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WO2025079386A1 - Hot-stamp molded body - Google Patents

Hot-stamp molded body Download PDF

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Publication number
WO2025079386A1
WO2025079386A1 PCT/JP2024/032794 JP2024032794W WO2025079386A1 WO 2025079386 A1 WO2025079386 A1 WO 2025079386A1 JP 2024032794 W JP2024032794 W JP 2024032794W WO 2025079386 A1 WO2025079386 A1 WO 2025079386A1
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WO
WIPO (PCT)
Prior art keywords
phase
content
less
plating layer
hot
Prior art date
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Pending
Application number
PCT/JP2024/032794
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French (fr)
Japanese (ja)
Inventor
将汰 林田
卓哉 光延
浩史 竹林
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Nippon Steel Corp
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Nippon Steel Corp
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Publication date
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Publication of WO2025079386A1 publication Critical patent/WO2025079386A1/en
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/10Alloys based on aluminium with zinc as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/60Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06Zinc or cadmium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12Aluminium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26After-treatment

Definitions

  • the present invention relates to a hot stamped body.
  • Hot stamping is known as a technique for press-forming difficult-to-form materials such as high-strength steel plates.
  • Hot stamping is a hot forming technique in which the material to be formed is heated and then shaped. With this technique, the material is heated before being shaped, so the steel is soft and has good formability when formed. Therefore, even high-strength steel can be precisely formed into complex shapes, and because the material is quenched at the same time as it is formed using a press die, the steel is known to have sufficient strength after forming.
  • Patent Document 1 describes a steel sheet coated with a metal coating having an Al/Zn ratio of greater than 2.9, comprising 2.0-24.0 wt. % zinc, 7.1-12.0 wt. % silicon, optional 1.1-8.0 wt. % magnesium, and optional additional elements selected from Pb, Ni, Zr, or Hf, with the weight content of each additional element being less than 0.3 wt. %, the balance being aluminum and optional unavoidable impurities and residual elements.
  • Patent Document 1 also teaches that metal coatings having an Al/Zn ratio of greater than 2.9 have high sacrificial protection.
  • Patent Document 2 describes an aluminum alloy plated steel sheet that includes a base steel sheet and an aluminum alloy plated layer formed on the base steel sheet, the aluminum alloy plated layer containing, by weight, 21-35% Zn, 1-6.9% Si, 2-12% Fe, the balance being Al and other unavoidable impurities. Patent Document 2 also teaches that weldability and corrosion resistance can be ensured by controlling the Al/(Zn+Si) of the aluminum alloy plated layer to 1.3-2.6.
  • the plated layer and the base steel may be alloyed during heating in the hot stamp forming, resulting in a decrease in corrosion resistance.
  • the present invention aims to provide a hot stamped body having an Al-containing plating layer that has improved corrosion resistance even after hot stamping.
  • the present inventors have conducted research, focusing particularly on the chemical composition and structure of the coating layer.
  • the present inventors have found that excellent corrosion resistance can be achieved in a hot stamped body by forming a coating layer made of an Al-Zn- Mg -Si system coating in a coating weight of at least a predetermined amount, forming a coating layer after hot stamping mainly of an Fe2Al5 phase , an Fe-Al phase formed on the Fe2Al5 phase and having a relatively low Fe content, and a surface oxide film modified with Mg, and further appropriately controlling the morphology of the Fe2Al5 phase, thereby completing the present invention.
  • a steel plate having a plating layer disposed on a surface of the steel plate The chemical composition of the plating layer is, in mass%, Zn: 2.5-40.0%, Si: 0.05-15.0%, Fe: 25.0-40.0%, Mg: 0.005-3.000%, Ni: 0 to 0.500%, Ca: 0-3.000%, Sb: 0 to 0.500%, Pb: 0 to 0.500%, Cu: 0 to 1.000%, Sn: 0-1.000%, Ti: 0 to 1.000%, Cr: 0-1.000%, Nb: 0 to 1.000%, Zr: 0 to 1.000%, Mn: 0 to 1.000%, Mo: 0-1.000%, Ag: 0-1.000%, Li: 0 to 1.000%, La: 0 to 0.500%, Ce: 0-0.500%, B: 0 to 0.500%, Y: 0 to 0.500%, Sr: 0-0.500%, In: 0
  • a hot stamped product characterized in that the coating weight of the plating layer is 20 g/m2 or more per side.
  • the chemical composition of the plating layer is, in mass%, Contains Zn: 5.0 to 35.0% and Si: 0.25 to 6.0%;
  • the hot stamped steel according to (1) above characterized in that the Mg content in the surface oxide film is 0.30 atomic % or more.
  • the present invention makes it possible to provide a hot stamped body having an Al-containing plating layer that has improved corrosion resistance even after hot stamping.
  • FIG. 1 is an example of a schematic cross-sectional view of a surface portion of a hot stamped steel according to an embodiment of the present invention, showing the projected length L i of an Fe—Al—Si phase and the length L 0 of the surface of a steel base material.
  • a hot stamped steel comprises a steel base material and a plating layer disposed on a surface of the steel base material,
  • the chemical composition of the plating layer is, in mass%, Zn: 2.5-40.0%, Si: 0.05-15.0%, Fe: 25.0-40.0%, Mg: 0.005-3.000%, Ni: 0 to 0.500%, Ca: 0-3.000%, Sb: 0 to 0.500%, Pb: 0 to 0.500%, Cu: 0 to 1.000%, Sn: 0-1.000%, Ti: 0 to 1.000%, Cr: 0-1.000%, Nb: 0 to 1.000%, Zr: 0 to 1.000%, Mn: 0 to 1.000%, Mo: 0-1.000%, Ag: 0-1.000%, Li: 0 to 1.000%, La: 0 to 0.500%, Ce: 0-0.500%, B: 0 to 0.500%, Y: 0 to 0.500%, Sr: 0-0.
  • the plated steel sheet and the base steel are alloyed during heating in the hot stamp forming, which may reduce the corrosion resistance.
  • the plated steel sheet and the base steel sheet are alloyed during high-temperature heating in the hot stamp forming (for example, heating at about 900°C or higher), and a plated steel sheet containing mainly the Fe 2 Al 5 phase is formed after hot stamp forming.
  • a relatively large amount of Fe-Al-based intermetallic compounds containing relatively large amounts of Si may also be formed in the plated steel sheet.
  • bimetallic corrosion galvanic corrosion
  • the present inventors conducted a study, focusing in particular on the chemical composition and form of the plating layer made of Al-Si-based plating before hot stamping, in order to provide a hot stamped body having an Al-containing plating layer having excellent corrosion resistance even after hot stamping.
  • the present inventors found that by appropriately preparing a plating layer made of Al-Zn-Mg-Si-based plating in which Zn and Mg are further added to the Al-Si plating and by appropriately selecting the heat treatment conditions for hot stamping, it is possible to suppress the formation of an Fe-Al-Si phase that may cause galvanic corrosion between the Fe 2 Al 5 phase in the plating layer formed after hot stamping, thereby improving the corrosion resistance of the formed body after hot stamping . Furthermore, the present inventors found that the red rust resistance of the hot stamped body can be improved by forming an Fe -Al phase having a relatively low Fe content, more specifically, an Fe content of 20 to 40 mass %, on the Fe 2 Al 5 phase. In addition, the addition of Mg makes it possible to appropriately modify the surface oxide film in the plating layer after hot stamp forming, thereby improving the chemical conversion treatability of the hot stamped body.
  • the present inventors first found that by setting the coating weight of the coating layer made of Al-Zn-Mg-Si-based coating to 20 g/ m2 or more per side and further appropriately selecting the heat treatment conditions for hot stamp forming, it is possible to form an Fe - Al phase having a lower Fe content than the Fe2Al5 phase on the Fe2Al5 phase on the steel base material side without alloying the entire coating layer to the Fe2Al5 phase during high-temperature heating in hot stamp forming.
  • Fe from the steel base material diffuses into the coating layer and is alloyed with Al, but by making the coating weight of the coating layer relatively large and appropriately weakening the degree of alloying, it is possible to form an Fe - Al phase having a lower Fe content than the Fe2Al5 phase, i.e., an Fe - Al phase having an Fe content of 20 to 40 mass %, on the surface side of the coating layer, although a sufficiently alloyed Fe2Al5 phase is formed on the steel base material side of the coating layer.
  • the improvement in red rust resistance due to the Fe-Al phase is due to the fact that the Fe-Al phase is less alloyed than the Fe2Al5 phase .
  • the present inventors have found that, as will be described in detail later in relation to the manufacturing method of a hot stamped body, by containing a predetermined amount of Si in the Fe-Al phase corresponding to the interface alloy layer formed at the interface between the base steel sheet and the coating layer before hot stamping, more specifically, by containing 3.0 mass% or more of Si in the interface alloy layer, it is possible to suppress the formation of a relatively large Fe-Al-Si phase in the Fe 2 Al 5 phase in the coating layer formed after hot stamping.
  • the present inventors have found that, in the coating layer after hot stamping, the relatively large Fe-Al-Si phase in the Fe 2 Al 5 phase formed on the steel base metal side of the coating layer is dispersed and present, that is, by controlling the projected length L i of the Fe-Al-Si phase having a Si content of 5 to 20 mass% and a circle equivalent diameter of 2 ⁇ m or more and the length L 0 of the surface of the steel base metal to satisfy ⁇ L i /L 0 ⁇ 0.70, the corrosion resistance of the coating layer after hot stamping can be significantly improved.
  • Fig. 1 is an example of a schematic cross-sectional view of a surface portion of a hot stamped steel according to an embodiment of the present invention, showing the projected length L i of the Fe-Al-Si phase and the length L 0 of the surface of the steel base material.
  • a hot stamped steel 1 according to an embodiment of the present invention includes a steel base material 2 and a coating layer 3 disposed on the surface of the steel base material 2, and the coating layer 3 includes, in order from the steel base material 2 side, an Fe 2 Al 5 phase 4 located on the steel base material 2, an Fe-Al phase 5 located on the Fe 2 Al 5 phase 4, more specifically, an Fe-Al phase 5 having an Fe content of 20 to 40 mass%, and a surface oxide film 6.
  • Fig. 1 is an example of a schematic cross-sectional view of a surface portion of a hot stamped steel according to an embodiment of the present invention, showing the projected length L i of the Fe-Al-Si phase and the length L 0 of the surface of the steel base material.
  • an Fe - Al-Si phase 7 having a Si content of 5 to 20 mass% and a circle equivalent diameter of 2 ⁇ m or more is present in the Fe 2 Al 5 phase 4.
  • the entire projected length including the overlapping portion is determined as one projected length. If the Fe-Al-Si phase 7 is present in a layered form in the Fe 2 Al 5 phase 4, it is considered that when galvanic corrosion occurs at the contact portion between the layered Fe-Al-Si phase 7 and the Fe 2 Al 5 phase 4, the corrosion will progress along the contact interface. As a result, the corrosion resistance of the plating layer 3 is significantly reduced.
  • the Fe-Al-Si phase 7 is dispersed in the Fe 2 Al 5 phase 4 so as to satisfy ⁇ L i /L 0 ⁇ 0.70, so that even if galvanic corrosion occurs at a contact portion between one or more Fe-Al-Si phases 7 and the Fe 2 Al 5 phase 4 present therearound, the corrosion will not progress from the corrosion at the contact portion to other Fe-Al-Si phases 7, thereby making it possible to significantly improve the corrosion resistance of the coating layer 3.
  • Zn is dissolved in the Fe 2 Al 5 phase 4 and the Fe-Al phase 5 in association with the addition of Zn to the coating layer, and therefore the corrosion resistance is further improved by the sacrificial anticorrosive action of Zn.
  • Mg is present in the surface oxide film 6 in an amount of 0.05 atomic % or more, and it is considered that the presence of Mg can modify the surface oxide film, thereby improving the chemical conversion treatability of the hot stamped body.
  • Mg is generally present in the plating layer as an Mg2Si phase or the like.
  • the plating layer 3 of the hot stamped body 1 according to the embodiment of the present invention contains a relatively large amount of Al, its surface is covered with an oxide film composed of Al-containing oxides and the like.
  • the Mg2Si phase has a relatively high melting point, it is difficult to be oxidized even during high-temperature heating in hot stamping, and therefore it is considered that it cannot act on the oxide film composed of Al-containing oxides and the like to modify the oxide film.
  • the present inventors have found that, as will be described in detail later in relation to the manufacturing method of a hot stamped body, by appropriately controlling the cooling after plating, it is possible to form an Mg-Al-Zn-Si intermetallic compound phase having a lower melting point and a tendency to be easily oxidized compared to the Mg 2 Si phase in the plating layer before hot stamp forming, more specifically, an Mg-Al-Zn-Si intermetallic compound phase having an Al content of 10 mass % or more, and that the presence of the Mg-Al-Zn-Si intermetallic compound phase is effective in modifying the surface oxide film.
  • the Mg-Al-Zn-Si intermetallic compound phase has a lower melting point and a tendency to be easily oxidized compared to the Mg 2 Si phase. Therefore, the Mg-Al-Zn-Si intermetallic compound phase melts during high-temperature heating in hot stamp forming, and the dissolved Mg can be introduced into the Al-containing oxide present on the surface in an amount of 0.05 atomic % or more. As a result, the oxide film formed on the surface of the formed body during hot stamp forming can be appropriately modified by Mg, which is believed to improve the chemical conversion treatability of the resulting hot stamped body.
  • the hot stamped steel according to the embodiment of the present invention it is possible to achieve excellent corrosion resistance by combining the effect of suppressing the formation of the Fe-Al- Si phase 7 that may cause galvanic corrosion between the Fe 2 Al 5 phase 4, more specifically, the effect of suppressing the progress of corrosion obtained by dispersing and forming a relatively large Fe-Al-Si phase 7, the effect of improving red rust resistance due to the formation of the Fe-Al phase 5, and the effect of improving chemical conversion treatability due to the modification of the surface oxide film by Mg.
  • the corrosion resistance of the hot stamped steel 1 can be improved by forming the coating layer 3 from the Fe 2 Al 5 phase 4, the Fe - Al phase 5 having a relatively low Fe content, and the surface oxide film 6 modified by Mg, and further by appropriately controlling the form of the Fe 2 Al 5 phase 4 as described above, was revealed for the first time by the present inventors. Therefore, the hot stamped steel according to the embodiment of the present invention is particularly useful in the automotive field where hot stamping is relatively often used.
  • the plating layer is disposed on the surface of the steel base material, for example, disposed on at least one, preferably both, surfaces of the steel base material.
  • the expression "disposed on the surface of the steel base material” includes not only the case where the plating layer is directly disposed on the surface of the steel base material, but also the case where the plating layer is indirectly disposed on the surface of the steel base material, for example, the case where a solid solution layer, which will be described later, is included between the steel base material and the plating layer.
  • the plating layer has the following chemical composition.
  • Zn has a sacrificial anticorrosive effect and is an element effective in improving the corrosion resistance of the plating layer.
  • Zn reacts with the treatment liquid during chemical conversion treatment to form a chemical conversion coating on the surface.
  • the Zn content is set to 2.5% or more.
  • the Zn content may be 3.5% or more, 5.0% or more, 8.0% or more, 10.0% or more, 12.0% or more, 15.0% or more, 18.0% or more, 20.0% or more, or 22.0% or more.
  • the Zn content is set to 40.0% or less.
  • the Zn content may be 38.0% or less, 35.0% or less, 32.0% or less, 30.0% or less, or 28.0% or less.
  • Si is an element effective in improving the adhesion of the plating layer.
  • the Si content is set to 0.05% or more.
  • the Si content may be 0.1% or more, 0.2% or more, 0.25% or more, 0.3% or more, 0.5% or more, 0.8% or more, 1.0% or more, 3.0% or more, or 5.0% or more.
  • the Si content is set to 15.0% or less.
  • the Si content may be 12.0% or less, 10.0% or less, 8.0% or less, or 6.0% or less.
  • Fe:25.0-40.0% When a plated steel sheet is heated during hot stamp forming, Fe from the steel base material diffuses into the plated layer and is alloyed with Al, etc., so that the plated layer inevitably contains Fe. Therefore, the Fe content is 25.0% or more, and may be, for example, 26.0% or more, 28.0% or more, 30.0% or more, or 32.0% or more. On the other hand, if the Fe content is too high, the red rust resistance may be reduced due to excessive alloying of the plated layer. Therefore, the Fe content is 40.0% or less, and may be, for example, 38.0% or less, 36.0% or less, or 34.0% or less.
  • Mg is an element effective in improving the corrosion resistance, particularly chemical conversion treatability, of the coating layer.
  • the Mg content is set to 0.005% or more.
  • the Mg content may be 0.010% or more, 0.020% or more, 0.030% or more, 0.050% or more, 0.080% or more, 0.100% or more, or 0.300% or more.
  • the Mg content is set to 3.000% or less.
  • the Mg content may be 2.500% or less, 2.000% or less, 1.500% or less, 1.000% or less, 0.800% or less, 0.600% or less, or 0.400% or less.
  • the plating layer may optionally contain Ni: 0-0.500%, Ca: 0-3.000%, Sb: 0-0.500%, Pb: 0-0.500%, Cu: 0-1.000%, Sn: 0-1.000%, Ti: 0-1.000%, Cr: 0-1.000%, Nb: 0-1.000%, Zr: 0-1.000%, Mn: 0-1.000%, Mo: 0-1.000 %, Ag: 0-1.000%, Li: 0-1.000%, La: 0-0.500%, Ce: 0-0.500%, B: 0-0.500%, Y: 0-0.500%, Sr: 0-0.500%, In: 0-0.500%, Co: 0-0.500%, Bi: 0-0.500%, P: 0-0.500%, and W: 0-0.500% may be contained.
  • the total content of these optional elements is 5.000% or less.
  • the total content of the optional elements may be 4.500% or less, 4.000% or less, 3.500% or less, 3.000% or less, 2.500% or less, 2.000% or less, 1.500% or less, 1.000% or less, 0.800% or less, 0.500% or less, 0.100% or less, or 0.050% or less.
  • the inclusion of these elements is not essential, and the total content of these elements may be 0%. If necessary, the lower limit of the total content of these elements may be 0.001%, 0.010%, 0.050%, or 0.080%.
  • Ni is an element effective for improving the corrosion resistance of the plating layer.
  • the Ni content may be 0%, but in order to obtain such an effect, the Ni content is preferably 0.001% or more.
  • the Ni content may be 0.003% or more, 0.005% or more, 0.008% or more, 0.010% or more, or 0.020% or more.
  • the Ni content is set to 0.500% or less, and may be, for example, 0.400% or less, 0.300% or less, 0.100% or less, 0.050% or less, or 0.030% or less.
  • Ca is an element effective in ensuring wettability of the plating bath.
  • the Ca content may be 0%, but in order to obtain such an effect, the Ca content is preferably 0.001% or more.
  • the Ca content may be 0.003% or more, 0.005% or more, or 0.010% or more.
  • the Ca content is preferably 3.000% or less.
  • the Ca content may be 2.000% or less, 1.000% or less, 0.500% or less, 0.300% or less, 0.100% or less, 0.050% or less, or 0.020% or less.
  • the content of Sb, Pb, La, Ce, B, Y, Sr, In, Co, Bi, P and W is preferably 0.500% or less, and may be, for example, 0.300% or less, 0.100% or less, 0.050% or less, or 0.020% or less.
  • the contents of Cu, Sn, Ti, Cr, Nb, Zr, Mn, Mo, Ag and Li are preferably 1.000% or less, and may be, for example, 0.800% or less, 0.500% or less, 0.100% or less, 0.050% or less, or 0.020% or less.
  • the remainder of the plating layer other than the above elements consists of Al and impurities.
  • Impurities in the plating layer are components that are mixed in due to various factors in the manufacturing process, including raw materials, when the plating layer is manufactured.
  • the Al content does not need to be specified in particular, but may be 10.0 to 72.45%. If necessary, the Al content may be 20.0% or more, 25.0% or more, 30.0% or more, 35.0% or more, 38.0% or more, 40.0% or more, or 42.0% or more, or 70.0% or less, 65.0% or less, 60.0% or less, 57.0% or less, 54.0% or less, 51.0% or less, or 48.0% or less.
  • the chemical composition of the plating layer is determined by dissolving only the plating layer in an acidic aqueous solution and chemically analyzing it. That is, the plating layer is dissolved in an acidic aqueous solution at room temperature containing an inhibitor that inhibits the dissolution of steel, for example, an acidic aqueous solution at room temperature containing 10% hydrochloric acid and 0.04% IBIT 710K (manufactured by Asahi Chemical Industry Co., Ltd.), and the resulting acidic aqueous solution is analyzed by ICP (inductively coupled plasma atomic emission spectroscopy) to obtain the chemical composition of the plating layer.
  • ICP inductively coupled plasma atomic emission spectroscopy
  • the coating layer contains an Fe2Al5 phase on the steel base metal side, and the projected length L i of the Fe - Al- Si phase having a Si content of 5-20 mass% and a circle equivalent diameter of 2 ⁇ m or more in the Fe2Al5 phase and the length L 0 of the surface of the steel base metal are controlled to satisfy ⁇ L i /L 0 ⁇ 0.70.
  • the Fe-Al-Si phase having a Si content of 5-20 mass% may cause galvanic corrosion between the Fe2Al5 phase and the Fe2Al5 phase.
  • the Fe-Al-Si phase is relatively large and exists continuously in a layered or nearly layered form, corrosion will progress along the contact interface between the Fe-Al- Si phase and the Fe2Al5 phase, and the corrosion resistance of the coating layer will be significantly reduced. Therefore, in order to suppress the progress of such corrosion and improve the corrosion resistance of the coating layer, it is necessary to have the Fe-Al-Si phase having a circle equivalent diameter of 2 ⁇ m or more dispersed in the Fe 2 Al 5 phase. Therefore, in the embodiment of the present invention, as shown in FIG.
  • the Fe-Al-Si phase is dispersed in the Fe 2 Al 5 phase so that the sum ⁇ L i of the projected lengths L i of each Fe-Al-Si phase having a circle equivalent diameter of 2 ⁇ m or more projected onto the surface of the steel base material and the length L 0 of the surface of the steel base material 2 satisfy ⁇ L i /L 0 ⁇ 0.70 , thereby improving the corrosion resistance of the coating layer.
  • the lower the value of ⁇ L i /L 0 the more preferable, and it may be, for example, 0.65 or less, 0.60 or less, 0.55 or less, 0.50 or less, 0.45 or less, or 0.40 or less.
  • the Fe-Al-Si phase having a circle equivalent diameter of less than 2 ⁇ m may not exist in the Fe 2 Al 5 phase. That is, the lower limit of ⁇ L i /L 0 may be 0. Although not particularly limited, for example, ⁇ L i /L 0 may be 0.05 or more, 0.10 or more, 0.15 or more, or 0.20 or more.
  • the plating layer includes an Fe - Al phase having a lower Fe content than the Fe 2 Al 5 phase (Fe content: more than 40 to 60 mass%), i.e., an Fe-Al phase having an Fe content of 20 to 40 mass%, on the surface side of the Fe 2 Al 5 phase.
  • the Fe-Al phase having an Fe content of 20 to 40 mass% has a lower degree of alloying than the Fe 2 Al 5 phase, and in this regard, can contribute to improving red rust resistance.
  • the Si content in the Fe-Al phase is less than 5 mass%.
  • the Fe-Al phase having an Fe content of 20 to 40 mass% may be simply referred to as the Fe-Al phase.
  • the plating layer includes a surface oxide film on its surface, and the Mg content in the surface oxide film is controlled to 0.05 atomic % or more. Since the plating layer of the hot stamped body according to the embodiment of the present invention contains a relatively large amount of Al, the surface is covered with an oxide film composed of Al-containing oxides and the like. By introducing Mg into such a surface oxide film in an amount of 0.05 atomic % or more, the surface oxide film can be appropriately modified, thereby improving the chemical conversion treatability of the hot stamped body.
  • the higher the Mg content in the surface oxide film the more preferable it is, and it may be, for example, 0.10 atomic % or more, 0.20 atomic % or more, 0.30 atomic % or more, 0.50 atomic % or more, 0.80 atomic % or more, 1.00 atomic % or more, or 1.50 atomic % or more.
  • the surface oxide film contains an excessive amount of Mg, the above effect is saturated.
  • the Mg content in the surface oxide film is preferably 6.00 atomic % or less, and may be, for example, 5.50 atomic % or less, 5.00 atomic % or less, 4.50 atomic % or less, or 4.00 atomic % or less.
  • the plating layer is analyzed as follows. First, five samples are taken from the hot stamped body so that the cross section of the plating layer can be observed. Next, for each sample, a rectangular range of 80 ⁇ m in the thickness direction and 100 ⁇ m in the direction perpendicular to the thickness direction is defined as one visual field, and five visual fields in total for the five samples are photographed at a magnification of 1500 times using SEM-EDS or EPMA to obtain a mapping image.
  • the positions of the Fe-Al phase having an Fe content of 20 to 40 mass%, the Fe 2 Al 5 phase, and the Fe - Al-Si phase having a Si content of 5 to 20 mass% and a circle equivalent diameter of 2 ⁇ m or more present inside the Fe 2 Al 5 phase, as well as the surface oxide film, are determined. More specifically, an element distribution image is obtained by SEM-EDS or EPMA with the measurement target elements being Fe, Al, Si, and Zn. In this element distribution image, the region that satisfies Fe: 20-40 mass% and Al: 58-78 mass% is defined as the Fe-Al phase having an Fe content of 20-40 mass%.
  • the concentration range of the color bar showing the concentration of each element in the element distribution image by color tone is set to Fe: 20-40 mass% and Al: 58-78 mass%, and the Fe-Al phase having an Fe content of 20-40 mass% (reference numeral 5 in FIG. 1) is specified by superimposing the element distribution images of Fe and Al with the color bar adjusted.
  • the region that satisfies Fe: more than 40 to 60 mass%, Al: 40 to less than 60 mass%, Si: 0 to less than 5 mass%, and Zn: 0 to 15 mass% is defined as the Fe 2 Al 5 phase (reference numeral 4 in FIG. 1).
  • the region in which the Si content is 5 to 20 mass% and the circle equivalent diameter is 2 ⁇ m or more and is surrounded by the Fe 2 Al 5 phase is defined as the Fe-Al-Si phase (reference numeral 7 in FIG. 1).
  • the Fe-Al-Si phase is projected onto the surface of the steel base material using image analysis software (for example, the "Analyze” function of "ImageJ"), and the sum of the projected lengths L i of each Fe-Al-Si phase (L 1 +L 2 +L 3 in FIG. 1) is calculated.
  • L i which is the length of the long side in the field, is also the distance between both ends of the measurement region (field) as shown in FIG. 1 (however, the distance in the direction parallel to the surface of the hot stamped body 1).
  • the Mg content in the surface oxide film is determined by measuring the concentration of elements constituting the surface oxide film for each of the five samples using SEM-EDS or EPMA, and averaging the measured values of the target element concentration for the five samples. More specifically, first, in each sample, the area that satisfies O: 30-70 mass%, Al: 30-70 mass%, and Mg: 0-2.5 mass% in the measurement by SEM-EDS or EPMA is determined to be the surface oxide (reference number 6 in Figure 1). Next, in each sample, the Mg content is measured at five measurement points spaced 50 ⁇ m apart in the direction parallel to the surface of the hot stamped body at the center position of the thickness of the area identified as the surface oxide, and the average value is determined to be the Mg content of each sample. The average value of the Mg contents in the five samples is determined to be the Mg content in the surface oxide film.
  • the plating layer having the above chemical composition, Fe2Al5 phase, Fe-Al phase, and surface oxide film may be a hot-dip plating layer. It is not necessary to exclude plating layers other than the hot-dip plating layer, but it may be limited to the hot-dip plating layer.
  • the coating weight of the coating layer is 20 g/m 2 or more per side.
  • the coating layer may be alloyed with the steel base material during high-temperature heating in hot stamp forming, resulting in a decrease in corrosion resistance.
  • the coating weight of the coating layer relatively large, specifically 20 g/m 2 or more per side, while appropriately weakening the degree of alloying, a sufficiently alloyed Fe 2 Al 5 phase is formed on the steel base material side of the coating layer, but an Fe-Al phase having a lower Fe content than the Fe 2 Al 5 phase, that is, an Fe-Al phase having an Fe content of 20 to 40 mass %, can be formed on the surface side of the coating layer.
  • the coating weight of the coating layer is small, the alloying of the coating layer may proceed too much during high-temperature heating in hot stamp forming, making it impossible to form an Fe-Al phase having a relatively low Fe content.
  • the coating weight of the plating layer is preferably 30 g/m 2 or more, 40 g/m 2 or more, or 50 g/m 2 or more, more preferably 60 g/m 2 or more, even more preferably 70 g/m 2 or more , and most preferably 80 g/m 2 or more per side.
  • the coating weight of the plating layer may be, for example, 200 g/m 2 or less, 190 g/m 2 or less, 180 g/m 2 or less, or 170 g/m 2 or less.
  • the coating weight of the plating layer is determined by dissolving only the plating layer in an acidic aqueous solution. That is, a 30 mm x 30 mm sample is taken from the hot stamped body, and then dissolved in an acidic aqueous solution containing an inhibitor that inhibits the dissolution of steel, for example, 0.04% Ibit 710K (manufactured by Asahi Chemical Industry Co., Ltd.) in 10% hydrochloric acid.
  • the plating layer is dissolved in an acidic aqueous solution at room temperature to which has been added, and the amount of plating layer attached is determined from the change in mass of the sample before and after dissolution of the plating layer.
  • the hot stamped product may further include a solid solution layer between the steel base material and the plating layer.
