performed at a cooling rate in the range of, for example, 10 to 100 ° C./sec.
- the ZnO region and the Ni—Fe—Zn alloy region are formed as the first region and the second region, and the concentration of each element in each region and the concentration of each element are formed.
- the thickness can be adjusted.
- a cold-rolled steel sheet having a plate thickness of 1.4 mm was immersed in a plating bath having the following plating bath composition, and Zn—Ni plating layers were formed on both sides of the cold-rolled steel sheet by electroplating.
- the pH of the plating bath was 2.0, the bath temperature was maintained at 60 ° C., and the current density was 30 to 50 A / dm 2 .
- All the steel sheets used were in mass%, C: 0.50%, Mn: 3.0%, Si: 0.50%, Al: 0.100%, P: 0.010%, S: It contained 0.020%, N: 0.003%, O: 0.003%, and B: 0.0010%, with the balance being iron and impurities.
- the plating bath composition nickel sulfate hexahydrate and zinc sulfate heptahydrate concentrations
- current density and energization time were adjusted. It was adjusted.
- the plating adhesion amount (g / m 2 ) and Zn / Ni ratio in the Zn—Ni alloy plating layer on the steel sheet obtained by electroplating were measured by ICP, and the measurement results are shown in Table 1.
- the amount of plating adhered indicates the amount of adhesion per side.
- sample No. In 13 and 14 overheating treatment was performed.
- the elements contained in the plating layer of each sample obtained after hot stamping were measured by quantitative analysis GDS in the depth direction (thickness direction) of the plating layer using GD-profiler2 of HORIBA, Ltd.
- the measurement conditions for GDS were a measurement diameter of 4 mm ⁇ , an Ar gas pressure of 600 Pa, a power of 35 W, a measurement time of 100 seconds, and the elements to be measured were Zn, Ni, Fe, Mn, Si and O.
- each sample is divided into a region having an oxygen concentration of 10% by mass or more and a region having an oxygen concentration of less than 10% by mass by GDS, and each is designated as a ZnO region and a Ni—Fe—Zn alloy region, and ZnO is used.
- the thickness of the area was determined. Further, from the concentration distribution of Zn, O, Mn and Si in the Ni—Fe—Zn alloy region, it was confirmed whether the concentration of these elements decreased from the surface side of the plating layer toward the steel plate side.
- the specified ZnO region was divided into 10 divisions at equal intervals, and the Fe concentration, Mn concentration, and Si concentration at the center position of each division were read from the GDS results, and the total of these concentrations was obtained in each division.
- the total average concentration of Fe, Mn and Si of each sample was determined.
- the Ni—Fe—Zn alloy region was divided into a region in which the Fe concentration was less than 60% by mass (first region) and a region in which the Fe concentration was 60% by mass or more (second region). Area) and.
- the maximum and minimum values of the Zn / Ni mass ratio were obtained from the Zn concentration and the Ni concentration in the first region, and the range of the Zn / Ni mass ratio in the first region was specified.
- the second region is divided into 10 sections at equal intervals, the Zn concentration and Ni concentration at the center position of each section are read to obtain the Zn / Ni mass ratio, and the obtained 10 Zn / Ni mass ratios are obtained. By averaging, the average Zn / Ni mass ratio in the second region was determined.
- Table 2 shows the total average concentration of Fe, Mn, and Si of each sample, the Zn / Ni mass ratio in the first region, the average Zn / Ni mass ratio in the second region, and the thickness of the ZnO region.
- the coating film peeling secondary adhesion of the hot stamped molded product was evaluated by the following procedure. First, the JASO-CCT test (M609-91), salt spray (5% NaCl, 35 ° C.): 2 without forming cross-cut flaws on the evaluation sample subjected to the above-mentioned chemical conversion treatment and electrodeposition coating. Time, drying (60 ° C., 20-30% RH): 4 hours, wetting (50 ° C., 95% RH): 2 hours were carried out for 200 cycles.
