WO2024214781A1 - めっき鋼材 - Google Patents

めっき鋼材 Download PDF

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Publication number
WO2024214781A1
WO2024214781A1 PCT/JP2024/014682 JP2024014682W WO2024214781A1 WO 2024214781 A1 WO2024214781 A1 WO 2024214781A1 JP 2024014682 W JP2024014682 W JP 2024014682W WO 2024214781 A1 WO2024214781 A1 WO 2024214781A1
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Prior art keywords
plating layer
steel material
phase
corrosion resistance
less
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PCT/JP2024/014682
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English (en)
French (fr)
Japanese (ja)
Inventor
将明 浦中
卓哉 光延
浩史 竹林
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Nippon Steel Corp
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Nippon Steel Corp
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Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Priority to JP2024545095A priority Critical patent/JP7606153B1/ja
Priority to AU2024251523A priority patent/AU2024251523A1/en
Priority to EP24788803.5A priority patent/EP4696806A4/en
Priority to CN202480022503.0A priority patent/CN120917175A/zh
Publication of WO2024214781A1 publication Critical patent/WO2024214781A1/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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • 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
    • C23C2/26—After-treatment
    • 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
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • 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
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas

Definitions

  • the present invention relates to a plated steel material.
  • This application claims priority based on Japanese Patent Application No. 2023-064064, filed on April 11, 2023, the contents of which are incorporated herein by reference.
  • Zn-Al-Mg plated steel material Steel material with a Zn plating layer containing Al and Mg formed on the surface (Zn-Al-Mg plated steel material) has excellent corrosion resistance. For this reason, Zn-Al-Mg plated steel material is widely used as a material for structural components that require corrosion resistance, such as building materials.
  • Patent Document 1 describes a plated steel sheet comprising a steel sheet and a plating layer formed on the surface of the steel sheet, the plating layer containing, in average composition, 0-90% by mass Al, 0-10% by mass Mg, with the remainder containing Zn and impurities, the plating layer having a patterned portion and a non-patterned portion arranged to have a predetermined shape, the patterned portion and the non-patterned portion each including one or two of a first region and a second region, the absolute value of the difference between the area ratio of the first region in the patterned portion and the area ratio of the first region in the non-patterned portion being 30% or more, the first region being a region having an orientation ratio of 3.5 or more, and the second region being a region having an orientation ratio of less than 3.5.
  • Patent Document 2 describes a Zn-Al-Mg-based plated steel sheet that includes a steel sheet and a plating layer that contains 4% to 22% by mass of Al, 1% to 5% by mass of Mg, and the remainder being Zn and unavoidable impurities, and in which the diffraction intensity ratio I(200)/I(111), which is the ratio of the X-ray diffraction intensity I(200) of the (200) plane of the Al phase to the X-ray diffraction intensity I(111) of the (111) plane of the Al phase, in a cross section of the plating layer parallel to the surface of the plating layer, is 0.8 or more.
  • Plated steel products are placed in a variety of environments. In areas where volcanic gases are generated or industrial areas, SOx gas in the atmosphere dissolves into rainwater and turns into acid rain, which can affect the corrosion resistance of plated steel products. However, in prior art, little consideration has been given to improving corrosion resistance in acidic environments.
  • Patent Document 1 describes that, when a region in which the intensity ratio between the diffraction peak intensity I0002 of the (0002) plane of the Zn phase and the diffraction peak intensity I10-11 of the (10-11) plane is 3.5 or more is defined as a first region, and a region in which the intensity ratio is less than 3.5 is defined as a second region, and by making the difference between the area ratio of the first region in the pattern portion and the area ratio of the first region in the non-pattern portion 30% or more, it is possible to intentionally make characters, designs, and the like appear on the surface of the plating layer; however, no consideration is given to corrosion resistance in acidic environments.
