WO2021039971A1 - ホットスタンプ成形体 - Google Patents

ホットスタンプ成形体 Download PDF

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Publication number
WO2021039971A1
WO2021039971A1 PCT/JP2020/032643 JP2020032643W WO2021039971A1 WO 2021039971 A1 WO2021039971 A1 WO 2021039971A1 JP 2020032643 W JP2020032643 W JP 2020032643W WO 2021039971 A1 WO2021039971 A1 WO 2021039971A1
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Prior art keywords
chemical conversion
plating layer
hot
conversion treatment
film
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PCT/JP2020/032643
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English (en)
French (fr)
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WO2021039971A9 (ja
Inventor
卓哉 光延
公平 ▲徳▼田
高橋　武寛
浩史 竹林
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日本製鉄株式会社
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Application filed by 日本製鉄株式会社 filed Critical 日本製鉄株式会社
Priority to MX2022002232A priority Critical patent/MX2022002232A/es
Priority to JP2021543047A priority patent/JP7332943B2/ja
Priority to CN202080059411.1A priority patent/CN114286869B/zh
Priority to US17/632,553 priority patent/US20220275481A1/en
Priority to EP20856236.3A priority patent/EP4023790A4/en
Priority to KR1020227005880A priority patent/KR102649501B1/ko
Publication of WO2021039971A1 publication Critical patent/WO2021039971A1/ja
Publication of WO2021039971A9 publication Critical patent/WO2021039971A9/ja

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
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    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
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    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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    • C22C—ALLOYS
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    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18—Removing excess of molten coatings from elongated material
    • C23C2/20—Strips; Plates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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    • C—CHEMISTRY; METALLURGY
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    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
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    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
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Definitions

  • the present invention relates to a hot stamped article.
  • the present application claims priority based on Japanese Patent Application No. 2019-157205 filed in Japan on August 29, 2019, the contents of which are incorporated herein by reference.
  • a material having high mechanical strength tends to have low shape freezing property in molding processing such as bending processing, and when processing into a complicated shape, the processing itself becomes difficult.
  • hot stamping method hot stamping method, high temperature pressing method, die quenching method
  • the material to be molded is once heated to a high temperature, and the material softened by heating is pressed and molded, or then cooled at the same time as molding.
  • the material is once heated to a high temperature to be softened and then pressed in a softened state, so that the material can be easily pressed. Therefore, by this hot press working, a press-molded product having both good shape freezing property and high mechanical strength can be obtained.
  • the mechanical strength of the press-molded product can be increased by the quenching effect of cooling after molding.
  • the steel sheet before hot stamping is coated with plating or the like to improve the corrosion resistance and omit the descaling step.
  • Patent Document 1 As such a plated steel material, for example, in Patent Document 1, an Al—Zn-based alloy plating layer containing Al: 20 to 95% by mass, Ca + Mg: 0.01 to 10% by mass, and Si is provided on the surface of the steel sheet.
  • a plated steel sheet for hot pressing which is characterized by having, is disclosed. According to Patent Document 1, scale formation is suppressed during heating before hot pressing, plating does not adhere to the mold during hot pressing, and the obtained hot press member has a good appearance. It is disclosed that it has excellent coating adhesion and corrosion resistance.
  • Patent Document 2 discloses a plated steel material in which a plating layer containing an Al—Fe alloy layer and a Zn—Mg—Al alloy layer is provided on the surface of the steel material, and the corrosion resistance is dramatically improved.
  • the members obtained by hot stamping the plated steel material as described above are often applied to automobile parts, and when applied as automobile parts, the members are generally subjected to chemical conversion treatment.
  • Patent Document 1 and Patent Document 2 no studies have been made on the characteristics when the chemical conversion treatment film is formed.
  • zinc phosphate treatment which is a general chemical conversion treatment for automobiles. It was found that the zinc phosphate film is difficult to form, or even if it is formed, the adhesion of the coating film when an electrodeposition coating film or the like is formed on the surface may not be sufficient.
  • Patent Document 3 discloses a method of treating the surface of a zinc-aluminum-magnesium alloy plated steel sheet with a metal surface treatment agent.
  • a reaction layer containing fluorides of Al and Mg is formed on the surface of the plating layer of the plated steel sheet by the chemical conversion treatment, and the chemical conversion film adheres to the surface of the plating layer. It is disclosed that the power can be further enhanced.
  • Patent Document 3 does not study the adhesion of the coating film when an electrodeposition coating film or the like is formed on the chemical conversion coating film.
  • An object of the present invention is to provide a hot stamped molded product having a chemical conversion-treated film having suppressed scale and excellent coating film adhesion.
  • the present inventions By controlling the composition balance of the plating layer of the molten Zn-Al-Mg plated steel sheet and the conditions at the time of manufacture, the present inventions have a chemical conversion-treated film in which scale is suppressed and the coating adhesion is excellent. It was found that a stamped product can be obtained.
  • the present invention has been completed based on the above findings, and the gist thereof is as follows.
  • the hot stamp molded body includes a base material made of steel, a plating layer formed on the surface of the base material, and a chemical conversion treatment film formed on the surface of the plating layer.
  • the chemical composition of the plating layer is, in terms of mass%, Al: 20.00 to 45.00%, Fe: 10.00 to 45.00%, Mg: 4.50 to 15.00%, Si: 0.10 to 3.00%, Ca: 0.05 to 3.00%, Sb: 0 to 0.50%, Pb: 0 to 0.50%, Cu: 0 to 1.00%, Sn: 0 ⁇ 1.00%, Ti: 0 to 1.00%, Sr: 0 to 0.50%, Cr: 0 to 1.00%, Ni: 0 to 1.00%, Mn: 0 to 1.00% Zinc phosphate crystal containing, the balance is Zn and impurities, and the chemical conversion coating film contains Mg: 5.0 to 50.0% and Ca: 0.5 to 5.0% in mass%.
  • the one-sided adhesion amount of the chemical conversion treatment film is 0.1 to 10.0 g / m 2 .
  • the chemical composition of the plating layer is mass%, Al: 25.00 to 35.00%, Mg: 6.00 to 10.00%. , 1 or 2 may be contained.
  • the amount of the chemical conversion-treated film adhered to one side may be 1.5 to 8.0 g / m 2.
  • the hot stamping compact 1 has a base material 2 made of steel, a plating layer 3 formed on the surface of the base material 2, and a chemical conversion formed on the surface of the plating layer 3.
  • the treatment film 4 is provided.
  • the plating layer 3 and the chemical conversion treatment film 4 are formed on only one side of the base material 2, but may be formed on both sides.
  • the base material 2 is made of steel.
  • the base material 2 is, for example, a hot stamping member obtained by hot stamping a steel plate. Therefore, although it has a plate shape in FIG. 1, the shape is not limited. Further, in the hot stamped molded product 1 according to the present embodiment, the plating layer 3 and the chemical conversion treatment film 4 are important, and the chemical composition of the base material 2 and the like are not particularly limited.
  • the steel to be subjected to plating, hot stamping, and chemical conversion treatment may be determined according to the applicable product, the required strength, the plate thickness, and the like.
  • a hot-rolled steel sheet described in JIS G3193: 2008 or a cold-rolled steel sheet described in JIS G3141: 2017 can be used.
  • Al 20.00-45.00%
  • Al is an essential element for improving the corrosion resistance of the plating layer 3.
  • Ca and Al are mainly used, which suppress the evaporation of Zn and Mg during the heating of the hot stamp and serve as a source of Ca to the chemical conversion treatment layer. Intermetallic compounds are not sufficiently formed on the surface of the plating layer. As a result, the scale of the chemical conversion treatment film 4 formed on the plating layer 3 becomes large. Therefore, the Al content is set to 20.00% or more. It is preferably 25.00% or more.