  • a solid solution may be formed between Fe diffusing from the steel base material to the plating layer and Al and/or Zn in the plating layer, and a solid solution layer containing a solid solution of these elements may be formed between the steel base material and the plating layer after hot stamping. Therefore, when the hot stamped product further includes a solid solution layer, the solid solution layer contains Fe and one or both of Al and Zn. More specifically, the solid solution layer includes an Fe-Al solid solution layer, an Fe-Zn solid solution layer, and/or an Fe-Al-Zn solid solution layer.
  • the presence of a solid solution layer can be confirmed as follows. First, the plating layer alone is dissolved in an acidic aqueous solution containing an inhibitor that inhibits the dissolution of steel, specifically, 10% hydrochloric acid plus 0.04% Ivit 710K (manufactured by Asahi Chemical Industry Co., Ltd.) at room temperature. Next, using a high-frequency glow discharge optical emission spectrometer (GDS), the surface of the hot stamped compact is placed in an Ar atmosphere, and a voltage is applied to generate glow plasma, and the surface of the hot stamped compact is sputtered and analyzed in the depth direction.
  • GDS glow discharge optical emission spectrometer
  • the elements contained in the material are identified from the element-specific emission spectrum wavelengths emitted by excited atoms in the glow plasma, and the emission intensity of the identified elements is estimated.
  • the data in the depth direction can be estimated from the sputtering time. Specifically, the relationship between sputtering time and sputtering depth is obtained in advance using a standard sample, so that the sputtering time can be converted to sputtering depth. Therefore, the sputtering depth converted from the sputtering time can be defined as the depth from the surface of the material.
  • the obtained emission intensity is converted to mass% by creating a calibration curve.
  • the present invention aims to provide a hot stamped product having an Al-containing plating layer having improved corrosion resistance even after hot stamp forming, and the object is achieved by optimizing the chemical composition and coating weight of the plating layer made of an Al-Zn-Mg-Si-based plating, configuring the plating layer mainly with an Fe 2 Al 5 phase, an Fe-Al phase formed on the Fe 2 Al 5 phase and having a relatively low Fe content, and a surface oxide film modified with Mg, and controlling the projected length L i of the Fe-Al-Si phase having a Si content of 5 to 20 mass% and a circle equivalent diameter of 2 ⁇ m or more in the Fe 2 Al 5 phase and the length L 0 of the surface of the steel base material so as to satisfy ⁇ L i /L 0 ⁇ 0.70.
  • the steel base material comprises, in mass %, C: 0.13-0.50%, Si: 0.001 to 3.000%, Mn: 0.30-3.00%, Al: 0.0002-2.000%, P: 0.100% or less, S: 0.1000% or less, N: 0.0100% or less, Nb: 0 to 0.15%, Ti: 0 to 0.15%, V: 0 to 0.15%, Mo: 0-1.0%, Cr: 0-1.0%, Cu: 0 to 1.0%, Ni: 0-1.0%, B: 0 to 0.0100%, W: 0-1.000%, Hf: 0 to 0.050%, Mg: 0 to 0.050%, Zr: 0 to 0.050%, Ca: 0-0.010%, REM: 0-0.30%, It is preferable that the chemical composition is Ir: 0 to 1.000%, and the balance: Fe and impurities. Each element will be described in more detail below.
  • C is an element that inexpensively increases tensile strength and is an important element for controlling the strength of steel.
  • the C content is preferably 0.13% or more.
  • the C content may be 0.15% or more, 0.20% or more, 0.30% or more, or 0.35% or more.
  • excessive C content may cause a decrease in elongation.
  • the C content is preferably 0.50% or less.
  • the C content may be 0.45% or less, or 0.40% or less.
  • Si acts as a deoxidizer and is an element that suppresses the precipitation of carbides during the cooling process during cold-rolled sheet annealing.
  • the Si content is preferably 0.001% or more.
  • the Si content may be 0.010% or more, 0.100% or more, or 0.200% or more.
  • excessive Si content may increase the steel strength and decrease the elongation. For this reason, the Si content is preferably 3.000% or less.
  • the Si content may be 2.500% or less, 2.000% or less, 1.500% or less, or 1.000% or less.
  • Mn is an element that enhances the hardenability of steel and is effective in increasing strength.
  • the Mn content is preferably 0.30% or more.
  • the Mn content may be 0.50% or more, 1.00% or more, or 1.30% or more.
  • excessive Mn content may increase the steel strength and decrease the elongation. For this reason, the Mn content is preferably 3.00% or less.
  • the Mn content may be 2.80% or less, 2.50% or less, or 2.00% or less.
  • Al acts as a deoxidizer for steel and is an element that has the effect of improving the soundness of steel.
  • the Al content is preferably 0.0002% or more.
  • the Al content may be 0.001% or more, 0.010% or more, 0.050% or more, or 0.100% or more.
  • the Al content is preferably 2.000% or less.
  • the Al content may be 1.500% or less, 1.000% or less, 0.800% or less, or 0.500% or less.
  • P 0.100% or less
  • P is an element that segregates at grain boundaries and promotes embrittlement of steel. Since the lower the P content, the better, it is ideally 0%. However, excessive reduction in the P content may lead to a significant increase in costs. For this reason, the P content may be 0.0001% or more, or may be 0.001% or more, or 0.005% or more. On the other hand, excessive inclusion of P may lead to embrittlement of steel due to grain boundary segregation as described above. Therefore, the P content is preferably 0.100% or less. The P content may be 0.050% or less, 0.030% or less, or 0.010% or less.
  • S is an element that generates nonmetallic inclusions such as MnS in steel, which leads to a decrease in the ductility of steel parts.
  • the S content may be 0.0001% or more, 0.0002% or more, 0.0010% or more, or 0.0050% or more.
  • the S content is preferably 0.1000% or less.
  • the S content may be 0.0500% or less, 0.0200% or less, or 0.0100% or less.
  • N is an element that forms coarse nitrides in the steel sheet and reduces the workability of the steel sheet. Since the lower the N content, the more preferable it is, the ideal N content is 0%. However, excessive reduction in the N content may lead to a significant increase in manufacturing costs. For this reason, the N content may be 0.0001% or more, 0.0005% or more, or 0.0010% or more. On the other hand, excessive N content may form coarse nitrides as described above, thereby reducing the workability of the steel sheet. Therefore, the N content is preferably 0.0100% or less. The N content may be 0.0080% or less, or 0.0050% or less.
  • the preferred basic chemical composition of the steel base material is as described above.
  • the steel base material may contain, as necessary, one or more elements selected from the group consisting of Nb: 0-0.15%, Ti: 0-0.15%, V: 0-0.15%, Mo: 0-1.0%, Cr: 0-1.0%, Cu: 0-1.0%, Ni: 0-1.0%, B: 0-0.0100%, W: 0-1.000%, Hf: 0-0.050%, Mg: 0-0.050%, Zr: 0-0.050%, Ca: 0-0.010%, REM: 0-0.30%, and Ir: 0-1.000%, in place of a portion of the remaining Fe.
  • Each of these elements may be 0.0001% or more, 0.0005% or more, 0.001% or more, or 0.01% or more.
  • the remainder of the steel base material other than the above elements consists of Fe and impurities.
  • Impurities in steel base material are components that are mixed in due to various factors in the manufacturing process, including raw materials such as ore and scrap, when the steel base material is industrially manufactured.
  • the chemical composition of the steel base material may be measured by a general analytical method.
  • the chemical composition of the steel base material may be measured by first removing the plating layer by mechanical grinding, and then using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) on the cutting chips in accordance with JIS G 1201:2014.
  • ICP-AES Inductively Coupled Plasma-Atomic Emission Spectrometry
  • a 35 mm square test piece may be obtained from the vicinity of the 1/2 position of the plate thickness of the steel base material, and the composition may be identified by measuring it under conditions based on a calibration curve created in advance using a Shimadzu ICPS-8100 or similar (measuring device).
  • C and S which cannot be measured by ICP-AES, may be measured using the combustion-infrared absorption method, N may be measured using the inert gas fusion-thermal conductivity method, and O may be measured using the inert gas fusion-non-dispersive infrared absorption method.
  • the thickness of the hot stamped steel is not particularly limited, and may be, for example, 0.2 mm or more, 0.3 mm or more, 0.6 mm or more, 1.0 mm or more, or 2.0 mm or more. Similarly, the thickness of the hot stamped steel may be, for example, 6.0 mm or less, 5.0 mm or less, or 4.0 mm or less.
  • the hot stamped product according to an embodiment of the present invention can be manufactured by, for example, carrying out a casting process in which molten steel with an adjusted chemical composition is cast to form a slab, a hot rolling process in which the slab is hot rolled to obtain a hot rolled steel sheet, a coiling process in which the hot rolled steel sheet is coiled, a cold rolling process in which the coiled hot rolled steel sheet is cold rolled to obtain a cold rolled steel sheet, an annealing process in which the cold rolled steel sheet is annealed, a cooling process in which the annealed cold rolled steel sheet is cooled, a plating process in which a plating layer is formed on the obtained steel base material, and a hot stamp forming process in which the obtained plated steel sheet is hot stamp formed.
  • the cold rolling process may be carried out directly after pickling without coiling after the hot rolling process. Each process will be described in detail below.
  • the conditions for the casting process are not particularly limited. For example, after melting in a blast furnace or an electric furnace, various secondary smelting processes may be carried out, and then casting may be carried out by a method such as ordinary continuous casting or casting by an ingot method.
  • the cast slab is hot-rolled to obtain a hot-rolled steel sheet.
  • the hot-rolling step is performed by reheating the cast slab directly or after cooling and then hot-rolling it.
  • the heating temperature of the slab may be, for example, 1100 to 1250°C.
  • rough rolling and finish rolling are usually performed.
  • the temperature and reduction of each rolling step can be appropriately determined according to the desired metal structure and plate thickness.
  • the end temperature of the finish rolling may be 900 to 1050°C, and the reduction of the finish rolling may be 10 to 50%.
  • the hot-rolled steel sheet can be coiled at a predetermined temperature.
  • the coiling temperature can be appropriately determined depending on the desired metal structure, etc., and may be, for example, 500 to 800°C.
  • the hot-rolled steel sheet may be subjected to a predetermined heat treatment by recoiling before or after coiling. Alternatively, the coiling step may be omitted, and the hot-rolled steel sheet may be pickled after the hot-rolling step and then subjected to the cold-rolling step described later.
  • the hot-rolled steel sheet After the hot-rolled steel sheet is subjected to pickling or the like, the hot-rolled steel sheet is cold-rolled to obtain a cold-rolled steel sheet.
  • the rolling reduction in the cold rolling can be appropriately determined according to the desired metal structure and sheet thickness, and may be, for example, 20 to 80%.
  • the steel sheet After the cold rolling step, the steel sheet may be cooled to room temperature, for example, by air cooling.
  • the annealing step includes heating the cold-rolled steel sheet to a temperature of 730 to 900 ° C. in an atmosphere with a dew point of -50 to 20 ° C. and holding the temperature for 10 to 300 seconds.
  • the surface layer of the cold-rolled steel sheet can be appropriately decarburized.
  • the atmosphere in the annealing step may be a reducing atmosphere, more specifically a reducing atmosphere containing nitrogen and hydrogen, for example a reducing atmosphere of 1 to 10% hydrogen (eg, 4% hydrogen and the balance nitrogen).
  • the cooling step may be performed at a cooling rate suitable for obtaining a desired metal structure from the heating temperature of the annealing step to the entry sheet temperature of the subsequent plating step.
  • the cooling step may be performed at an average cooling rate of 10° C./s or more from the heating temperature of the annealing step to the entry sheet temperature of the plating step.
  • a plating layer is formed on at least one, preferably both, surfaces of the cold-rolled steel sheet (steel base material). More specifically, the plating step is carried out using a plating bath having a predetermined chemical composition, for example, a plating bath containing Zn: 5.0 to 50.0%, Si: 0.1 to 18.0%, Mg: 0.010 to 3.000%, and the balance: Al and impurities (plating bath temperature: 650°C or higher, for example, 650 to 680°C), so that the temperature of the steel base material entering the plating bath is 500°C or lower, and after plating, the steel is primarily cooled to 480°C at an average cooling rate of 20°C/s or higher, and then secondary cooled from 480°C to 300°C at an average cooling rate of 10°C/s or lower.
  • a plating bath having a predetermined chemical composition for example, a plating bath containing Zn: 5.0 to 50.0%, Si: 0.1 to 18.0%, Mg: 0.0
  • the plating step is important for obtaining a desired chemical composition of the Fe-Al phase corresponding to the interface alloy layer formed at the interface with the steel base material, and is also important for forming an Mg-Al-Zn-Si-based intermetallic compound phase in the plating layer. This will be explained in detail below.
  • the plating process is carried out so that the entry sheet temperature is the same as or approximately the same as the plating bath temperature.
  • the difference between the entry sheet temperature of the steel base material into the plating bath and the plating bath temperature i.e., plating bath temperature - entry sheet temperature
  • the entry sheet temperature is higher than 500°C, or if the plating bath temperature is lower than 650°C
  • the Si content of the Fe-Al phase becomes less than 3.0%.
  • the plating bath temperature is controlled to 650°C or more and the entry sheet temperature is controlled to 500°C or less to ensure that the entry sheet temperature is 150°C or more lower than the plating bath temperature, thereby crystallizing the interface alloy layer (Fe-Al phase) at a low temperature and changing the phase type to one suitable for containing 3.0 mass% or more of Si in the interface alloy layer. It is considered that by containing 3.0 mass% or more of Si in the interface alloy layer, it is possible to trap much of the Si present in the plating layer before hot stamp forming in the interface alloy layer.
  • the Fe-Al-Si phase after hot stamp forming is an intermetallic compound containing a relatively large amount of Si, it is considered that by trapping much of Si in the interface alloy layer before hot stamp forming, it is possible to suppress the formation of the Fe-Al-Si phase in the Fe 2 Al 5 phase during high-temperature heating in hot stamp forming. As a result, it is believed possible to manufacture a hot stamped steel in which the Fe--Al--Si phase is dispersed in the Fe 2 Al 5 phase so as to satisfy ⁇ L i /L 0 ⁇ 0.70.
  • the entry sheet temperature is controlled to be the same as or to the same extent as the plating bath temperature as described above, and even if the entry sheet temperature is different from the plating bath temperature, the entry sheet temperature is generally controlled within a range of ⁇ 20°C relative to the plating bath temperature. The reason for this is that, although the sheet temperature rises to the plating bath temperature when immersed in the plating bath, there is no need to take the manufacturing cost to cool and control the entry sheet temperature to a lower temperature, and the plating bath may solidify due to the entry sheet temperature being lower than the plating bath temperature.
  • the corrosion resistance of the plating layer after hot stamp forming can be improved by controlling the plating bath temperature to 650°C or higher and the entry sheet temperature to 500°C or lower, as in this manufacturing method, to ensure that the entry sheet temperature is 150°C or lower than the plating bath temperature.
  • the lower limit of the entry sheet temperature is not particularly limited, but for example, the entry sheet temperature of the steel base material into the plating bath may be 380°C or higher. Conventional wisdom would suggest that controlling the entry sheet temperature to 500°C or less could lead to the plating bath solidifying due to its composition.
  • the plating process is carried out, for example, by hot-dip plating.
  • Other conditions of the plating process may be appropriately set in consideration of the thickness and adhesion amount of the plating layer.
  • a cold-rolled steel sheet is immersed in a plating bath, then pulled out, and immediately sprayed with N2 gas or air by a gas wiping method, and then cooled, so that the adhesion amount of the plating layer can be adjusted to a predetermined range, for example, within the range of 20 to 200 g/ m2 per side.
  • the plated steel sheet is primarily cooled to 480°C at an average cooling rate of 20°C/s or more, and then secondary cooled from 480°C to 300°C at an average cooling rate of 10°C/s or less.
  • the Mg 2 Si phase is generally likely to crystallize.
  • the plated steel sheet is rapidly cooled to 480°C at an average cooling rate of 20°C/s or more, so that the composition of the liquid phase can be made suitable for the crystallization of the Mg- Al -Zn-Si intermetallic compound phase while suppressing the crystallization of the Mg 2 Si phase.
  • the steel sheet is slowly cooled from 480°C to 300°C at an average cooling rate of 10°C/s or less, whereby the Mg-Al-Zn-Si intermetallic compound phase can be stably and slowly crystallized, and it is possible to form a plating layer containing 0.010% or more of the Mg-Al-Zn-Si intermetallic compound phase with an Al content of 10% or more by area ratio in the plating layer.
  • the Mg-Al-Zn-Si intermetallic compound phase with an Al content of 10% or more by mass has a relatively low melting point and is easily oxidized.
  • the Mg-Al-Zn-Si intermetallic compound phase can be dissolved during high-temperature heating in hot stamp forming, and the oxide film formed on the surface of the formed body during hot stamp forming can be appropriately modified by the dissolved Mg.
  • the Mg content in the surface oxide of the obtained hot stamped body becomes 0.05 atomic % or more, making it possible to improve the chemical conversion treatability of the hot stamped body.
  • the liquid phase composition becomes suitable for the crystallization of the ⁇ -(Al, Mg, Zn) phase, i.e., Mg is dissolved in the ⁇ -Al phase, and the desired amount of Mg-Al-Zn-Si intermetallic compound phase cannot be crystallized.
  • Mg the oxide film formed on the surface of the formed body during high-temperature heating in hot stamp forming
  • the Mg content in the surface oxide becomes less than 0.05 atomic %, and the desired chemical conversion treatability cannot be obtained.
  • the upper limit of the average cooling rate for the primary cooling is not particularly limited, but may be, for example, 50°C/s or less.
  • the lower limit of the secondary cooling is not particularly limited, but may be, for example, 3°C/s or more.
  • the obtained plated steel sheet is hot stamped in a hot stamp forming process to produce a hot stamped body including a desired plated layer.
  • a hot stamp forming process it is preferable to load the plated steel sheet into a furnace at 800 to 1000°C, and hold the plated steel sheet in the furnace for 5 to 50 seconds after the temperature of the plated steel sheet reaches a predetermined temperature, for example, 900°C. If the holding time is 50 seconds or more, the alloying of the plated steel layer progresses too much, and it may become impossible to form an Fe-Al phase having a relatively low Fe content.
  • the heating atmosphere is not particularly limited, and may be under normal conditions, for example, in air, a gas combustion atmosphere with a controlled ratio of air to fuel, or a nitrogen atmosphere, and the dew point may be controlled in these gases.
  • Examples of the heating method include electric heating, high-frequency heating, and induction heating.
  • the coating weight of the coating layer is 20 g/m 2 or more per side
  • the coating layer is mainly composed of an Fe 2 Al 5 phase, an Fe-Al phase formed on the Fe 2 Al 5 phase and effective for improving red rust resistance, and a surface oxide film modified with Mg, and further, the Fe-Al-Si phase in the Fe 2 Al 5 phase is dispersed so as to satisfy ⁇ L i /L 0 ⁇ 0.70.
  • hot stamped bodies according to embodiments of the present invention were manufactured under various conditions, and the properties of the manufactured hot stamped bodies were investigated.
  • molten steel was cast by continuous casting to form a slab having a chemical composition by mass of C: 0.20%, Si: 0.012%, Mn: 1.30%, Al: 0.030%, P: 0.005%, S: 0.0020%, and N: 0.0030%, with the balance being Fe and impurities.
  • the slab was once cooled, then reheated to 1200°C and hot rolled, and then coiled at a temperature of 600°C or less.
  • the hot rolling was performed by rough rolling and finish rolling, with the finishing temperature of the finish rolling being 900-1050°C and the reduction ratio of the finish rolling being 30%.
  • the obtained hot-rolled steel sheet was pickled and then cold rolled at a reduction ratio of 50% to obtain a cold-rolled steel sheet having a thickness of 1.6 mm.
  • the obtained cold-rolled steel sheet was subjected to an annealing process under the conditions shown in Table 1 in a mixed gas atmosphere of 4% hydrogen and the balance of nitrogen in a furnace with an oxygen concentration of 20 ppm or less, and then cooled at an average cooling rate of 10°C/s or more to produce a steel base material.
  • the produced steel base material was cut into 100 mm x 200 mm, and the steel base material was plated using a batch-type hot-dip plating test device manufactured by our company. More specifically, the produced steel base material was first introduced into a plating bath having various chemical compositions and plating bath temperatures shown in Table 1 at the entry sheet temperature shown in Table 1 and immersed for about 3 seconds, then pulled up at a pulling speed of 20 to 200 mm/s, and the coating weight of the plating layer was adjusted to the value shown in Table 1 by N2 gas wiping.
  • the steel base material with the plating layer attached was primarily cooled to 480°C at the average cooling rate shown in Table 1 using nitrogen gas as a cooling gas, and then secondarily cooled from 480°C to 300°C at the average cooling rate shown in Table 1, thereby obtaining a plated steel sheet with a plating layer formed on both sides of the steel base material.
  • the sheet temperature was measured using a thermocouple spot-welded to the center of the steel base material.
  • the chemical composition of the plating layer after hot stamp forming was determined as follows. First, the plated steel sheet was heated by electrical heating, and after the temperature of the plated steel sheet reached 900°C, it was held for 10 seconds. Next, the plated steel sheet was removed from the furnace, and the plated steel sheet was sandwiched between flat plate dies at about room temperature and quenched to obtain a hot stamped body having a plating layer including, from the steel base metal side, an Fe 2 Al 5 phase, an Fe-Al phase having an Fe content of 20 to 40 mass%, and a surface oxide film.
  • the plated layer of the sample cut into 30 mm x 30 mm of the hot stamped body after heating and quenching was dissolved in an acidic aqueous solution at room temperature containing 10% hydrochloric acid and 0.04% IBIT 710K (manufactured by Asahi Chemical Industry Co., Ltd.), and the obtained acid solution was measured by ICP emission spectroscopy to determine the chemical composition of the plating layer.
  • the mass of the sample before and after the pickling and peeling was measured, and the adhesion amount of the plating layer was determined from the change in mass. The results are shown in Table 1.
  • the Fe2Al5 phase, the Fe-Al phase having an Fe content of 20 to 40 mass%, the Fe-Al-Si phase having an Si content of 5 to 20 mass% and an equivalent circle diameter of 2 ⁇ m or more, and the surface oxide film were identified by the above-mentioned method, and the Mg content of the surface oxide film was determined by the above-mentioned method. Furthermore, the value of ⁇ L i /L 0 was determined by the above-mentioned method.
  • the Fe2Al5 phase, the Fe-Al phase having an Fe content of 20 to 40 mass%, and the surface oxide film were present in this order from the side of the steel base material.
  • the red rust resistance after hot stamp forming was evaluated as follows. First, the plated steel sheet was heated by electrical heating, and after the temperature of the plated steel sheet reached 900°C, it was held for 10 seconds. Next, the plated steel sheet was removed from the furnace, and the plated steel sheet was sandwiched between flat molds at about room temperature and quenched. A sample of the hot stamp formed body after heating and quenching, 50 mm x 100 mm, was subjected to Zn phosphate treatment (SD5350 system: Nippon Paint Industrial Coating Co., Ltd. standard), and then electrocoating (PN110 Powernics Gray: Nippon Paint Industrial Coating Co., Ltd.
  • the chemical conversion treatability was evaluated as follows. First, the plated steel sheet was heated by electrical heating, and after the temperature of the plated steel sheet reached 900°C, it was held for 10 seconds. Next, the plated steel sheet was removed from the furnace, and the plated steel sheet was sandwiched between flat molds at about room temperature and quenched. A sample of 50 mm x 100 mm of the hot stamped body after heating and quenching was subjected to Zn phosphate treatment (SD5350 system: standard manufactured by Nippon Paint Industrial Coating Co., Ltd.) to form a chemical conversion coating. Next, the P intensity was measured by fluorescent X-ray analysis, and the calibration curve was used to convert it into the adhesion amount of the chemical conversion coating.
  • Zn phosphate treatment SD5350 system: standard manufactured by Nippon Paint Industrial Coating Co., Ltd.
  • the chemical conversion treatability of the hot stamped body was evaluated according to the following evaluation criteria according to the adhesion amount of the chemical conversion coating.
  • AA Adhesion amount 0.9 g/ m2 or more
  • A Adhesion amount 0.1 to less than 0.9 g/ m2
  • B Adhesion amount less than 0.1 g/ m2
  • the coating blister was evaluated as follows. First, a sample of 50 mm x 100 mm of the hot stamped body after heating and quenching in the same manner as in the case of red rust resistance was subjected to Zn phosphate treatment (SD5350 system: Nippon Paint Industrial Coating Co., Ltd. standard), then electrocoating (PN110 Powernics Gray: Nippon Paint Industrial Coating Co., Ltd. standard) was performed at 20 ⁇ m, and baking treatment was performed at a temperature of 150 ° C and 20 minutes. Next, a cut reaching the base steel (steel base material) was introduced in the center of the sample.
  • Zn phosphate treatment SD5350 system: Nippon Paint Industrial Coating Co., Ltd. standard
  • electrocoating PN110 Powernics Gray: Nippon Paint Industrial Coating Co., Ltd. standard
  • baking treatment was performed at a temperature of 150 ° C and 20 minutes.
  • a cut reaching the base steel was introduced in the center of the sample.
  • the hot stamped body was evaluated as having an Al-containing plating layer with improved corrosion resistance even after hot stamping. The results are shown in Table 1.
  • Comparative Example 32 it is considered that the desired Si content was not obtained in the interface alloy layer in the coating layer before hot stamp forming because the entry sheet temperature in the coating process was high. As a result, the formation of the Fe-Al-Si phase in the Fe 2 Al 5 phase in the coating layer after hot stamp forming became significant, the value of ⁇ L i /L 0 became large, and the corrosion resistance after hot stamp forming deteriorated. In Comparative Example 33, it is considered that the average cooling rate in the primary cooling from after coating to 480°C was slow, so that a large amount of Mg 2 Si phase was formed in the coating layer before hot stamp forming, and the Mg-Al-Zn-Si intermetallic compound phase could not be sufficiently formed.
  • Comparative Example 36 since the Si content in the plating layer was high, the formation of the Fe-Al-Si phase became significant, the value of ⁇ L i /L 0 became large, and the corrosion resistance after hot stamp forming was reduced.
  • Comparative Example 37 since the Si content in the plating layer was low, the adhesion of the plating layer was reduced, and the corrosion resistance after hot stamp forming was reduced.
  • Comparative Example 38 since the Mg content in the plating layer was low, Mg could not be sufficiently introduced into the surface oxide after hot stamp forming, and the chemical conversion treatability was reduced.
  • Comparative Example 39 since the adhesion amount of the plating layer was insufficient, the corrosion resistance after hot stamp forming was reduced.
  • Comparative Example 40 the Fe content in the plating layer was high due to excessive alloying, and it was not possible to form an Fe-Al phase having an Fe content of 20 to 40 mass%. As a result, the red rust resistance after hot stamp forming was reduced.
  • Comparative Example 41 since the plating bath temperature was low, the plating bath solidified when the steel base material was immersed in the plating bath, and the plating layer could not be properly formed. For this reason, the subsequent production was stopped, and analysis and performance evaluation were not performed.
  • the chemical composition of the entire plating layer was controlled within a prescribed range, the coating weight of the plating layer was set to 20 g/ m2 or more per side, the plating layer was composed mainly of an Fe2Al5 phase, an Fe-Al phase, and a surface oxide film modified with Mg, and the Fe-Al-Si phase in the Fe2Al5 phase was dispersed so as to satisfy ⁇ L i /L 0 ⁇ 0.70.
  • the corrosion resistance of the hot stamped steel was significantly improved by a combination of the corrosion progression inhibition effect obtained by dispersing and forming an Fe-Al-Si phase in the Fe2Al5 phase, the effect of improving red rust resistance due to the formation of the Fe-Al phase, and the effect of improving chemical conversion treatability due to the modification of the surface oxide film with Mg.
  • the cross sections of the plated layers were measured for element concentration by EPMA, and the Si content in the interface alloy layer was higher than that in Comparative Example 32, being 3.0 mass% or more in all the Examples.
  • the element distribution images of the mapping images obtained by EPMA were measured, and it was found that the Mg-Al-Zn-Si-based intermetallic compound phase having an Al content of 10 mass% or more was contained in the plated layer in an amount significantly exceeding 0.010% in terms of area ratio.
  • the Mg-Al-Zn-Si-based intermetallic compound phase was not contained in the plated layers before hot stamp forming.

