WO2021235083A1 - Ａｌめっきホットスタンプ鋼材 - Google Patents

Ａｌめっきホットスタンプ鋼材 Download PDF

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Publication number
WO2021235083A1
WO2021235083A1 PCT/JP2021/012395 JP2021012395W WO2021235083A1 WO 2021235083 A1 WO2021235083 A1 WO 2021235083A1 JP 2021012395 W JP2021012395 W JP 2021012395W WO 2021235083 A1 WO2021235083 A1 WO 2021235083A1
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Prior art keywords
chemical conversion
steel
plated
content
zinc phosphate
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Ceased
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PCT/JP2021/012395
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English (en)
French (fr)
Japanese (ja)
Inventor
伸一 山口
宗士 藤田
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Nippon Steel Corp
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Nippon Steel Corp
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Priority to JP2022524293A priority Critical patent/JP7453583B2/ja
Priority to EP21809842.4A priority patent/EP4155427B1/en
Priority to KR1020227036786A priority patent/KR102892579B1/ko
Priority to US17/910,289 priority patent/US11905600B2/en
Priority to MX2022014404A priority patent/MX2022014404A/es
Priority to CN202180031244.4A priority patent/CN115443350B/zh
Publication of WO2021235083A1 publication Critical patent/WO2021235083A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • 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
    • 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
    • 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
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • 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
    • 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
    • C23C22/73—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 characterised by the process
    • 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
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/48—Electroplating: Baths therefor from solutions of gold

Definitions

  • the plated steel sheet is provided with a surface treatment layer containing a specific compound such as zinc oxide (ZnO). It is known to provide.
  • the zirconia particle size is 5nm or more 500nm or less, lanthanum oxide, cerium oxide and one or more oxides per side 0.2 g / m 2 or more 2g selected from neodymium oxide / m 2
  • Patent Document 1 teaches that the presence of magnesium oxide, calcium oxide or zinc oxide on the surface layer of the surface treatment layer after hot pressing improves the phosphate treatment property.
  • a ZnO aqueous dispersion (A) and an aqueous dispersible organic resin (B) are contained, and the ZnO aqueous dispersion (A) contains water and ZnO particles having an average particle size of 10 to 300 nm.
  • the water-dispersible organic resin (B) has an emulsion average particle size of 5 ⁇ 300 nm
  • the mass of ZnO particles of the ZnO aqueous dispersion with (W a) the solid content of the water-dispersible organic resin
  • the mass ratio of the mass (W B) of (W a / W B) is surface-treatment liquid of the hot-press coated steel sheet is described which is 30 / 70-95 / 5.
  • an Al-based plated steel sheet for hot stamping Fe is diffused from the steel base material (base iron) by hot stamping to form an alloy layer containing Al and Fe, and in some cases Si, on the steel base material.
  • a plating layer containing the mixture is formed, and then a chemical conversion treatment is generally performed to form a chemical conversion treatment film such as a phosphate film, which is further coated by electrodeposition coating or the like.
  • a chemical conversion treatment film such as a phosphate film, which is further coated by electrodeposition coating or the like.
  • an Al-based plating hot having a plating layer including the alloy layer and further subjected to chemical conversion treatment. It is known that the stamped steel material is less likely to have flaws reaching the steel base material and is generally excellent in corrosion resistance after painting.
  • the present invention has been made in view of the above, and an object of the present invention is to provide improved post-painting corrosion resistance in an Al-plated hot stamped steel material which has been subjected to chemical conversion treatment after hot stamping.
  • Al is formed by forming a chemical conversion-treated film containing a zinc phosphate-based crystal and a Ce-based compound adhering to the surface of the zinc phosphate-based crystal, and further appropriately controlling the amount of these adhering amounts and the like. Even if the plated hot stamped steel has a flaw that reaches the steel base material, Ce is eluted from the above Ce-based compound in the flawed portion, and a protective film is applied to the cathode reaction region of the exposed portion of the steel base material. Therefore, it is possible to suppress the progress of the cathode reaction in the exposed portion of the steel base material.
  • a plating layer containing Al and Si is generally formed on the steel base material (base iron) at the beginning, and by performing hot stamping, Fe is obtained from the steel base material. Is diffused to form a plating layer containing an alloy layer made of Al—Fe—Si or the like on the steel base material, and then a chemical conversion treatment is generally performed to form a chemical conversion treatment film such as a phosphate film. Furthermore, painting is applied by electrodeposition coating or the like. As described above, since the alloy layer formed on the steel base material during hot stamping is relatively hard, Al is provided with a plating layer containing the alloy layer and further subjected to chemical conversion treatment.
  • system-plated hot stamped steel material is less likely to have flaws reaching the steel base material and is generally excellent in corrosion resistance after painting.