- coating film peeling resistance was ⁇ or ⁇ (excluding the evaluation of coating film peeling secondary adhesion), it was evaluated as a hot stamp molded product having improved coating film peeling resistance.
- sample No. in 1, 2, 4 to 10, 13 and 14 the concentrations of Zn, O, Mn and Si in the Ni—Fe—Zn alloy region are from the surface side of the plating layer to the steel plate side in the Ni—Fe—Zn alloy region. It decreased, and the Zn / Ni mass ratio in the first region was 2.0 or more and 15.0 or less, and the average Zn / Ni mass ratio in the second region was 0.5 or more and 2.0 or less. Partial corrosion resistance was good.
- Sample No. In No. 3 since the total average concentration of Fe, Mn, and Si in the ZnO region was less than 5% by mass, the ZnO region did not have sufficient strength and the coating film peeling resistance was insufficient.
- sample No. In No. 11 since the total average density of Fe, Mn, and Si in the ZnO region was more than 30% by mass, a large amount of Fe and the like were easily corroded on the surface layer of the hot stamped molded product, and as a result, the coating film peeling resistance was poor. It became enough.
- Sample No. 15 since the temperature rising rate was too slow, Fe diffused excessively on the surface, and the total average density of Fe, Mn, and Si in the ZnO region exceeded 30% by mass, resulting in coating film peeling resistance. It became insufficient. Sample No. In No. 16, the appearance of the plating layer was poor due to the temperature rise rate being too fast, and sufficient quality as a product could not be obtained. Therefore, the plating layer was not analyzed and the characteristics of the sample were not evaluated.
- the present invention it is possible to provide a hot stamp molded product having improved strength of the ZnO region existing on the surface side of the plating layer, preventing peeling or breaking of ZnO itself, and having improved peeling resistance of the coating film.