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Abstract

The present invention provides a hot-stamp molded body comprising a steel base material, and a plating layer disposed on the surface of the steel base material, the hot-stamp molded bod being characterized in that: the plating layer has a predetermined chemical composition; the plating layer includes, in order from the steel base material side, an Fe2Al5 phase, an Fe-Al phase having an Fe content of 20-40 mass%, and a surface oxide film; in a cross-section of the plating layer, a projection length Li of an Fe-Al-Si phase in which the Si content in the Fe2Al5 phase is 5-20 mass% and an equivalent circle diameter is 2 μm or more, and a length L0 of the surface of the steel base material satisfy ΣLi/L0≤0.70; the Mg content in the surface oxide film is 0.05 atom% or more; and the adhesion amount of the plating layer is 20 g/m2 or more per surface.

Description

ホットスタンプ成形体Hot stamped compact

 本発明は、ホットスタンプ成形体に関する。 The present invention relates to a hot stamped body.

 近年、自動車業界では、燃費向上の観点から車体の軽量化が求められている。車体の軽量化と衝突安全性を両立するためには、骨格部品等において使用する鋼板の高強度化が有効な方法の一つであり、このような背景から高強度鋼板の開発が進められている。 In recent years, the automotive industry has been seeking to reduce the weight of vehicle bodies in order to improve fuel efficiency. In order to achieve both a lighter vehicle body and crashworthiness, one effective method is to increase the strength of the steel plates used in structural components, etc., and against this background, the development of high-strength steel plates is underway.

 高強度鋼板のような成形が困難な材料をプレス成形する技術としてホットスタンプ(熱間プレス)が知られている。ホットスタンプは、成形に供される材料を加熱してから成形する熱間成形技術である。この技術では、材料を加熱してから成形するため、成形時には鋼材が軟質で良好な成形性を有する。したがって、高強度の鋼材であっても複雑な形状に精度よく成形することが可能であり、また、プレス金型によって成形と同時に焼き入れを行うため、成形後の鋼材は十分な強度を有することが知られている。 Hot stamping is known as a technique for press-forming difficult-to-form materials such as high-strength steel plates. Hot stamping is a hot forming technique in which the material to be formed is heated and then shaped. With this technique, the material is heated before being shaped, so the steel is soft and has good formability when formed. Therefore, even high-strength steel can be precisely formed into complex shapes, and because the material is quenched at the same time as it is formed using a press die, the steel is known to have sufficient strength after forming.

 これに関連して、Al含有めっきを施したホットスタンプ成形体や当該ホットスタンプ成形体用のめっき鋼板についても様々な検討がされている。 In relation to this, various studies are being conducted on hot stamped bodies with Al-containing plating and plated steel sheets for such hot stamped bodies.

 例えば、特許文献1では、2.0~24.0重量%の亜鉛、7.1~12.0重量%のケイ素、任意の1.1~8.0重量%のマグネシウム、及び任意にPb、Ni、Zr又はHfから選択される追加の元素を含み、各追加の元素の重量含有率が0.3重量%より低く、残部がアルミニウム並びに任意の不可避的不純物及び残留元素であり、ここで、Al/Zn比が2.9を超える金属コーティングで被覆された鋼板が記載されている。また、特許文献1では、Al/Zn比が2.9を超える金属コーティングは、高い犠牲保護を有すると教示されている。 For example, Patent Document 1 describes a steel sheet coated with a metal coating having an Al/Zn ratio of greater than 2.9, comprising 2.0-24.0 wt. % zinc, 7.1-12.0 wt. % silicon, optional 1.1-8.0 wt. % magnesium, and optional additional elements selected from Pb, Ni, Zr, or Hf, with the weight content of each additional element being less than 0.3 wt. %, the balance being aluminum and optional unavoidable impurities and residual elements. Patent Document 1 also teaches that metal coatings having an Al/Zn ratio of greater than 2.9 have high sacrificial protection.

 特許文献2では、素地鋼板、及び前記素地鋼板上に形成されたアルミニウム合金めっき層を含み、前記アルミニウム合金めっき層は、重量%で、Zn:21~35%、Si:1~6.9%、Fe:2~12%、残部Al及びその他の不可避不純物を含むアルミニウム合金めっき鋼板が記載されている。また、特許文献2では、上記アルミニウム合金めっき層のAl/(Zn+Si)を1.3~2.6に制御することで溶接性及び耐食性を確保することができると教示されている。 Patent Document 2 describes an aluminum alloy plated steel sheet that includes a base steel sheet and an aluminum alloy plated layer formed on the base steel sheet, the aluminum alloy plated layer containing, by weight, 21-35% Zn, 1-6.9% Si, 2-12% Fe, the balance being Al and other unavoidable impurities. Patent Document 2 also teaches that weldability and corrosion resistance can be ensured by controlling the Al/(Zn+Si) of the aluminum alloy plated layer to 1.3-2.6.

特表2018-528324号公報Special table 2018-528324 publication 特表2022-550142号公報Special Publication No. 2022-550142

 例えば、特許文献1及び2に記載されるようなめっき鋼板、より具体的にはめっき層中の成分としてAlを比較的多く含有するめっき鋼板をホットスタンプ成形において使用すると、当該ホットスタンプ成形における加熱の際にめっき層と地鉄(母材鋼板)が合金化することで耐食性が低下する場合がある。 For example, when plated steel sheets as described in Patent Documents 1 and 2, more specifically plated steel sheets containing a relatively large amount of Al as a component in the plated layer, are used in hot stamp forming, the plated layer and the base steel (base steel sheet) may be alloyed during heating in the hot stamp forming, resulting in a decrease in corrosion resistance.

 そこで、本発明は、ホットスタンプ成形後においても、改善された耐食性を有するAl含有めっき層を備えたホットスタンプ成形体を提供することを目的とする。 The present invention aims to provide a hot stamped body having an Al-containing plating layer that has improved corrosion resistance even after hot stamping.

 本発明者らは、上記目的を達成するために、特にめっき層の化学組成及び組織に着目して検討を行った。その結果、本発明者らは、Al-Zn-Mg-Si系めっきからなるめっき層を所定量以上の付着量において形成するとともに、ホットスタンプ成形後に形成されるめっき層を主としてFe2Al5相と、当該Fe2Al5相上に形成されかつ比較的低いFe含有量を有するFe-Al相と、Mgで改質された表面酸化膜とによって構成し、さらにFe2Al5相の形態を適切に制御することで、ホットスタンプ成形体において優れた耐食性を達成することができることを見出し、本発明を完成させた。 In order to achieve the above object, the present inventors have conducted research, focusing particularly on the chemical composition and structure of the coating layer. As a result, the present inventors have found that excellent corrosion resistance can be achieved in a hot stamped body by forming a coating layer made of an Al-Zn- Mg -Si system coating in a coating weight of at least a predetermined amount, forming a coating layer after hot stamping mainly of an Fe2Al5 phase , an Fe-Al phase formed on the Fe2Al5 phase and having a relatively low Fe content, and a surface oxide film modified with Mg, and further appropriately controlling the morphology of the Fe2Al5 phase, thereby completing the present invention.

 上記目的を達成し得た本発明は下記のとおりである。
 (1)鋼母材と、前記鋼母材の表面に配置されためっき層とを備え、
 前記めっき層の化学組成が、質量%で、
 Zn:2.5~40.0%、
 Si:0.05~15.0%、
 Fe:25.0~40.0%、
 Mg:0.005~3.000%、
 Ni:0~0.500%、
 Ca:0~3.000%、
 Sb:0~0.500%、
 Pb:0~0.500%、
 Cu:0~1.000%、
 Sn:0~1.000%、
 Ti:0~1.000%、
 Cr:0~1.000%、
 Nb:0~1.000%、
 Zr:0~1.000%、
 Mn:0~1.000%、
 Mo:0~1.000%、
 Ag:0~1.000%、
 Li:0~1.000%、
 La:0~0.500%、
 Ce:0~0.500%、
 B :0~0.500%、
 Y :0~0.500%、
 Sr:0~0.500%、
 In:0~0.500%、
 Co:0~0.500%、
 Bi:0~0.500%、
 P :0~0.500%、
 W :0~0.500%、並びに
 残部:Al及び不純物であり、かつ、
 Ni、Ca、Sb、Pb、Cu、Sn、Ti、Cr、Nb、Zr、Mn、Mo、Ag、Li、La、Ce、B、Y、Sr、In、Co、Bi、P、及びWの合計含有量が5.000%以下であり、
 前記めっき層が、前記鋼母材の側から順に、Fe2Al5相と、20~40質量%のFe含有量を有するFe-Al相と、表面酸化膜とを含み、
 前記めっき層の断面において、前記Fe2Al5相中のSi含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相の投影長さLiと、前記鋼母材の表面の長さL0がΣLi/L0≦0.70を満たし、
 前記表面酸化膜中のMg含有量が0.05原子%以上であり、
 前記めっき層の付着量が片面当たり20g/m2以上であることを特徴とする、ホットスタンプ成形体。
 (2)前記めっき層の化学組成が、質量%で、
 Zn:5.0~35.0%、及び
 Si:0.25~6.0%を含有し、
 前記表面酸化膜中のMg含有量が0.30原子%以上であることを特徴とする、上記(1)に記載のホットスタンプ成形体。
 (3)ΣLi/L0≦0.50であることを特徴とする、上記(1)又は(2)に記載のホットスタンプ成形体。
The present invention, which has achieved the above object, is as follows.
(1) A steel plate having a plating layer disposed on a surface of the steel plate,
The chemical composition of the plating layer is, in mass%,
Zn: 2.5-40.0%,
Si: 0.05-15.0%,
Fe: 25.0-40.0%,
Mg: 0.005-3.000%,
Ni: 0 to 0.500%,
Ca: 0-3.000%,
Sb: 0 to 0.500%,
Pb: 0 to 0.500%,
Cu: 0 to 1.000%,
Sn: 0-1.000%,
Ti: 0 to 1.000%,
Cr: 0-1.000%,
Nb: 0 to 1.000%,
Zr: 0 to 1.000%,
Mn: 0 to 1.000%,
Mo: 0-1.000%,
Ag: 0-1.000%,
Li: 0 to 1.000%,
La: 0 to 0.500%,
Ce: 0-0.500%,
B: 0 to 0.500%,
Y: 0 to 0.500%,
Sr: 0-0.500%,
In: 0 to 0.500%,
Co: 0 to 0.500%,
Bi: 0-0.500%,
P: 0 to 0.500%,
W: 0 to 0.500%, and the balance: Al and impurities,
The total content of Ni, Ca, Sb, Pb, Cu, Sn, Ti, Cr, Nb, Zr, Mn, Mo, Ag, Li, La, Ce, B, Y, Sr, In, Co, Bi, P, and W is 5.000% or less;
the plating layer includes, in order from the steel base material side, an Fe2Al5 phase, an Fe-Al phase having an Fe content of 20 to 40 mass %, and a surface oxide film;
In a cross section of the coating layer, a projected length L i of an Fe-Al-Si phase having a Si content of 5 to 20 mass % in the Fe 2 Al 5 phase and an equivalent circle diameter of 2 μm or more and a length L 0 of the surface of the steel base material satisfy ΣL i /L 0 ≦0.70,
The Mg content in the surface oxide film is 0.05 atomic % or more,
1. A hot stamped product, characterized in that the coating weight of the plating layer is 20 g/m2 or more per side.
(2) The chemical composition of the plating layer is, in mass%,
Contains Zn: 5.0 to 35.0% and Si: 0.25 to 6.0%;
The hot stamped steel according to (1) above, characterized in that the Mg content in the surface oxide film is 0.30 atomic % or more.
(3) The hot stamped steel according to (1) or (2) above, characterized in that ΣL i /L 0 ≦0.50.

 本発明によれば、ホットスタンプ成形後においても、改善された耐食性を有するAl含有めっき層を備えたホットスタンプ成形体を提供することができる。 The present invention makes it possible to provide a hot stamped body having an Al-containing plating layer that has improved corrosion resistance even after hot stamping.

本発明の実施形態に係るホットスタンプ成形体における表面部分の断面概略図の一例であり、Fe-Al-Si相の投影長さLi及び鋼母材の表面の長さL0を示すものである。FIG. 1 is an example of a schematic cross-sectional view of a surface portion of a hot stamped steel according to an embodiment of the present invention, showing the projected length L i of an Fe—Al—Si phase and the length L 0 of the surface of a steel base material.

<ホットスタンプ成形体>
 本発明の実施形態に係るホットスタンプ成形体は、鋼母材と、前記鋼母材の表面に配置されためっき層とを備え、
 前記めっき層の化学組成が、質量%で、
 Zn:2.5~40.0%、
 Si:0.05~15.0%、
 Fe:25.0~40.0%、
 Mg:0.005~3.000%、
 Ni:0~0.500%、
 Ca:0~3.000%、
 Sb:0~0.500%、
 Pb:0~0.500%、
 Cu:0~1.000%、
 Sn:0~1.000%、
 Ti:0~1.000%、
 Cr:0~1.000%、
 Nb:0~1.000%、
 Zr:0~1.000%、
 Mn:0~1.000%、
 Mo:0~1.000%、
 Ag:0~1.000%、
 Li:0~1.000%、
 La:0~0.500%、
 Ce:0~0.500%、
 B :0~0.500%、
 Y :0~0.500%、
 Sr:0~0.500%、
 In:0~0.500%、
 Co:0~0.500%、
 Bi:0~0.500%、
 P :0~0.500%、
 W :0~0.500%、並びに
 残部:Al及び不純物であり、かつ、
 Ni、Ca、Sb、Pb、Cu、Sn、Ti、Cr、Nb、Zr、Mn、Mo、Ag、Li、La、Ce、B、Y、Sr、In、Co、Bi、P、及びWの合計含有量が5.000%以下であり、
 前記めっき層が、前記鋼母材の側から順に、Fe2Al5相と、20~40質量%のFe含有量を有するFe-Al相と、表面酸化膜とを含み、
 前記めっき層の断面において、前記Fe2Al5相中のSi含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相の投影長さLiと、前記鋼母材の表面の長さL0がΣLi/L0≦0.70を満たし、
 前記表面酸化膜中のMg含有量が0.05原子%以上であり、
 前記めっき層の付着量が片面当たり20g/m2以上であることを特徴としている。
<Hot stamped body>
A hot stamped steel according to an embodiment of the present invention comprises a steel base material and a plating layer disposed on a surface of the steel base material,
The chemical composition of the plating layer is, in mass%,
Zn: 2.5-40.0%,
Si: 0.05-15.0%,
Fe: 25.0-40.0%,
Mg: 0.005-3.000%,
Ni: 0 to 0.500%,
Ca: 0-3.000%,
Sb: 0 to 0.500%,
Pb: 0 to 0.500%,
Cu: 0 to 1.000%,
Sn: 0-1.000%,
Ti: 0 to 1.000%,
Cr: 0-1.000%,
Nb: 0 to 1.000%,
Zr: 0 to 1.000%,
Mn: 0 to 1.000%,
Mo: 0-1.000%,
Ag: 0-1.000%,
Li: 0 to 1.000%,
La: 0 to 0.500%,
Ce: 0-0.500%,
B: 0 to 0.500%,
Y: 0 to 0.500%,
Sr: 0-0.500%,
In: 0 to 0.500%,
Co: 0 to 0.500%,
Bi: 0-0.500%,
P: 0 to 0.500%,
W: 0 to 0.500%, and the balance: Al and impurities,
The total content of Ni, Ca, Sb, Pb, Cu, Sn, Ti, Cr, Nb, Zr, Mn, Mo, Ag, Li, La, Ce, B, Y, Sr, In, Co, Bi, P, and W is 5.000% or less;
the plating layer includes, in order from the steel base material side, an Fe2Al5 phase, an Fe-Al phase having an Fe content of 20 to 40 mass %, and a surface oxide film;
In a cross section of the coating layer, a projected length L i of an Fe-Al-Si phase having a Si content of 5 to 20 mass % in the Fe 2 Al 5 phase and an equivalent circle diameter of 2 μm or more and a length L 0 of the surface of the steel base material satisfy ΣL i /L 0 ≦0.70,
The Mg content in the surface oxide film is 0.05 atomic % or more,
The plating layer is characterized in that the coating weight per side is 20 g/ m2 or more.

 先に述べたとおり、めっき層中の成分としてAlを比較的多く含有するめっき鋼板をホットスタンプ成形において使用すると、当該ホットスタンプ成形における加熱の際にめっき層と地鉄(母材鋼板)が合金化することで耐食性が低下する場合がある。より詳しく説明すると、例えば、従来のAl-Si系めっきからなるめっき層を備えためっき鋼板をホットスタンプ成形した場合には、ホットスタンプ成形における高温加熱時(例えば約900℃又はそれよりも高い温度における加熱時)にめっき層と母材鋼板が合金化して、ホットスタンプ成形後に主としてFe2Al5相を含むめっき層が形成される。しかしながら、めっき層中にはFe2Al5相以外にも、Siを比較的多く含むFe-Al系金属間化合物、特にSiを5質量%以上含むFe-Al-Si相も比較的多く形成される場合がある。このような場合には、Fe2Al5相と当該Fe-Al-Si相との間で異種金属接触腐食(ガルバニック腐食)が生じることがあり、ホットスタンプ成形体の耐食性が低下することとなる。 As mentioned above, when a plated steel sheet containing a relatively large amount of Al as a component in the plated layer is used in hot stamp forming, the plated steel sheet and the base steel (base steel sheet) are alloyed during heating in the hot stamp forming, which may reduce the corrosion resistance. To explain in more detail, for example, when a plated steel sheet having a plated layer made of a conventional Al-Si-based plating is hot stamp formed, the plated steel sheet and the base steel sheet are alloyed during high-temperature heating in the hot stamp forming (for example, heating at about 900°C or higher), and a plated steel sheet containing mainly the Fe 2 Al 5 phase is formed after hot stamp forming. However, in addition to the Fe 2 Al 5 phase, a relatively large amount of Fe-Al-based intermetallic compounds containing relatively large amounts of Si, particularly Fe-Al-Si phases containing 5 mass% or more of Si, may also be formed in the plated steel sheet. In such a case, bimetallic corrosion (galvanic corrosion) may occur between the Fe 2 Al 5 phase and the Fe-Al-Si phase, which may reduce the corrosion resistance of the hot stamped body.

 そこで、本発明者らは、ホットスタンプ成形後においても優れた耐食性を有するAl含有めっき層を備えたホットスタンプ成形体を提供すべく、特にホットスタンプ成形前のAl-Si系めっきからなるめっき層の化学組成及び形態に着目して検討を行った。その結果、本発明者らは、Al-Si系めっきにさらにZn及びMgを加えたAl-Zn-Mg-Si系めっきからなるめっき層を適切に作り込むとともに、ホットスタンプ成形の熱処理条件を適切に選択することで、ホットスタンプ成形後に形成されるめっき層において、Fe2Al5相との間でガルバニック腐食を生じさせ得るFe-Al-Si相の形成を抑制することができ、それによってホットスタンプ成形後の成形体において耐食性を改善することができることを見出した。さらに、本発明者らは、当該Fe2Al5相上に比較的低いFe含有量、より具体的には20~40質量%のFe含有量を有するFe-Al相を形成することで、ホットスタンプ成形体の耐赤さび性を改善することができることを見出した。加えて、本発明者らは、Mgの添加に起因してホットスタンプ成形後のめっき層における表面酸化膜を適切に改質することができ、それによってホットスタンプ成形体の化成処理性を向上させることができることを見出した。 Therefore, the present inventors conducted a study, focusing in particular on the chemical composition and form of the plating layer made of Al-Si-based plating before hot stamping, in order to provide a hot stamped body having an Al-containing plating layer having excellent corrosion resistance even after hot stamping. As a result, the present inventors found that by appropriately preparing a plating layer made of Al-Zn-Mg-Si-based plating in which Zn and Mg are further added to the Al-Si plating and by appropriately selecting the heat treatment conditions for hot stamping, it is possible to suppress the formation of an Fe-Al-Si phase that may cause galvanic corrosion between the Fe 2 Al 5 phase in the plating layer formed after hot stamping, thereby improving the corrosion resistance of the formed body after hot stamping . Furthermore, the present inventors found that the red rust resistance of the hot stamped body can be improved by forming an Fe -Al phase having a relatively low Fe content, more specifically, an Fe content of 20 to 40 mass %, on the Fe 2 Al 5 phase. In addition, the present inventors have found that the addition of Mg makes it possible to appropriately modify the surface oxide film in the plating layer after hot stamp forming, thereby improving the chemical conversion treatability of the hot stamped body.