  • Patent Document 2 the orientation of the Al phase in the plating layer is controlled to give the plating layer a fine, smooth, pear-skin appearance with many shiny areas, but corrosion resistance in acidic environments is not examined.
  • the present invention was made in consideration of the above circumstances, and aims to provide a plated steel material that has excellent sacrificial corrosion resistance and corrosion resistance in acidic environments.
  • a steel material; A plating layer on the steel material; The chemical composition of the plating layer is, in mass%, Al: 6.0-30.0%, Mg: 3.0 to 15.0%, Fe: 0.01-15.00%, Si: 0-2.0%, Ca: 0 to 2.00%; Sb: 0-0.50%, Pb: 0-0.50%, Cu: 0-1.00%, Sn: 0-1.00%, Ti: 0-1.00%, Cr: 0-1.00%, Nb: 0-1.00%, Zr: 0-1.00%, Ni: 0-1.000%, Mn: 0-1.00%, Mo: 0-1.0 0%, Ag: 0-1.00%, Li: 0-1.00%, La: 0-1.000%, C
  • the steel sheet contains one or more elements selected from the group consisting of e: 0-1.000%, B: 0-0.500%, Y: 0-0.50%, P: 0-0.50%, Sr: 0-0.50%, Co: 0-0.500%,
  • a plated steel material wherein a diffraction intensity obtained from an X-ray diffraction measurement of the plating layer satisfies the following formula (1): 0.5 ⁇ I(002) Zn / ⁇ I(100) Zn +I(101) Zn ⁇ 25.0 ...(1)
  • I(002) Zn is the diffraction intensity of (002) in the ⁇ -Zn phase
  • I(100) Zn is the diffraction intensity of (100) in the ⁇ -Zn phase
  • I(101) Zn is the diffraction intensity of (101) in the ⁇ -Zn phase.
  • the Sn content of the plating layer is, in mass%, Sn: 0.05 to 0.50%,
  • the present invention provides plated steel with excellent corrosion resistance in acidic environments.
  • FIG. 1 is a cross-sectional schematic diagram of a plated steel material according to an embodiment of the present invention.
  • the inventors therefore conducted extensive research to improve the corrosion resistance of Zn plating layers containing Al and Mg in acidic environments.
  • the ⁇ -Zn phase contained in the plating layer has a hexagonal crystal structure, which includes various crystal orientation planes.
  • the corrosion resistance of these crystal orientation planes is not uniform across all orientation planes.
  • the (002) plane of the ⁇ -Zn phase is a dense crystal orientation plane with a relatively high Zn atomic density, so Zn itself is relatively difficult to dissolve, and the corrosion resistance of Zn itself is considered to be relatively high.
  • the (100) plane of the ⁇ -Zn phase is a crystal orientation plane with a lower Zn atomic density than the (002) plane, so Zn itself is relatively easy to dissolve, and although the corrosion resistance of Zn itself is low, the base steel is protected from corrosion by the corrosion products generated by the corrosion of Zn, so the sacrificial corrosion protection of the base steel is considered to be high. Therefore, it was thought that by orienting the (002) plane of the ⁇ -Zn phase parallel to the surface of the plating layer, it would be possible to improve the corrosion resistance in acidic environments of the Zn plating layer containing Al and Mg.
  • the present inventors have attempted to orient the (002) plane of the ⁇ -Zn phase contained in the plating layer parallel to the surface of the plating layer.
  • a Zn plating layer containing Al and Mg is solidified from a molten state, an ⁇ phase is first crystallized, followed by MgZn 2 phase and ⁇ -Zn phase, and then a ternary eutectic structure containing an ⁇ phase, MgZn 2 phase and ⁇ -Zn phase is formed.
  • the ternary eutectic temperature which is a guide for the start of formation of the ternary eutectic structure, can be roughly predicted based on the chemical composition of the plating layer.
  • the (002) plane of the ⁇ -Zn phase in the ternary eutectic structure is oriented parallel to the surface of the plating layer.