- This makes it possible to provide an automobile member having high coating film peeling resistance and excellent corrosion resistance. Therefore, it can be said that the present invention has extremely high industrial value.
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Abstract
Description
(1)
鋼板と、前記鋼板の少なくとも片面に形成されためっき層とを有し、前記めっき層が、前記めっき層の表面側に存在し、酸素濃度が10質量%以上であるZnO領域と、前記めっき層の鋼板側に存在し、酸素濃度が10質量%未満であるNi-Fe-Zn合金領域とからなり、前記ZnO領域において、Fe、Mn及びSiの合計の平均濃度が5質量%以上30質量%以下である、ホットスタンプ成形体。
(2)
前記Ni-Fe-Zn合金領域において、Zn、O、Mn及びSiの各濃度が、前記めっき層の表面側から鋼板側に向けて減少する、(1)に記載のホットスタンプ成形体。
(3)
前記Ni-Fe-Zn合金領域が、前記めっき層の表面側から順に、Fe濃度が60質量%未満である第1の領域と、Fe濃度が60質量%以上である第2の領域とからなり、前記第1の領域におけるZn/Ni質量比が2.0以上15.0以下の範囲であり、前記第2の領域における平均Zn/Ni質量比が0.5以上2.0以下である、(1)又は(2)に記載のホットスタンプ成形体。
(4)
前記第2の領域における平均Zn/Ni質量比が0.8以上1.2以下である、(3)に記載のホットスタンプ成形体。
(5)
前記ZnO領域の厚さが1.0μm以上5.0μm以下である、(1)~(4)のいずれかに記載のホットスタンプ成形体。
本発明に係るホットスタンプ成形体は、鋼板と、鋼板の少なくとも片面に形成されためっき層とを有する。好ましくは、めっき層は鋼板の両面に形成される。
本発明における鋼板の成分組成は、特に限定されず、ホットスタンプ後のホットスタンプ成形体の強度やホットスタンプ時の焼入れ性を考慮して決定すればよい。以下では、本発明における鋼板に含まれ得る元素について説明する。なお、成分組成についての各元素の含有量を表す「%」は特に断りがない限り質量%を意味する。
C(炭素)は、鋼板の強度を向上させるのに有効な元素である。自動車用部材には、例えば980MPa以上の高強度が求められる場合がある。強度を十分に確保するためには、C含有量を0.05%以上とすることが好ましい。一方、Cを過度に含有すると鋼板の加工性が低下する場合があるため、C含有量を0.70%以下とすることが好ましい。C含有量の下限は、好ましくは0.10%、より好ましくは0.12%、さらに好ましくは0.15%、最も好ましくは0.20%である。また、C含有量の上限は、好ましくは0.65%、より好ましくは0.60%、さらに好ましくは0.55%、最も好ましくは0.50%である。
Mn(マンガン)は、ホットスタンプの際の焼入れ性を向上させるのに有効な元素である。この効果を確実に得るためには、Mn含有量を0.5%以上とすることが好ましい。一方、Mnを過度に含有すると、Mnが偏析してホットスタンプ後の成形体の強度等が不均一になるおそれがあるため、Mn含有量を11.0%以下とすることが好ましい。Mn含有量の下限は、好ましくは1.0%、より好ましくは2.0%、さらに好ましくは2.5%、よりさらに好ましくは3.0%、最も好ましくは3.5%である。Mn含有量の上限は、好ましくは10.0%、より好ましくは9.5%、さらに好ましくは9.0%、よりさらに好ましくは8.5%、最も好ましくは8.0%である。