  • Al-plated hot stamped steel material once a flaw reaches the steel base material, corrosion of the steel base material progresses and the corrosion resistance after painting deteriorates. There is a risk.
  • the exposed part of the steel base becomes the cathode and the Al-plated part becomes the anode. It occurs at the interface between the steel base and the plating.
  • the exposed portions of the steel base material the cathode reaction (O 2 + 2H 2 O + 4e - ⁇ 4OH -) of dissolved oxygen for fast progression, which in connection with progress corrosion of the plating interface between the steel base material This may cause swelling of the coating film.
  • the present inventors perform a chemical conversion treatment obtained by chemical conversion treatment of an Al-plated hot stamped steel material provided with a surface treatment layer containing zinc (Zn).
  • the components in the film were examined.
  • the present inventors have found that it is effective to include cerium (Ce) as a corrosion inhibitor (inhibitor) in the chemical conversion treatment film. More specifically, the present inventors add Ce to the surface-treated layer containing Zn and perform chemical conversion treatment on the Ce to adhere to the surface of the zinc phosphate-based crystal and the zinc phosphate-based crystal.
  • Ce ions particularly trivalent and / or tetravalent Ce ions
  • the eluted Ce ions, cathode reaction (O 2 + 2H 2 O + 4e - ⁇ 4OH -) believed to move in order to maintain electrical neutrality towards the steel base metal exposed portion became alkaline environment with the progress of the ..
  • the Ce ion since the Ce ion is stable to exist in the form of a hydroxide under an alkaline environment, it precipitates as cerium hydroxide composed of Ce (OH) 3 and / or Ce (OH) 4, and further.
  • the steel base material according to the embodiment of the present invention may be any steel material having a thickness and a chemical composition generally used in a hot stamped compact. More specifically, the present invention aims to provide improved post-coating corrosion resistance in an Al-based plated hot stamped steel material that has been subjected to chemical conversion treatment after hot stamping as described above, and is intended to provide improved post-coating corrosion resistance of an Al-plated layer.
  • a chemical conversion-treated film containing a zinc phosphate-based crystal and a Ce-based compound adhering to the surface of the zinc phosphate-based crystal is formed on the film, and the amount of the zinc phosphate-based crystal adhered and the area ratio of the Ce-based compound are appropriately adjusted. By controlling it, the purpose is achieved.
  • Carbon (C) is an element that is inevitably contained in steel and / or is contained in order to secure the desired mechanical strength. Excessive reduction of the C content increases the refining cost, so the C content is preferably 0.01% or more. Further, if the C content is low, it is necessary to contain a large amount of other alloying elements in order to secure the mechanical strength. Therefore, from the viewpoint of ensuring the mechanical strength, the C content is 0.05%. As mentioned above, it is preferably 0.10% or more or 0.20% or more. On the other hand, if C is excessively contained, the steel material can be further hardened, but it may become brittle and melt cracking may occur. Therefore, the C content is preferably 0.55% or less, and more preferably 0.50% or less, 0.40% or less, or 0.30% or less from the viewpoint of preventing melt cracking.
  • Si is an element that is inevitably contained in the refining process of steel, such as being added as a deoxidizing agent, and also has an effect of improving strength.
  • the Si content may be 0%, but is preferably 0.01% or more from the viewpoint of improving the strength.
  • the Si content may be 0.05% or more or 0.10% or more.
  • an excessive content of Si may cause a decrease in ductility in the hot spreading step at the time of manufacturing a steel sheet, or may deteriorate the surface texture as a result. Therefore, the Si content is preferably 2.00% or less.
  • the Si content may be 1.50% or less or 1.00% or less.
  • Si is also an easily oxidizable element and forms an oxide film on the surface of the steel sheet. Therefore, if the Si content is relatively high, the wettability is lowered during hot-dip plating, and non-plating may occur. There is. Therefore, more preferably, the Si content is 0.60% or less.
  • Aluminum (Al) is an element used as a deoxidizing agent during steelmaking, and the lower limit of the Al content is preferably 0.001% from the refining limit.
  • the Al content may be 0.005% or more or 0.010% or more.
  • the upper limit of the Al content is preferably 0.100%.
  • the Al content may be 0.080% or less or 0.050% or less.
  • N Nitrogen (N) is also an element that is inevitably contained. However, if the amount is too large, the production cost is expected to increase. Therefore, the upper limit of the N content is preferably 0.020%. For example, the N content may be 0.015% or less or 0.010% or less. On the other hand, the lower limit of the N content may be 0%, but is preferably 0.001% from the viewpoint of manufacturing cost. For example, the N content may be 0.002% or more or 0.003% or more.