 より具体的には、まず、本発明者らは、Al-Zn-Mg-Si系めっきからなるめっき層の付着量を片面当たり20g/m2以上とし、さらにホットスタンプ成形の熱処理条件を適切に選択することで、ホットスタンプ成形における高温加熱時にめっき層全体をFe2Al5相まで合金化することなく、鋼母材側のFe2Al5相上に、当該Fe2Al5相よりもFe含有量が低いFe-Al相を形成することができることを見出した。より詳しく説明すると、ホットスタンプ成形における高温加熱時には鋼母材からのFeがめっき層中に拡散してAlと合金化することになるが、めっき層の付着量を比較的多くしつつ、合金化の程度を適度に弱めることで、めっき層の鋼母材側には十分に合金化されたFe2Al5相が形成されるものの、めっき層の表面側にはFe2Al5相よりもFe含有量が低いFe-Al相、すなわち20~40質量%のFe含有量を有するFe-Al相を形成することが可能となる。何ら特定の理論に束縛されることを意図するものではないが、Fe-Al相による耐赤さび性の向上は、当該Fe-Al相がFe2Al5相に比べて合金化の程度が低いという事実に起因しているものと考えられる。 More specifically, the present inventors first found that by setting the coating weight of the coating layer made of Al-Zn-Mg-Si-based coating to 20 g/ m2 or more per side and further appropriately selecting the heat treatment conditions for hot stamp forming, it is possible to form an Fe - Al phase having a lower Fe content than the Fe2Al5 phase on the Fe2Al5 phase on the steel base material side without alloying the entire coating layer to the Fe2Al5 phase during high-temperature heating in hot stamp forming. To explain in more detail, during high-temperature heating in hot stamp forming, Fe from the steel base material diffuses into the coating layer and is alloyed with Al, but by making the coating weight of the coating layer relatively large and appropriately weakening the degree of alloying, it is possible to form an Fe - Al phase having a lower Fe content than the Fe2Al5 phase, i.e., an Fe - Al phase having an Fe content of 20 to 40 mass %, on the surface side of the coating layer, although a sufficiently alloyed Fe2Al5 phase is formed on the steel base material side of the coating layer. Without intending to be bound by any particular theory, it is believed that the improvement in red rust resistance due to the Fe-Al phase is due to the fact that the Fe-Al phase is less alloyed than the Fe2Al5 phase .

 次に、本発明者らは、ホットスタンプ成形体の製造方法に関連して後で詳しく説明されるように、ホットスタンプ成形前の母材鋼板とめっき層の界面に形成される界面合金層に相当するFe-Al相中にSiを所定の量で含有させること、より具体的には界面合金層中にSiを3.0質量%以上含有させることで、ホットスタンプ成形後に形成されるめっき層において、上記Fe2Al5相中で比較的大きなFe-Al-Si相の形成を抑制することができることを見出した。より具体的には、本発明者らは、ホットスタンプ成形後のめっき層において、当該めっき層の鋼母材側に形成されるFe2Al5相中の比較的大きなFe-Al-Si相を分散させて存在させること、すなわちSi含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相の投影長さLiと、鋼母材の表面の長さL0がΣLi/L0≦0.70を満たすように制御することで、ホットスタンプ成形後のめっき層の耐食性を顕著に改善することができることを見出した。 Next, the present inventors have found that, as will be described in detail later in relation to the manufacturing method of a hot stamped body, by containing a predetermined amount of Si in the Fe-Al phase corresponding to the interface alloy layer formed at the interface between the base steel sheet and the coating layer before hot stamping, more specifically, by containing 3.0 mass% or more of Si in the interface alloy layer, it is possible to suppress the formation of a relatively large Fe-Al-Si phase in the Fe 2 Al 5 phase in the coating layer formed after hot stamping. More specifically, the present inventors have found that, in the coating layer after hot stamping, the relatively large Fe-Al-Si phase in the Fe 2 Al 5 phase formed on the steel base metal side of the coating layer is dispersed and present, that is, by controlling the projected length L i of the Fe-Al-Si phase having a Si content of 5 to 20 mass% and a circle equivalent diameter of 2 μm or more and the length L 0 of the surface of the steel base metal to satisfy ΣL i /L 0 ≦0.70, the corrosion resistance of the coating layer after hot stamping can be significantly improved.

 図1は、本発明の実施形態に係るホットスタンプ成形体における表面部分の断面概略図の一例であり、Fe-Al-Si相の投影長さLi及び鋼母材の表面の長さL0を示すものである。図1を参照すると、本発明の実施形態に係るホットスタンプ成形体1は、鋼母材2と、当該鋼母材2の表面に配置されためっき層3とを備え、当該めっき層3は、鋼母材2の側から順に、鋼母材2の上に位置するFe2Al5相4と、当該Fe2Al5相4の上に位置するFe-Al相5、より具体的には20~40質量%のFe含有量を有するFe-Al相5と、表面酸化膜6とを含む。また、図1においては、Fe2Al5相4中に、Si含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相7が存在している。ここで、各Fe-Al-Si相7を鋼母材2の表面に投影した投影長さLiの合計ΣLi(図1では、ΣLi=L1+L2+L3)と、鋼母材2の表面の長さL0がΣLi/L0≦0.70を満たしており、それゆえ比較的大きなFe-Al-Si相7がFe2Al5相4中で分散して存在している。複数のFe-Al-Si相7の投影長さが部分的に重複している場合には、重複部分を含めた全体の投影長さが1つの投影長さとして決定される。仮にFe-Al-Si相7がFe2Al5相4中で層状に存在していると、層状のFe-Al-Si相7とFe2Al5相4との接触部でガルバニック腐食が生じた場合に、接触界面に沿って腐食が進行していくことになると考えられる。その結果として、めっき層3の耐食性が大きく低下することとなる。これに対し、本発明の実施形態に係るホットスタンプ成形体1においては、ΣLi/L0≦0.70を満たすようにFe-Al-Si相7をFe2Al5相4中で分散して存在させることにより、仮に1つ又は複数のFe-Al-Si相7とその周りに存在するFe2Al5相4との接触部でガルバニック腐食が生じたとしても、当該接触部での腐食を起点に他のFe-Al-Si相7へと腐食が進行していくことがなく、それゆえめっき層3の耐食性を顕著に改善することが可能となる。加えて、本発明の実施形態に係るホットスタンプ成形体1においては、めっき層中へのZnの添加に関連してFe2Al5相4及びFe-Al相5中にZnが固溶しており、したがってZnの犠牲防食作用によっても耐食性がさらに改善される。 Fig. 1 is an example of a schematic cross-sectional view of a surface portion of a hot stamped steel according to an embodiment of the present invention, showing the projected length L i of the Fe-Al-Si phase and the length L 0 of the surface of the steel base material. Referring to Fig. 1, a hot stamped steel 1 according to an embodiment of the present invention includes a steel base material 2 and a coating layer 3 disposed on the surface of the steel base material 2, and the coating layer 3 includes, in order from the steel base material 2 side, an Fe 2 Al 5 phase 4 located on the steel base material 2, an Fe-Al phase 5 located on the Fe 2 Al 5 phase 4, more specifically, an Fe-Al phase 5 having an Fe content of 20 to 40 mass%, and a surface oxide film 6. In Fig. 1, an Fe - Al-Si phase 7 having a Si content of 5 to 20 mass% and a circle equivalent diameter of 2 µm or more is present in the Fe 2 Al 5 phase 4. Here, the sum ΣL i of the projected lengths L i of each Fe-Al-Si phase 7 projected onto the surface of the steel base material 2 (in FIG. 1, ΣL i = L 1 + L 2 + L 3 ) and the length L 0 of the surface of the steel base material 2 satisfy ΣL i /L 0 ≦0.70, and therefore the relatively large Fe-Al-Si phase 7 is dispersed and present in the Fe 2 Al 5 phase 4. When the projected lengths of the multiple Fe-Al-Si phases 7 overlap partially, the entire projected length including the overlapping portion is determined as one projected length. If the Fe-Al-Si phase 7 is present in a layered form in the Fe 2 Al 5 phase 4, it is considered that when galvanic corrosion occurs at the contact portion between the layered Fe-Al-Si phase 7 and the Fe 2 Al 5 phase 4, the corrosion will progress along the contact interface. As a result, the corrosion resistance of the plating layer 3 is significantly reduced. In contrast, in the hot stamped steel 1 according to the embodiment of the present invention, the Fe-Al-Si phase 7 is dispersed in the Fe 2 Al 5 phase 4 so as to satisfy ΣL i /L 0 ≦0.70, so that even if galvanic corrosion occurs at a contact portion between one or more Fe-Al-Si phases 7 and the Fe 2 Al 5 phase 4 present therearound, the corrosion will not progress from the corrosion at the contact portion to other Fe-Al-Si phases 7, thereby making it possible to significantly improve the corrosion resistance of the coating layer 3. In addition, in the hot stamped steel 1 according to the embodiment of the present invention, Zn is dissolved in the Fe 2 Al 5 phase 4 and the Fe-Al phase 5 in association with the addition of Zn to the coating layer, and therefore the corrosion resistance is further improved by the sacrificial anticorrosive action of Zn.

 また、図1においては、表面酸化膜6中にMgが0.05原子%以上の量で存在しており、Mgの存在に起因して表面酸化膜を改質することができ、ホットスタンプ成形体の化成処理性を向上させることが可能になるものと考えられる。より詳しく説明すると、一般的に、Mgはめっき層中でMg2Si相などとして存在している。一方で、本発明の実施形態に係るホットスタンプ成形体1のめっき層3はAlを比較的多く含有しているため、その表面がAl含有酸化物等から構成される酸化膜によって覆われている。ここで、Mg2Si相は融点が比較的高いために、ホットスタンプ成形の高温加熱時においても酸化されにくく、それゆえAl含有酸化物等から構成される酸化膜に作用して当該酸化膜を改質することができないものと考えられる。これに対し、本発明者らは、ホットスタンプ成形体の製造方法に関連して後で詳しく説明されるように、めっき後の冷却を適切に制御することで、ホットスタンプ成形前のめっき層中においてMg2Si相と比較して融点が低く、酸化されやすい性質を有するMg-Al-Zn-Si系金属間化合物相、より具体的にはAl含有量が10質量%以上のMg-Al-Zn-Si系金属間化合物相を形成することができ、当該Mg-Al-Zn-Si系金属間化合物相の存在が表面酸化膜の改質に有効であることを見出した。Mg-Al-Zn-Si系金属間化合物相は、上記のとおりMg2Si相と比較して融点が低く、酸化されやすい性質を有する。このため、ホットスタンプ成形の高温加熱時において当該Mg-Al-Zn-Si系金属間化合物相が溶解し、溶解したMgを表面に存在するAl含有酸化物中に0.05原子%以上の量で導入することが可能となる。その結果として、ホットスタンプ成形の際に成形体表面に形成される酸化膜をMgによって適切に改質することができるので、得られるホットスタンプ成形体の化成処理性を向上させることが可能になるものと考えられる。一般に、化成処理性が低下すると、スケと呼ばれる化成処理皮膜が形成していない領域が生じることがあり、このような場合には塗装後の耐食性が低下する。逆に言えば、ホットスタンプ成形体の化成処理性を向上させることで、当該ホットスタンプ成形体における塗装後の耐食性を向上させることが可能となる。 In addition, in Fig. 1, Mg is present in the surface oxide film 6 in an amount of 0.05 atomic % or more, and it is considered that the presence of Mg can modify the surface oxide film, thereby improving the chemical conversion treatability of the hot stamped body. To explain in more detail, Mg is generally present in the plating layer as an Mg2Si phase or the like. On the other hand, since the plating layer 3 of the hot stamped body 1 according to the embodiment of the present invention contains a relatively large amount of Al, its surface is covered with an oxide film composed of Al-containing oxides and the like. Here, since the Mg2Si phase has a relatively high melting point, it is difficult to be oxidized even during high-temperature heating in hot stamping, and therefore it is considered that it cannot act on the oxide film composed of Al-containing oxides and the like to modify the oxide film. In response to this, the present inventors have found that, as will be described in detail later in relation to the manufacturing method of a hot stamped body, by appropriately controlling the cooling after plating, it is possible to form an Mg-Al-Zn-Si intermetallic compound phase having a lower melting point and a tendency to be easily oxidized compared to the Mg 2 Si phase in the plating layer before hot stamp forming, more specifically, an Mg-Al-Zn-Si intermetallic compound phase having an Al content of 10 mass % or more, and that the presence of the Mg-Al-Zn-Si intermetallic compound phase is effective in modifying the surface oxide film. As described above, the Mg-Al-Zn-Si intermetallic compound phase has a lower melting point and a tendency to be easily oxidized compared to the Mg 2 Si phase. Therefore, the Mg-Al-Zn-Si intermetallic compound phase melts during high-temperature heating in hot stamp forming, and the dissolved Mg can be introduced into the Al-containing oxide present on the surface in an amount of 0.05 atomic % or more. As a result, the oxide film formed on the surface of the formed body during hot stamp forming can be appropriately modified by Mg, which is believed to improve the chemical conversion treatability of the resulting hot stamped body. In general, when the chemical conversion treatability is reduced, a region where the chemical conversion coating is not formed, called a "sk", may be generated, and in such a case, the corrosion resistance after painting is reduced. In other words, by improving the chemical conversion treatability of the hot stamped body, it is possible to improve the corrosion resistance of the hot stamped body after painting.

 したがって、本発明の実施形態に係るホットスタンプ成形体によれば、Fe2Al5相4との間でガルバニック腐食を生じさせ得るFe-Al-Si相7の形成を抑制すること、より具体的には比較的大きなFe-Al-Si相7を分散して形成することによって得られる腐食の進行抑制効果と、Fe-Al相5の形成に起因する耐赤さび性向上効果と、Mgによる表面酸化膜の改質に起因する化成処理性向上効果との組み合わせにより、優れた耐食性を達成することが可能となる。とりわけ、めっき層3をFe2Al5相4と、比較的低いFe含有量を有するFe-Al相5と、Mgで改質された表面酸化膜6とによって構成し、さらにFe2Al5相4の形態を上記のように適切に制御することでホットスタンプ成形体1の耐食性を向上させることができるという事実は、今回、本発明者らによって初めて明らかにされたことである。したがって、本発明の実施形態に係るホットスタンプ成形体は、ホットスタンプ成形が比較的多く適用される自動車分野での利用において特に有用である。 Therefore, according to the hot stamped steel according to the embodiment of the present invention, it is possible to achieve excellent corrosion resistance by combining the effect of suppressing the formation of the Fe-Al- Si phase 7 that may cause galvanic corrosion between the Fe 2 Al 5 phase 4, more specifically, the effect of suppressing the progress of corrosion obtained by dispersing and forming a relatively large Fe-Al-Si phase 7, the effect of improving red rust resistance due to the formation of the Fe-Al phase 5, and the effect of improving chemical conversion treatability due to the modification of the surface oxide film by Mg. In particular, the fact that the corrosion resistance of the hot stamped steel 1 can be improved by forming the coating layer 3 from the Fe 2 Al 5 phase 4, the Fe - Al phase 5 having a relatively low Fe content, and the surface oxide film 6 modified by Mg, and further by appropriately controlling the form of the Fe 2 Al 5 phase 4 as described above, was revealed for the first time by the present inventors. Therefore, the hot stamped steel according to the embodiment of the present invention is particularly useful in the automotive field where hot stamping is relatively often used.

 以下、本発明の実施形態に係るホットスタンプ成形体についてより詳しく説明する。以下の説明において、各元素の含有量の単位である「%」は、特に断りがない限り「質量%」を意味するものである。また、本明細書において、数値範囲を示す「~」とは、特に断りがない場合、その前後に記載される数値を下限値及び上限値として含む意味で使用される。 The hot stamped body according to an embodiment of the present invention will be described in more detail below. In the following description, the unit of content of each element, "%", means "mass%" unless otherwise specified. Furthermore, in this specification, "to" indicating a numerical range is used to mean that the numerical values before and after it are included as the lower and upper limits, unless otherwise specified.

[めっき層]
 本発明の実施形態によれば、めっき層は鋼母材の表面に配置され、例えば鋼母材の少なくとも一方、好ましくは両方の表面に配置される。ここで、「鋼母材の表面に配置される」との表現は、めっき層が鋼母材の表面に直接的に配置される場合だけでなく、めっき層が鋼母材の表面に間接的に配置される場合、例えば、鋼母材とめっき層との間に後で説明する固溶体層等を含む場合も包含するものである。めっき層は下記の化学組成を有する。
[Plating layer]
According to an embodiment of the present invention, the plating layer is disposed on the surface of the steel base material, for example, disposed on at least one, preferably both, surfaces of the steel base material. Here, the expression "disposed on the surface of the steel base material" includes not only the case where the plating layer is directly disposed on the surface of the steel base material, but also the case where the plating layer is indirectly disposed on the surface of the steel base material, for example, the case where a solid solution layer, which will be described later, is included between the steel base material and the plating layer. The plating layer has the following chemical composition.

[Zn:2.5~40.0%]
 Znは、犠牲防食作用を有し、めっき層の耐食性を向上させるのに有効な元素である。また、Znは、化成処理の際に処理液と反応し、表面上に化成処理皮膜を形成する作用を有する。これらの効果を十分に得るために、Zn含有量は2.5%以上とする。Zn含有量は3.5%以上、5.0%以上、8.0%以上、10.0%以上、12.0%以上、15.0%以上、18.0%以上、20.0%以上又は22.0%以上であってもよい。一方で、Znを過度に含有すると、ホットスタンプ成形の高温加熱時におけるZnの溶融が顕著となり、溶融したZnが鋼中に侵入して液体金属脆化(LME)割れを引き起こす場合がある。したがって、Zn含有量は40.0%以下とする。Zn含有量は38.0%以下、35.0%以下、32.0%以下、30.0%以下又は28.0%以下であってもよい。
[Zn: 2.5-40.0%]
Zn has a sacrificial anticorrosive effect and is an element effective in improving the corrosion resistance of the plating layer. In addition, Zn reacts with the treatment liquid during chemical conversion treatment to form a chemical conversion coating on the surface. In order to fully obtain these effects, the Zn content is set to 2.5% or more. The Zn content may be 3.5% or more, 5.0% or more, 8.0% or more, 10.0% or more, 12.0% or more, 15.0% or more, 18.0% or more, 20.0% or more, or 22.0% or more. On the other hand, if Zn is excessively contained, the melting of Zn during high-temperature heating in hot stamp forming becomes significant, and the molten Zn may penetrate into the steel and cause liquid metal embrittlement (LME) cracking. Therefore, the Zn content is set to 40.0% or less. The Zn content may be 38.0% or less, 35.0% or less, 32.0% or less, 30.0% or less, or 28.0% or less.

[Si:0.05~15.0%]
 Siは、めっき層の密着性を向上させるのに有効な元素である。このような効果を十分に得るために、Si含有量は0.05%以上とする。Si含有量は0.1%以上、0.2%以上、0.25%以上、0.3%以上、0.5%以上、0.8%以上、1.0%以上、3.0%以上又は5.0%以上であってもよい。一方で、Siを過度に含有すると、Fe2Al5相中のFe-Al-Si相の形成が顕著となり、耐食性が低下する場合がある。したがって、Si含有量は15.0%以下とする。Si含有量は12.0%以下、10.0%以下、8.0%以下又は6.0%以下であってもよい。
[Si: 0.05-15.0%]
Si is an element effective in improving the adhesion of the plating layer. In order to fully obtain such an effect, the Si content is set to 0.05% or more. The Si content may be 0.1% or more, 0.2% or more, 0.25% or more, 0.3% or more, 0.5% or more, 0.8% or more, 1.0% or more, 3.0% or more, or 5.0% or more. On the other hand, if Si is contained excessively, the formation of the Fe-Al-Si phase in the Fe 2 Al 5 phase becomes significant, and the corrosion resistance may decrease. Therefore, the Si content is set to 15.0% or less. The Si content may be 12.0% or less, 10.0% or less, 8.0% or less, or 6.0% or less.

[Fe:25.0~40.0%]
 ホットスタンプ成形時にめっき鋼板を加熱すると、鋼母材からのFeがめっき層中に拡散してAl等と合金化するため、当該めっき層には必然的にFeが含有される。したがって、Fe含有量は25.0%以上であり、例えば26.0%以上、28.0%以上、30.0%以上又は32.0%以上であってもよい。一方で、Fe含有量が高くなりすぎると、めっき層の過度な合金化に起因して耐赤さび性が低下する場合がある。したがって、Fe含有量は40.0%以下とし、例えば38.0%以下、36.0%以下又は34.0%以下であってもよい。
[Fe:25.0-40.0%]
When a plated steel sheet is heated during hot stamp forming, Fe from the steel base material diffuses into the plated layer and is alloyed with Al, etc., so that the plated layer inevitably contains Fe. Therefore, the Fe content is 25.0% or more, and may be, for example, 26.0% or more, 28.0% or more, 30.0% or more, or 32.0% or more. On the other hand, if the Fe content is too high, the red rust resistance may be reduced due to excessive alloying of the plated layer. Therefore, the Fe content is 40.0% or less, and may be, for example, 38.0% or less, 36.0% or less, or 34.0% or less.

[Mg:0.005~3.000%]
 Mgは、めっき層の耐食性、特に化成処理性を向上させるのに有効な元素である。このような効果を十分に得るために、Mg含有量は0.005%以上とする。Mg含有量は0.010%以上、0.020%以上、0.030%以上、0.050%以上、0.080%以上、0.100%以上又は0.300%以上であってもよい。一方で、加工性向上の観点から、Mg含有量は3.000%以下とする。Mg含有量は2.500%以下、2.000%以下、1.500%以下、1.000%以下、0.800%以下、0.600%以下又は0.400%以下であってもよい。
[Mg: 0.005-3.000%]
Mg is an element effective in improving the corrosion resistance, particularly chemical conversion treatability, of the coating layer. In order to fully obtain such an effect, the Mg content is set to 0.005% or more. The Mg content may be 0.010% or more, 0.020% or more, 0.030% or more, 0.050% or more, 0.080% or more, 0.100% or more, or 0.300% or more. On the other hand, from the viewpoint of improving workability, the Mg content is set to 3.000% or less. The Mg content may be 2.500% or less, 2.000% or less, 1.500% or less, 1.000% or less, 0.800% or less, 0.600% or less, or 0.400% or less.

 さらに、めっき層は、任意選択で、Ni:0~0.500%、Ca:0~3.000%、Sb:0~0.500%、Pb:0~0.500%、Cu:0~1.000%、Sn:0~1.000%、Ti:0~1.000%、Cr:0~1.000%、Nb:0~1.000%、Zr:0~1.000%、Mn:0~1.000%、Mo:0~1.000%、Ag:0~1.000%、Li:0~1.000%、La:0~0.500%、Ce:0~0.500%、B:0~0.500%、Y:0~0.500%、Sr:0~0.500%、In:0~0.500%、Co:0~0.500%、Bi:0~0.500%、P:0~0.500%、及びW:0~0.500%の少なくとも1種を含有してもよい。これらの任意選択元素の合計含有量(つまり、これらの元素の含有量の合計)は、5.000%以下である。任意選択元素の合計含有量は、4.500%以下、4.000%以下、3.500%以下、3.000%以下、2.500%以下、2.000%以下、1.500%以下、1.000%以下、0.800%以下、0.500%以下、0.100%以下又は0.050%以下であってもよい。これらの元素の含有は必須でなく、これらの元素の含有量の合計は0%であってもよい。必要に応じて、これらの元素の含有量の合計の下限を0.001%、0.010%、0.050%又は0.080%としてもよい。以下、これらの任意選択元素について詳しく説明する。 Furthermore, the plating layer may optionally contain Ni: 0-0.500%, Ca: 0-3.000%, Sb: 0-0.500%, Pb: 0-0.500%, Cu: 0-1.000%, Sn: 0-1.000%, Ti: 0-1.000%, Cr: 0-1.000%, Nb: 0-1.000%, Zr: 0-1.000%, Mn: 0-1.000%, Mo: 0-1.000 %, Ag: 0-1.000%, Li: 0-1.000%, La: 0-0.500%, Ce: 0-0.500%, B: 0-0.500%, Y: 0-0.500%, Sr: 0-0.500%, In: 0-0.500%, Co: 0-0.500%, Bi: 0-0.500%, P: 0-0.500%, and W: 0-0.500% may be contained. The total content of these optional elements (i.e., the total content of these elements) is 5.000% or less. The total content of the optional elements may be 4.500% or less, 4.000% or less, 3.500% or less, 3.000% or less, 2.500% or less, 2.000% or less, 1.500% or less, 1.000% or less, 0.800% or less, 0.500% or less, 0.100% or less, or 0.050% or less. The inclusion of these elements is not essential, and the total content of these elements may be 0%. If necessary, the lower limit of the total content of these elements may be 0.001%, 0.010%, 0.050%, or 0.080%. These optional elements will be described in detail below.

[Ni:0~0.500%]
 Niは、めっき層の耐食性を向上させるのに有効な元素である。Ni含有量は0%であってもよいが、このような効果を得るためには、Ni含有量は0.001%以上であることが好ましい。Ni含有量は0.003%以上、0.005%以上、0.008%以上、0.010%以上又は0.020%以上であってもよい。上限は特に限定されないが、製造コスト等の観点から、Ni含有量は0.500%以下とし、例えば0.400%以下、0.300%以下、0.100%以下、0.050%以下又は0.030%以下であってもよい。
[Ni: 0-0.500%]
Ni is an element effective for improving the corrosion resistance of the plating layer. The Ni content may be 0%, but in order to obtain such an effect, the Ni content is preferably 0.001% or more. The Ni content may be 0.003% or more, 0.005% or more, 0.008% or more, 0.010% or more, or 0.020% or more. Although there is no particular upper limit, from the viewpoint of manufacturing costs, etc., the Ni content is set to 0.500% or less, and may be, for example, 0.400% or less, 0.300% or less, 0.100% or less, 0.050% or less, or 0.030% or less.