Si(ケイ素)は、鋼板の強度を向上させるのに有効な元素である。強度を十分に確保するためには、Si含有量を0.05%以上とすることが好ましい。一方、Siを過度に含有すると、加工性が低下する場合があるため、Si含有量を2.50%以下とすることが好ましい。Si含有量の下限は、好ましくは0.10%、より好ましくは0.15%、さらに好ましくは0.20%、最も好ましくは0.30%である。Si含有量の上限は、好ましくは2.00%、より好ましくは1.80%、さらに好ましくは1.50%、最も好ましくは1.20%である。
Al(アルミニウム)は、脱酸元素として作用する元素である。脱酸の効果を得るためには、Al含有量を0.001%以上とすることが好ましい。一方、Alを過剰に含有すると加工性が低下するおそれがあるため、Al含有量を1.500%以下とすることが好ましい。Al含有量の下限は、好ましくは0.010%、より好ましくは0.020%、さらに好ましくは0.050%、最も好ましくは0.100%である。Al含有量の上限は、好ましくは1.000%、より好ましくは0.800%、さらに好ましくは0.700%、最も好ましくは0.500%である。
(S:0.100%以下)
(N:0.010%以下)
(O:0.010%以下)
P(リン)、S(硫黄)、N(窒素)及び酸素(O)は不純物であり、少ない方が好ましいため、これらの元素の下限は特に限定されない。ただし、これらの元素の含有量を0.000%超又は0.001%以上としてもよい。一方、これらの元素を過剰に含有すると、靭性、延性及び/又は加工性が劣化するおそれがあるため、P及びSの上限を0.100%、N及びOの上限を0.010%とすることが好ましい。P及びSの上限は、好ましくは0.080%、より好ましくは0.050%である。N及びOの上限は、好ましくは0.008%、より好ましくは0.005%である。
B(ホウ素)は、ホットスタンプの際の焼入れ性を向上させるのに有効な元素である。B含有量は0%であってもよいが、この効果を確実に得るためには、B含有量を0.0005%以上とすることが好ましい。一方、Bを過度に含有すると、鋼板の加工性が低下するおそれがあるため、B含有量を0.0040%以下とすることが好ましい。B含有量の下限は、好ましくは0.0008%、より好ましくは0.0010%、さらに好ましくは0.0015%である。また、B含有量の上限は、好ましくは0.0035%、より好ましくは0.0030%である。
Cr(クロム)は、ホットスタンプの際の焼入れ性を向上させるのに有効な元素である。Cr含有量は0%であってもよいが、この効果を確実に得るためには、Cr含有量は0.01%以上とすることが好ましい。Cr含有量は0.10%以上、0.50%以上又は0.70%以上であってもよい。一方、Crを過度に含有すると、鋼材の熱的安定性が低下する場合がある。したがって、Cr含有量は2.00%以下とすることが好ましい。Cr含有量は1.50%以下、1.20%以下又は1.00%以下であってもよい。
(Nb:0%以上0.300%以下)
(V:0%以上0.300%以下)
(Zr:0%以上0.300%以下)
Ti(チタン)、Nb(ニオブ)、V(バナジウム)及びZr(ジルコニウム)は金属組織の微細化を通じ、引張強さを向上させる元素である。これらの元素の含有量は0%であってもよいが、この効果を確実に得るためには、Ti、Nb、V及びZr含有量は0.001%以上とすることが好ましく、0.010%以上、0.020%以上又は0.030%以上であってもよい。一方、Ti、Nb、V及びZrを過度に含有すると、効果が飽和するとともに製造コストが上昇する。このため、Ti、Nb、V及びZr含有量は0.300%以下とすることが好ましく、0.150%以下、0.100%以下又は0.060%以下であってもよい。
(Cu:0%以上2.000%以下)
(Ni:0%以上2.000%以下)
Mo(モリブデン)、Cu(銅)及びNi(ニッケル)は、引張強さを高める作用を有する。これらの元素の含有量は0%であってもよいが、この効果を確実に得るためには、Mo、Cu及びNi含有量は0.001%以上とすることが好ましく、0.010%以上、0.050%以上又は0.100%以上であってもよい。一方、Mo、Cu及びNiを過度に含有すると、鋼材の熱的安定性が低下する場合がある。したがって、Mo、Cu及びNi含有量は2.000%以下とすることが好ましく、1.500%以下、1.000%以下又は0.800%以下であってもよい。