  • the basic chemical composition of the steel base material suitable for use in the present invention is as described above. Further, the steel base material is optionally Ti: 0 to 0.100%, B: 0 to 0.0100%, Cr: 0 to 1.00%, Ni: 0 to 5.00%, Mo :. 0 to 2.000%, Cu: 0 to 1.000%, Nb: 0 to 1.000%, Sn: 0 to 1.000%, Ca: 0 to 0.1000% and REM: 0 to 0.0100. May contain 1 or more of%.
  • these optional elements will be described in detail.
  • B is an element that acts during quenching and has the effect of improving the strength of steel materials.
  • the B content may be 0%, but in order to obtain such an effect, the B content is preferably 0.0001% or more.
  • the B content may be 0.0003% or more, 0.0010% or more, or 0.0020% or more.
  • inclusions for example, BN, carbon boride, etc.
  • the B content is preferably 0.0100% or less.
  • the B content may be 0.0080% or less or 0.0060% or less.
  • Chromium (Cr) is a nitride formed at the interface of the Al-based plating layer, and has an effect of suppressing the formation of a nitride that causes peeling of the Al-based plating layer.
  • Cr is also an element that improves wear resistance and hardenability.
  • the Cr content may be 0%, but in order to obtain these effects, the Cr content is preferably 0.01% or more.
  • the Cr content may be 0.05% or more or 0.10% or more.
  • the Cr content is preferably 1.00% or less.
  • the Cr content may be 0.80% or less or 0.50% or less.
  • Nickel (Ni) has the effect of improving the quenching property during hot pressing, and also has the effect of improving the corrosion resistance of the steel material itself.
  • the Ni content may be 0%, but in order to obtain these effects, the Ni content is preferably 0.01% or more.
  • the Ni content may be 0.05% or more or 0.10% or more.
  • the Ni content is preferably 5.00% or less.
  • the Ni content may be 3.00% or less or 2.00% or less.
  • Molybdenum has the effect of improving the quenching property during hot pressing, and also has the effect of improving the corrosion resistance of the steel material itself.
  • the Mo content may be 0%, but in order to obtain these effects, the Mo content is preferably 0.001% or more.
  • the Mo content may be 0.005% or more, 0.010% or more, or 0.100% or more.
  • the Mo content is preferably 2.000% or less.
  • the Mo content may be 1.500% or less or 1.000% or less.
  • Copper (Cu) has the effect of improving the quenching property during hot pressing, and also has the effect of improving the corrosion resistance of the steel material itself.
  • the Cu content may be 0%, but in order to obtain these effects, the Cu content is preferably 0.001% or more.
  • the Cu content may be 0.005% or more, 0.010% or more, or 0.050% or more.
  • the Cu content is preferably 1.000% or less.
  • the Cu content may be 0.500% or less or 0.200% or less.
  • Niobium (Nb) is an element that contributes to strengthening precipitation and the like.
  • the Nb content may be 0%, but in order to obtain such an effect, the Nb content is preferably 0.001% or more.
  • the Nb content may be 0.005% or more or 0.010% or more.
  • the Nb content is preferably 1.000% or less.
  • the Nb content may be 0.500% or less or 0.200% or less.
  • Ca 0 to 0.1000%
  • Ca is an element for inclusion control.
  • the Ca content may be 0%, but in order to obtain such an effect, the Ca content is preferably 0.0001% or more.
  • the Ca content may be 0.0002% or more, 0.0010% or more, or 0.0020% or more.
  • the alloy cost increases, so that the Ca content is preferably 0.1000% or less.
  • the Ca content may be 0.0500% or less or 0.0100% or less.
  • REM 0 to 0.0100%
  • REM (rare earth metal) is an element for inclusion control.
  • the REM content may be 0%, but in order to obtain such an effect, the REM content is preferably 0.0001% or more.
  • the REM content may be 0.0002% or more, 0.0005% or more, or 0.0010% or more.
  • the REM content is preferably 0.0100% or less.
  • the REM content may be 0.0080% or less or 0.0050% or less.
  • REM is a group consisting of atomic number 21 scandium (Sc), atomic number 39 yttrium (Y), and lanthanoid atomic number 57 lanthanum (La) to atomic number 71 lutetium (Lu). It is one or more elements selected from, and the REM content is the total content of these elements.
  • an Al plating layer is formed on at least one side of the steel base material, that is, on one side or both sides of the steel base material.
  • the "Al plating layer” refers to a plating layer having a chemical composition immediately after plating containing Al as a main component, and more specifically, a plating layer having a chemical composition immediately after plating of more than 50% by mass. It is a thing.
  • Fe diffuses from the steel base material into the Al plating layer, so that the chemical composition of the Al plating layer changes depending on the heat treatment conditions (heating temperature, holding time, etc.) at the time of hot stamping.