[Ca:0~3.000%]
 Caは、めっき浴の濡れ性を確保するのに有効な元素である。Ca含有量は0%であってもよいが、このような効果を得るためには、Ca含有量は0.001%以上であることが好ましい。Ca含有量は0.003%以上、0.005%以上又は0.010%以上であってもよい。一方で、Caを過度に含有すると、めっき層中に硬い金属間化合物を多量に形成して、めっき層が脆くなり、鋼板との密着性を低下させる場合がある。したがって、Ca含有量は3.000%以下であることが好ましい。Ca含有量は2.000%以下、1.000%以下、0.500%以下、0.300%以下、0.100%以下、0.050%以下又は0.020%以下であってもよい。
[Ca: 0-3.000%]
Ca is an element effective in ensuring wettability of the plating bath. The Ca content may be 0%, but in order to obtain such an effect, the Ca content is preferably 0.001% or more. The Ca content may be 0.003% or more, 0.005% or more, or 0.010% or more. On the other hand, if Ca is contained excessively, a large amount of hard intermetallic compounds may be formed in the plating layer, making the plating layer brittle and reducing the adhesion to the steel sheet. Therefore, the Ca content is preferably 3.000% or less. The Ca content may be 2.000% or less, 1.000% or less, 0.500% or less, 0.300% or less, 0.100% or less, 0.050% or less, or 0.020% or less.

[Sb:0~0.500%、Pb:0~0.500%、Cu:0~1.000%、Sn:0~1.000%、Ti:0~1.000%、Cr:0~1.000%、Nb:0~1.000%、Zr:0~1.000%、Mn:0~1.000%、Mo:0~1.000%、Ag:0~1.000%、Li:0~1.000%、La:0~0.500%、Ce:0~0.500%、B:0~0.500%、Y:0~0.500%、Sr:0~0.500%、In:0~0.500%、Co:0~0.500%、Bi:0~0.500%、P:0~0.500%及びW:0~0.500%]
 Sb、Pb、Cu、Sn、Ti、Cr、Nb、Zr、Mn、Mo、Ag、Li、La、Ce、B、Y、Sr、In、Co、Bi、P及びWは、めっき層中に含まれなくてもよいが、0.0001%以上、0.001%以上又は0.01%以上の量においてめっき層中に存在し得る。これらの元素は、所定の含有量の範囲内であれば、ホットスタンプ成形体としての性能に悪影響は及ぼさない。しかしながら、各元素の含有量が過剰な場合には耐食性を低下させる場合がある。したがって、Sb、Pb、La、Ce、B、Y、Sr、In、Co、Bi、P及びWの含有量は0.500%以下であることが好ましく、例えば0.300%以下、0.100%以下、0.050%以下又は0.020%以下であってもよい。同様に、Cu、Sn、Ti、Cr、Nb、Zr、Mn、Mo、Ag及びLiの含有量は1.000%以下であることが好ましく、例えば0.800%以下、0.500%以下、0.100%以下、0.050%以下又は0.020%以下であってもよい。
[Sb: 0 to 0.500%, Pb: 0 to 0.500%, Cu: 0 to 1.000%, Sn: 0 to 1.000%, Ti: 0 to 1.000%, Cr: 0 ~1.000%, Nb: 0-1.000%, Zr: 0-1.000%, Mn: 0-1.000%, Mo: 0-1.000%, Ag: 0-1.000 %, Li: 0-1.000%, La: 0-0.500%, Ce: 0-0.500%, B: 0-0.500%, Y: 0-0.500%, Sr: 0- 0.500%, In: 0 to 0.500%, Co: 0 to 0.500%, Bi: 0 to 0.500%, P: 0 to 0.500% and W: 0 to 0.500%]
Sb, Pb, Cu, Sn, Ti, Cr, Nb, Zr, Mn, Mo, Ag, Li, La, Ce, B, Y, Sr, In, Co, Bi, P and W may not be contained in the plating layer, but may be present in the plating layer in an amount of 0.0001% or more, 0.001% or more, or 0.01% or more. These elements do not adversely affect the performance of the hot stamped body as long as they are within a predetermined content range. However, if the content of each element is excessive, the corrosion resistance may be reduced. Therefore, the content of Sb, Pb, La, Ce, B, Y, Sr, In, Co, Bi, P and W is preferably 0.500% or less, and may be, for example, 0.300% or less, 0.100% or less, 0.050% or less, or 0.020% or less. Similarly, the contents of Cu, Sn, Ti, Cr, Nb, Zr, Mn, Mo, Ag and Li are preferably 1.000% or less, and may be, for example, 0.800% or less, 0.500% or less, 0.100% or less, 0.050% or less, or 0.020% or less.

 めっき層において、上記の元素以外の残部はAl及び不純物からなる。めっき層における不純物とは、めっき層を製造する際に、原料を始めとして、製造工程の種々の要因によって混入する成分等である。なお、Al含有量を特に規定する必要はないが、10.0~72.45%としてもよい。必要に応じて、Al含有量は、20.0%以上、25.0%以上、30.0%以上、35.0%以上、38.0%以上、40.0%以上又は42.0%以上であってもよく、70.0%以下、65.0%以下、60.0%以下、57.0%以下、54.0%以下、51.0%以下又は48.0%以下であってもよい。 The remainder of the plating layer other than the above elements consists of Al and impurities. Impurities in the plating layer are components that are mixed in due to various factors in the manufacturing process, including raw materials, when the plating layer is manufactured. The Al content does not need to be specified in particular, but may be 10.0 to 72.45%. If necessary, the Al content may be 20.0% or more, 25.0% or more, 30.0% or more, 35.0% or more, 38.0% or more, 40.0% or more, or 42.0% or more, or 70.0% or less, 65.0% or less, 60.0% or less, 57.0% or less, 54.0% or less, 51.0% or less, or 48.0% or less.

[めっき層の化学組成の測定]
 めっき層の化学組成は、酸性水溶液でめっき層のみを溶解し、化学分析することで決定される。すなわち、鋼の溶解を抑制するインヒビターを含有した酸性水溶液、例えば10%の塩酸に0.04%のイビット710K(朝日化学工業製)を加えた室温の酸性水溶液でめっき層を溶解し、得られた酸性水溶液をICP(高周波誘導結合プラズマ発光分光法)分析することで、めっき層の化学組成が得られる。
[Measurement of chemical composition of plating layer]
The chemical composition of the plating layer is determined by dissolving only the plating layer in an acidic aqueous solution and chemically analyzing it. That is, the plating layer is dissolved in an acidic aqueous solution at room temperature containing an inhibitor that inhibits the dissolution of steel, for example, an acidic aqueous solution at room temperature containing 10% hydrochloric acid and 0.04% IBIT 710K (manufactured by Asahi Chemical Industry Co., Ltd.), and the resulting acidic aqueous solution is analyzed by ICP (inductively coupled plasma atomic emission spectroscopy) to obtain the chemical composition of the plating layer.

[Fe2Al5相]
[ΣLi/L0≦0.70]
 本発明の実施形態において、めっき層は鋼母材の側にFe2Al5相を含み、当該Fe2Al5相中のSi含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相の投影長さLiと、鋼母材の表面の長さL0がΣLi/L0≦0.70を満たすように制御される。先に述べたとおり、Si含有量が5~20質量%のFe-Al-Si相は、Fe2Al5相との間でガルバニック腐食を生じさせ得る。とりわけ、当該Fe-Al-Si相が比較的大きく、層状又は層状に近い形態で連続的に存在すると、Fe-Al-Si相とFe2Al5相との接触界面に沿って腐食が進行していくことになり、めっき層の耐食性が大きく低下してしまう。このため、このような腐食の進行を抑制して、めっき層の耐食性を高めるためには、円相当直径が2μm以上のFe-Al-Si相をFe2Al5相中で分散して存在させることが必要となる。そこで、本発明の実施形態においては、図1に示すように、円相当直径が2μm以上の各Fe-Al-Si相を鋼母材の表面に投影した投影長さLiの合計ΣLiと、鋼母材2の表面の長さL0がΣLi/L0≦0.70を満たすように、Fe-Al-Si相をFe2Al5相中で分散して存在させることにより、めっき層の耐食性を向上させている。耐食性向上効果をさらに高める観点からは、ΣLi/L0の値は低いほど好ましく、例えば0.65以下、0.60以下、0.55以下、0.50以下、0.45以下、又は0.40以下であってもよい。
[ Fe2Al5 phase ]
[ΣL i /L 0 ≦0.70]
In an embodiment of the present invention, the coating layer contains an Fe2Al5 phase on the steel base metal side, and the projected length L i of the Fe - Al- Si phase having a Si content of 5-20 mass% and a circle equivalent diameter of 2 μm or more in the Fe2Al5 phase and the length L 0 of the surface of the steel base metal are controlled to satisfy ΣL i /L 0 ≦0.70. As described above, the Fe-Al-Si phase having a Si content of 5-20 mass% may cause galvanic corrosion between the Fe2Al5 phase and the Fe2Al5 phase. In particular, if the Fe-Al-Si phase is relatively large and exists continuously in a layered or nearly layered form, corrosion will progress along the contact interface between the Fe-Al- Si phase and the Fe2Al5 phase, and the corrosion resistance of the coating layer will be significantly reduced. Therefore, in order to suppress the progress of such corrosion and improve the corrosion resistance of the coating layer, it is necessary to have the Fe-Al-Si phase having a circle equivalent diameter of 2 μm or more dispersed in the Fe 2 Al 5 phase. Therefore, in the embodiment of the present invention, as shown in FIG. 1, the Fe-Al-Si phase is dispersed in the Fe 2 Al 5 phase so that the sum ΣL i of the projected lengths L i of each Fe-Al-Si phase having a circle equivalent diameter of 2 μm or more projected onto the surface of the steel base material and the length L 0 of the surface of the steel base material 2 satisfy ΣL i /L 00.70 , thereby improving the corrosion resistance of the coating layer. From the viewpoint of further improving the corrosion resistance improvement effect, the lower the value of ΣL i /L 0 , the more preferable, and it may be, for example, 0.65 or less, 0.60 or less, 0.55 or less, 0.50 or less, 0.45 or less, or 0.40 or less.

 一方で、円相当直径が2μm未満のFe-Al-Si相は仮に腐食が生じても、当該腐食を起点に他のFe-Al-Si相へと腐食がさらに進行することがない。このため、円相当直径が2μm未満のFe-Al-Si相が存在しても、ホットスタンプ成形体の耐食性には必ずしも不利に影響しない。これに関連して、さらなる耐食性向上の観点から、円相当直径が2μm以上のFe-Al-Si相がFe2Al5相中に存在しないようにしてもよい。すなわち、ΣLi/L0の下限は0であってもよい。特に限定されないが、例えば、ΣLi/L0は0.05以上、0.10以上、0.15以上又は0.20以上であってもよい。 On the other hand, even if corrosion occurs in the Fe-Al-Si phase having a circle equivalent diameter of less than 2 μm, the corrosion does not proceed further from the corrosion to other Fe-Al-Si phases. Therefore, even if an Fe-Al-Si phase having a circle equivalent diameter of less than 2 μm exists, it does not necessarily have a detrimental effect on the corrosion resistance of the hot stamped body. In this regard, from the viewpoint of further improving the corrosion resistance, the Fe-Al-Si phase having a circle equivalent diameter of 2 μm or more may not exist in the Fe 2 Al 5 phase. That is, the lower limit of ΣL i /L 0 may be 0. Although not particularly limited, for example, ΣL i /L 0 may be 0.05 or more, 0.10 or more, 0.15 or more, or 0.20 or more.

[20~40質量%のFe含有量を有するFe-Al相]
 本発明の実施形態において、めっき層は、上記Fe2Al5相の表面側に当該Fe2Al5相(Fe含有量:40超~60質量%)よりもFe含有量が低いFe-Al相、すなわち20~40質量%のFe含有量を有するFe-Al相を含む。20~40質量%のFe含有量を有するFe-Al相は、Fe2Al5相に比べて合金化の程度が低く、これに関連して耐赤さび性の向上に寄与し得る。Fe-Al相中のSi含有量は5質量%未満である。なお、本明細書において、20~40質量%のFe含有量を有するFe-Al相を、単にFe-Al相ということがある。
[Fe-Al phase having an Fe content of 20 to 40 mass %]
In an embodiment of the present invention, the plating layer includes an Fe - Al phase having a lower Fe content than the Fe 2 Al 5 phase (Fe content: more than 40 to 60 mass%), i.e., an Fe-Al phase having an Fe content of 20 to 40 mass%, on the surface side of the Fe 2 Al 5 phase. The Fe-Al phase having an Fe content of 20 to 40 mass% has a lower degree of alloying than the Fe 2 Al 5 phase, and in this regard, can contribute to improving red rust resistance. The Si content in the Fe-Al phase is less than 5 mass%. In this specification, the Fe-Al phase having an Fe content of 20 to 40 mass% may be simply referred to as the Fe-Al phase.

[表面酸化膜中のMg含有量:0.05原子%以上]
 本発明の実施形態において、めっき層は、図1に示すように、その表面に表面酸化膜を含み、当該表面酸化膜中のMg含有量が0.05原子%以上に制御される。本発明の実施形態に係るホットスタンプ成形体のめっき層はAlを比較的多く含有しているため、その表面がAl含有酸化物等から構成される酸化膜によって覆われている。このような表面酸化膜にMgを0.05原子%以上の量で導入することにより、当該表面酸化膜を適切に改質することができ、それによってホットスタンプ成形体の化成処理性を向上させることができる。化成処理性向上効果をさらに高める観点からは、表面酸化膜中のMg含有量は高いほど好ましく、例えば0.10原子%以上、0.20原子%以上、0.30原子%以上、0.50原子%以上、0.80原子%以上、1.00原子%以上、又は1.50原子%以上であってもよい。一方で、表面酸化膜中にMgを過度に含有しても上記効果は飽和する。したがって、特に限定されないが、表面酸化膜中のMg含有量は6.00原子%以下とすることが好ましく、例えば5.50原子%以下、5.00原子%以下、4.50原子%以下、又は4.00原子%以下であってもよい。
[Mg content in surface oxide film: 0.05 atomic % or more]
In an embodiment of the present invention, as shown in FIG. 1, the plating layer includes a surface oxide film on its surface, and the Mg content in the surface oxide film is controlled to 0.05 atomic % or more. Since the plating layer of the hot stamped body according to the embodiment of the present invention contains a relatively large amount of Al, the surface is covered with an oxide film composed of Al-containing oxides and the like. By introducing Mg into such a surface oxide film in an amount of 0.05 atomic % or more, the surface oxide film can be appropriately modified, thereby improving the chemical conversion treatability of the hot stamped body. From the viewpoint of further enhancing the effect of improving the chemical conversion treatability, the higher the Mg content in the surface oxide film, the more preferable it is, and it may be, for example, 0.10 atomic % or more, 0.20 atomic % or more, 0.30 atomic % or more, 0.50 atomic % or more, 0.80 atomic % or more, 1.00 atomic % or more, or 1.50 atomic % or more. On the other hand, even if the surface oxide film contains an excessive amount of Mg, the above effect is saturated. Therefore, although not particularly limited, the Mg content in the surface oxide film is preferably 6.00 atomic % or less, and may be, for example, 5.50 atomic % or less, 5.00 atomic % or less, 4.50 atomic % or less, or 4.00 atomic % or less.

[めっき層の分析]
 めっき層の分析は、以下のようにして行われる。まず、めっき層の断面が観察できるように、ホットスタンプ成形体から5つのサンプルを採取する。次いで、各サンプルについて、厚さ方向に80μm、厚さ方向と直角方向に100μmの矩形の範囲を1視野とし、5つのサンプルの合計で5視野についてSEM-EDS又はEPMAを用いて1500倍の倍率で撮影し、マッピング像を得る。このマッピング像の元素分布像から、20~40質量%のFe含有量を有するFe-Al相、Fe2Al5相及び当該Fe2Al5相の内部に存在するSi含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相、並びに表面酸化膜の位置を決定する。より具体的には、測定対象元素をFe、Al、Si及びZnとしてSEM-EDS又はEPMAによる元素分布像を得る。この元素分布像において、Fe:20~40質量%及びAl:58~78質量%を満たす領域を20~40質量%のFe含有量を有するFe-Al相とする。当該Fe-Al相の領域は、元素分布像における各元素の濃度を色調で示すカラーバーの濃度範囲をFe:20~40質量%及びAl:58~78質量%と設定し、カラーバーを調整したFeとAlの元素分布像を重ね合わせることで20~40質量%のFe含有量を有するFe-Al相(図1中の符号5)を特定する。この元素分布像において、Fe:40超~60質量%、Al:40~60質量%未満、Si:0~5質量%未満、及びZn:0~15質量%を満たす領域をFe2Al5相(図1中の符号4)とする。Si含有量が5~20質量%でかつ円相当直径が2μm以上の領域であって、その領域がFe2Al5相により囲まれている領域をFe-Al-Si相(図1中の符号7)とする。次に、Fe-Al-Si相を、画像解析ソフト(例えば、「ImageJ」の「Analyze」機能)を用いて鋼母材の表面に投影し、各Fe-Al-Si相の投影長さLiの合計(図1では、L1+L2+L3)を算出する。最後に、5つのサンプルについて得られたLiの合計の平均を算出してΣLiとし、対応する鋼母材の表面の長さL0(各視野中の長辺の長さ:100μm)との比ΣLi/L0を算出する。ここで、視野中の長辺の長さであるL0は、図1のとおり、測定領域(視野)の両端の間隔(ただし、ホットスタンプ成形体1の表面に平行な方向の間隔)でもある。
[Analysis of plating layer]
The plating layer is analyzed as follows. First, five samples are taken from the hot stamped body so that the cross section of the plating layer can be observed. Next, for each sample, a rectangular range of 80 μm in the thickness direction and 100 μm in the direction perpendicular to the thickness direction is defined as one visual field, and five visual fields in total for the five samples are photographed at a magnification of 1500 times using SEM-EDS or EPMA to obtain a mapping image. From the element distribution image of this mapping image, the positions of the Fe-Al phase having an Fe content of 20 to 40 mass%, the Fe 2 Al 5 phase, and the Fe - Al-Si phase having a Si content of 5 to 20 mass% and a circle equivalent diameter of 2 μm or more present inside the Fe 2 Al 5 phase, as well as the surface oxide film, are determined. More specifically, an element distribution image is obtained by SEM-EDS or EPMA with the measurement target elements being Fe, Al, Si, and Zn. In this element distribution image, the region that satisfies Fe: 20-40 mass% and Al: 58-78 mass% is defined as the Fe-Al phase having an Fe content of 20-40 mass%. The concentration range of the color bar showing the concentration of each element in the element distribution image by color tone is set to Fe: 20-40 mass% and Al: 58-78 mass%, and the Fe-Al phase having an Fe content of 20-40 mass% (reference numeral 5 in FIG. 1) is specified by superimposing the element distribution images of Fe and Al with the color bar adjusted. In this element distribution image, the region that satisfies Fe: more than 40 to 60 mass%, Al: 40 to less than 60 mass%, Si: 0 to less than 5 mass%, and Zn: 0 to 15 mass% is defined as the Fe 2 Al 5 phase (reference numeral 4 in FIG. 1). The region in which the Si content is 5 to 20 mass% and the circle equivalent diameter is 2 μm or more and is surrounded by the Fe 2 Al 5 phase is defined as the Fe-Al-Si phase (reference numeral 7 in FIG. 1). Next, the Fe-Al-Si phase is projected onto the surface of the steel base material using image analysis software (for example, the "Analyze" function of "ImageJ"), and the sum of the projected lengths L i of each Fe-Al-Si phase (L 1 +L 2 +L 3 in FIG. 1) is calculated. Finally, the average of the sums of L i obtained for the five samples is calculated as ΣL i , and the ratio ΣL i /L 0 to the length L 0 of the corresponding steel base material surface (length of the long side in each field: 100 μm) is calculated. Here, L 0 , which is the length of the long side in the field, is also the distance between both ends of the measurement region (field) as shown in FIG. 1 (however, the distance in the direction parallel to the surface of the hot stamped body 1).

 表面酸化膜中のMg含有量は、上記5つのサンプルのそれぞれについてSEM-EDS又はEPMAを用いて表面酸化膜を構成する元素濃度を測定し、対象とする元素濃度の5つのサンプルの測定値を平均することで決定される。より具体的には、まず、各サンプルにて、SEM-EDS又はEPMAによる測定において、O:30~70質量%、Al:30~70質量%、及びMg:0~2.5質量%を満たす領域を表面酸化物(図1中の符号6)とする。次に、各サンプルにおいて、表面酸化物と同定された領域の厚さの中央の位置において、ホットスタンプ成形体の表面に平行な方向に50μm間隔の5つの測定点におけるMg含有量を測定し、その平均値を各サンプルのMg含有量とする。5つのサンプルにおけるMg含有量の平均値を表面酸化膜中のMg含有量とする。 The Mg content in the surface oxide film is determined by measuring the concentration of elements constituting the surface oxide film for each of the five samples using SEM-EDS or EPMA, and averaging the measured values of the target element concentration for the five samples. More specifically, first, in each sample, the area that satisfies O: 30-70 mass%, Al: 30-70 mass%, and Mg: 0-2.5 mass% in the measurement by SEM-EDS or EPMA is determined to be the surface oxide (reference number 6 in Figure 1). Next, in each sample, the Mg content is measured at five measurement points spaced 50 μm apart in the direction parallel to the surface of the hot stamped body at the center position of the thickness of the area identified as the surface oxide, and the average value is determined to be the Mg content of each sample. The average value of the Mg contents in the five samples is determined to be the Mg content in the surface oxide film.

 上記の化学組成、Fe2Al5相、Fe-Al相及び表面酸化膜を有するめっき層としては、溶融めっき層があり得る。溶融めっき層以外のめっき層を排除する必要はないが、溶融めっき層に限定してもよい。 The plating layer having the above chemical composition, Fe2Al5 phase, Fe-Al phase, and surface oxide film may be a hot-dip plating layer. It is not necessary to exclude plating layers other than the hot-dip plating layer, but it may be limited to the hot-dip plating layer.

[めっき層の付着量:片面当たり20g/m2以上]
 本発明の実施形態に係るホットスタンプ成形体においては、めっき層の付着量は片面当たり20g/m2以上である。一般に、めっき層は、ホットスタンプ成形における高温加熱時に鋼母材と合金化して耐食性が低下する場合がある。しかしながら、本発明の実施形態によれば、めっき層の付着量を比較的多くしつつ、具体的には片面当たり20g/m2以上としつつ、合金化の程度を適度に弱めることで、めっき層の鋼母材側には十分に合金化されたFe2Al5相が形成されるものの、めっき層の表面側にはFe2Al5相よりもFe含有量が低いFe-Al相、すなわち20~40質量%のFe含有量を有するFe-Al相を形成することが可能となる。一方で、めっき層の付着量が少ないと、ホットスタンプ成形における高温加熱時にめっき層の合金化が進行しすぎてしまい、比較的低いFe含有量を有するFe-Al相を形成することができなくなる場合がある。この場合には、Fe-Al相の形成に起因する耐赤さび性向上効果が得られなくなる。あるいはまた、めっき層の付着量が少ないと、犠牲防食作用を有するZnをめっき層中に添加した効果が十分に得られなくなる場合があり、この場合には、ホットスタンプ成形後の耐食性が低下してしまう。耐食性向上の観点からは、めっき層の付着量は、片面当たり好ましくは30g/m2以上、40g/m2以上又は50g/m2以上、より好ましくは60g/m2以上、さらにより好ましくは70g/m2以上、最も好ましくは80g/m2以上である。上限は特に限定されないが、めっき層の付着量は、例えば200g/m2以下、190g/m2以下、180g/m2以下又は170g/m2以下であってもよい。
[Plating layer deposition weight: 20 g/ m2 or more per side]
In the hot stamped product according to the embodiment of the present invention, the coating weight of the coating layer is 20 g/m 2 or more per side. In general, the coating layer may be alloyed with the steel base material during high-temperature heating in hot stamp forming, resulting in a decrease in corrosion resistance. However, according to the embodiment of the present invention, by making the coating weight of the coating layer relatively large, specifically 20 g/m 2 or more per side, while appropriately weakening the degree of alloying, a sufficiently alloyed Fe 2 Al 5 phase is formed on the steel base material side of the coating layer, but an Fe-Al phase having a lower Fe content than the Fe 2 Al 5 phase, that is, an Fe-Al phase having an Fe content of 20 to 40 mass %, can be formed on the surface side of the coating layer. On the other hand, if the coating weight of the coating layer is small, the alloying of the coating layer may proceed too much during high-temperature heating in hot stamp forming, making it impossible to form an Fe-Al phase having a relatively low Fe content. In this case, the effect of improving red rust resistance due to the formation of an Fe-Al phase cannot be obtained. Alternatively, if the coating weight of the plating layer is small, the effect of adding Zn having a sacrificial anticorrosive effect to the plating layer may not be fully obtained, and in this case, the corrosion resistance after hot stamp forming is reduced. From the viewpoint of improving corrosion resistance, the coating weight of the plating layer is preferably 30 g/m 2 or more, 40 g/m 2 or more, or 50 g/m 2 or more, more preferably 60 g/m 2 or more, even more preferably 70 g/m 2 or more , and most preferably 80 g/m 2 or more per side. Although there is no particular upper limit, the coating weight of the plating layer may be, for example, 200 g/m 2 or less, 190 g/m 2 or less, 180 g/m 2 or less, or 170 g/m 2 or less.

[めっき付着量の測定]
 めっき層の付着量は、酸性水溶液でめっき層のみを溶解することで決定される。すなわち、ホットスタンプ成形体から30mm×30mmのサンプルを採取し、次いで鋼の溶解を抑制するインヒビターを含有した酸性水溶液、例えば10%の塩酸に0.04%のイビット710K(朝日化学工業製)
を加えた室温の酸性水溶液でめっき層を溶解し、めっき層の溶解前後のサンプルの質量変化からめっき層の付着量が決定される。
[Measurement of plating weight]
The coating weight of the plating layer is determined by dissolving only the plating layer in an acidic aqueous solution. That is, a 30 mm x 30 mm sample is taken from the hot stamped body, and then dissolved in an acidic aqueous solution containing an inhibitor that inhibits the dissolution of steel, for example, 0.04% Ibit 710K (manufactured by Asahi Chemical Industry Co., Ltd.) in 10% hydrochloric acid.
The plating layer is dissolved in an acidic aqueous solution at room temperature to which has been added, and the amount of plating layer attached is determined from the change in mass of the sample before and after dissolution of the plating layer.