Sb(アンチモン)は、めっきの濡れ性や密着性を向上させるのに有効な元素である。Sb含有量は0%であってもよいが、この効果を確実に得るためには、Sb含有量は0.001%以上とすることが好ましい。Sb含有量は0.005%以上、0.010%以上又は0.020%以下であってもよい。一方、Sbを過度に含有すると、靭性の低下を引き起す場合がある。したがって、Sb含有量は0.100%以下とすることが好ましい。Sb含有量は0.080%以下、0.060%以下又は0.050%以下であってもよい。
(Mg:0%以上0.0100%以下)
(REM:0%以上0.1000%以下)
Ca(カルシウム)、Mg(マグネシウム)及びREM(希土類金属)は、介在物の形状を調整することによりホットスタンプ後の靭性を向上させる元素である。これらの元素の含有量は0%であってもよいが、この効果を確実に得るためには、Ca、Mg及びREM含有量は0.0001%以上とすることが好ましく、0.0010%以上、0.0020%以上又は0.0040%以上であってもよい。一方、Ca、Mg及びREMを過度に含有すると、効果が飽和するとともに製造コストが上昇する。このため、Ca及びMg含有量は0.0100%以下とすることが好ましく、0.0080%以下、0.0060%以下又は0.0050%以下であってもよい。同様に、REM含有量は0.1000%以下とすることが好ましく、0.0800%以下、0.0500%以下0.0100%以下であってもよい。
本発明におけるめっき層は、ZnO領域と、Ni-Fe-Zn合金領域とからなる。ZnO領域は、当該めっき層の表面側に存在し、酸素濃度が10質量%以上である領域をいう。めっき層の残りの領域がNi-Fe-Zn合金領域であり、すなわち、Ni-Fe-Zn合金領域は、当該めっき層の鋼板側に存在し、酸素濃度が10%未満である領域をいう。したがって、ZnO領域とNi-Fe-Zn合金領域とは接するように存在しており、この2つの領域でめっき層を構成する。本発明におけるめっき層においては、Oはホットスタンプ時にめっき層に取り込まれるものであるため、めっき層の表面側が最も酸素濃度が高く、鋼板側に進むにつれて酸素濃度が減少する。したがって、ホットスタンプ成形体の表面から酸素濃度が10質量%の位置までがZnO領域であり、めっき層の残りの部分がNi-Fe-Zn合金領域となる。
本発明に係るホットスタンプ成形体において、めっき層は、当該めっき層の表面側に酸素濃度が10質量%以上であるZnO領域を有する。当該ZnO領域は、典型的に、ホットスタンプ前に形成されていためっき層中のZnと、ホットスタンプ時の雰囲気中のOとが結合する、すなわちZnが酸化されてZnOになることで形成される領域である。
本発明に係るホットスタンプ成形体は、めっき層の鋼板側に、上述したZnO領域に接し、酸素濃度が10質量%未満であるNi-Fe-Zn合金領域を有する。好ましくは、当該合金領域には、Zn、Ni、O、Fe、Mn及びSiが存在する。当該Ni-Fe-Zn合金領域は、典型的に、ホットスタンプの加熱時に、鋼板中のFeがめっき層中に拡散することで、ホットスタンプ前のめっき層に含まれるZn及びNiと、鋼板中から拡散したFeとが合金化した領域である。また、鋼板中のMn及びSiもFeと同時にNi-Fe-Zn合金領域に拡散し、合金化する。
本発明に係るホットスタンプ成形体の製造方法の例を以下で説明する。本発明に係るホットスタンプ成形体は、鋼板の少なくとも片面、好ましくは両面に、例えば、電気めっきによりZn-Niめっき層を形成した後に、得られためっき鋼板を所定の条件でホットスタンプすることで得ることができる。Zn-Niめっき層の代わりに、Znめっき層及びNiめっき層を形成することも可能である。以下では、Zn-Niめっき層を形成する場合について説明する。
本発明に係るホットスタンプ成形体を製造するのに使用される鋼板の製造方法は特に限定されない。例えば、溶鋼の成分組成を所望の範囲に調整し、熱間圧延し、巻取り、さらに冷間圧延を行うことで鋼板を得ることができる。本発明における鋼板の板厚は、例えば、0.1mm~3.2mmであればよい。本発明における鋼板は、上述したように、Fe等の鋼板成分をめっき層中に拡散させて本発明に係るホットスタンプ成形体を得るために、鋼板の表面粗さRaを1.0μm以上3.0μm以下にしておくことが好ましい。このような表面粗さを得る方法は特に限定されなく、当業者に公知の方法で行うことができる。