  • the Al-plated layer according to the embodiment of the present invention preferably contains Si.
  • Fe diffuses from the steel base material during the plating process, and the diffused Fe reacts with Al in the plating layer to form Al- at the interface between the plating layer and the steel base material. It is known that an Fe alloy layer is formed. Since the Al—Fe alloy layer is a hard layer, if the Al—Fe alloy layer is excessively formed, for example, the formability of the steel sheet during cold working may be impaired.
  • Si in the Al plating layer is known to have a function of suppressing the formation of such an Al—Fe alloy layer.
  • the Al plating layer according to the embodiment of the present invention after hot stamping is alloyed with Fe diffused from the steel base material into the Al plating layer during hot stamping.
  • a relatively hard Al—Fe—Si alloy layer can be included. As a result, it is possible to reliably maintain high resistance to the formation of flaws that reach the steel base material in the finally obtained Al-plated hot stamped steel material.
  • FIG. 1 is a schematic view showing an Al-plated hot stamped steel material according to an embodiment of the present invention.
  • FIG. 1 for simplification, only one side portion of the Al-plated hot stamped steel material is shown, but of course, the Al-plated hot stamped steel material according to the embodiment of the present invention is not only on one side but also on both sides of the steel base material. It may have an Al plating layer or the like. Referring to FIG.
  • the exposed portions of the steel base material the cathode reaction (O 2 + 2H 2 O + 4e - ⁇ 4OH -) of dissolved oxygen for fast progression, which in connection with progress corrosion of the plating interface between the steel base material This may cause swelling of the coating film.
  • a Ce-based compound is further attached to the zinc phosphate-based crystal and contained in the chemical conversion-treated film containing the zinc phosphate-based crystal.
  • the cerium component more specifically the Ce ion, particularly the trivalent and / /
  • tetravalent Ce ions may be eluted to form a protective film, more specifically, a protective film consisting of Ce (OH) 3 and / or Ce (OH) 4 in the cathode reaction region of the exposed portion of the steel base material.
  • the chemical conversion-treated film according to the embodiment of the present invention may contain a Zn-containing compound such as zinc oxide (for example, zinc oxide particles). This is because, as will be described in detail later, since the chemical conversion treatment film is produced by, for example, a chemical conversion treatment of a film containing a Zn-containing compound, a part of Zn is contained during the chemical conversion treatment. This is because the compound may not react and may remain in the final chemical conversion treatment film.
  • a Zn-containing compound such as zinc oxide (for example, zinc oxide particles).
  • the amount of zinc phosphate crystals adhered to the chemical conversion coating film is small, it may not be possible to fully exert the effect of improving the adhesion of the coating film, and in such a case, the corrosion resistance after coating is deteriorated. .. Therefore, the amount of zinc phosphate crystals attached is 0.3 g / m 2 or more in terms of metallic Zn, preferably 1.0 g / m 2 or more, more preferably 1.5 g / m 2 or more, and most preferably 2. It is 0 g / m 2 or more.
  • the amount of zinc phosphate-based crystals attached is 4.0 g / m 2 or less in terms of metallic Zn, for example, 3.5 g / m 2 or less, 3.0 g / m 2 or less, or 2.5 g / m 2 or less. There may be.
  • the amount of zinc phosphate-based crystals adhered to the chemical conversion coating is determined by measuring the amount of metal Zn adhering to the chemical conversion coating by a fluorescent X-ray analysis method in accordance with JIS G 3314: 2011. Will be done.
  • the zinc phosphate crystals may be any suitable compounds known to those skilled in the art, but are not limited to, for example, Hopeito (Zn 3 (PO 4) 2 ⁇ 4H 2 O) and phosphophyllite ( Zn 2 Fe 2+ (PO 4) preferably includes a 2 ⁇ 4H least one compound of the 2 O).
  • Hopeito Zn 3 (PO 4) 2 ⁇ 4H 2 O
  • phosphophyllite Zn 2 Fe 2+ (PO 4) preferably includes a 2 ⁇ 4H least one compound of the 2 O).
  • the Al-plated hot stamped steel material according to the embodiment of the present invention may be left as it is after chemical conversion treatment, or may be coated by electrodeposition coating or the like after chemical conversion treatment.
  • the zinc phosphate-based crystal is not only a compound such as hopate and phosphophyllite, but also a Zn-containing compound derived from these compounds, that is, Zn 6 Al 2 (OH) derived from hopate. also like 16 CO 3 ⁇ 4H 2 O is intended to cover.
  • Ce-based compound In the Al-plated hot stamped steel material according to the embodiment of the present invention, as described above, mainly by adjusting the amount of zinc phosphate-based crystals adhered to the chemical conversion coating to an appropriate amount, the adhesion to the coating film is improved. , Ce-based compounds improve post-coating corrosion resistance.