  • the Al content is set to 45.00% or less. It is preferably 35.00% or less.
  • Fe 10.00-45.00%
  • the Fe content is set to 10.00% or more.
  • the Fe content is set to 45.00% or less.
  • Mg 4.50 to 15.00%
  • Mg is an element that contributes to the improvement of the corrosion resistance of the plating layer 3. Further, Mg has an effect of suppressing LME cracking because it binds to the Zn component in the plating layer 3 to prevent the generation of liquid phase Zn when the hot stamp is heated. Further, in the hot stamp molded product 1 according to the present embodiment, Mg is an element that diffuses into the chemical conversion treatment film 4 to enhance the adhesion of the coating film. In order to obtain these effects, the Mg content is set to 4.50% or more. If the Mg content is less than 4.50%, the coating film adhesion is lowered. The Mg content is preferably 6.0% or more.
  • the Mg content exceeds 15.00%, sacrificial anticorrosion works excessively, and the corrosion resistance of the plating layer 3 tends to decrease. Further, a large amount of Mg-based intermetallic compounds that reduce the chemical conversion treatment property are formed in the plating layer 3, and as a result, the scale of the chemical conversion treatment film 4 is increased and the coating film adhesion is lowered. Therefore, the Mg content is set to 15.00% or less. It is preferably 10.00% or less.
  • Si 0.10 to 3.00%
  • Si is an element that forms a compound together with Mg and contributes to the improvement of corrosion resistance. Further, Si suppresses the formation of an excessively thick alloy layer formed between the surface of the steel sheet and the plating layer when the plating layer is formed on the steel sheet, and the adhesion between the steel sheet and the plating layer is suppressed. It is also an element that has the effect of increasing the plating. If the Si content is less than 0.10%, these effects cannot be sufficiently obtained. Therefore, the Si content is set to 0.10% or more.
  • the Si content exceeds 3.00%, Mg 2 Si, Mg 2 Ca, or (Mg, Ca) 2 Si is formed, and the Mg content and Ca content contained in the chemical conversion coating film 4 are formed. Is insufficient, and the adhesion of the coating film is lowered. Further, if the Si phase is excessively generated, the chipping resistance and the seizure resistance are lowered. Therefore, the Si content is set to 3.00% or less.
  • Ca 0.05 to 3.00%
  • Ca is an element that diffuses into the chemical conversion treatment film 4 and enhances the adhesion of the coating film. If the Ca content is less than 0.05%, the scale of the chemical conversion treatment film 4 becomes large. Therefore, the Ca content is set to 0.05% or more. On the other hand, when the Ca content exceeds 3.00%, an intermetallic compound containing Ca as a main component, which lowers the chemical conversion treatment property, is formed, so that the Mg content and Ca content of the chemical conversion treatment film become insufficient. The scale becomes large and the adhesion of the coating film decreases. Therefore, the Ca content is set to 3.00% or less.
  • the plating layer 3 of the hot stamping molded product 1 basically contains the above elements, and the balance is made of Zn and impurities.
  • the plating layer 3 may contain Sb, Pb, Cu, Sn, Ti, Sr, Cr, Ni, and Mn in the following range in addition to the above elements. Since these elements do not necessarily have to be contained, the lower limit is 0%. The total content of these elements is preferably 5.00% or less.
  • the contents of Sb and Pb are set to 0.50% or less, and the contents of Cu, Sn and Ti are set to 1.00% or less, respectively.
  • the content of Sb and Pb is preferably 0.20% or less.
  • the content of Cu, Sn and Ti is preferably 0.80% or less, more preferably 0.50% or less.
  • Sr 0 to 0.50%
  • Sr is an element effective for suppressing the formation of top dross formed on the plating bath during production. Further, Sr is an element that suppresses color change of the plated steel sheet after the heat treatment because it suppresses atmospheric oxidation during the heat treatment of hot stamping. Therefore, Sr may be contained. In order to obtain the above effects, the Sr content is preferably 0.05% or more. On the other hand, when the content of Sr is excessive, it adversely affects the coating film swelling width and flow rust in the corrosion test. Therefore, the Sr content is set to 0.50% or less. The Sr content is preferably 0.30% or less, and more preferably 0.10% or less.
  • Ni, and Mn are elements that are concentrated in the vicinity of the interface between the plating layer and the base material in the plated steel sheet and have an effect of eliminating spangles on the surface of the plating layer. Therefore, one or more selected from Cr, Ni and Mn may be contained in the plating layer 3.
  • the contents of Cr, Ni and Mn are preferably 0.01% or more, respectively.
  • the contents of Cr, Ni and Mn are set to 1.00% or less, respectively.
  • the contents of Cr, Ni and Mn are each preferably 0.50% or less, and more preferably 0.10% or less.
  • the average composition of the plating layer is measured by melting and peeling the plating layer and then analyzing the content of elements contained in the peeled plating layer by inductively coupled plasma atomic emission (ICP) analysis.
  • the plating layer may be peeled off by immersing it in 10% hydrochloric acid containing an inhibitor that suppresses corrosion of the base iron (pickling suppression inhibitor: manufactured by Asahi Chemical Co., Ltd.), and determining that the dissolution is complete when the foaming stops. ..
  • the structure of the plating layer is not limited, but includes, for example, a Fe—Al phase, a Zn—Mg phase, and a Zn—Al—Mg phase.
  • the amount of the plating layer adhered is not limited, but is preferably 10 to 120 g / m 2.
  • the amount of adhesion of the plating layer can be determined from the weight change before and after melting the plating layer at room temperature by the above method.
  • ⁇ Chemical conversion coating> [Consists of zinc phosphate crystals containing Mg: 5.0 to 50.0% and Ca: 0.5 to 5.0% in mass%]
  • an oxide mainly composed of Al 2 O 3 is formed on the surface (surface of the plating layer) of the hot stamped molded product obtained by hot stamping a steel material having a plating layer containing Al. Since Al 2 O 3 formed on the plating layer surface prevents the formation of chemical conversion film, when the chemical conversion treatment to the plated steel materials Al 2 O 3 is formed on the surface, in the hot stamping material, the chemical conversion coating The ratio of plating increases.
  • oxides mainly composed of Ca and Mg are formed on the surface of the plated steel material after hot stamping to be subjected to chemical conversion treatment. A film is formed.
  • Mg and Ca are diffused in the chemical conversion treatment film, and by mass%, Mg: 5.0 to 50.0% and Ca: 0.5 to 5
  • a chemical conversion-treated film 4 composed of zinc phosphate crystals containing 0.0% is formed.
  • FIG. 2 shows a typical microstructure photograph of the chemical conversion-treated film 4 of the hot stamped molded product 1 according to the present embodiment.
  • the chemical conversion-treated film 4 is composed of zinc phosphate crystals 11 containing Mg: 5.0 to 50.0% and Ca: 0.5 to 5.0%, and the zinc phosphate crystals 11 have a crystal grain size. It is scaly with a major axis of 10 ⁇ m or less and a minor axis of 5 ⁇ m or less. Further, when such zinc phosphate crystals 11 are formed, the ratio of the scale is 10% or less. Further, since the chemical conversion-treated film containing Mg is excellent in corrosion resistance by itself, it contributes to the improvement of post-coating adhesion (coating film adhesion) as compared with the chemical conversion-treated film not containing Mg.