Zn-Niめっき層の形成方法は、特に限定されないが、電気めっきにより形成することが好ましい。また、このめっきの形成前にプレめっきとしてNiなどをめっきしてもよい。以下では、Zn-Niめっき層を電気めっきにより形成した場合を説明する。
次いで、Zn-Niめっき層を形成した鋼板にホットスタンプを行う。ホットスタンプの加熱温度は、鋼板をオーステナイト域の温度に加熱できればよく、例えば、800℃以上1000℃以下の範囲である。昇温速度は、2~10℃/秒であることが好ましく、3~5℃/秒であることがより好ましい。昇温速度が遅すぎると、Feが過度に表面に拡散し、最終的に得られるZnO領域におけるFe、Mn及びSiの合計の平均濃度が30質量%を超えるか及び/又はZnO領域が厚くなりすぎる場合がある。一方で、昇温速度が速すぎると、最終的に得られるめっき層の外観を劣化させ、製品として十分な品質を確保することができない場合がある。加熱後の保持時間は、0.5分間以上5.0分間以下で適宜設定することができる。より好ましくは1.0分間以上4.0分間以下、最も好ましくは2.0分間以上4.0分間以下である。保持時間が短すぎると所望量の拡散が起こらないおそれがあり、反対に長すぎると、ZnO領域が厚くなりすぎるおそれがある。加熱温度、昇温速度及び保持時間は、鋼板からめっき層への鋼板成分の拡散及びZnO領域の形成等に対して相互に関係している。このため、各パラメータの値を単に上記の範囲内に制御しただけでは、所望のめっき層の構成が得られない場合がある。例えば、昇温速度が比較的遅い場合やオーバーヒート処理を行う場合には、加熱後の保持時間は比較的短くてもよいが、昇温速度が比較的速い場合やオーバーヒート処理を行わない場合には、所望のめっき層の構成を得るためには、加熱後の保持時間は比較的長くする必要がある。加えて、加熱温度、昇温速度及び保持時間の具体的な値は、めっきの組成及び付着量、鋼板の板厚並びにオーバーヒート処理の有無などによっても影響を受ける。さらに、同じ加熱温度及び保持時間であっても、鋼板を加熱炉から取り出した直後に比較的高温のままホットスタンプを行うか又は所定の温度まで放冷した後にホットスタンプを行うかによっても、最終的に得られるめっき層の特徴は変化し得る。したがって、同じ加熱温度、昇温速度及び保持時間であっても、めっきの組成及び付着量、鋼板の板厚並びにオーバーヒート処理の有無、実際にホットスタンプを行う際の温度などに応じてめっき層の特徴が変化し得る。このため、加熱温度、昇温速度及び保持時間等の具体的な値は、めっきの組成及び付着量、鋼板の板厚並びにオーバーヒート処理の有無、実際にホットスタンプを行う際の温度などの条件を考慮して適切に選択することが好ましい。
板厚1.4mmの冷延鋼板を以下のめっき浴組成を有するめっき浴に浸漬し、電気めっきにより当該冷延鋼板上の両面にZn-Niめっき層を形成した。めっき浴のpHは2.0とし、浴温を60℃で維持し、電流密度は30~50A/dm2とした。なお、使用した全ての鋼板は、質量%で、C:0.50%、Mn:3.0%、Si:0.50%、Al:0.100%、P:0.010%、S:0.020%、N:0.003%、O:0.003%、及びB:0.0010%を含有し、残部が鉄及び不純物であった。また、全ての鋼板は表面粗さRa=1.5μmであった。
めっき浴組成
・硫酸ニッケル・6水和物:25~250g/L(可変)
・硫酸亜鉛・7水和物:10~150g/L(可変)
・硫酸ナトリウム:50g/L(固定)
次いで、得られたZn-Niめっき鋼板を、表1に示す条件でホットスタンプを行った。より具体的には、ホットスタンプは、表1に示す温度及び時間による加熱保持直後に800℃を超える温度で行い、焼入れは冷却速度:30℃/秒で行った。試料No.3については、加熱時の雰囲気を、酸素濃度約5%の低酸素雰囲気(低露点雰囲気)とした。それ以外の試料については大気雰囲気下(酸素濃度約20%)でホットスタンプした。試料No.1~12、15及び17では炉加熱により加熱し、試料No.16では通電加熱により加熱した。試料No.16の昇温速度は30℃/秒であるが、本試料では900℃の目標温度に達する前に昇温速度を徐々に下げてオーバーヒートしないようにした。