  • the Ce-based compound exists in a state of being attached to the surface of the zinc phosphate-based crystal in the chemical conversion treatment film. More specifically, the chemical conversion-treated film has a structure in which a Ce-based compound smaller than the zinc phosphate-based crystal is attached to the surface of the zinc phosphate-based crystal.
  • FIG. 2 shows an observation image of the chemical conversion-treated film with a scanning electron microscope (SEM), and FIG.
  • FIG. 2 (a) shows the chemical conversion-treated film according to the embodiment of the present invention containing a zinc phosphate-based crystal and a Ce-based compound. An SEM observation image is shown, and FIG. 2B shows a cross-sectional SEM observation image of a chemical conversion-treated coating containing only zinc phosphate-based crystals and no Ce-based compound.
  • the zinc phosphate-based crystals 4 exist in a relatively tightly aggregated state regardless of the presence or absence of the Ce-based compound.
  • the chemical conversion-treated film according to the embodiment of the present invention has a Ce-based film smaller than the zinc phosphate-based crystal on the surface of the zinc phosphate-based crystal 4 as shown by an arrow.
  • the compound 5 has a structure to which the compound 5 is attached. By having such a structure, the zinc phosphate crystals 4 can be aggregated relatively densely and the gap between the zinc phosphate crystals 4 can be reduced, so that Ce adhered to the surface of these crystals.
  • the chemical conversion-treated film according to the embodiment of the present invention it is sufficient that at least a part of the Ce-based compound 5 is attached to the surface of the zinc phosphate-based crystal 4, that is, all of the Ce-based compound 5 is not necessarily zinc phosphate. It does not have to be attached to the surface of the system crystal 4. For example, some Ce-based compounds 5 may be incorporated into the zinc phosphate-based crystal 4.
  • the Ce-based compound 5 when the Ce-based compound 5 is incorporated into the zinc phosphate-based crystal 4, it becomes relatively difficult to elute the Ce from the Ce-based compound 5 into the cathode reaction region of the exposed portion of the steel base material. Therefore, there is a risk that sufficient corrosion resistance after painting cannot be achieved. Therefore, from the viewpoint of improving the corrosion resistance after coating, it is extremely important that the chemical conversion coating film contains a Ce-based compound adhering to the surface of the zinc phosphate-based crystal.
  • the area ratio of the Ce-based compound in the chemical conversion treatment film is controlled to 0.5 to 25%. If the area ratio of the Ce-based compound in the chemical conversion treatment film is low, the effect obtained by adding the Ce-based compound, that is, the effect of improving the corrosion resistance after coating cannot be sufficiently exhibited. On the other hand, if the area ratio of the Ce-based compound in the chemical conversion-treated film is too large, the amount of the elution-based Ce-based compound adhered to the chemical conversion-treated film increases, that is, the amount of the Ce ion eluted increases. The adhesive interface of the coating film is reduced, and the adhesion of the coating film is lowered.
  • the area ratio of the Ce-based compound in the chemical conversion-treated film is such that the surface of the chemical conversion-treated film has a beam diameter of 10 ⁇ m, a step interval of 10 ⁇ m, and the number of steps is 500 points ⁇ 500 points using an EPMA (electron probe microanalyzer). It is determined by measuring under the above conditions and calculating the percentage of the Ce-based compound in the whole (500 points ⁇ 500 points).
  • EPMA electron probe microanalyzer
  • the amount of the Ce-based compound adhered to the chemical conversion-treated film is preferably 1.0 to 280 mg / m 2 in terms of metal Ce.
  • the amount of the Ce-based compound adhered to the chemical conversion coating is small, the effect obtained by adding the Ce-based compound, that is, the effect of improving the corrosion resistance after coating, is sufficiently exhibited as in the case of the area ratio of the Ce-based compound. May not be possible.
  • the amount of the Ce-based compound adhered to the chemical conversion coating film is too large, the amount of Ce ions eluted from the chemical conversion coating film increases, so that the adhesion interface with the coating film decreases and the adhesion to the coating film deteriorates.
  • the corrosion resistance after painting may be deteriorated.
  • the area ratio of the Ce-based compound in the chemical conversion coating may be controlled within the range of 0.5 to 25%, and in addition, the amount of the Ce-based compound adhered may be controlled.
  • the adhesion amount of the Ce-based compound is within the range of 1.0 to 280 mg / m 2.
  • the amount of the Ce-based compound adhered to the chemical conversion coating may be 5 mg / m 2 or more, 10 mg / m 2 or more, 30 mg / m 2 or more, 50 mg / m 2 or 100 mg / m 2 or more, and / Alternatively, it may be 250 mg / m 2 or less, 220 mg / m 2 or less, 200 mg / m 2 or less, 180 mg / m 2 or less, or 150 mg / m 2 or less.