  • the oxide film of Mg and Ca is not sufficiently formed on the surface of the steel material to be subjected to the chemical conversion treatment, Al oxide is generated and the scale of the chemical conversion treatment film 4 becomes large. If the content of Mg and Ca in the chemical conversion treatment film is low, the corrosion resistance of the chemical conversion treatment film is lowered, so that the coating film adhesion is lowered. On the other hand, if the content of Mg and Ca is high, the corrosion resistance of the chemical conversion coating film is rather lowered, so that the adhesion of the coating film is lowered. Depending on the hot stamping conditions and the thickness of the plating layer, Fe diffused into the plating layer by alloying may be present in the chemical conversion treatment film of zinc phosphate crystals.
  • the chemical composition of the chemical conversion coating is such that the plating layer is not dissolved and only the chemical conversion coating is dissolved, for example, a solution dissolved in 20% chromium acid and the chemical conversion coating is dissolved is analyzed by ICP, and the average of the chemical conversion coating is averaged. Obtained by measuring the composition. Alternatively, it can be measured by preparing a calibration curve in advance and quantitatively analyzing it with fluorescent X-rays.
  • the amount of adhesion on one side is set to 0.1 to 10 g / m 2 .
  • it is 1.5 to 8.0 g / m 2 .
  • the opposite surface and end surface other than the surface to be measured are sealed with tape and immersed in the solution to obtain a release solution for only the measurement surface before and after dissolution. It can be obtained from the change in weight.
  • the amount of adhesion on only one side is required.
  • an oxide film may be further provided between the plating layer 3 and the chemical conversion treatment film 4.
  • This oxide film is made of, for example, calcium oxide or magnesium oxide.
  • the hot stamped molded article according to the present embodiment can obtain the effect as long as it has the above characteristics regardless of the manufacturing method.
  • stable production can be performed, which is preferable.
  • the hot stamp molded body according to this embodiment is (I) A plating step of immersing a steel material in a plating bath to obtain a plated steel material having a plating layer, (II) A hot stamping process for hot stamping the plated steel material after the plating process, and (III) A chemical conversion treatment process for performing a chemical conversion treatment on the plated steel material after hot stamping, and With (IV) In the plating step, in the cooling process after immersion in the plating bath, the average cooling rate of the bath temperature to 450 ° C.
  • the average cooling rate of 450 to 350 ° C. is set to 7 ° C./sec or less, and 350. Cool to room temperature so that the average cooling rate at ⁇ 150 ° C is 4 ° C / sec or less. It can be obtained by a manufacturing method.
  • ⁇ Plating process> [Immersion in plating bath]
  • a steel material such as a steel plate to be a base plate is immersed in a plating bath to form a plating layer on the surface.
  • the conditions of immersion in the plating bath for example, the surface of the plated original plate at 600 ⁇ 940 ° C. heat reduction treatment, after the temperature of the steel was air-cooled with N 2 gas has reached the bath temperature + 20 °C, 500 ⁇ 750 Immerse in a plating bath at a bath temperature of ° C. for about 0.2 to 6 seconds. If the immersion time is less than 0.2 seconds, the plating layer may not be sufficiently formed.
  • the immersion time exceeds 6 seconds, the plating layer and the steel material are excessively alloyed, and a large amount of Fe is contained in the plating layer.
  • excess Fe is contained in the plating layer, it becomes difficult to suppress the evaporation of Zn and Mg during the heating of the hot stamp. Therefore, when the immersion time exceeds 6 seconds, the chemical conversion treatment film having a predetermined composition cannot be obtained by the subsequent chemical conversion treatment step, and the coating film adhesion of the hot stamp molded product is lowered.
  • the plating bath may be set to contain Zn, Al, Mg and other elements according to the composition of the target plating layer 3.
  • the composition of the plating bath contains, for example, Al: 30.00 to 75.00%, Mg: 4.00 to 17.00%, Si: 0.20 to 2.00%, and is added to the plating layer as needed. It contains arbitrary elements to be contained, and the balance is Zn and impurities.
  • the average cooling rate in the temperature range up to 450 ° C after pulling the plated steel material from the plating bath is Cool to 10 ° C./sec or higher.
  • Average cooling rate of 450 to 350 ° C.: 7 ° C./sec or less Following the above cooling, cooling is performed so that the average cooling rate in the temperature range of 450 ° C. to 350 ° C. is 7 ° C./sec or less.
  • oxides of Mg and Ca having a low Al content for example, 10% or less
  • a chemical conversion treatment film containing Mg and Ca can be obtained with less scale.
  • Zn (zinc) evaporates due to hot stamping, but in the solidified structure controlled as described above, although the detailed mechanism is not clear, an element having a high vapor pressure.
  • Al, Zn, Ca and / or Si-containing intermetallic compounds having the effect of suppressing the evaporation of Zn and Mg are preferentially generated in the vicinity of the surface of the plating layer, whereby the heating of the hot stamp is continued. Evaporation of Zn and Mg at that time can be suppressed.
  • Average cooling rate of 350 to 150 ° C: 4 ° C / sec or less Following the above cooling, if the average cooling rate of 350 ° C to 150 ° C is 4 ° C / sec or less, the solid solution of Al and Zn contained in the solidified structure will be formed. Separation into the Al phase and the Zn phase lowers the melting point of the plating layer, and the intermetallic compound containing Al, Zn, Ca and / or Si moves to the surface of the plating layer in a molten state during hot stamp heating. It will be easier to do. As a result, it becomes possible to suppress the evaporation of Zn and Mg more efficiently, and it becomes possible to form a chemical conversion treatment film containing Mg and Ca.
  • the average cooling rate of 350 ° C. to 150 ° C. is 4 ° C./sec or less, if the cooling rate in a part of the temperature range is high, a preferable metal structure cannot be obtained. Therefore, the average cooling rate of 350 ° C. to 150 ° C. is 4 ° C./sec or less, the average cooling rate of 350 ° C. to 250 ° C. is 4 ° C./sec or less, and the average cooling rate of 250 to 150 ° C. is 4 ° C./sec. It is preferably less than a second.
  • Hot stamping is performed on the plated steel material (a steel material having a base material and a plating layer formed on the surface thereof) after the plating process.
  • the conditions for hot stamping are not limited, but for example, a method of heating a plated steel sheet to 750 to 1200 ° C., holding it for 0 to 8 minutes, and then sandwiching the plated steel sheet with a flat plate mold at a temperature of about room temperature to quench it can be mentioned. Be done.
  • a chemical conversion treatment is performed on the molded product after hot stamping.
  • the chemical conversion treatment is not limited, and a known zinc phosphate treatment may be used.
  • Tables 1 to 3 show examples disclosed in the present invention.
  • Various Zn-Al-Mg-based plating baths were built and subjected to hot stamp heating.
  • a steel plate having a thickness of 1.6 mm (including C: 0.2% and Mn: 1.3%) was used as the plating original plate.
  • plating was performed with a batch-type hot-dip galvanizing test apparatus manufactured in-house. The plate temperature was measured using a thermocouple spot-welded to the center of the original plating plate.
  • oxygen concentration 20ppm heat reduction treatment be plated surface at 800 ° C.
  • the galvanized steel sheet is inserted into a heating furnace at 900 ° C., and after the temperature of the galvanized steel sheet reaches the furnace temperature of -10 ° C, it is retained for 0 to 8 minutes, and then the flat plate mold is at a temperature of about room temperature.
  • a molded product was produced by sandwiching a plated steel sheet with and quenching it.
  • the chemical composition of the plating layer after hot stamping was as shown in Table 1. No. No. 31 was hot stamped on a commercially available alloyed hot-dip galvanized steel sheet.