[固溶体層]
 本発明の実施形態においては、ホットスタンプ成形体は、鋼母材とめっき層との間に固溶体層をさらに含んでいてもよい。ホットスタンプ成形前のめっき組成やホットスタンプ条件によっては、鋼母材からめっき層に拡散するFeとめっき層中のAl及び/又はZnとの間で固溶体化が進み、ホットスタンプ成形後に鋼母材とめっき層との間にこれら元素の固溶体を含む固溶体層が形成される場合がある。したがって、ホットスタンプ成形体が固溶体層をさらに含む場合には、当該固溶体層は、FeとAl及びZnのうち一方又は両方とを含む。より具体的には、固溶体層は、Fe-Al固溶体層、Fe-Zn固溶体層、及び/又はFe-Al-Zn固溶体層を含む。
[Solid solution layer]
In an embodiment of the present invention, the hot stamped product may further include a solid solution layer between the steel base material and the plating layer. Depending on the plating composition before hot stamping and the hot stamping conditions, a solid solution may be formed between Fe diffusing from the steel base material to the plating layer and Al and/or Zn in the plating layer, and a solid solution layer containing a solid solution of these elements may be formed between the steel base material and the plating layer after hot stamping. Therefore, when the hot stamped product further includes a solid solution layer, the solid solution layer contains Fe and one or both of Al and Zn. More specifically, the solid solution layer includes an Fe-Al solid solution layer, an Fe-Zn solid solution layer, and/or an Fe-Al-Zn solid solution layer.

 固溶体層の存在は以下のようにして確認することができる。まず、鋼の溶解を抑制するインヒビターを含有した酸性水溶液、具体的には10%の塩酸に0.04%のイビット710K(朝日化学工業製)を加えた室温の酸性水溶液でめっき層のみを溶解する。次に、高周波グロー放電発光分析装置(GDS)を用い、ホットスタンプ成形体の表面をAr雰囲気にし、電圧をかけてグロープラズマを発生させた状態で、ホットスタンプ成形体の表面をスパッタリングさせながら深さ方向に分析する。そして、グロープラズマ中で原子が励起されて発せられる元素特有の発光スペクトル波長から、材料に含まれる元素を同定し、同定した元素の発光強度を見積もる。深さ方向のデータは、スパッタ時間から見積もることができる。具体的には、予め標準サンプルを用いてスパッタ時間とスパッタ深さとの関係を求めておくことで、スパッタ時間をスパッタ深さに変換することができる。したがって、スパッタ時間から変換したスパッタ深さを、材料の表面からの深さと定義することができる。得られた発光強度は検量線を作製することで質量%に換算する。このようにしてホットスタンプ成形体をGDS測定した場合に、深さ方向にAl濃度が1.00質量%超でかつ鋼母材のAl含有量の1.10倍以上となる領域を固溶体層として決定する。 The presence of a solid solution layer can be confirmed as follows. First, the plating layer alone is dissolved in an acidic aqueous solution containing an inhibitor that inhibits the dissolution of steel, specifically, 10% hydrochloric acid plus 0.04% Ivit 710K (manufactured by Asahi Chemical Industry Co., Ltd.) at room temperature. Next, using a high-frequency glow discharge optical emission spectrometer (GDS), the surface of the hot stamped compact is placed in an Ar atmosphere, and a voltage is applied to generate glow plasma, and the surface of the hot stamped compact is sputtered and analyzed in the depth direction. Then, the elements contained in the material are identified from the element-specific emission spectrum wavelengths emitted by excited atoms in the glow plasma, and the emission intensity of the identified elements is estimated. The data in the depth direction can be estimated from the sputtering time. Specifically, the relationship between sputtering time and sputtering depth is obtained in advance using a standard sample, so that the sputtering time can be converted to sputtering depth. Therefore, the sputtering depth converted from the sputtering time can be defined as the depth from the surface of the material. The obtained emission intensity is converted to mass% by creating a calibration curve. When the hot stamped body is subjected to GDS measurement in this manner, the region in the depth direction where the Al concentration is greater than 1.00 mass% and is 1.10 times or more the Al content of the steel base material is determined to be the solid solution layer.

[鋼母材の好ましい化学組成]
 本発明は、上記のとおり、ホットスタンプ成形後においても、改善された耐食性を有するAl含有めっき層を備えたホットスタンプ成形体を提供することを目的とするものであって、Al-Zn-Mg-Si系めっきからなるめっき層においてその化学組成及び付着量を適正化するとともに、当該めっき層を主としてFe2Al5相と、当該Fe2Al5相上に形成されかつ比較的低いFe含有量を有するFe-Al相と、Mgで改質された表面酸化膜とによって構成し、さらに上記Fe2Al5相中のSi含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相の投影長さLiと、鋼母材の表面の長さL0がΣLi/L0≦0.70を満たすように制御することによって当該目的を達成するものである。したがって、鋼母材の化学組成自体は、本発明の目的を達成する上で必須の技術的特徴でないことは明らかである。以下、本発明の実施形態に係るホットスタンプ成形体において使用される鋼母材の好ましい化学組成について詳しく説明するが、これらの説明は、ホットスタンプ成形体のための鋼母材の好ましい化学組成の単なる例示を意図するものであり、本発明をこのような特定の化学組成を有する鋼母材を使用したものに限定することを意図するものではない。
[Preferable chemical composition of steel base material]
As described above, the present invention aims to provide a hot stamped product having an Al-containing plating layer having improved corrosion resistance even after hot stamp forming, and the object is achieved by optimizing the chemical composition and coating weight of the plating layer made of an Al-Zn-Mg-Si-based plating, configuring the plating layer mainly with an Fe 2 Al 5 phase, an Fe-Al phase formed on the Fe 2 Al 5 phase and having a relatively low Fe content, and a surface oxide film modified with Mg, and controlling the projected length L i of the Fe-Al-Si phase having a Si content of 5 to 20 mass% and a circle equivalent diameter of 2 μm or more in the Fe 2 Al 5 phase and the length L 0 of the surface of the steel base material so as to satisfy ΣL i /L 0 ≦0.70. Therefore, it is clear that the chemical composition of the steel base material itself is not an essential technical feature for achieving the object of the present invention. Hereinafter, preferred chemical compositions of the steel base material used in the hot stamped body according to the embodiment of the present invention will be described in detail. However, these descriptions are intended to merely exemplify preferred chemical compositions of the steel base material for the hot stamped body, and are not intended to limit the present invention to the use of a steel base material having such a specific chemical composition.

 本発明の実施形態において、例えば、鋼母材は、質量%で、
 C:0.13~0.50%、
 Si:0.001~3.000%、
 Mn:0.30~3.00%、
 Al:0.0002~2.000%、
 P :0.100%以下、
 S :0.1000%以下、
 N :0.0100%以下、
 Nb:0~0.15%、
 Ti:0~0.15%、
 V :0~0.15%、
 Mo:0~1.0%、
 Cr:0~1.0%、
 Cu:0~1.0%、
 Ni:0~1.0%、
 B :0~0.0100%、
 W :0~1.000%、
 Hf:0~0.050%、
 Mg:0~0.050%、
 Zr:0~0.050%、
 Ca:0~0.010%、
 REM:0~0.30%、
 Ir:0~1.000%、並びに
 残部:Fe及び不純物
からなる化学組成を有することが好ましい。以下、各元素についてより詳しく説明する。
In an embodiment of the present invention, for example, the steel base material comprises, in mass %,
C: 0.13-0.50%,
Si: 0.001 to 3.000%,
Mn: 0.30-3.00%,
Al: 0.0002-2.000%,
P: 0.100% or less,
S: 0.1000% or less,
N: 0.0100% or less,
Nb: 0 to 0.15%,
Ti: 0 to 0.15%,
V: 0 to 0.15%,
Mo: 0-1.0%,
Cr: 0-1.0%,
Cu: 0 to 1.0%,
Ni: 0-1.0%,
B: 0 to 0.0100%,
W: 0-1.000%,
Hf: 0 to 0.050%,
Mg: 0 to 0.050%,
Zr: 0 to 0.050%,
Ca: 0-0.010%,
REM: 0-0.30%,
It is preferable that the chemical composition is Ir: 0 to 1.000%, and the balance: Fe and impurities. Each element will be described in more detail below.

[C:0.13~0.50%]
 Cは、安価に引張強度を増加させる元素であり、鋼の強度を制御するために重要な元素である。このような効果を十分に得るために、C含有量は0.13%以上とすることが好ましい。C含有量は0.15%以上、0.20%以上、0.30%以上又は0.35%以上であってもよい。一方で、Cを過度に含有すると、伸びの低下を招く場合がある。このため、C含有量は0.50%以下とすることが好ましい。C含有量は0.45%以下又は0.40%以下であってもよい。
[C:0.13-0.50%]
C is an element that inexpensively increases tensile strength and is an important element for controlling the strength of steel. In order to fully obtain such an effect, the C content is preferably 0.13% or more. The C content may be 0.15% or more, 0.20% or more, 0.30% or more, or 0.35% or more. On the other hand, excessive C content may cause a decrease in elongation. For this reason, the C content is preferably 0.50% or less. The C content may be 0.45% or less, or 0.40% or less.

[Si:0.001~3.000%]
 Siは、脱酸剤として作用し、冷間圧延板焼鈍中の冷却過程における炭化物の析出を抑制する元素である。このような効果を十分に得るために、Si含有量は0.001%以上とすることが好ましい。Si含有量は0.010%以上、0.100%以上又は0.200%以上であってもよい。一方で、Siを過度に含有すると、鋼強度の増加とともに伸びの低下を招く場合がある。このため、Si含有量は3.000%以下とすることが好ましい。Si含有量は2.500%以下、2.000%以下、1.500%以下又は1.000%以下であってもよい。
[Si: 0.001 to 3.000%]
Si acts as a deoxidizer and is an element that suppresses the precipitation of carbides during the cooling process during cold-rolled sheet annealing. In order to fully obtain such effects, the Si content is preferably 0.001% or more. The Si content may be 0.010% or more, 0.100% or more, or 0.200% or more. On the other hand, excessive Si content may increase the steel strength and decrease the elongation. For this reason, the Si content is preferably 3.000% or less. The Si content may be 2.500% or less, 2.000% or less, 1.500% or less, or 1.000% or less.

[Mn:0.30~3.00%]
 Mnは、鋼の焼入れ性を高める元素であり、強度上昇に有効な元素である。このような効果を十分に得るために、Mn含有量は0.30%以上とすることが好ましい。Mn含有量は0.50%以上、1.00%以上又は1.30%以上であってもよい。一方で、Mnを過度に含有すると、鋼強度の増加とともに伸びの低下を招く場合がある。このため、Mn含有量は3.00%以下とすることが好ましい。Mn含有量は2.80%以下、2.50%以下又は2.00%以下であってもよい。
[Mn: 0.30-3.00%]
Mn is an element that enhances the hardenability of steel and is effective in increasing strength. In order to fully obtain such an effect, the Mn content is preferably 0.30% or more. The Mn content may be 0.50% or more, 1.00% or more, or 1.30% or more. On the other hand, excessive Mn content may increase the steel strength and decrease the elongation. For this reason, the Mn content is preferably 3.00% or less. The Mn content may be 2.80% or less, 2.50% or less, or 2.00% or less.

[Al:0.0002~2.000%]
 Alは、鋼の脱酸剤として作用し、鋼を健全化する作用を有する元素である。このような効果を十分に得るために、Al含有量は0.0002%以上とすることが好ましい。Al含有量は0.001%以上、0.010%以上、0.050%以上又は0.100%以上であってもよい。一方で、Alを過度に含有すると、粗大なAl酸化物が生成して鋼板の伸びが低下する場合がある。このため、Al含有量は2.000%以下とすることが好ましい。Al含有量は1.500%以下、1.000%以下、0.800%以下又は0.500%以下であってもよい。
[Al: 0.0002-2.000%]
Al acts as a deoxidizer for steel and is an element that has the effect of improving the soundness of steel. In order to fully obtain such an effect, the Al content is preferably 0.0002% or more. The Al content may be 0.001% or more, 0.010% or more, 0.050% or more, or 0.100% or more. On the other hand, if Al is contained excessively, coarse Al oxides may be generated and the elongation of the steel sheet may decrease. For this reason, the Al content is preferably 2.000% or less. The Al content may be 1.500% or less, 1.000% or less, 0.800% or less, or 0.500% or less.

[P:0.100%以下]
 Pは、粒界に偏析して鋼の脆化を促す元素である。P含有量は少ないほど好ましいため、理想的には0%である。しかしながら、P含有量の過度な低減はコストの大幅な増加を招く場合がある。このため、P含有量は0.0001%以上としてもよく、0.001%以上又は0.005%以上であってもよい。一方で、Pを過度に含有すると、上記のとおり粒界偏析により鋼の脆化を招く場合がある。したがって、P含有量は0.100%以下とすることが好ましい。P含有量は0.050%以下、0.030%以下又は0.010%以下であってもよい。
[P: 0.100% or less]
P is an element that segregates at grain boundaries and promotes embrittlement of steel. Since the lower the P content, the better, it is ideally 0%. However, excessive reduction in the P content may lead to a significant increase in costs. For this reason, the P content may be 0.0001% or more, or may be 0.001% or more, or 0.005% or more. On the other hand, excessive inclusion of P may lead to embrittlement of steel due to grain boundary segregation as described above. Therefore, the P content is preferably 0.100% or less. The P content may be 0.050% or less, 0.030% or less, or 0.010% or less.

[S:0.1000%以下]
 Sは、鋼中でMnS等の非金属介在物を生成し、鋼材部品の延性の低下を招く元素である。S含有量は少ないほど好ましいため、理想的には0%である。しかしながら、S含有量の過度な低減はコストの大幅な増加を招く場合がある。このため、S含有量は0.0001%以上としてもよく、0.0002%以上、0.0010%以上又は0.0050%以上であってもよい。一方で、Sを過度に含有すると、冷間成形時に非金属介在物を起点とした割れの発生を招く場合がある。したがって、S含有量は0.1000%以下とすることが好ましい。S含有量は0.0500%以下、0.0200%以下又は0.0100%以下であってもよい。
[S: 0.1000% or less]
S is an element that generates nonmetallic inclusions such as MnS in steel, which leads to a decrease in the ductility of steel parts. The lower the S content, the better, so ideally it is 0%. However, excessive reduction in the S content may lead to a significant increase in costs. For this reason, the S content may be 0.0001% or more, 0.0002% or more, 0.0010% or more, or 0.0050% or more. On the other hand, excessive S content may lead to the occurrence of cracks originating from nonmetallic inclusions during cold forming. Therefore, the S content is preferably 0.1000% or less. The S content may be 0.0500% or less, 0.0200% or less, or 0.0100% or less.

[N:0.0100%以下]
 Nは、鋼板中で粗大な窒化物を形成し、鋼板の加工性を低下させる元素である。N含有量は少ないほど好ましいため、理想的には0%である。しかしながら、N含有量の過度な低減は製造コストの大幅な増加を招く場合がある。このため、N含有量は0.0001%以上としてもよく、0.0005%以上又は0.0010%以上であってもよい。一方で、Nを過度に含有すると、上記のとおり粗大な窒化物を形成して鋼板の加工性を低下させる場合がある。したがって、N含有量は0.0100%以下とすることが好ましい。N含有量は0.0080%以下又は0.0050%以下であってもよい。
[N: 0.0100% or less]
N is an element that forms coarse nitrides in the steel sheet and reduces the workability of the steel sheet. Since the lower the N content, the more preferable it is, the ideal N content is 0%. However, excessive reduction in the N content may lead to a significant increase in manufacturing costs. For this reason, the N content may be 0.0001% or more, 0.0005% or more, or 0.0010% or more. On the other hand, excessive N content may form coarse nitrides as described above, thereby reducing the workability of the steel sheet. Therefore, the N content is preferably 0.0100% or less. The N content may be 0.0080% or less, or 0.0050% or less.

 鋼母材の好ましい基本化学組成は上記のとおりである。さらに、鋼母材は、必要に応じて、残部のFeの一部に代えて、Nb:0~0.15%、Ti:0~0.15%、V:0~0.15%、Mo:0~1.0%、Cr:0~1.0%、Cu:0~1.0%、Ni:0~1.0%、B:0~0.0100%、W:0~1.000%、Hf:0~0.050%、Mg:0~0.050%、Zr:0~0.050%、Ca:0~0.010%、REM:0~0.30%、及びIr:0~1.000%からなる群より選択される1種又は2種以上を含有してもよい。これらの元素はそれぞれ0.0001%以上、0.0005%以上、0.001%以上又は0.01%以上であってもよい。 The preferred basic chemical composition of the steel base material is as described above. Furthermore, the steel base material may contain, as necessary, one or more elements selected from the group consisting of Nb: 0-0.15%, Ti: 0-0.15%, V: 0-0.15%, Mo: 0-1.0%, Cr: 0-1.0%, Cu: 0-1.0%, Ni: 0-1.0%, B: 0-0.0100%, W: 0-1.000%, Hf: 0-0.050%, Mg: 0-0.050%, Zr: 0-0.050%, Ca: 0-0.010%, REM: 0-0.30%, and Ir: 0-1.000%, in place of a portion of the remaining Fe. Each of these elements may be 0.0001% or more, 0.0005% or more, 0.001% or more, or 0.01% or more.

 鋼母材において、上記の元素以外の残部はFe及び不純物からなる。鋼母材における不純物とは、鋼母材を工業的に製造する際に、鉱石やスクラップ等のような原料を始めとして、製造工程の種々の要因によって混入する成分等である。 The remainder of the steel base material other than the above elements consists of Fe and impurities. Impurities in steel base material are components that are mixed in due to various factors in the manufacturing process, including raw materials such as ore and scrap, when the steel base material is industrially manufactured.

 鋼母材の化学組成は、一般的な分析方法によって測定すればよい。例えば、鋼母材の化学組成は、まず機械研削によりめっき層を除去し、次いでJIS G 1201:2014に準じて切粉に対するICP-AES(Inductively Coupled Plasma-Atomic Emission Spectrometry)を用いて測定すればよい。具体的には、例えば、鋼母材の板厚1/2位置付近から35mm角の試験片を取得し、島津製作所製ICPS-8100等(測定装置)により、予め作成した検量線に基づいた条件で測定することにより特定することができる。ICP-AESで測定できないC及びSは燃焼-赤外線吸収法を用い、Nは不活性ガス融解-熱伝導度法を用い、Oは不活性ガス融解-非分散型赤外線吸収法を用いて測定すればよい。 The chemical composition of the steel base material may be measured by a general analytical method. For example, the chemical composition of the steel base material may be measured by first removing the plating layer by mechanical grinding, and then using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) on the cutting chips in accordance with JIS G 1201:2014. Specifically, for example, a 35 mm square test piece may be obtained from the vicinity of the 1/2 position of the plate thickness of the steel base material, and the composition may be identified by measuring it under conditions based on a calibration curve created in advance using a Shimadzu ICPS-8100 or similar (measuring device). C and S, which cannot be measured by ICP-AES, may be measured using the combustion-infrared absorption method, N may be measured using the inert gas fusion-thermal conductivity method, and O may be measured using the inert gas fusion-non-dispersive infrared absorption method.

[ホットスタンプ成形体の板厚]
 ホットスタンプ成形体の板厚は、特に限定されないが、例えば0.2mm以上であり、0.3mm以上、0.6mm以上、1.0mm以上又は2.0mm以上であってもよい。同様に、ホットスタンプ成形体の板厚は、例えば6.0mm以下であり、5.0mm以下又は4.0mm以下であってもよい。
[Thickness of hot stamped body]
The thickness of the hot stamped steel is not particularly limited, and may be, for example, 0.2 mm or more, 0.3 mm or more, 0.6 mm or more, 1.0 mm or more, or 2.0 mm or more. Similarly, the thickness of the hot stamped steel may be, for example, 6.0 mm or less, 5.0 mm or less, or 4.0 mm or less.

<ホットスタンプ成形体の製造方法>
 次に、本発明の実施形態に係るホットスタンプ成形体の好ましい製造方法について説明する。以下の説明は、本発明の実施形態に係るホットスタンプ成形体を製造するための特徴的な方法の例示を意図するものであって、当該ホットスタンプ成形体を以下に説明するような製造方法によって製造されるものに限定することを意図するものではない。
<Method of Manufacturing Hot Stamped Product>
Next, a preferred method for producing the hot stamped steel according to the embodiment of the present invention will be described. The following description is intended to exemplify a characteristic method for producing the hot stamped steel according to the embodiment of the present invention, but is not intended to limit the hot stamped steel to one produced by the production method described below.

 本発明の実施形態に係るホットスタンプ成形体は、例えば、化学組成を調整した溶鋼を鋳造してスラブを形成する鋳造工程、スラブを熱間圧延して熱間圧延鋼板を得る熱間圧延工程、熱間圧延鋼板を巻取る巻取工程、巻取った熱間圧延鋼板を冷間圧延して冷間圧延鋼板を得る冷間圧延工程、冷間圧延鋼板を焼鈍する焼鈍工程、焼鈍された冷間圧延鋼板を冷却する冷却工程、得られた鋼母材にめっき層を形成するめっき工程、及び得られためっき鋼板をホットスタンプ成形するホットスタンプ成形工程を行うことで製造することができる。代替的に、熱間圧延工程後に巻き取らず、酸洗してそのまま冷間圧延工程を行ってもよい。以下、各工程について詳しく説明する。 The hot stamped product according to an embodiment of the present invention can be manufactured by, for example, carrying out a casting process in which molten steel with an adjusted chemical composition is cast to form a slab, a hot rolling process in which the slab is hot rolled to obtain a hot rolled steel sheet, a coiling process in which the hot rolled steel sheet is coiled, a cold rolling process in which the coiled hot rolled steel sheet is cold rolled to obtain a cold rolled steel sheet, an annealing process in which the cold rolled steel sheet is annealed, a cooling process in which the annealed cold rolled steel sheet is cooled, a plating process in which a plating layer is formed on the obtained steel base material, and a hot stamp forming process in which the obtained plated steel sheet is hot stamp formed. Alternatively, the cold rolling process may be carried out directly after pickling without coiling after the hot rolling process. Each process will be described in detail below.

[鋳造工程]
 鋳造工程の条件は特に限定されない。例えば、高炉や電炉等による溶製に引き続き、各種の二次製錬を行い、次いで、通常の連続鋳造、インゴット法による鋳造などの方法で鋳造すればよい。
[Casting process]
The conditions for the casting process are not particularly limited. For example, after melting in a blast furnace or an electric furnace, various secondary smelting processes may be carried out, and then casting may be carried out by a method such as ordinary continuous casting or casting by an ingot method.

[熱間圧延工程]
 鋳造したスラブを熱間圧延して熱間圧延鋼板を得ることができる。熱間圧延工程は、鋳造したスラブを直接又は一旦冷却した後に再加熱して熱間圧延することにより行われる。再加熱を行う場合には、スラブの加熱温度は、例えば1100~1250℃であってよい。熱間圧延工程においては、通常、粗圧延と仕上げ圧延とが行われる。各圧延の温度や圧下率は、所望の金属組織や板厚に応じて適宜決定することができる。例えば仕上げ圧延の終了温度は900~1050℃であってよく、仕上げ圧延の圧下率は10~50%であってよい。
[Hot rolling process]
The cast slab is hot-rolled to obtain a hot-rolled steel sheet. The hot-rolling step is performed by reheating the cast slab directly or after cooling and then hot-rolling it. When reheating is performed, the heating temperature of the slab may be, for example, 1100 to 1250°C. In the hot-rolling step, rough rolling and finish rolling are usually performed. The temperature and reduction of each rolling step can be appropriately determined according to the desired metal structure and plate thickness. For example, the end temperature of the finish rolling may be 900 to 1050°C, and the reduction of the finish rolling may be 10 to 50%.

[巻取工程]
 熱間圧延鋼板は所定の温度で巻取ることができる。巻取温度は、所望の金属組織等に応じて適宜決定することができ、例えば500~800℃であってよい。巻取る前又は巻取った後に巻き戻して、熱間圧延鋼板に所定の熱処理を与えてもよい。代替的に、巻取工程は行わずに熱間圧延工程後に酸洗して後述する冷間圧延工程を行うこともできる。
[Winding process]
The hot-rolled steel sheet can be coiled at a predetermined temperature. The coiling temperature can be appropriately determined depending on the desired metal structure, etc., and may be, for example, 500 to 800°C. The hot-rolled steel sheet may be subjected to a predetermined heat treatment by recoiling before or after coiling. Alternatively, the coiling step may be omitted, and the hot-rolled steel sheet may be pickled after the hot-rolling step and then subjected to the cold-rolling step described later.

[冷間圧延工程]
 熱間圧延鋼板に酸洗等を行った後、熱間圧延鋼板を冷間圧延して冷間圧延鋼板を得ることができる。冷間圧延の圧下率は、所望の金属組織や板厚に応じて適宜決定することができ、例えば20~80%であってよい。冷間圧延工程後は、例えば空冷して室温まで冷却してもよい。
[Cold rolling process]
After the hot-rolled steel sheet is subjected to pickling or the like, the hot-rolled steel sheet is cold-rolled to obtain a cold-rolled steel sheet. The rolling reduction in the cold rolling can be appropriately determined according to the desired metal structure and sheet thickness, and may be, for example, 20 to 80%. After the cold rolling step, the steel sheet may be cooled to room temperature, for example, by air cooling.