一方で、試料No.13及び14では、オーバーヒート処理を行った。当該オーバーヒート処理については、炉加熱と通電加熱を併用して実施した。まず炉加熱により加熱し、次いで900℃直前から通電加熱との併用により温度を950℃まで一気に上昇させ、950℃に到達後に通電加熱を終了し、炉加熱のみで保持して900℃に戻し(超過温度=50℃)、オーバーヒート時間は4秒とした。したがって、試料No.13及び14において、超過温度とオーバーヒート時間との積は200であった(当該値は、表1中では「オーバーヒート条件」と示した)。表1中の試料No.13及び14の昇温速度はオーバーヒート処理を行う前の昇温速度を示している。
ホットスタンプ後に得た各試料のめっき層に含まれる元素を堀場製作所のGD-profiler2を用いて、めっき層の深さ方向(厚み方向)に定量分析GDSにより測定した。GDSの測定条件は、測定径4mmφ、Arガス圧力:600Pa、電力:35W、測定時間:100秒間とし、測定対象元素は、Zn、Ni、Fe、Mn、Si及びOとした。具体的には、まず、各試料について、GDSにより酸素濃度が10質量%以上の領域と酸素濃度が10質量%未満の領域に分け、それぞれをZnO領域とNi-Fe-Zn合金領域とし、ZnO領域の厚さを決定した。また、Ni-Fe-Zn合金領域におけるZn、O、Mn及びSiの濃度分布から、これらの元素の濃度がめっき層の表面側から鋼板側に向けて減少しているかを確認した。次いで、特定したZnO領域を等間隔に10個の区分に分け、各区分の中心位置のFe濃度、Mn濃度及びSi濃度をGDS結果から読み取り各区分でこれらの濃度の合計を求め、得られた10個のFe、Mn及びSiの合計濃度の値を平均化することで、各試料のFe、Mn及びSiの合計の平均濃度を決定した。次いで、得られたGDS結果から、Ni-Fe-Zn合金領域を、Fe濃度が60質量%未満である領域(第1の領域)と、Fe濃度が60質量%以上である領域(第2の領域)とに分けた。第1の領域におけるZn濃度及びNi濃度からZn/Ni質量比の最大値と最小値を求め、第1の領域におけるZn/Ni質量比の範囲を特定した。また、第2の領域を等間隔に10個の区分に分け、各区分の中心位置のZn濃度及びNi濃度を読み取りZn/Ni質量比を求め、得られた10個のZn/Ni質量比を平均化することで、第2の領域における平均Zn/Ni質量比を決定した。各試料のFe、Mn及びSiの合計の平均濃度、第1の領域におけるZn/Ni質量比、第2の領域における平均Zn/Ni質量比及びZnO領域の厚さを表2に示す。なお、表2中の「Ni-Fe-Zn合金領域のZn、O、Mn及びSiの濃度分布」については、これらの元素全てがNi-Fe-Zn合金領域においてめっき層の表面側から鋼板側に向けて減少していた場合は「〇」、そうでない場合は「×」と示した。
各試料から100mm×100mmの大きさの評価用サンプルを切り出し、当該サンプルを化成処理液(日本パーカライジング(株)社製PB-SX35)にて化成処理した後、これに電着塗料(日本ペイント(株)社製パワーニクス110)を膜厚が10μmとなるよう塗装して200℃で焼き付けた。その後、評価用サンプルの表面に1mm間隔で縦横に11本ずつ切込みを入れ、合計100個の碁盤目状の切込みに対して、粘着テープによる剥離テストを行い、耐塗膜剥離性を評価した。剥離した個数が20個未満であれば耐塗膜剥離性評価「◎」、20個以上30個未満であれば耐塗膜剥離性評価「〇」、30個以上であれば耐塗膜剥離性評価「×」とした。各試料の評価結果を表2に示す。
長期的な耐塗膜剥離性を評価するため、以下の手順でホットスタンプ成形体の耐塗膜剥離二次密着性を評価した。まず、上述した化成処理及び電着塗料を施した評価用サンプルに、クロスカット疵を形成することなしに、JASO-CCT試験(M609-91)、塩水噴霧(5%NaCl、35℃):2時間、乾燥(60℃、20~30%RH):4時間、湿潤(50℃、95%RH):2時間を200サイクル実施した。次いで、200サイクル後の各評価用サンプルの表面に1mm間隔で縦横に11本ずつ切込みを入れ、合計100個の碁盤目状の切込みに対して、粘着テープによる剥離テストを行い、耐塗膜剥離二次密着性を評価した。剥離した個数が10個未満であれば耐塗膜剥離二次密着性評価「☆」、剥離した個数が10個以上30個未満であれば耐塗膜剥離二次密着性評価「◎」、30個以上50個未満であれば耐塗膜剥離二次密着性評価「〇」、50個以上であれば耐塗膜剥離二次密着性評価「×」とした。各試料の評価結果を表2に示す。