  • the sample after the chemical conversion treatment was cut into 25 mm (C direction) ⁇ 15 mm (L direction) to obtain an SEM image of the sample surface. Based on this SEM image, the shape of zinc phosphate crystals was observed. As a result, in the example of the invention, it was confirmed that the zinc phosphate crystal had a scaly shape having a major axis of 10 ⁇ m or less and a minor axis of 5 ⁇ m or less.
  • the electrodeposition coating film was peeled off by tape peeling, and the area ratio of the peeled part and red rust were generated. Evaluated from the situation. "AA” when the peeling area is 5% or less, “A” when the peeling area is more than 5% to 10%, and “B” when the peeling area is more than 10% or red rust has occurred. did.
  • FIG. 2 shows No. 1 in Tables 1 to 3.
  • SEM images BSE images.
  • Zinc phosphate crystals were formed on the surface of the sample, and no skeleton without zinc phosphate crystals was observed.
  • zinc phosphate crystals contained 33.5% of Mg and 2.6% of Ca.
  • the composition of the chemical conversion coating film and / or the area ratio of the scale was large, and the coating film adhesion was low.
  • the zinc phosphate film 13 did not contain Ca and Mg, and a large amount of scale 12 was also observed.

Abstract

このホットスタンプ成形体は、鋼からなる母材と、前記母材の表面に形成されためっき層と、前記めっき層の表面に形成された化成処理皮膜と、を備え、前記めっき層の化学組成が、質量％で、Ａｌ：２０．００～４５．００％、Ｆｅ：１０．００～４５．００％、Ｍｇ：４．５０～１５．００％、Ｓｉ：０．１０～３．００％、Ｃａ：０．０５～３．００％、Ｓｂ：０～０．５０％、Ｐｂ：０～０．５０％、Ｃｕ：０～１．００％、Ｓｎ：０～１．００％、Ｔｉ：０～１．００％、Ｓｒ：０～０．５０％、Ｃｒ：０～１．００％、Ｎｉ：０～１．００％、Ｍｎ：０～１．００％、を含み、残部がＺｎおよび不純物であり、前記化成処理皮膜が、質量％で、Ｍｇ：５．０～５０．０％、Ｃａ：０．５～５．０％を含有するりん酸亜鉛結晶からなり、前記化成処理皮膜の片面付着量が、０．１～１０．０ｇ／ｍ２である。

Description

ホットスタンプ成形体
　本発明は、ホットスタンプ成形体に関する。
　本願は、２０１９年０８月２９日に、日本に出願された特願２０１９－１５７２０５号に基づき優先権を主張し、その内容をここに援用する。
　近年、環境保護及び地球温暖化の防止のために、化学燃料の消費を抑制することが要請されている。このような要請は、例えば、移動手段として日々の生活や活動に欠かせない自動車についても例外ではない。このような要請に対し、自動車では、車体の軽量化などによる燃費の向上等が検討されている。自動車の構造の多くは、鉄、特に鋼板により形成されているので、この鋼板を薄くして重量を低減することが、車体の軽量化にとって効果が大きい。しかしながら、単純に鋼板の厚みを薄くして鋼板の重量を低減すると、構造物としての強度が低下し、安全性が低下することが懸念される。そのため、鋼板の厚みを薄くするためには、構造物の強度を低下させないように、使用される鋼板の機械的強度を高くすることが求められる。
　よって、鋼板の機械的強度を高めることにより、以前使用されていた鋼板より薄くしても機械的強度を維持又は高めることが可能な鋼板について、研究開発が行われている。このような鋼板に対する要請は、自動車製造業のみならず、様々な製造業でも同様になされている。
　一般的に、高い機械的強度を有する材料は、曲げ加工等の成形加工において、形状凍結性が低い傾向にあり、複雑な形状に加工する場合、加工そのものが困難となる。この成形性についての問題を解決する手段の一つとして、いわゆる「熱間プレス方法（ホットスタンプ法、高温プレス法、ダイクエンチ法）」が挙げられる。この熱間プレス方法では、成形対象である材料を一旦高温に加熱して、加熱により軟化した材料に対してプレス加工を行って成形した後に、または成形と同時に、冷却する。
　この熱間プレス方法によれば、材料を一旦高温に加熱して軟化させ、材料が軟化した状態でプレス加工するので、材料を容易にプレス加工することができる。従って、この熱間プレス加工により、良好な形状凍結性と高い機械的強度とを両立したプレス成形品が得られる。特に材料が鋼の場合、成形後の冷却による焼入れ効果により、プレス成形品の機械的強度を高めることができる。
　しかしながら、この熱間プレス方法を鋼板に適用した場合、例えば８００℃以上の高温に加熱することにより、表面の鉄などが酸化してスケール（酸化物）が発生する。従って、熱間プレス加工を行った後に、このスケールを除去する工程（デスケーリング工程）が必要となり、生産性が低下する。また、耐食性を必要とする部材等では、加工後に部材表面へ防錆処理や金属被覆をする必要があるので、表面清浄化工程、表面処理工程が必要となり、やはり生産性が低下する。
　このような生産性の低下を抑制する方法の例として、ホットスタンプ前の鋼板にめっき等の被覆を施すことで、耐食性を高めるとともに、デスケーリング工程を省略することが考えられている。
　このようなめっき鋼材として、例えば、特許文献１には、鋼板表面に、Ａｌ：２０～９５質量％、Ｃａ＋Ｍｇ：０．０１～１０質量％、およびＳｉを含有するＡｌ－Ｚｎ系合金めっき層を有することを特徴とする熱間プレス用めっき鋼板が開示されている。特許文献１によれば、熱間プレス前の加熱時にスケールの生成が抑制され、かつ熱間プレス時に金型にめっきが凝着することなく、また、得られる熱間プレス部材は、外観が良好であり、優れた塗装密着性や耐食性を有すると開示されている。