  • the amount of the Ce-based compound adhered to the chemical conversion-treated film is determined by measuring the amount of the metal Ce adhered to the chemical conversion-treated film by a fluorescent X-ray analysis method in accordance with JIS G 3314: 2011. ..
  • the Ce-based compound may be any suitable compound capable of eluting Ce ions, and is not particularly limited.
  • cerium hydroxide (IV) (Ce (OH) 4 ) preferably containing at least one compound selected from the group consisting of Ce (OH) 3 and Ce (OH) 4 . It is more preferable to contain a compound, and most preferably to contain Ce (OH) 3.
  • Ce-based compounds even if the Al-plated hot-stamped steel material has a flaw that reaches the steel base material, a trivalent or tetravalent Ce from the Ce-based compound is present in the flawed portion.
  • ions can be eluted to form a protective film composed of Ce (OH) 3 and / or Ce (OH) 4 in the cathode reaction region of the exposed steel base material, the cathode reaction in the exposed steel base material can be formed. It is possible to suppress further progress.
  • Ce (OH) 3 and / or Ce (OH) as a Ce-based compound in the chemical conversion coating film.
  • the progress of corrosion is considered to be suppressed by the following mechanism.
  • the corroded environment becomes acidic, and the acidity is used as a driving force to elute Ce ions from Ce (OH) 3 and / or Ce (OH) 4 in the chemical conversion coating.
  • cathode reaction (O 2 + 2H 2 O + 4e - ⁇ 4OH -) proceeds by moving to keep the electrical neutrality towards the steel base metal exposed portion became alkaline environment.
  • Ce ions since it is stable that Ce ions exist in the form of hydroxide under an alkaline environment, cerium hydroxide composed of Ce (OH) 3 and / or Ce (OH) 4 is formed again. It precipitates, and this precipitate film acts as a protective film to suppress further progress of the cathode reaction in the exposed portion of the steel base material.
  • CeO 2 when CeO 2 is present as a Ce-based compound in the chemical conversion-treated film , CeO 2 can elute Ce ions without any particular restrictions on the acidic environment or alkaline environment, and thus after elution of Ce ions. Can suppress further progress of the cathode reaction in the exposed portion of the steel base material by the same mechanism as when Ce (OH) 3 and / or Ce (OH) 4 is contained as the Ce-based compound.
  • the Al-plated hot stamped steel material according to the embodiment of the present invention having the above characteristics is The process of forming an Al plating layer on at least one side of a steel sheet, It can be manufactured by a method comprising a step of hot-pressing the steel sheet and a step of forming a chemical conversion treatment film on the hot-pressed steel material.
  • a method comprising a step of hot-pressing the steel sheet and a step of forming a chemical conversion treatment film on the hot-pressed steel material.
  • the cold-rolled steel sheet N 2 -H 2 mixed gas atmosphere for example at a temperature of 750 - 850 ° C. 10 seconds to 5 minutes
  • the inert atmosphere such as a nitrogen atmosphere
  • this steel sheet is immersed in an Al plating bath containing 3 to 15% by mass of Si at a temperature of 600 to 750 ° C. for 0.1 to 60 seconds, then pulled up and immediately subjected to N 2 gas or air by a gas wiping method.
  • a hot press (hot press) is applied to the steel sheet on which the Al plating layer is formed.
  • the above hot press can be carried out by any method known to those skilled in the art, and is not particularly limited. It can be heated to a temperature, generally about 850-1000 ° C., and then hot pressed for a predetermined time. Here, if the heating temperature is less than 850 ° C., sufficient quenching hardness may not be obtained, which is not preferable. Further, if the heating temperature exceeds 1000 ° C., the alloying of Al and Fe may proceed too much due to the excessive diffusion of Fe from the steel base material to the Al plating layer. In such a case, the corrosion resistance after painting is achieved.
  • quenching with a die during hot pressing is not particularly limited, but for example, after leaving the heating furnace, it is cooled at an average cooling speed of 30 ° C./sec or more until the temperature drops to 400 ° C.
  • a chemical conversion treatment film is formed on the Al plating layer.
  • the chemical conversion-treated film can be formed by various methods and is not particularly limited. For example, after a hot pressing step, a film containing a Zn-containing compound and / or a Ce-containing compound is formed, and then the film is subjected to the conversion. It may be formed by chemical conversion treatment, or a film containing a Zn-containing compound and / or a Ce-containing compound is formed in advance before the hot pressing step, and the film is subjected to hot pressing. It may be formed by subjecting it to a chemical conversion treatment.