[焼鈍工程]
 次に、得られた冷間圧延鋼板に焼鈍を行う。焼鈍工程は、冷間圧延鋼板を露点が-50~20℃の雰囲気中730~900℃の温度に加熱して10~300秒間保持することを含む。とりわけ、-10~20℃の比較的高露点の条件下で焼鈍工程を実施することにより、冷間圧延鋼板の表層部を適切に脱炭することができる。この場合には、理由は必ずしも明らかではないが、最終的に得られるホットスタンプ成形体のめっき層において、Fe-Al-Si相をFe2Al5相中でより分散して存在させることが可能となる。その結果として、露点が-10℃未満の条件下で焼鈍工程を実施した場合と比較して、ΣLi/L0の値を小さくすることができ、例えばΣLi/L0を0.50以下まで低減することができ、ホットスタンプ成形後の耐食性をさらに向上させることが可能となる。焼鈍工程における雰囲気は、還元雰囲気、より具体的には窒素及び水素を含む還元雰囲気、例えば水素1~10%の還元雰囲気(例えば、水素4%及び窒素バランス)であってよい。
[Annealing process]
Next, the obtained cold-rolled steel sheet is annealed. The annealing step includes heating the cold-rolled steel sheet to a temperature of 730 to 900 ° C. in an atmosphere with a dew point of -50 to 20 ° C. and holding the temperature for 10 to 300 seconds. In particular, by carrying out the annealing step under conditions of a relatively high dew point of -10 to 20 ° C., the surface layer of the cold-rolled steel sheet can be appropriately decarburized. In this case, although the reason is not necessarily clear, it is possible to make the Fe-Al-Si phase more dispersed in the Fe 2 Al 5 phase in the coating layer of the finally obtained hot stamped body. As a result, the value of ΣL i /L 0 can be reduced compared to the case where the annealing step is carried out under conditions of a dew point of less than -10 ° C., and for example, ΣL i /L 0 can be reduced to 0.50 or less, and the corrosion resistance after hot stamping can be further improved. The atmosphere in the annealing step may be a reducing atmosphere, more specifically a reducing atmosphere containing nitrogen and hydrogen, for example a reducing atmosphere of 1 to 10% hydrogen (eg, 4% hydrogen and the balance nitrogen).

[冷却工程]
 冷却工程は、焼鈍工程の加熱温度から次のめっき工程の侵入板温まで所望の金属組織を得るのに適した冷却速度にて実施すればよい。特に限定されないが、例えば、冷却工程は、焼鈍工程の加熱温度からめっき工程の侵入板温まで10℃/s以上の平均冷却速度で実施してもよい。
[Cooling process]
The cooling step may be performed at a cooling rate suitable for obtaining a desired metal structure from the heating temperature of the annealing step to the entry sheet temperature of the subsequent plating step. Although not particularly limited, for example, the cooling step may be performed at an average cooling rate of 10° C./s or more from the heating temperature of the annealing step to the entry sheet temperature of the plating step.

[めっき工程]
 次に、めっき工程において、冷間圧延鋼板(鋼母材)の少なくとも一方、好ましくは両方の表面にめっき層が形成される。より具体的には、めっき工程は、所定の化学組成を有するめっき浴、例えば、Zn:5.0~50.0%、Si:0.1~18.0%、Mg:0.010~3.000%、並びに残部:Al及び不純物を含有するめっき浴(めっき浴温:650℃以上、例えば650~680℃)を用いて、鋼母材のめっき浴への侵入板温が500℃以下となるようにして実施され、めっき後480℃まで20℃/s以上の平均冷却速度で1次冷却され、次いで480℃から300℃まで10℃/s以下の平均冷却速度で2次冷却される。めっき工程は、鋼母材との界面に形成される界面合金層に相当するFe-Al相の所望の化学組成を得るのに重要であり、さらにめっき層中にMg-Al-Zn-Si系金属間化合物相を形成させるのに重要である。以下、詳しく説明される。
[Plating process]
Next, in the plating step, a plating layer is formed on at least one, preferably both, surfaces of the cold-rolled steel sheet (steel base material). More specifically, the plating step is carried out using a plating bath having a predetermined chemical composition, for example, a plating bath containing Zn: 5.0 to 50.0%, Si: 0.1 to 18.0%, Mg: 0.010 to 3.000%, and the balance: Al and impurities (plating bath temperature: 650°C or higher, for example, 650 to 680°C), so that the temperature of the steel base material entering the plating bath is 500°C or lower, and after plating, the steel is primarily cooled to 480°C at an average cooling rate of 20°C/s or higher, and then secondary cooled from 480°C to 300°C at an average cooling rate of 10°C/s or lower. The plating step is important for obtaining a desired chemical composition of the Fe-Al phase corresponding to the interface alloy layer formed at the interface with the steel base material, and is also important for forming an Mg-Al-Zn-Si-based intermetallic compound phase in the plating layer. This will be explained in detail below.

 一般的には、めっき工程は、侵入板温がめっき浴温と同じか又は同程度となるようにして実施される。しかしながら、鋼母材のめっき浴への侵入板温とめっき浴温との差(すなわち、めっき浴温-侵入板温)が150℃未満である場合、侵入板温が500℃よりも高い場合、又はめっき浴温が650℃よりも低い場合、適切な相種のFe-Al相を形成することができなくなる。具体的には、これらの場合、Fe-Al相のSi含有量が3.0%未満となってしまう。その結果として、そのようなめっき鋼板に(ホットスタンプ成形の)高温加熱が施されると、その高温加熱中にFe2Al5相中のFe-Al-Si相の形成を十分に抑制することができなくなる。この場合には、ΣLi/L0の値が大きくなるため、ホットスタンプ成形後のめっき層の耐食性が大きく低下する。そこで、本製造方法においては、めっき浴温を650℃以上かつ侵入板温を500℃以下に制御して侵入板温がめっき浴温よりも150℃以上低くなることを確実にすることにより、低温で界面合金層(Fe-Al相)を晶出させるとともに、当該界面合金層中にSiを3.0質量%以上含有させるのに適した相種に変化させている。この界面合金層中にSiを3.0質量%以上含有させることで、ホットスタンプ成形前のめっき層中に存在するSiの多くを当該界面合金層中にトラップすることができると考えられる。ホットスタンプ成形後のFe-Al-Si相はSiを比較的多く含む金属間化合物であるため、ホットスタンプ成形前の界面合金層中にSiの多くをトラップすることで、ホットスタンプ成形の高温加熱時におけるFe2Al5相中のFe-Al-Si相の形成を抑制することが可能になるものと考えられる。その結果として、Fe2Al5相中のFe-Al-Si相がΣLi/L0≦0.70を満たすよう分散されたホットスタンプ成形体を製造することが可能になるものと考えられる。 Generally, the plating process is carried out so that the entry sheet temperature is the same as or approximately the same as the plating bath temperature. However, if the difference between the entry sheet temperature of the steel base material into the plating bath and the plating bath temperature (i.e., plating bath temperature - entry sheet temperature) is less than 150°C, if the entry sheet temperature is higher than 500°C, or if the plating bath temperature is lower than 650°C, it becomes impossible to form an appropriate phase type of Fe-Al phase. Specifically, in these cases, the Si content of the Fe-Al phase becomes less than 3.0%. As a result, when such a plated steel sheet is subjected to high-temperature heating (hot stamp forming), it becomes impossible to sufficiently suppress the formation of the Fe-Al-Si phase in the Fe 2 Al 5 phase during the high-temperature heating. In this case, the value of ΣL i /L 0 becomes large, and the corrosion resistance of the plating layer after hot stamp forming is greatly reduced. Therefore, in the present manufacturing method, the plating bath temperature is controlled to 650°C or more and the entry sheet temperature is controlled to 500°C or less to ensure that the entry sheet temperature is 150°C or more lower than the plating bath temperature, thereby crystallizing the interface alloy layer (Fe-Al phase) at a low temperature and changing the phase type to one suitable for containing 3.0 mass% or more of Si in the interface alloy layer. It is considered that by containing 3.0 mass% or more of Si in the interface alloy layer, it is possible to trap much of the Si present in the plating layer before hot stamp forming in the interface alloy layer. Since the Fe-Al-Si phase after hot stamp forming is an intermetallic compound containing a relatively large amount of Si, it is considered that by trapping much of Si in the interface alloy layer before hot stamp forming, it is possible to suppress the formation of the Fe-Al-Si phase in the Fe 2 Al 5 phase during high-temperature heating in hot stamp forming. As a result, it is believed possible to manufacture a hot stamped steel in which the Fe--Al--Si phase is dispersed in the Fe 2 Al 5 phase so as to satisfy ΣL i /L 0 ≦0.70.

 一般的に、侵入板温は上記のとおりめっき浴温と同じか又は同程度に制御され、仮に侵入板温がめっき浴温と異なる場合であっても、当該侵入板温は一般にめっき浴温に対して±20℃の範囲内に制御される。この理由としては、めっき浴への浸漬時に板温がめっき浴温まで上昇するにもかかわらず、あえて製造コストをかけて侵入板温をより低い温度に冷却及び制御する必要がないこと、並びに侵入板温がめっき浴温に対してより低いことに起因してめっき浴が凝固する場合があることなどが挙げられる。したがって、本製造方法のように、めっき浴温を650℃以上かつ侵入板温を500℃以下に制御して侵入板温がめっき浴温よりも150℃以上低くなることを確実にすることにより、ホットスタンプ成形後のめっき層の耐食性を向上させることができるという事実は極めて意外であり、また驚くべきことである。侵入板温の下限は特に限定されないが、例えば、鋼母材のめっき浴への侵入板温は380℃以上であってもよい。なお、従来の常識では、侵入板温を500℃以下に制御することで、めっき浴の組成等に起因して当該めっき浴が凝固する可能性があると考えられる。しかし、本実施形態においては、侵入板温とめっき浴温との差を従来の常識を大きく超える150℃以上とすることにより、つまり、侵入板温を500℃以下としめっき浴温の650℃という高温化などにより、めっき浴の凝固を防止することができることを見出した。なお、めっき浴の凝固を防ぐため、めっき浴内の撹拌によりめっき液を対流させることが好ましい。 Generally, the entry sheet temperature is controlled to be the same as or to the same extent as the plating bath temperature as described above, and even if the entry sheet temperature is different from the plating bath temperature, the entry sheet temperature is generally controlled within a range of ±20°C relative to the plating bath temperature. The reason for this is that, although the sheet temperature rises to the plating bath temperature when immersed in the plating bath, there is no need to take the manufacturing cost to cool and control the entry sheet temperature to a lower temperature, and the plating bath may solidify due to the entry sheet temperature being lower than the plating bath temperature. Therefore, it is quite unexpected and surprising that the corrosion resistance of the plating layer after hot stamp forming can be improved by controlling the plating bath temperature to 650°C or higher and the entry sheet temperature to 500°C or lower, as in this manufacturing method, to ensure that the entry sheet temperature is 150°C or lower than the plating bath temperature. The lower limit of the entry sheet temperature is not particularly limited, but for example, the entry sheet temperature of the steel base material into the plating bath may be 380°C or higher. Conventional wisdom would suggest that controlling the entry sheet temperature to 500°C or less could lead to the plating bath solidifying due to its composition. However, in this embodiment, it has been discovered that by setting the difference between the entry sheet temperature and the plating bath temperature to 150°C or more, which is significantly greater than conventional wisdom, that is, by setting the entry sheet temperature to 500°C or less and setting the plating bath temperature to a high temperature of 650°C, it is possible to prevent the plating bath from solidifying. In order to prevent the plating bath from solidifying, it is preferable to circulate the plating solution by stirring the plating bath.

 めっき工程は、例えば溶融めっき処理により行われる。めっき工程の他の条件は、めっき層の厚さ及び付着量等を考慮して適宜設定すればよい。例えば、冷間圧延鋼板をめっき浴に浸漬した後、これを引き上げ、ガスワイピング法により直ちにN2ガス又は空気を吹き付け、その後冷却するようにすることでめっき層の付着量を所定の範囲内、例えば、片面当たり20~200g/m2の範囲内に調整することができる。 The plating process is carried out, for example, by hot-dip plating. Other conditions of the plating process may be appropriately set in consideration of the thickness and adhesion amount of the plating layer. For example, a cold-rolled steel sheet is immersed in a plating bath, then pulled out, and immediately sprayed with N2 gas or air by a gas wiping method, and then cooled, so that the adhesion amount of the plating layer can be adjusted to a predetermined range, for example, within the range of 20 to 200 g/ m2 per side.

[めっき後の冷却]
 めっき後の鋼板は、上記のとおり、480℃まで20℃/s以上の平均冷却速度で1次冷却され、次いで480℃から300℃まで10℃/s以下の平均冷却速度で2次冷却される。めっき後の鋼板をこのような比較的速い平均冷却速度(20℃/s以上)による1次冷却と比較的遅い平均冷却速度(10℃/s以下)による2次冷却との組み合わせに基づいて冷却することで、めっき層中にMg-Al-Zn-Si系金属間化合物相を形成させることが可能となる。より詳しく説明すると、めっき中にMgを添加した場合には、一般にMg2Si相が晶出しやすい。しかしながら、まず、1次冷却において、めっき後の鋼板を480℃まで20℃/s以上の平均冷却速度で急冷することにより、Mg2Si相の晶出を抑制しつつ、液相の組成をMg-Al-Zn-Si系金属間化合物相の晶出に適した組成にすることができる。次いで、2次冷却において、鋼板を480℃から300℃まで10℃/s以下の平均冷却速度で徐冷することにより、Mg-Al-Zn-Si系金属間化合物相を安定的にゆっくりと晶出させることができ、めっき層中にAl含有量が10質量%以上のMg-Al-Zn-Si系金属間化合物相を面積率で0.010%以上含むめっき層を形成することが可能となる。Al含有量が10質量%以上のMg-Al-Zn-Si系金属間化合物相は融点が比較的低く、酸化されやすい性質を有する。このため、Mg-Al-Zn-Si系金属間化合物相をめっき層中に面積率で0.010%以上含めることで、ホットスタンプ成形の高温加熱時に当該Mg-Al-Zn-Si系金属間化合物相を溶解させ、ホットスタンプ成形の際に成形体表面に形成される酸化膜を、溶解したMgによって適切に改質することができる。その結果、得られるホットスタンプ成形体の表面酸化物中のMg含有量が0.05原子%以上となり、当該ホットスタンプ成形体の化成処理性を向上させることが可能となる。
[Cooling after plating]
As described above, the plated steel sheet is primarily cooled to 480°C at an average cooling rate of 20°C/s or more, and then secondary cooled from 480°C to 300°C at an average cooling rate of 10°C/s or less. By cooling the plated steel sheet based on such a combination of primary cooling at a relatively fast average cooling rate (20°C/s or more) and secondary cooling at a relatively slow average cooling rate (10°C/s or less), it is possible to form an Mg-Al-Zn-Si intermetallic compound phase in the plated layer. To explain in more detail, when Mg is added during plating, the Mg 2 Si phase is generally likely to crystallize. However, first, in the primary cooling, the plated steel sheet is rapidly cooled to 480°C at an average cooling rate of 20°C/s or more, so that the composition of the liquid phase can be made suitable for the crystallization of the Mg- Al -Zn-Si intermetallic compound phase while suppressing the crystallization of the Mg 2 Si phase. Next, in the secondary cooling, the steel sheet is slowly cooled from 480°C to 300°C at an average cooling rate of 10°C/s or less, whereby the Mg-Al-Zn-Si intermetallic compound phase can be stably and slowly crystallized, and it is possible to form a plating layer containing 0.010% or more of the Mg-Al-Zn-Si intermetallic compound phase with an Al content of 10% or more by area ratio in the plating layer. The Mg-Al-Zn-Si intermetallic compound phase with an Al content of 10% or more by mass has a relatively low melting point and is easily oxidized. For this reason, by containing 0.010% or more of the Mg-Al-Zn-Si intermetallic compound phase by area ratio in the plating layer, the Mg-Al-Zn-Si intermetallic compound phase can be dissolved during high-temperature heating in hot stamp forming, and the oxide film formed on the surface of the formed body during hot stamp forming can be appropriately modified by the dissolved Mg. As a result, the Mg content in the surface oxide of the obtained hot stamped body becomes 0.05 atomic % or more, making it possible to improve the chemical conversion treatability of the hot stamped body.

 一方で、480℃から300℃までの間も引き続き急冷するか又は10℃/s超の平均冷却速度で冷却すると、液相の組成がα-(Al,Mg,Zn)相の晶出に適した組成となってしまい、すなわちMgがα-Al相中に固溶されてしまい、Mg-Al-Zn-Si系金属間化合物相を所望の量で晶出させることができなくなる。この場合には、当然ながら、ホットスタンプ成形の高温加熱時に成形体表面に形成される酸化膜をMgによって改質することができなくなり、その結果として表面酸化物中のMg含有量が0.05原子%未満となり、所望の化成処理性を得ることができなくなる。1次冷却の平均冷却速度の上限は特に限定されないが、例えば50℃/s以下であってもよい。同様に、2次冷却の下限は特に限定されないが、例えば3℃/s以上であってもよい。 On the other hand, if the material is rapidly cooled from 480°C to 300°C or cooled at an average cooling rate of more than 10°C/s, the liquid phase composition becomes suitable for the crystallization of the α-(Al, Mg, Zn) phase, i.e., Mg is dissolved in the α-Al phase, and the desired amount of Mg-Al-Zn-Si intermetallic compound phase cannot be crystallized. In this case, it is natural that the oxide film formed on the surface of the formed body during high-temperature heating in hot stamp forming cannot be modified by Mg, and as a result, the Mg content in the surface oxide becomes less than 0.05 atomic %, and the desired chemical conversion treatability cannot be obtained. The upper limit of the average cooling rate for the primary cooling is not particularly limited, but may be, for example, 50°C/s or less. Similarly, the lower limit of the secondary cooling is not particularly limited, but may be, for example, 3°C/s or more.

[ホットスタンプ成形工程]
 最後に、得られためっき鋼板は、ホットスタンプ成形工程においてホットスタンプ成形されて所望のめっき層を含むホットスタンプ成形体が製造される。所望のめっき層を得る観点からは、めっき鋼板を800~1000℃の炉内に装入し、めっき鋼板の温度が所定の温度、例えば900℃に到達した後、炉内で5~50秒間保持することが好ましい。保持時間が50秒以上になると、めっき層の合金化が進行しすぎてしまい、比較的低いFe含有量を有するFe-Al相を形成することができなくなる場合がある。加熱雰囲気は特に限定されず、通常の条件でよく、例えば、大気中や、空気と燃料の比率を制御したガス燃焼雰囲気や、窒素雰囲気であればよく、これらガスにおいて露点を制御してもよい。加熱方法としては、例えば、通電加熱、高周波加熱、誘導加熱等が挙げられる。炉内での加熱保持後、めっき鋼板を炉から取り出し、次いでめっき鋼板が所定の温度、例えば850℃以下の所定の温度に到達した後、通常の条件下でホットスタンプ成形を行うことができる。ホットスタンプ成形後には、特に限定されないが、例えば250℃以下の温度域まで20℃/秒以上の平均冷却速度で冷却すればよい。
[Hot stamp forming process]
Finally, the obtained plated steel sheet is hot stamped in a hot stamp forming process to produce a hot stamped body including a desired plated layer. From the viewpoint of obtaining a desired plated layer, it is preferable to load the plated steel sheet into a furnace at 800 to 1000°C, and hold the plated steel sheet in the furnace for 5 to 50 seconds after the temperature of the plated steel sheet reaches a predetermined temperature, for example, 900°C. If the holding time is 50 seconds or more, the alloying of the plated steel layer progresses too much, and it may become impossible to form an Fe-Al phase having a relatively low Fe content. The heating atmosphere is not particularly limited, and may be under normal conditions, for example, in air, a gas combustion atmosphere with a controlled ratio of air to fuel, or a nitrogen atmosphere, and the dew point may be controlled in these gases. Examples of the heating method include electric heating, high-frequency heating, and induction heating. After heating and holding in the furnace, the plated steel sheet is removed from the furnace, and then the plated steel sheet reaches a predetermined temperature, for example, a predetermined temperature of 850°C or less, and hot stamp forming can be performed under normal conditions. After hot stamp forming, the material may be cooled to a temperature range of, for example, 250° C. or lower at an average cooling rate of 20° C./sec or higher, although this is not particularly limited.

 本製造方法によれば、めっき層全体の化学組成を所定の範囲内に制御しかつめっき層の付着量を片面当たり20g/m2以上とするとともに、当該めっき層が主としてFe2Al5相と、当該Fe2Al5相上に形成されかつ耐赤さび性の向上に有効なFe-Al相と、Mgで改質された表面酸化膜とによって構成され、さらにFe2Al5相中のFe-Al-Si相がΣLi/L0≦0.70を満たすよう分散されたホットスタンプ成形体を製造することができる。それゆえ、Fe2Al5相中にFe-Al-Si相を分散して形成することによって得られる腐食の進行抑制効果と、Fe-Al相の形成に起因する耐赤さび性向上効果と、Mgによる表面酸化膜の改質に起因する化成処理性向上効果との組み合わせにより、ホットスタンプ成形体の耐食性を顕著に向上させることが可能となる。したがって、このようなホットスタンプ成形体によれば、従来のホットスタンプ成形体と比較して、優れた耐食性を実現することが可能となる。このため、自動車や建築材料用途において長寿命化を通して、産業の発展に貢献することができる。 According to this manufacturing method, it is possible to manufacture a hot stamped body in which the chemical composition of the entire coating layer is controlled within a predetermined range, the coating weight of the coating layer is 20 g/m 2 or more per side, the coating layer is mainly composed of an Fe 2 Al 5 phase, an Fe-Al phase formed on the Fe 2 Al 5 phase and effective for improving red rust resistance, and a surface oxide film modified with Mg, and further, the Fe-Al-Si phase in the Fe 2 Al 5 phase is dispersed so as to satisfy ΣL i /L 0 ≦0.70. Therefore, it is possible to significantly improve the corrosion resistance of the hot stamped body by combining the effect of inhibiting the progress of corrosion obtained by dispersing and forming the Fe-Al-Si phase in the Fe 2 Al 5 phase, the effect of improving red rust resistance due to the formation of the Fe-Al phase, and the effect of improving chemical conversion treatability due to the modification of the surface oxide film by Mg. Therefore, according to such a hot stamped body, it is possible to realize superior corrosion resistance compared to conventional hot stamped bodies. This will contribute to industrial development by extending the service life of automobiles and building materials.

 以下、実施例によって本発明をより詳細に説明するが、以下の実施例は本発明の一例にすぎず、本発明はこれらの実施例に何ら限定されるものではない。本発明は、本発明の要旨を逸脱しない範囲で任意に変更可能であることは言うまでもない。 The present invention will be described in more detail below with reference to examples. However, the following examples are merely examples of the present invention, and the present invention is in no way limited to these examples. It goes without saying that the present invention can be modified as desired without departing from the gist of the present invention.

 以下の実施例では、本発明の実施形態に係るホットスタンプ成形体を種々の条件下で製造し、製造されたホットスタンプ成形体の特性について調べた。 In the following examples, hot stamped bodies according to embodiments of the present invention were manufactured under various conditions, and the properties of the manufactured hot stamped bodies were investigated.

 まず、溶鋼を連続鋳造法にて鋳造して、質量%でC:0.20%、Si:0.012%、Mn:1.30%、Al:0.030%、P:0.005%、S:0.0020%及びN:0.0030%、並びに残部:Fe及び不純物からなる化学組成を有するスラブを形成し、当該スラブを一旦冷却した後、1200℃に再加熱して熱間圧延し、次いで600℃以下の温度で巻き取った。熱間圧延は、粗圧延と仕上げ圧延を行うことにより実施し、仕上げ圧延の終了温度は900~1050℃、仕上げ圧延の圧下率は30%であった。次に、得られた熱間圧延鋼板に酸洗を施し、次いで圧下率50%で冷間圧延して、1.6mmの板厚を有する冷間圧延鋼板を得た。次に、得られた冷間圧延鋼板に対し、酸素濃度20ppm以下の炉内において水素4%及び窒素バランスの混合ガス雰囲気中、表1に示す条件下で焼鈍工程を実施し、次いで10℃/s以上の平均冷却速度で冷却して鋼母材を製造した。 First, molten steel was cast by continuous casting to form a slab having a chemical composition by mass of C: 0.20%, Si: 0.012%, Mn: 1.30%, Al: 0.030%, P: 0.005%, S: 0.0020%, and N: 0.0030%, with the balance being Fe and impurities. The slab was once cooled, then reheated to 1200°C and hot rolled, and then coiled at a temperature of 600°C or less. The hot rolling was performed by rough rolling and finish rolling, with the finishing temperature of the finish rolling being 900-1050°C and the reduction ratio of the finish rolling being 30%. Next, the obtained hot-rolled steel sheet was pickled and then cold rolled at a reduction ratio of 50% to obtain a cold-rolled steel sheet having a thickness of 1.6 mm. Next, the obtained cold-rolled steel sheet was subjected to an annealing process under the conditions shown in Table 1 in a mixed gas atmosphere of 4% hydrogen and the balance of nitrogen in a furnace with an oxygen concentration of 20 ppm or less, and then cooled at an average cooling rate of 10°C/s or more to produce a steel base material.

 次に、製造した鋼母材を100mm×200mmに切断し、自社製のバッチ式溶融めっき試験装置を用いて当該鋼母材にめっきを施した。より具体的には、まず、製造した鋼母材を種々の化学組成及び表1に示すめっき浴温を有するめっき浴に表1に示す侵入板温で導入して約3秒間浸漬し、次いでこれを引上速度20~200mm/sで引き上げ、N2ガスワイピングによりめっき層の付着量を表1に示す値に調整した。次に、めっき層を付着した鋼母材を、冷却ガスとして窒素ガスを用いて480℃まで表1に示す平均冷却速度で1次冷却し、次いで480℃から300℃まで表1に示す平均冷却速度で2次冷却することにより、鋼母材の両面にめっき層が形成されためっき鋼板を得た。板温は鋼母材の中心部にスポット溶接した熱電対を用いて測定した。 Next, the produced steel base material was cut into 100 mm x 200 mm, and the steel base material was plated using a batch-type hot-dip plating test device manufactured by our company. More specifically, the produced steel base material was first introduced into a plating bath having various chemical compositions and plating bath temperatures shown in Table 1 at the entry sheet temperature shown in Table 1 and immersed for about 3 seconds, then pulled up at a pulling speed of 20 to 200 mm/s, and the coating weight of the plating layer was adjusted to the value shown in Table 1 by N2 gas wiping. Next, the steel base material with the plating layer attached was primarily cooled to 480°C at the average cooling rate shown in Table 1 using nitrogen gas as a cooling gas, and then secondarily cooled from 480°C to 300°C at the average cooling rate shown in Table 1, thereby obtaining a plated steel sheet with a plating layer formed on both sides of the steel base material. The sheet temperature was measured using a thermocouple spot-welded to the center of the steel base material.