　また、特許文献２には、鋼材表面に、Ａｌ－Ｆｅ合金層とＺｎ－Ｍｇ－Ａｌ合金層とを含むめっき層が備えられた、耐食性を飛躍的に向上しためっき鋼材が開示されている。
　上述のようなめっき鋼材をホットスタンプして得られる部材は自動車部品に適用されることが多く、自動車部品として適用される場合、部材には一般に化成処理が施される。しかしながら、特許文献１及び特許文献２では、化成処理皮膜を形成した場合の特性については何ら検討されていない。
　本発明者らが検討した結果、ＡｌやＺｎを含むめっき層を有する鋼板にホットスタンプを行って得られた部材に、自動車用として一般的な化成処理であるりん酸亜鉛処理を行っても、りん酸亜鉛皮膜が形成されにくい、または形成されたとしても、さらに表面に電着塗膜等を形成した際の塗膜密着性が十分でない場合があることが分かった。
　特許文献３には、亜鉛－アルミニウム－マグネシウム合金めっき鋼板の表面を、金属表面処理剤を用いて処理する方法が開示されている。特許文献３では、化成処理液にフッ素化合物を含有させることで、化成処理によってめっき鋼板のめっき層表面にＡｌおよびＭｇのフッ化物を含む反応層が形成され、化成皮膜とめっき層表面との密着力をより高めることができると開示されている。
　しかしながら、特許文献３では化成処理皮膜に電着塗膜等を形成した場合の塗膜密着性については検討されていない。
日本国特開２０１２－１１２０１０号公報 日本国特開２０１７－６６４５９号公報 日本国特開２０１６－８９２３２号公報
　本発明は、上記の課題に鑑みてなされた。本発明は、スケが抑制されかつ塗膜密着性に優れた化成処理皮膜を有する、ホットスタンプ成形体を提供することを課題とする。
　本発明らは、溶融Ｚｎ－Ａｌ－Ｍｇめっき鋼板のめっき層の組成バランスと製造時の条件とを制御することで、スケが抑制されかつ塗膜密着性に優れた化成処理皮膜を有する、ホットスタンプ成形体が得られることを知見した。
　本発明は上記知見に基づいて完成され、その要旨は以下の通りである。
（１）本発明の一態様に係るホットスタンプ成形体は、鋼からなる母材と、前記母材の表面に形成されためっき層と、前記めっき層の表面に形成された化成処理皮膜と、を備え、前記めっき層の化学組成が、質量％で、Ａｌ：２０．００～４５．００％、Ｆｅ：１０．００～４５．００％、Ｍｇ：４．５０～１５．００％、Ｓｉ：０．１０～３．００％、Ｃａ：０．０５～３．００％、Ｓｂ：０～０．５０％、Ｐｂ：０～０．５０％、Ｃｕ：０～１．００％、Ｓｎ：０～１．００％、Ｔｉ：０～１．００％、Ｓｒ：０～０．５０％、Ｃｒ：０～１．００％、Ｎｉ：０～１．００％、Ｍｎ：０～１．００％、を含み、残部がＺｎおよび不純物であり、前記化成処理皮膜が、質量％で、Ｍｇ：５．０～５０．０％、Ｃａ：０．５～５．０％を含有するりん酸亜鉛結晶からなり、前記化成処理皮膜の片面付着量が、０．１～１０．０ｇ／ｍ２である。
（２）上記（１）に記載のホットスタンプ成形体は、前記めっき層の前記化学組成が、質量％で、Ａｌ：２５．００～３５．００％、Ｍｇ：６．００～１０．００％、の１種または２種を含有してもよい。
（３）上記（１）または（２）に記載のホットスタンプ成形体は、前記化成処理皮膜の前記片面付着量が、１．５～８．０ｇ／ｍ２であってもよい。
　本発明の上記態様によれば、スケが抑制されかつ塗膜密着性に優れた化成処理皮膜を有するホットスタンプ成形体を提供することができる。
本実施形態に係るホットスタンプ成形体を示す模式図である。 本実施形態に係るホットスタンプ成形体の化成処理皮膜の組織の一例を示す図である。 実施例Ｎｏ．１２（比較例）のホットスタンプ成形体の化成処理皮膜の組織の一例を示す図である。
　本発明の一実施形態に係るホットスタンプ成形体（本実施形態に係るホットスタンプ成形体）について、図面を参照しながら説明する。
　図１を参照し、本実施形態に係るホットスタンプ成形体１は、鋼からなる母材２と、母材２の表面に形成されためっき層３と、めっき層３の表面に形成された化成処理皮膜４とを備える。図１では、めっき層３と化成処理皮膜４とは母材２の片面にのみ形成されているが、両面に形成されていてもよい。
＜母材＞
　母材２は、鋼からなる。母材２は、例えば鋼板をホットスタンプして得られるホットスタンプ部材である。そのため、図１では、板形状をしているが、その形状は限定されない。
　また、本実施形態に係るホットスタンプ成形体１は、めっき層３及び化成処理皮膜４が重要であり、母材２の化学組成等については特に限定されない。母材２は、適用される製品や要求される強度や板厚等によってめっき、ホットスタンプ及び化成処理に供する鋼を決定すればよい。例えば、母材としては、ＪＩＳ　Ｇ３１９３：２００８に記載された熱延鋼板やＪＩＳ　Ｇ３１４１：２０１７に記載された冷延鋼板を用いることができる。
＜めっき層＞
［化学組成］
　以下、めっき層、化成処理皮膜の化学組成に関する％は、断りがない限り質量％である。
Ａｌ：２０．００～４５．００％、
　Ａｌは、めっき層３の耐食性を向上させるために必須な元素である。また、Ａｌ含有量が２０．００％未満であると、ホットスタンプの加熱中にＺｎ及びＭｇの蒸発を抑制するとともに化成処理層へのＣａの供給源となる、ＣａとＡｌとを主体とした金属間化合物が、めっき層の表面に十分に生成されなくなる。その結果、めっき層３上に形成される化成処理皮膜４のスケが大きくなる。そのため、Ａｌ含有量を２０．００％以上とする。好ましくは２５．００％以上である。
　一方、Ａｌ含有量が４５．００％を超えても、ホットスタンプの加熱中に、めっき層３表面にＣａとＡｌとを主体とした金属間化合物が生成しにくくなる。その結果、化成処理皮膜４のスケが大きくなる。そのため、Ａｌ含有量を４５．００％以下とする。好ましくは３５．００％以下である。
Ｆｅ：１０．００～４５．００％
　ホットスタンプ時に、めっき鋼板を加熱すると、Ｆｅが母材２からめっき層３に拡散するので、ホットスタンプ成形体１のめっき層３には必ずＦｅが含まれる。
　Ｆｅ含有量が１０．０％未満である場合、スポット溶接性、および溶着性が悪化する傾向にあるので、Ｆｅ含有量を、１０．００％以上とする。
　一方、Ｆｅ含有量が高すぎる場合、耐食性が悪化する傾向にあるので、Ｆｅ含有量を、４５．００％以下とする。
Ｍｇ：４．５０～１５．００％
　Ｍｇは、めっき層３の耐食性の向上に寄与する元素である。また、Ｍｇは、ホットスタンプの加熱時に、めっき層３中のＺｎ成分と結合して液相Ｚｎの発生を防止するので、ＬＭＥ割れを抑制する効果も有する。また、本実施形態に係るホットスタンプ成形体１では、Ｍｇは化成処理皮膜４に拡散し、塗膜密着性を高める元素である。これらの効果を得るため、Ｍｇ含有量を４．５０％以上とする。Ｍｇ含有量が４．５０％未満であると、塗膜密着性が低下する。Ｍｇ含有量は好ましくは６．０％以上である。
　一方、Ｍｇ含有量が１５．００％を超えると、過度に犠牲防食が働き、めっき層３の耐食性が低下する傾向がある。また、めっき層３中に化成処理性を低下させるＭｇ系の金属間化合物が多量に形成し、その結果、化成処理皮膜４のスケが大きくなるとともに、塗膜密着性が低下する。そのため、Ｍｇ含有量を１５．００％以下とする。好ましくは１０．００％以下である。