上述した化成処理及び電着塗料を施した評価用サンプルに、下地の鋼板まで到達する対角線長さ70mmのクロスカット疵を形成し、その後、JASO-CCT試験(M609-91)、塩水噴霧(5%NaCl、35℃):2時間、乾燥(60℃、20~30%RH):4時間、湿潤(50℃、95%RH):2時間を180サイクル実施し、疵部耐食性を評価した。180サイクル後の評価用サンプルにおいて、膨れ幅2mm以下であれば疵部耐食性評価「〇」、2mm超であれば疵部耐食性評価「×」とした。各試料の評価結果を表2に示す。
Claims (5)
- 鋼板と、前記鋼板の少なくとも片面に形成されためっき層とを有し、前記めっき層が、前記めっき層の表面側に存在し、酸素濃度が10質量%以上であるZnO領域と、前記めっき層の鋼板側に存在し、酸素濃度が10質量%未満であるNi-Fe-Zn合金領域とからなり、前記ZnO領域において、Fe、Mn及びSiの合計の平均濃度が5質量%以上30質量%以下である、ホットスタンプ成形体。
- 前記Ni-Fe-Zn合金領域において、Zn、O、Mn及びSiの各濃度が、前記めっき層の表面側から鋼板側に向けて減少する、請求項1に記載のホットスタンプ成形体。
- 前記Ni-Fe-Zn合金領域が、前記めっき層の表面側から順に、Fe濃度が60質量%未満である第1の領域と、Fe濃度が60質量%以上である第2の領域とからなり、前記第1の領域におけるZn/Ni質量比が2.0以上15.0以下の範囲であり、前記第2の領域における平均Zn/Ni質量比が0.5以上2.0以下である、請求項1又は2に記載のホットスタンプ成形体。
- 前記第2の領域における平均Zn/Ni質量比が0.8以上1.2以下である、請求項3に記載のホットスタンプ成形体。
- 前記ZnO領域の厚さが1.0μm以上5.0μm以下である、請求項1~4のいずれか1項に記載のホットスタンプ成形体。
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JP2005113233A (ja) * | 2003-10-09 | 2005-04-28 | Nippon Steel Corp | 熱間プレス用Zn系めっき鋼材 |
JP2013503254A (ja) * | 2009-08-25 | 2013-01-31 | 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 | 腐食に対する保護を与える金属コーティングが施された鋼部材を製造する方法、および鋼部材 |
JP2014014834A (ja) * | 2012-07-09 | 2014-01-30 | Nippon Steel & Sumitomo Metal | 高強度鋼成形部材の製造方法 |
KR20150061410A (ko) * | 2013-11-27 | 2015-06-04 | 주식회사 포스코 | 가공성이 우수한 열간 프레스 성형용 강판 및 이의 제조방법 |
JP2015104753A (ja) * | 2013-12-02 | 2015-06-08 | 新日鐵住金株式会社 | ホットスタンプ鋼材の製造方法及びホットスタンプ鋼材 |
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JP7277823B2 (ja) | 2023-05-19 |
KR20220002429A (ko) | 2022-01-06 |
CN113939610A (zh) | 2022-01-14 |
CN113939610B (zh) | 2024-02-02 |
JPWO2020241864A1 (ja) | 2020-12-03 |
US20220213609A1 (en) | 2022-07-07 |
KR102608759B1 (ko) | 2023-12-04 |
US11795560B2 (en) | 2023-10-24 |
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