  • the former a film containing a Zn-containing compound and / or a Ce-containing compound is formed after the hot pressing step, and then a chemical conversion treatment is performed
  • electrolytic Zn plating is performed on the Al plating layer after the hot pressing step.
  • a predetermined amount of an aqueous solution of cerium oxide sol is applied in a spray form and air-dried, and then subjected to normal chemical conversion treatment to generate crystalline zinc phosphate crystals from the Zn-containing compound and the phosphorus. It is possible to form a chemical conversion-treated film having a structure in which a Ce-based compound is attached to the surface of a zinc acid-based crystal.
  • the chemical conversion treatment film according to the embodiment of the present invention can be formed.
  • the metal-equivalent adhesion amount of Zn can be controlled within a desired range by appropriately adjusting the concentration of the zinc oxide gel aqueous solution, the coating amount, and the like, and similarly, the Ce-based compound.
  • the Ce-based compound when the Ce-based compound is applied by immersing the steel material in an aqueous solution containing the Ce-based compound instead of applying the Ce-based compound by spraying, the Ce-based compound is applied.
  • the amount of adhesion becomes too large, and it becomes impossible to control within an appropriate range.
  • the area ratio of the Ce-based compound in the finally obtained chemical conversion-treated film may greatly exceed 25% and reach 100%.
  • the adhesive interface with the coating film is reduced, resulting in a decrease in the adhesion of the coating film.
  • the amount of the Ce-based compound adhered becomes too large, and the finally obtained chemical conversion-treated film is Ce-based.
  • the area ratio of the compound may greatly exceed 25% and reach 100%.
  • a film containing no Zn-containing compound is subjected to chemical conversion treatment, an amorphous phosphoric acid compound is formed, and the chemical conversion-treated film containing zinc phosphate-based crystals according to the embodiment of the present invention is formed. It cannot be formed.
  • the Al-plated hot stamped steel material that has undergone chemical conversion treatment may be coated by electrodeposition coating or the like, if necessary.
  • the painting process can be carried out under any suitable conditions known to those skilled in the art.
  • the Al-plated hot stamped steel material according to the embodiment of the present invention may be left as it is after chemical conversion treatment, or may be coated by electrodeposition coating or the like after chemical conversion treatment as described above. Further, in the Al-plated hot stamped steel material according to the embodiment of the present invention, the composition of the chemical conversion treatment film does not change before and after coating, and in addition, the chemical conversion is performed even after the coating is peeled off with a release liquid or the like after coating. The composition of the treated film is essentially unchanged. Therefore, the Al-plated hot stamped steel material according to the embodiment of the present invention is not only the Al-plated hot-stamped steel material that has been coated as it is and after the chemical conversion treatment, but also the Al-plated hot stamped steel material that has been once coated with the coating. It also includes steel materials.
  • steel materials corresponding to the Al-plated hot stamped steel materials according to the present invention were manufactured under various conditions, and their coating film adhesion and post-coating corrosion resistance were investigated.
  • N Al plating layer on both sides of a cold-rolled steel sheet (plate thickness 1.4 mm) having a chemical composition of 0.001%, Ti: 0.020%, B: 0.0030%, and the balance: Fe and impurities by the Zenzimer method. Formed. More specifically, first, the above-mentioned cold-rolled steel sheet N 2 -H 2 mixture gas (H 2 4%, N 2 balance) was annealed 1 minute at 800 ° C. in an atmosphere, a nitrogen atmosphere to near the plating bath temperature Cooled with.
  • this steel sheet was immersed in an Al plating bath containing 9% by mass of Si at a temperature of 670 ° C. for 3 seconds, then pulled up and immediately sprayed with N 2 gas by the gas wiping method to increase the amount of Al plating adhered.
  • the temperature was adjusted to 160 g / m 2 on both sides (80 g / m 2 on one side).
  • an Al plating layer was applied to both sides of the steel sheet by blowing air on the steel sheet to cool the steel sheet.
  • the cooled Al-plated steel sheet is cut into a size of 120 mm ⁇ 200 mm and placed in a furnace simulating a hot stamp, and then installed on a 70 mm ⁇ 70 mm SiC pedestal with the evaluation surface facing up. Then, it was held at 900 ° C. ⁇ 10 ° C. for 1 minute. Immediately after taking out the Al-plated steel sheet from the furnace, it was sandwiched between stainless steel dies and rapidly cooled at a cooling rate of about 150 ° C./sec, and the edges of the obtained steel were sheared to a size of 70 mm x 150 mm from the center. Obtained the steel material of.
  • the obtained steel material was immersed in a 10% aqueous hydrochloric acid solution for 5 seconds, and then pickled and washed with water.
  • 30 A / dm in an electrolytic Zn plating solution (Zn 2 SO 4 : 200 g / L + ZnCl 2 : 100 g / L + (NH 4 ) 2 SO 4 : 30 g / L) at 50 ° C. on the surface of the Al plating layer.