Ｓｉ：０．１０～３．００％
　Ｓｉは、Ｍｇとともに化合物を形成して、耐食性の向上に寄与する元素である。また、Ｓｉは、鋼板上にめっき層を形成するにあたり、鋼板表面とめっき層との間に形成される合金層が過剰に厚く形成されることを抑制して、鋼板とめっき層との密着性を高める効果を有する元素でもある。Ｓｉ含有量が０．１０％未満ではこれらの効果が十分に得られない。そのため、Ｓｉ含有量を０．１０％以上とする。
　一方、Ｓｉ含有量が３．００％を超えると、Ｍｇ２Ｓｉ、Ｍｇ２Ｃａ、あるいは（Ｍｇ，Ｃａ）２Ｓｉが形成されて、化成処理皮膜４に含有されるＭｇ含有量ならびにＣａ含有量が不足し、塗膜密着性が低下する。また、Ｓｉ相が過剰に生成すると、耐チッピング性、耐焼付き性が低下する。そのため、Ｓｉ含有量を３．００％以下とする。
Ｃａ：０．０５～３．００％
　本実施形態に係るホットスタンプ成形体１では、Ｃａは化成処理皮膜４に拡散し、塗膜密着性を高める元素である。Ｃａ含有量が０．０５％未満では、化成処理皮膜４のスケが大きくなる。そのため、Ｃａ含有量を０．０５％以上とする。
　一方、Ｃａ含有量が３．００％を超えると、化成処理性を低下させるＣａを主体とする金属間化合物が形成されることで、化成処理皮膜のＭｇ含有量、Ｃａ含有量が不足するとともにスケが大きくなり、塗膜密着性が低下する。そのため、Ｃａ含有量を３．００％以下とする。
　本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、上記の元素を含有し、残部がＺｎ及び不純物からなることを基本とする。
　しかしながら、めっき層３は、上記の元素に加えて、Ｓｂ、Ｐｂ、Ｃｕ、Ｓｎ、Ｔｉ、Ｓｒ、Ｃｒ、Ｎｉ、Ｍｎを下記の範囲で含有してもよい。これらの元素は必ずしも含有する必要がないので、下限は０％である。また、これらの元素の合計含有量は、５．００％以下であることが好ましい。
Ｓｂ：０～０．５０％
Ｐｂ：０～０．５０％
Ｃｕ：０～１．００％
Ｓｎ：０～１．００％
Ｔｉ：０～１．００％
　Ｓｂ、Ｐｂ、Ｃｕ、ＳｎおよびＴｉは、めっき層３中でＺｎと置換され、ＭｇＺｎ２相内で固溶体を形成するが、所定の含有量の範囲内であれば、ホットスタンプ成形体１の特性に悪影響を及ぼさない。よって、これらの元素がめっき層３中に含まれていてもよい。しかしながら、それぞれの元素の含有量が過剰な場合、ホットスタンプの加熱時に、これらの元素の酸化物が析出し、ホットスタンプ成形体１の表面性状が悪化して化成処理性が低下する傾向がある。また、Ｐｂ、Ｓｎの含有量が過剰な場合には、溶着性および耐ＬＭＥ性も劣化する。
　そのため、ＳｂおよびＰｂの含有量は、それぞれ０．５０％以下、Ｃｕ、ＳｎおよびＴｉの含有量はそれぞれ１．００％以下とする。ＳｂおよびＰｂの含有量は０．２０％以下とするのが好ましい。Ｃｕ、ＳｎおよびＴｉの含有量は、０．８０％以下が好ましく、０．５０％以下がより好ましい。
Ｓｒ：０～０．５０％
　Ｓｒは、製造時にめっき浴上に形成されるトップドロスの生成を抑制するために有効な元素である。また、Ｓｒは、ホットスタンプの熱処理時に、大気酸化を抑制するので、熱処理後のめっき鋼板の色変化を抑制する元素である。そのため、Ｓｒを含有させてもよい。上記の効果を得るためには、Ｓｒ含有量は０．０５％以上とするのが好ましい。
　一方、Ｓｒは、含有量が過剰な場合、腐食試験において塗膜膨れ幅および流れ錆に悪影響を与える。そのため、Ｓｒ含有量は０．５０％以下とする。Ｓｒ含有量は、０．３０％以下とするのが好ましく、０．１０％以下とするのがより好ましい。
Ｃｒ：０～１．００％
Ｎｉ：０～１．００％
Ｍｎ：０～１．００％
　Ｃｒ、ＮｉおよびＭｎは、めっき鋼板においては、めっき層と母材との界面付近に濃化し、めっき層表面のスパングルを消失させるなどの効果を有する元素である。よって、Ｃｒ、ＮｉおよびＭｎから選択される一種以上が、めっき層３中に含まれていてもよい。これらの効果を得る場合、Ｃｒ、ＮｉおよびＭｎの含有量は、それぞれ０．０１％以上とするのが好ましい。
　一方、これらの元素の含有量が過剰な場合には、塗膜膨れ幅および流れ錆が大きくなり、耐食性が悪化する傾向にある。よって、Ｃｒ、ＮｉおよびＭｎの含有量は、それぞれ１．００％以下とする。Ｃｒ、ＮｉおよびＭｎの含有量は、それぞれ、０．５０％以下とするのが好ましく、０．１０％以下とするのがより好ましい。
　めっき層の平均組成は、めっき層を溶解して剥離した後、誘導結合プラズマ発光（ＩＣＰ）分析法により、剥離されためっき層に含まれる元素の含有量を分析することで測定する。めっき層の剥離は、例えば、地鉄の腐食を抑制するインヒビター（酸洗抑制防止剤：朝日化学製）を加えた１０％塩酸に浸漬し、発泡が停止したところを溶解完了と判断すればよい。
　めっき層の組織は限定されないが、例えばＦｅ－Ａｌ相、Ｚｎ－Ｍｇ相、Ｚｎ－Ａｌ－Ｍｇ相を含んでいる。また、めっき層の付着量は限定されないが、１０～１２０ｇ／ｍ２が好ましい。めっき層の付着量は、上述の方法でめっき層を室温で溶解し、溶解前後の重量変化から求めることができる。
＜化成処理皮膜＞
［質量％で、Ｍｇ：５．０～５０．０％、Ｃａ：０．５～５．０％を含有するりん酸亜鉛結晶からなる］
　通常、Ａｌを含むめっき層を有する鋼材をホットスタンプして得られたホットスタンプ成形体の表面（めっき層の表面）には、主としてＡｌ２Ｏ３からなる酸化物が形成される。めっき層表面に形成されたＡｌ２Ｏ３は化成処理皮膜の形成を妨げるので、表面にＡｌ２Ｏ３が形成されためっき鋼材に化成処理を行うと、ホットスタンプ成形体において、化成処理皮膜のスケの割合が大きくなる。
　これに対し、本実施形態に係るホットスタンプ成形体では、後述するような方法でめっきを行うことで、化成処理に供するホットスタンプ後のめっき鋼材の表面に、Ｃａ、Ｍｇを主体とする酸化物皮膜が形成される。この鋼材に対し、りん酸亜鉛処理（化成処理）を行うと、化成処理皮膜にＭｇ及びＣａが拡散し、質量％で、Ｍｇ：５．０～５０．０％、Ｃａ：０．５～５．０％を含有するりん酸亜鉛結晶からなる化成処理皮膜４が形成される。図２に本実施形態に係るホットスタンプ成形体１の化成処理皮膜４の代表的な組織写真を示す。この化成処理皮膜４は、Ｍｇ：５．０～５０．０％、Ｃａ：０．５～５．０％を含有するりん酸亜鉛結晶１１からなり、りん酸亜鉛結晶１１は、結晶粒径が長径１０μｍ以下、短径５μｍ以下の鱗片状である。また、このようなりん酸亜鉛結晶１１が形成される場合、スケの割合が１０％以下になる。また、Ｍｇを含有する化成処理皮膜は、それ自体が耐食性に優れるので、Ｍｇを含有しない化成処理皮膜に比べて塗装後密着性（塗膜密着性）の向上に寄与する。
　化成処理を行う鋼材の表面にＭｇ、Ｃａの酸化物皮膜が十分に形成されないと、Ａｌ酸化物が生成し、化成処理皮膜４のスケが大きくなる。化成処理皮膜中のＭｇ、Ｃａ含有量が少ないと、化成処理皮膜の耐食性が低下するので、塗膜密着性が低下する。
　一方、Ｍｇ、Ｃａ含有量が多いと、化成処理皮膜の耐食性がかえって低下するので、塗膜密着性が低下する。
　ホットスタンプの条件やめっき層の厚みによっては、合金化によってめっき層に拡散したＦｅが、りん酸亜鉛結晶の化成処理皮膜中に存在することがある。