[めっき層の化学組成分析など]
 ホットスタンプ成形後のめっき層の化学組成は以下のようにして決定した。まず、めっき鋼板を通電加熱により加熱し、めっき鋼板の温度が900℃に到達した後、10秒間保持した。次に、めっき鋼板を炉から取り出し、室温程度の温度にある平板金型でめっき鋼板を挟み込み急冷し、鋼母材側から順にFe2Al5相と、20~40質量%のFe含有量を有するFe-Al相と、表面酸化膜とを含むめっき層を備えたホットスタンプ成形体を得た。加熱及び急冷後のホットスタンプ成形体を30mm×30mmに切断したサンプルのめっき層を、10%の塩酸に0.04%のイビット710K(朝日化学工業製)を加えた室温の酸性水溶液で溶解し、得られた酸溶液をICP発光分光法によって測定することによりめっき層の化学組成を決定した。また、この酸洗剥離前後のサンプルの質量を測定し、その質量の変化からめっき層の付着量を決定した。その結果を表1に示す。
[Chemical composition analysis of plating layer, etc.]
The chemical composition of the plating layer after hot stamp forming was determined as follows. First, the plated steel sheet was heated by electrical heating, and after the temperature of the plated steel sheet reached 900°C, it was held for 10 seconds. Next, the plated steel sheet was removed from the furnace, and the plated steel sheet was sandwiched between flat plate dies at about room temperature and quenched to obtain a hot stamped body having a plating layer including, from the steel base metal side, an Fe 2 Al 5 phase, an Fe-Al phase having an Fe content of 20 to 40 mass%, and a surface oxide film. The plated layer of the sample cut into 30 mm x 30 mm of the hot stamped body after heating and quenching was dissolved in an acidic aqueous solution at room temperature containing 10% hydrochloric acid and 0.04% IBIT 710K (manufactured by Asahi Chemical Industry Co., Ltd.), and the obtained acid solution was measured by ICP emission spectroscopy to determine the chemical composition of the plating layer. In addition, the mass of the sample before and after the pickling and peeling was measured, and the adhesion amount of the plating layer was determined from the change in mass. The results are shown in Table 1.

[めっき層の組織分析]
 前述の方法により、Fe2Al5相、20~40質量%のFe含有量を有するFe-Al相、Si含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相、及び表面酸化膜を同定し、表面酸化膜については、同様に前述の方法によりMg含有量を決定した。さらに、前述の方法によりΣLi/L0の値を決定した。なお、20~40質量%のFe含有量を有するFe-Al相がない実施例(具体的には、比較例40)を除き、前記鋼母材の側から順に、Fe2Al5相と、20~40質量%のFe含有量を有するFe-Al相と、表面酸化膜とが、存在していた。
[Structural analysis of plating layer]
The Fe2Al5 phase, the Fe-Al phase having an Fe content of 20 to 40 mass%, the Fe-Al-Si phase having an Si content of 5 to 20 mass% and an equivalent circle diameter of 2 μm or more, and the surface oxide film were identified by the above-mentioned method, and the Mg content of the surface oxide film was determined by the above-mentioned method. Furthermore, the value of ΣL i /L 0 was determined by the above-mentioned method. Note that, except for the example that did not have an Fe-Al phase having an Fe content of 20 to 40 mass% (specifically, Comparative Example 40), the Fe2Al5 phase, the Fe-Al phase having an Fe content of 20 to 40 mass%, and the surface oxide film were present in this order from the side of the steel base material.

[耐赤さび性]
 ホットスタンプ成形後の耐赤さび性は以下のようにして評価した。まず、めっき鋼板を通電加熱により加熱し、めっき鋼板の温度が900℃に到達した後、10秒間保持した。次に、めっき鋼板を炉から取り出し、室温程度の温度にある平板金型でめっき鋼板を挟み込み急冷した。加熱及び急冷後のホットスタンプ成形体のサンプル50mm×100mmを、りん酸Zn処理(SD5350システム:日本ペイント・インダストリアルコーディング社製規格)に従い実施し、次いで電着塗装(PN110パワーニクスグレー:日本ペイント・インダストリアルコーディング社製規格)を20μmで実施して、温度150℃及び20分で焼き付け処理を行った。次に、サンプル中央に地鉄(鋼母材)へ到達するカットを導入した。次いで、JIS H 8502:1999の8.1で規定される中性塩水噴霧サイクル試験を実施してカット部から赤さびが発生するサイクル数を測定し、以下のようにして耐食性を評価した。
  A  :3サイクル以上
  B  :3サイクル未満
[Red rust resistance]
The red rust resistance after hot stamp forming was evaluated as follows. First, the plated steel sheet was heated by electrical heating, and after the temperature of the plated steel sheet reached 900°C, it was held for 10 seconds. Next, the plated steel sheet was removed from the furnace, and the plated steel sheet was sandwiched between flat molds at about room temperature and quenched. A sample of the hot stamp formed body after heating and quenching, 50 mm x 100 mm, was subjected to Zn phosphate treatment (SD5350 system: Nippon Paint Industrial Coating Co., Ltd. standard), and then electrocoating (PN110 Powernics Gray: Nippon Paint Industrial Coating Co., Ltd. standard) was performed at 20 μm, and baking treatment was performed at a temperature of 150°C and 20 minutes. Next, a cut reaching the base steel (steel base material) was introduced into the center of the sample. Next, a neutral salt spray cycle test as specified in JIS H 8502:1999, 8.1 was carried out to measure the number of cycles until red rust was generated from the cut portion, and the corrosion resistance was evaluated as follows.
A: 3 or more cycles B: Less than 3 cycles

[化成処理性]
 化成処理性は以下のようにして評価した。まず、めっき鋼板を通電加熱により加熱し、めっき鋼板の温度が900℃に到達した後、10秒間保持した。次に、めっき鋼板を炉から取り出し、室温程度の温度にある平板金型でめっき鋼板を挟み込み急冷した。加熱及び急冷後のホットスタンプ成形体のサンプル50mm×100mmを、りん酸Zn処理(SD5350システム:日本ペイント・インダストリアルコーディング社製規格)に従い実施し、化成処理皮膜を形成させた。次に、蛍光X線分析によってP強度を測定し、検量線を用いて、化成処理皮膜の付着量へ換算した。化成処理皮膜の付着量に応じて、以下の評価基準によりホットスタンプ成形体の化成処理性を評価した。
  AA:付着量0.9g/m2以上
  A :付着量0.1~0.9g/m2未満
  B :付着量0.1g/m2未満
[Chemical conversion treatment properties]
The chemical conversion treatability was evaluated as follows. First, the plated steel sheet was heated by electrical heating, and after the temperature of the plated steel sheet reached 900°C, it was held for 10 seconds. Next, the plated steel sheet was removed from the furnace, and the plated steel sheet was sandwiched between flat molds at about room temperature and quenched. A sample of 50 mm x 100 mm of the hot stamped body after heating and quenching was subjected to Zn phosphate treatment (SD5350 system: standard manufactured by Nippon Paint Industrial Coating Co., Ltd.) to form a chemical conversion coating. Next, the P intensity was measured by fluorescent X-ray analysis, and the calibration curve was used to convert it into the adhesion amount of the chemical conversion coating. The chemical conversion treatability of the hot stamped body was evaluated according to the following evaluation criteria according to the adhesion amount of the chemical conversion coating.
AA: Adhesion amount 0.9 g/ m2 or more A: Adhesion amount 0.1 to less than 0.9 g/ m2 B: Adhesion amount less than 0.1 g/ m2

[塗膜膨れ]
 塗膜膨れは以下のようにして評価した。まず、耐赤さび性の場合と同様に加熱及び急冷した後のホットスタンプ成形体のサンプル50mm×100mmを、りん酸Zn処理(SD5350システム:日本ペイント・インダストリアルコーディング社製規格)に従い実施し、次いで電着塗装(PN110パワーニクスグレー:日本ペイント・インダストリアルコーディング社製規格)を20μmで実施して、温度150℃及び20分で焼き付け処理を行った。次に、サンプル中央に地鉄(鋼母材)へ到達するカットを導入した。次いで、JIS H 8502:1999の8.1で規定される中性塩水噴霧サイクル試験を120サイクル実施して塗膜膨れ幅を測定し、以下のようにして耐食性を評価した。
  AAA:2mm以下
  AA :2超~3mm
  A  :3超~4mm
  B  :4mm超
[Paint blister]
The coating blister was evaluated as follows. First, a sample of 50 mm x 100 mm of the hot stamped body after heating and quenching in the same manner as in the case of red rust resistance was subjected to Zn phosphate treatment (SD5350 system: Nippon Paint Industrial Coating Co., Ltd. standard), then electrocoating (PN110 Powernics Gray: Nippon Paint Industrial Coating Co., Ltd. standard) was performed at 20 μm, and baking treatment was performed at a temperature of 150 ° C and 20 minutes. Next, a cut reaching the base steel (steel base material) was introduced in the center of the sample. Next, a neutral salt spray cycle test specified in 8.1 of JIS H 8502:1999 was performed for 120 cycles to measure the coating blister width, and the corrosion resistance was evaluated as follows.
AAA: 2mm or less AA: More than 2 to 3mm
A: More than 3 to 4 mm
B: More than 4 mm

 耐赤さび性の評価がAであり、化成処理性の評価がAA及びAであり、塗膜膨れの評価がAAA、AA及びAである場合を、ホットスタンプ成形後においても改善された耐食性を有するAl含有めっき層を備えたホットスタンプ成形体として評価した。その結果を表1に示す。  If the red rust resistance rating was A, the chemical conversion treatability ratings were AA and A, and the paint blister ratings were AAA, AA and A, the hot stamped body was evaluated as having an Al-containing plating layer with improved corrosion resistance even after hot stamping. The results are shown in Table 1.

 表1を参照すると、比較例32では、めっき工程の侵入板温が高かったために、ホットスタンプ成形前のめっき層中の界面合金層において所望のSi含有量が得られなかったと考えられる。その結果として、ホットスタンプ成形後のめっき層においてFe2Al5相中のFe-Al-Si相の形成が顕著となってΣLi/L0の値が大きくなり、ホットスタンプ成形後の耐食性が低下した。比較例33では、めっき後から480℃までの1次冷却における平均冷却速度が遅かったために、ホットスタンプ成形前のめっき層中にMg2Si相が多く形成し、Mg-Al-Zn-Si系金属間化合物相を十分に形成させることができなかったと考えられる。その結果として、ホットスタンプ成形後の表面酸化物中にMgを十分に導入することができず、化成処理性が低下した。比較例34では、480℃から300℃までの2次冷却における平均冷却速度が速かったために、ホットスタンプ成形前のめっき層におけるMgの多くがα-Al相中に固溶されてしまい、同様にMg-Al-Zn-Si系金属間化合物相を十分に形成させることができなかったと考えられる。その結果として、ホットスタンプ成形後の表面酸化物中にMgを十分に導入することができず、化成処理性が低下した。比較例35では、めっき層中のZn含有量が低かったために、化成処理の際にりん酸との反応が十分に進行せず、化成処理性が低下した。比較例36では、めっき層中のSi含有量が高く、Fe-Al-Si相の形成が顕著となってΣLi/L0の値が大きくなり、ホットスタンプ成形後の耐食性が低下した。比較例37では、めっき層中のSi含有量が低かったために、めっき層の密着性が低下して、ホットスタンプ成形後の耐食性が低下した。比較例38では、めっき層中のMg含有量が低かったために、ホットスタンプ成形後の表面酸化物中にMgを十分に導入することができず、化成処理性が低下した。比較例39では、めっき層の付着量が十分でなかったために、ホットスタンプ成形後の耐食性が低下した。比較例40では、過度な合金化に起因してめっき層中のFe含有量が高くなり、20~40質量%のFe含有量を有するFe-Al相を形成することができなかった。その結果としてホットスタンプ成形後の耐赤さび性が低下した。比較例41では、めっき浴温が低かったために、鋼母材をめっき浴に浸漬したときにめっき浴が凝固してしまい、めっき層を適切に形成することができなかった。このため、その後の製造を停止し、分析及び性能評価は行わなかった。 With reference to Table 1, in Comparative Example 32, it is considered that the desired Si content was not obtained in the interface alloy layer in the coating layer before hot stamp forming because the entry sheet temperature in the coating process was high. As a result, the formation of the Fe-Al-Si phase in the Fe 2 Al 5 phase in the coating layer after hot stamp forming became significant, the value of ΣL i /L 0 became large, and the corrosion resistance after hot stamp forming deteriorated. In Comparative Example 33, it is considered that the average cooling rate in the primary cooling from after coating to 480°C was slow, so that a large amount of Mg 2 Si phase was formed in the coating layer before hot stamp forming, and the Mg-Al-Zn-Si intermetallic compound phase could not be sufficiently formed. As a result, Mg could not be sufficiently introduced into the surface oxide after hot stamp forming, and the chemical conversion treatability deteriorated. In Comparative Example 34, since the average cooling rate in the secondary cooling from 480°C to 300°C was fast, most of the Mg in the plating layer before hot stamp forming was dissolved in the α-Al phase, and it is considered that the Mg-Al-Zn-Si intermetallic compound phase could not be sufficiently formed. As a result, Mg could not be sufficiently introduced into the surface oxide after hot stamp forming, and the chemical conversion treatability was reduced. In Comparative Example 35, since the Zn content in the plating layer was low, the reaction with phosphoric acid did not proceed sufficiently during the chemical conversion treatment, and the chemical conversion treatability was reduced. In Comparative Example 36, since the Si content in the plating layer was high, the formation of the Fe-Al-Si phase became significant, the value of ΣL i /L 0 became large, and the corrosion resistance after hot stamp forming was reduced. In Comparative Example 37, since the Si content in the plating layer was low, the adhesion of the plating layer was reduced, and the corrosion resistance after hot stamp forming was reduced. In Comparative Example 38, since the Mg content in the plating layer was low, Mg could not be sufficiently introduced into the surface oxide after hot stamp forming, and the chemical conversion treatability was reduced. In Comparative Example 39, since the adhesion amount of the plating layer was insufficient, the corrosion resistance after hot stamp forming was reduced. In Comparative Example 40, the Fe content in the plating layer was high due to excessive alloying, and it was not possible to form an Fe-Al phase having an Fe content of 20 to 40 mass%. As a result, the red rust resistance after hot stamp forming was reduced. In Comparative Example 41, since the plating bath temperature was low, the plating bath solidified when the steel base material was immersed in the plating bath, and the plating layer could not be properly formed. For this reason, the subsequent production was stopped, and analysis and performance evaluation were not performed.

 これとは対照的に、全ての実施例に係るホットスタンプ成形体においてめっき層全体の化学組成を所定の範囲内に制御しかつめっき層の付着量を片面当たり20g/m2以上とするとともに、当該めっき層を主としてFe2Al5相と、Fe-Al相と、Mgで改質された表面酸化膜とによって構成し、さらに当該Fe2Al5相中のFe-Al-Si相をΣLi/L0≦0.70を満たすように分散させることで、900℃の高温下にさらされた場合であっても、Fe2Al5相中にFe-Al-Si相を分散して形成することによって得られる腐食の進行抑制効果と、Fe-Al相の形成に起因する耐赤さび性向上効果と、Mgによる表面酸化膜の改質に起因する化成処理性向上効果との組み合わせにより、ホットスタンプ成形体の耐食性を顕著に向上させることができた。また、全ての実施例に係るホットスタンプ成形前のめっき鋼板について、めっき層の断面をEPMAによって元素濃度測定したところ、界面合金層中のSi含有量は比較例32よりも高く、いずれも3.0質量%以上であった。また、全ての実施例に係るホットスタンプ成形前のめっき層について、EPMAを用いて得られたマッピング像の元素分布像から測定したところ、Al含有量が10質量%以上のMg-Al-Zn-Si系金属間化合物相がめっき層中に面積率で0.010%を大きく超える量で含まれていた。一方で、比較例33及び34では、ホットスタンプ成形前のめっき層中に当該Mg-Al-Zn-Si系金属間化合物相は含まれていなかった。とりわけ、めっき層全体の化学組成がZn:5.0~35.0%及びSi:0.25~6.0%を含有し、表面酸化膜中のMg含有量が0.30原子%以上であり、さらにΣLi/L0≦0.50の関係を満足するように制御した実施例27~31では、耐赤さび性の評価がA、化成処理性の評価がAAであることに加えて、塗膜膨れの評価がAAAとなり、耐食性をより一層向上させることができた。また、各ホットスタンプ成形体についてGDS測定を行ったところ、全ての実施例に係るホットスタンプ成形体において、鋼母材とめっき層との間に、Fe-Al固溶体層、Fe-Zn固溶体層、及び/又はFe-Al-Zn固溶体層を含む固溶体層の存在を確認した。 In contrast to this, in all of the hot stamped steels according to the present invention, the chemical composition of the entire plating layer was controlled within a prescribed range, the coating weight of the plating layer was set to 20 g/ m2 or more per side, the plating layer was composed mainly of an Fe2Al5 phase, an Fe-Al phase, and a surface oxide film modified with Mg, and the Fe-Al-Si phase in the Fe2Al5 phase was dispersed so as to satisfy ΣL i /L 0 ≦0.70. As a result, even when exposed to a high temperature of 900°C, the corrosion resistance of the hot stamped steel was significantly improved by a combination of the corrosion progression inhibition effect obtained by dispersing and forming an Fe-Al-Si phase in the Fe2Al5 phase, the effect of improving red rust resistance due to the formation of the Fe-Al phase, and the effect of improving chemical conversion treatability due to the modification of the surface oxide film with Mg. In addition, for the plated steel sheets according to all the Examples before hot stamp forming, the cross sections of the plated layers were measured for element concentration by EPMA, and the Si content in the interface alloy layer was higher than that in Comparative Example 32, being 3.0 mass% or more in all the Examples. In addition, for the plated layers according to all the Examples before hot stamp forming, the element distribution images of the mapping images obtained by EPMA were measured, and it was found that the Mg-Al-Zn-Si-based intermetallic compound phase having an Al content of 10 mass% or more was contained in the plated layer in an amount significantly exceeding 0.010% in terms of area ratio. On the other hand, in Comparative Examples 33 and 34, the Mg-Al-Zn-Si-based intermetallic compound phase was not contained in the plated layers before hot stamp forming. In particular, in Examples 27 to 31 in which the chemical composition of the entire plating layer contained 5.0 to 35.0% Zn and 0.25 to 6.0% Si, the Mg content in the surface oxide film was 0.30 atomic % or more, and the relationship ΣL i /L 0 ≦0.50 was satisfied, the red rust resistance was rated A, the chemical conversion treatability was rated AA, and the coating blistering was rated AAA, thereby further improving the corrosion resistance. Furthermore, when GDS measurement was performed on each hot stamped product, the presence of a solid solution layer containing an Fe-Al solid solution layer, an Fe-Zn solid solution layer, and/or an Fe-Al-Zn solid solution layer was confirmed between the steel base material and the plating layer in the hot stamped products of all the Examples.

 1  ホットスタンプ成形体
 2  鋼母材
 3  めっき層
 4  Fe2Al5
 5  20~40質量%のFe含有量を有するFe-Al相
 6  表面酸化膜
 7  Si含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相
REFERENCE SIGNS LIST 1 Hot stamped body 2 Steel base material 3 Coating layer 4 Fe 2 Al 5 phase 5 Fe-Al phase having an Fe content of 20 to 40 mass % 6 Surface oxide film 7 Fe-Al-Si phase having a Si content of 5 to 20 mass % and an equivalent circle diameter of 2 μm or more

Claims (3)

 鋼母材と、前記鋼母材の表面に配置されためっき層とを備え、
 前記めっき層の化学組成が、質量%で、
 Zn:2.5~40.0%、
 Si:0.05~15.0%、
 Fe:25.0~40.0%、
 Mg:0.005~3.000%、
 Ni:0~0.500%、
 Ca:0~3.000%、
 Sb:0~0.500%、
 Pb:0~0.500%、
 Cu:0~1.000%、
 Sn:0~1.000%、
 Ti:0~1.000%、
 Cr:0~1.000%、
 Nb:0~1.000%、
 Zr:0~1.000%、
 Mn:0~1.000%、
 Mo:0~1.000%、
 Ag:0~1.000%、
 Li:0~1.000%、
 La:0~0.500%、
 Ce:0~0.500%、
 B :0~0.500%、
 Y :0~0.500%、
 Sr:0~0.500%、
 In:0~0.500%、
 Co:0~0.500%、
 Bi:0~0.500%、
 P :0~0.500%、
 W :0~0.500%、並びに
 残部:Al及び不純物であり、かつ、
 Ni、Ca、Sb、Pb、Cu、Sn、Ti、Cr、Nb、Zr、Mn、Mo、Ag、Li、La、Ce、B、Y、Sr、In、Co、Bi、P、及びWの合計含有量が5.000%以下であり、
 前記めっき層が、前記鋼母材の側から順に、Fe2Al5相と、20~40質量%のFe含有量を有するFe-Al相と、表面酸化膜とを含み、
 前記めっき層の断面において、前記Fe2Al5相中のSi含有量が5~20質量%でかつ円相当直径が2μm以上のFe-Al-Si相の投影長さLiと、前記鋼母材の表面の長さL0がΣLi/L0≦0.70を満たし、
 前記表面酸化膜中のMg含有量が0.05原子%以上であり、
 前記めっき層の付着量が片面当たり20g/m2以上であることを特徴とする、ホットスタンプ成形体。
A steel base material and a plating layer disposed on a surface of the steel base material,
The chemical composition of the plating layer is, in mass%,
Zn: 2.5-40.0%,
Si: 0.05-15.0%,
Fe: 25.0-40.0%,
Mg: 0.005-3.000%,
Ni: 0 to 0.500%,
Ca: 0-3.000%,
Sb: 0 to 0.500%,
Pb: 0 to 0.500%,
Cu: 0 to 1.000%,
Sn: 0-1.000%,
Ti: 0 to 1.000%,
Cr: 0-1.000%,
Nb: 0 to 1.000%,
Zr: 0 to 1.000%,
Mn: 0 to 1.000%,
Mo: 0-1.000%,
Ag: 0-1.000%,
Li: 0 to 1.000%,
La: 0 to 0.500%,
Ce: 0-0.500%,
B: 0 to 0.500%,
Y: 0 to 0.500%,
Sr: 0-0.500%,
In: 0 to 0.500%,
Co: 0 to 0.500%,
Bi: 0-0.500%,
P: 0 to 0.500%,
W: 0 to 0.500%, and the balance: Al and impurities,
The total content of Ni, Ca, Sb, Pb, Cu, Sn, Ti, Cr, Nb, Zr, Mn, Mo, Ag, Li, La, Ce, B, Y, Sr, In, Co, Bi, P, and W is 5.000% or less;
the plating layer includes, in order from the steel base material side, an Fe2Al5 phase, an Fe-Al phase having an Fe content of 20 to 40 mass %, and a surface oxide film;
In a cross section of the coating layer, a projected length L i of an Fe-Al-Si phase having a Si content of 5 to 20 mass % in the Fe 2 Al 5 phase and an equivalent circle diameter of 2 μm or more and a length L 0 of the surface of the steel base material satisfy ΣL i /L 0 ≦0.70,
The Mg content in the surface oxide film is 0.05 atomic % or more,
A hot stamped product, characterized in that the coating weight of the plating layer per side is 20 g/m2 or more .
 前記めっき層の化学組成が、質量%で、
 Zn:5.0~35.0%、及び
 Si:0.25~6.0%を含有し、
 前記表面酸化膜中のMg含有量が0.30原子%以上であることを特徴とする、請求項1に記載のホットスタンプ成形体。
The chemical composition of the plating layer is, in mass%,
Contains Zn: 5.0 to 35.0% and Si: 0.25 to 6.0%;
2. The hot stamped steel according to claim 1, wherein the surface oxide film has a Mg content of 0.30 atomic % or more.
 ΣLi/L0≦0.50であることを特徴とする、請求項1又は2に記載のホットスタンプ成形体。 The hot stamped steel according to claim 1 or 2, characterized in that ΣL i /L 0 ≦0.50.
PCT/JP2024/032794 2023-10-12 2024-09-13 Hot-stamp molded body Pending WO2025079386A1 (en)

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JP2023-176662 2023-10-12

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019180853A1 (en) * 2018-03-20 2019-09-26 日本製鉄株式会社 Hot stamp molded body
JP2020510755A (en) * 2017-02-28 2020-04-09 タタ、スティール、アイモイデン、ベスローテン、フェンノートシャップTata Steel Ijmuiden Bv Manufacturing method of hot formed coated steel products
WO2022161049A1 (en) * 2021-01-28 2022-08-04 宝山钢铁股份有限公司 Aluminum plated steel sheet, thermoformed component, and manufacturing methods
JP2023532501A (en) * 2020-06-30 2023-07-28 ヒュンダイ スチール カンパニー Steel plate for hot press and manufacturing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020510755A (en) * 2017-02-28 2020-04-09 タタ、スティール、アイモイデン、ベスローテン、フェンノートシャップTata Steel Ijmuiden Bv Manufacturing method of hot formed coated steel products
WO2019180853A1 (en) * 2018-03-20 2019-09-26 日本製鉄株式会社 Hot stamp molded body
JP2023532501A (en) * 2020-06-30 2023-07-28 ヒュンダイ スチール カンパニー Steel plate for hot press and manufacturing method thereof
WO2022161049A1 (en) * 2021-01-28 2022-08-04 宝山钢铁股份有限公司 Aluminum plated steel sheet, thermoformed component, and manufacturing methods

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