  • Cathode electrolysis was performed in step 2.
  • the metal equivalent adhesion amount of Zn was adjusted by the number of energized Coulombs.
  • the obtained steel material was subjected to chemical conversion treatment with a chemical conversion treatment liquid (PB-SX35 manufactured by Nihon Parkerizing Co., Ltd.).
  • PB-SX35 manufactured by Nihon Parkerizing Co., Ltd.
  • a 70 mm ⁇ 150 mm steel material with a thermocouple welded into the furnace set at 900 ° C was charged, and the temperature up to 900 ° C was measured to calculate the average temperature rise rate.
  • the average temperature rise rate was 5 ° C / sec. rice field.
  • the chemical conversion-treated steel material was coated with an electrodeposition paint (Powernics 110 manufactured by Nippon Paint Co., Ltd.) so that the film thickness was 15 ⁇ m, and baked at 170 ° C.
  • the amount of zinc phosphate crystals attached to the chemical conversion coating in terms of metal Zn
  • the amount of Ce-based compounds attached in terms of metal Ce
  • the film adhesion and post-coating corrosion resistance were evaluated.
  • the area ratio of the Ce-based compound in the chemical conversion coating film is the beam diameter of the surface of the chemical conversion coating film in each steel material after the coating film is peeled off using an EPMA (electron probe microanalyzer). Measured under the conditions of 10 ⁇ m, current value 10 -6 A, step interval 10 ⁇ m, and number of steps 500 points ⁇ 500 points, Ce-based compound (number of points with intensity of 10 cps or more) occupying the whole (500 points ⁇ 500 points). ) was determined by calculating the percentage.
  • EPMA electron probe microanalyzer
  • the amount of zinc phosphate crystals and Ce-based compounds attached and the area ratio of Ce-based compounds shown in Table 1 were measured for the chemical conversion-treated film in a state where the coating was once applied and then peeled off. The value of was equivalent to the value separately measured separately for the steel material as it was subjected to chemical conversion treatment.
  • Corrosion resistance after coating was evaluated by conducting a SAE J2334 test on each coated steel material and measuring the swelling width of the coating film. More specifically, the coating film was cut (scratched) with an acrylic cutter. For the steel material for which it was confirmed that the cut reached the steel substrate, the width of the coating film swelling from the cut portion after 200 cycles in the SAE J2334 test (maximum value on one side) was measured. Here, the smaller the value of the "coating film swelling width" in Table 1, the better the corrosion resistance of the steel material after coating. Table 1 also shows the test results of a steel material provided with a chemical conversion treatment film containing no Ce-based compound as a comparative example (Comparative Example 1 in Table 1).
  • the coating film swelling width (maximum value on one side) was 6 mm when the same test was performed. A case where the coating film swelling width was 6 mm or less was regarded as acceptable, and a case where the coating film swelling width was more than 6 mm was regarded as unacceptable. The results are shown in Table 1.
  • Comparative Example 1 in which the chemical conversion coating film does not contain a Ce-based compound, the effect of improving the corrosion resistance after coating by adding the Ce-based compound is naturally not obtained, and as a result, the coating film swelling width is 8 mm. It showed lower corrosion resistance after painting compared to 6 mm of GA material. In Comparative Example 6, since the amount of zinc phosphate-based crystals adhered was low, the corrosion resistance after coating was lowered. It is considered that the result of Comparative Example 6 is due to the fact that the evaluation of the coating film adhesion was passed with a score of 1, but the coating film adhesion was relatively low within the range of the score 1. ..
  • Comparative Example 14 since the area ratio of the Ce compound was high, the amount of the elution Ce-based compound adhered to the chemical conversion coating film increased, the coating film adhesion decreased, and the corrosion resistance after coating decreased in connection with this. bottom.
  • Comparative Example 15 the amount of zinc phosphate-based crystals adhered was large, so that the corrosion resistance after coating was lowered. It is considered that as a result of the thickening of the chemical conversion coating, the elution of Ce into the cathode reaction region of the exposed portion of the steel base material was inhibited.

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US17/910,289 US11905600B2 (en) 2020-05-18 2021-03-24 Al-plated hot stamped steel material
MX2022014404A MX2022014404A (es) 2020-05-18 2021-03-24 Material de acero estampado en caliente enchapado con al.
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WO2025234462A1 (ja) * 2024-05-10 2025-11-13 日本製鉄株式会社 ホットスタンプ用アルミめっき鋼板およびその製造方法

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WO2025234462A1 (ja) * 2024-05-10 2025-11-13 日本製鉄株式会社 ホットスタンプ用アルミめっき鋼板およびその製造方法

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