　化成処理皮膜の化学組成は、めっき層は溶解せず化成処理皮膜のみを溶解する薬剤、例えば、２０％クロム酸で溶解し、化成処理皮膜が溶解した溶液をＩＣＰ分析し、化成処理皮膜の平均組成を測定することで得られる。または、予め検量線を作成し、蛍光Ｘ線で定量分析することでも測定できる。
［片面付着量が、０．１～１０ｇ／ｍ２］
　化成処理皮膜４の片面付着量が０．１ｇ／ｍ２未満では、塗膜密着性（化成処理皮膜の表面に塗膜を形成した際の密着性）の向上効果が十分に得られない。一方、片面付着量が１０ｇ／ｍ２を超えると、曲げ加工などを受けた際に化成処理皮膜内で亀裂を生じやすくなり、塗膜剥離の原因となる。そのため、片面付着量を０．１～１０ｇ／ｍ２とする。好ましくは、１．５～８．０ｇ／ｍ２である。
　片面付着量を溶解する方法で求める場合、測定する面以外の、反対側の面及び端面をテープでシールして、溶解液に浸漬することで測定面のみの剥離液を得て、溶解前後の重量変化から求めることができる。
　蛍光Ｘ線で測定する場合は、片面のみの付着量が求められる。
　本実施形態に係るホットスタンプ成形体１では、めっき層３と化成処理皮膜４との間に、さらに酸化物皮膜を備えていてもよい。この酸化物皮膜は、例えば、酸化カルシウムや酸化マグネシウムからなる。
＜製造方法＞
　本実施形態に係るホットスタンプ成形体は、製造方法に依らず、上記の特徴を有していればその効果が得られる。しかしながら、以下の工程を含む製造方法によれば安定して製造することができるので好ましい。
　すなわち、本実施形態に係るホットスタンプ成形体は、
（Ｉ）鋼材をめっき浴に浸漬してめっき層を有するめっき鋼材を得るめっき工程と、
（ＩＩ）めっき工程後のめっき鋼材にホットスタンプを行うホットスタンプ工程と、
（ＩＩＩ）ホットスタンプ後のめっき鋼材に化成処理を行う化成処理工程と、
を備え、
（ＩＶ）めっき工程において、めっき浴浸漬後の冷却過程で、浴温～４５０℃の平均冷却速度を１０℃／秒以上とし、４５０～３５０℃の平均冷却速度を７℃／秒以下とし、３５０～１５０℃の平均冷却速度を４℃／秒以下とするように、室温まで冷却する、
製造方法によって得ることができる。
＜めっき工程＞
［めっき浴への浸漬］
　めっき工程では、原板となる鋼板等の鋼材を、めっき浴に浸漬することで、表面にめっき層を形成させる。
　めっき浴への浸漬の条件については、例えば、６００～９４０℃でめっき原板の表面を加熱還元処理し、Ｎ２ガスで空冷して鋼材の温度が浴温＋２０℃に到達した後、５００～７５０℃の浴温のめっき浴に約０．２～６秒浸漬する。
　浸漬時間が０．２秒未満では、めっき層が十分に形成されない場合がある。一方、浸漬時間が６秒超では、めっき層と鋼材とが過剰に合金化し、めっき層中に多量のＦｅが含有されることとなる。過剰のＦｅがめっき層に含有された場合、ホットスタンプの加熱中にＺｎ及びＭｇの蒸発を抑制することが困難となる。そのため、浸漬時間が６秒超の場合には、その後の化成処理工程によって、所定の組成を有する化成処理皮膜が得られなくなり、ホットスタンプ成形体の塗膜密着性が低下する。
　めっき浴は目的とするめっき層３の組成に応じて、Ｚｎ、Ａｌ、Ｍｇ及びその他の元素を含むように設定すればよい。めっき浴の組成は、例えば、Ａｌ：３０．００～７５．００％、Ｍｇ：４．００～１７．００％、Ｓｉ：０．２０～２．００％を含み、必要に応じてめっき層に含有させたい任意元素を含み、残部がＺｎと不純物である。
［冷却］
浴温～４５０℃の平均冷却速度：１０℃／秒以上
　本実施形態に係るホットスタンプ成形体の製造方法では、めっき浴からめっき鋼材を引上げた後、４５０℃までの温度域の平均冷却速度が１０℃／秒以上となるように冷却する。この温度域での平均冷却速度を１０℃／秒以上とすることで、めっき鋼材の表面にＡｌ酸化物が形成されることを抑制できる。
４５０～３５０℃の平均冷却速度：７℃／秒以下
　上記冷却に引き続き、４５０℃～３５０℃の温度域の平均冷却速度が７℃／秒以下となるように冷却を行う。
　この温度域での冷却速度を低くして凝固組織を制御することで、引き続いて行われるホットスタンプ工程において、表面にＡｌ含有量の少ない（例えば１０％以下）、Ｍｇ、Ｃａの酸化物が形成される。その結果、化成処理を行った場合に、スケが少なく、Ｍｇ、Ｃａを含む化成処理皮膜が得られる。
　また、亜鉛系のめっき層の場合、ホットスタンプによってＺｎ（亜鉛）が蒸発することが懸念されるが、上記の通り制御された凝固組織では、詳細な機構は明らかでないものの、蒸気圧が高い元素であるＺｎ及びＭｇの蒸発を抑制する効果を有するＡｌ、Ｚｎ、Ｃａ及び／またはＳｉを含有する金属間化合物がめっき層の表面近傍に優先的に生成することで、引き続き行われるホットスタンプの加熱時のＺｎ及びＭｇの蒸発を抑制することができる。
３５０～１５０℃の平均冷却速度：４℃／秒以下
　上記冷却に引き続き、３５０℃～１５０℃の平均冷却速度を４℃／秒以下とすると、凝固組織に含有されるＡｌとＺｎとの固溶体がＡｌ相とＺｎ相とに分離することでめっき層の融点が低下し、Ａｌ、Ｚｎ、Ｃａ及び／またはＳｉを含有する金属間化合物がホットスタンプ加熱中に溶融状態にあるめっき層の表面に移動しやすくなる。その結果として、より効率的にＺｎ及びＭｇの蒸発を抑制することが可能となり、ＭｇとＣａとを含有した化成処理皮膜の形成が可能となる。
　ただし、３５０℃～１５０℃の平均冷却速度が４℃／秒以下であっても、一部の温度域の冷却速度が速いと好ましい金属組織が得られなくなる。そのため、３５０℃～１５０℃の平均冷却速度が４℃／秒以下であって、３５０℃～２５０℃の平均冷却速度が４℃／秒以下、かつ２５０～１５０℃の平均冷却速度が４℃／秒以下であることが好ましい。
＜ホットスタンプ工程＞
　めっき工程後のめっき鋼材（母材とその表面上に形成されためっき層とを有する鋼材）にホットスタンプを行う。
　ホットスタンプの条件は限定されないが、例えば、めっき鋼板を７５０～１２００℃に加熱し、０～８分保持した後、室温程度の温度にある平板金型でめっき鋼板を挟み込んで急冷する方法が挙げられる。
＜化成処理工程＞
　ホットスタンプ後の成形体に対して、化成処理を行う。化成処理については限定されず、公知のりん酸亜鉛処理とすればよい。
　上記の製造方法によれば、本実施形態に係るホットスタンプ成形体を得ることができる。
　以下、実施例によって本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
　表１～表３に本発明で開示する実施例を示す。種々のＺｎ－Ａｌ－Ｍｇ系めっき浴を建浴し、ホットスタンプ加熱に供した。めっき原板には、板厚１．６ｍｍの鋼板(Ｃ：０．２％、Ｍｎ：１．３％を含む)を用いた。原板を１００ｍｍ×２００ｍｍに切断した後、自社製のバッチ式の溶融めっき試験装置でめっきを施した。板温はめっき原板中心部にスポット溶接した熱電対を用いて測定した。
　めっき浴浸漬前、酸素濃度２０ｐｐｍ以下の炉内においてＮ２－５％Ｈ２ガス雰囲気にて８００℃でめっき原板表面を加熱還元処理し、Ｎ２ガスで空冷して浸漬板温度が浴温＋２０℃に到達した後、表２に示す浴温のめっき浴に約３秒浸漬した。めっき浴浸漬後、引上速度２０～２００ｍｍ／秒で引上げた。
　引上げ時、Ｎ２ワイピングガスでめっき付着量を表２のように制御した。めっき浴から鋼板を引上げた後、表２に示す条件でめっき浴温から室温まで冷却した。
　作製しためっき鋼板に対し、ホットスタンプ加熱と金型急冷とを施した。加熱条件は、９００℃の加熱炉中にめっき鋼板を挿入し、めっき鋼板の温度が炉内温度－１０℃に到達してから０～８分保定した後、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、急冷することで成形品を作製した。
　上述した方法で調査した結果、ホットスタンプ後のめっき層の化学組成は、表１に示す通りであった。
　Ｎｏ．３１は、市販の合金化溶融亜鉛めっき鋼板に対しホットスタンプを行った。
　その後、ホットスタンプ後の鋼材から、５０×１００ｍｍ（×板厚）のサンプルを採取し、このサンプルに、りん酸亜鉛処理を(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。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
＜化成処理皮膜の評価＞
　化成処理皮膜を調査するため、作製したサンプルを２０％クロム酸で溶解し、化成処理皮膜が溶解した溶液をＩＣＰ分析し、化成処理皮膜の平均組成を測定した。また、溶解前後の重量変化から片面当たり付着量を測定した。
　また、化成処理皮膜が形成されためっき鋼板の表面をＳＥＭ観察することで、化成処理皮膜のスケの割合（面積％）を測定した。その際、ＳＥＭ観察視野において、鋼板が露出した領域の面積率をスケの割合と定義した。スケの割合が１０面積％以下であれば、スケが抑制されていると判断した。
　なお、化成処理後のサンプルを２５ｍｍ（Ｃ方向）×１５ｍｍ（Ｌ方向）に切断し、サンプル表面のＳＥＭ像を得た。このＳＥＭ像に基づいて、りん酸亜鉛結晶の形状を観察した。その結果、発明例では、りん酸亜鉛結晶の、結晶粒径が長径１０μｍ以下、短径５μｍ以下の鱗片状であることが確認された。
＜塗膜密着性（耐ＳＤＴ性）＞
　ホットスタンプ成形体の塗膜密着性は、上述のようにサンプル５０×１００ｍｍを、りん酸亜鉛処理(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)に従い実施した後、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、塗膜厚が２０μｍとなるように実施して、焼き付け温度１５０℃、２０分で焼き付けを行った後、地鉄に到達するクロスカット傷(４０×√２ｍｍ　２本)を付けた塗装めっき鋼板を、５５℃の５％ＮａＣｌ塩水に１０００ｈ浸漬した後、テープ剥離により電着塗膜を剥離させ、剥離が生じた部分の面積率と赤錆発生状況とから評価した。
　剥離面積が５％以下の場合は「ＡＡ」、剥離面積が５％超～１０％の場合は、「Ａ」、剥離面積が１０％超の場合または赤錆が生じていた場合は「Ｂ」とした。
　結果を表３に示す。
Figure JPOXMLDOC01-appb-T000003
　本発明例であるＮｏ．３、５～１０、１７～２０、２３～２６、２８、２９においては適切な製造条件でめっき鋼板を作製し、ホットスタンプすることで、ＭｇとＣａとを含有した化成処理皮膜がめっき層上に形成されていた。その結果、優れた塗膜密着性を有していた。
　図２は、表１～表３中、Ｎｏ．１０のＳＥＭ像(ＢＳＥ像)である。サンプル表面にはりん酸亜鉛結晶が形成されており、りん酸亜鉛結晶が形成されていないスケは見られなかった。ＩＣＰ分析した結果、りん酸亜鉛結晶にはＭｇが３３．５％、Ｃａが２．６％含有されていた。
　一方、めっき層の化学組成が本発明範囲外、または、製造方法が好ましくなかった比較例では、化成処理皮膜の組成及び／またはスケの面積率が大きくなり、塗膜密着性が低かった。例えば、Ｎｏ．１２では、図３に示すように、りん酸亜鉛皮膜１３にはＣａ、Ｍｇが含まれず、またスケ１２も多く見られた。
　また、市販の合金化溶融亜鉛めっき鋼板に対しホットスタンプを行ったＮｏ．２８でも塗膜密着性は劣位であった。
　　１　ホットスタンプ成形体
　　２　母材
　　３　めっき層
　　４　化成処理皮膜
　　１１　ＭｇとＣａとを含有するりん酸亜鉛結晶
　　１２　スケ
　　１３　ＭｇとＣａとを含有しないりん酸亜鉛結晶

Claims (3)

  1. 　鋼からなる母材と、
    　前記母材の表面に形成されためっき層と、
    　前記めっき層の表面に形成された化成処理皮膜と、
    を備え、
    　前記めっき層の化学組成が、質量％で、
    　Ａｌ：２０．００～４５．００％、
    　Ｆｅ：１０．００～４５．００％、
    　Ｍｇ：４．５０～１５．００％、
    　Ｓｉ：０．１０～３．００％、
    　Ｃａ：０．０５～３．００％、
    　Ｓｂ：０～０．５０％、
    　Ｐｂ：０～０．５０％、
    　Ｃｕ：０～１．００％、
    　Ｓｎ：０～１．００％、
    　Ｔｉ：０～１．００％、
    　Ｓｒ：０～０．５０％、
    　Ｃｒ：０～１．００％、
    　Ｎｉ：０～１．００％、
    　Ｍｎ：０～１．００％、
    を含み、残部がＺｎおよび不純物であり、
    　前記化成処理皮膜が、質量％で、Ｍｇ：５．０～５０．０％、Ｃａ：０．５～５．０％を含有するりん酸亜鉛結晶からなり、
    　前記化成処理皮膜の片面付着量が、０．１～１０．０ｇ／ｍ２である、
    ことを特徴とするホットスタンプ成形体。
  2. 　前記めっき層の前記化学組成が、質量％で、
    　Ａｌ：２５．００～３５．００％、
    　Ｍｇ：６．００～１０．００％、
    の１種または２種を含有することを特徴とする、
    請求項１に記載のホットスタンプ成形体。
  3. 　前記化成処理皮膜の前記片面付着量が、１．５～８．０ｇ／ｍ２である、
    ことを特徴とする請求項１または２に記載のホットスタンプ成形体。
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JP2012112010A (ja) 2010-11-26 2012-06-14 Jfe Steel Corp 熱間プレス用めっき鋼板、それを用いた熱間プレス部材の製造方法および熱間プレス部材
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JP2018090879A (ja) * 2016-12-06 2018-06-14 株式会社神戸製鋼所 熱間プレス成形用鋼板、熱間プレス成形品の製造方法、および熱間プレス成形品
WO2018139620A1 (ja) * 2017-01-27 2018-08-02 新日鐵住金株式会社 めっき鋼材
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WO2022153840A1 (ja) * 2021-01-14 2022-07-21 日本製鉄株式会社 自動車構造部材用めっき鋼板
WO2023063048A1 (ja) * 2021-10-12 2023-04-20 日本製鉄株式会社 ホットスタンプ成形体

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