  • the immersion temperature when the steel material is immersed in the plating bath and the cooling conditions after the steel material is pulled out of the plating bath it is possible to cause the eutectic reaction to occur at a temperature lower than the expected ternary eutectic temperature, and to orient the (002) plane of the ⁇ -Zn phase parallel to the surface of the plating layer.
  • the plated steel material of this embodiment comprises a steel material and a plating layer disposed on the surface of the steel material, and the chemical composition of the plating layer contains, in mass%, Al: 6.0-30.0%, Mg: 3.0-15.0%, Fe: 0.01-15.00%, Si: 0-2.0%, Ca: 0-2.00%, Sb: 0-0.50%, Pb: 0-0.50%, Cu: 0-1.00%, Sn: 0-1.00%, Ti: 0-1.00%, Cr: 0-1.00%, Nb: 0-1.00%, Zr: 0-1.00%, Ni: 0-1.000%, Mn: 0-1.00%, Mo: 0-1.00%, Ag: 0-1.
  • the surface of the steel material referred to here is the interface between the plating layer and the steel material.
  • I(002) Zn is the diffraction intensity of (002) in the ⁇ -Zn phase
  • I(100) Zn is the diffraction intensity of (100) in the ⁇ -Zn phase
  • I(101) Zn is the diffraction intensity of (101) in the ⁇ -Zn phase.
  • the "%" of the content of each element in the chemical composition means “mass %".
  • the content of an element in the chemical composition may be expressed as element concentration (e.g., Zn concentration, Mg concentration, etc.).
  • element concentration e.g., Zn concentration, Mg concentration, etc.
  • “Corrosion resistance in acidic environments” refers to the property of the plating layer (specifically, the Zn-Al-Mg alloy layer) being resistant to corrosion in an acidic environment.
  • “Corrosion resistance of flat surfaces” refers to the property of the plating layer (specifically, the Zn-Al-Mg alloy layer) itself being resistant to corrosion.
  • “Sacrificial corrosion resistance” refers to the property of suppressing corrosion of the steel material at exposed parts (e.g., cut end surfaces of plated steel material, cracked parts of the plating layer during processing, and parts where the steel material is exposed due to peeling of the plating layer).
  • “Plating layer” refers to the plating film produced by the so-called hot-dip plating process.
  • the plated steel material 1 has a steel material 11.
  • the steel material 11 may also be a formed base steel material such as a steel pipe, civil engineering and construction material (fences, corrugated pipes, drainage ditch covers, sand prevention boards, bolts, wire mesh, guardrails, water cut-off walls, etc.), home appliance parts (casings for air conditioner outdoor units, etc.), and automobile parts (suspension parts, etc.).
  • Forming is, for example, various plastic processing techniques such as pressing, roll forming, and bending.
  • the steel material 11 can be various steel materials such as general steel, Al-killed steel, extra-low carbon steel, high carbon steel, various high tensile steels, some high alloy steels (steels containing strengthening elements such as Ni and Cr, etc.).
  • the steel material 11 may also be a hot-rolled steel plate, hot-rolled steel strip, cold-rolled steel plate, cold-rolled steel strip, etc. described in JIS G 3302:2010.
  • the manufacturing method of the steel plate hot rolling method, pickling method, cold rolling method, etc.
  • the steel material 11 serving as the plating base sheet may be a pre-plated steel material in which the surface of the steel material 11 is pre-plated.
  • An example of the pre-plated steel material is Ni pre-plated steel material having Ni plating on the steel material 11.
  • the pre-plated steel material is obtained, for example, by electrolytic treatment or displacement plating.
  • the electrolytic treatment is performed by immersing the base steel material in a sulfate bath or chloride bath containing metal ions of various pre-plating components and performing electrolytic treatment.
  • the displacement plating is performed by immersing the base steel material in an aqueous solution containing metal ions of various pre-plating components and having the pH adjusted with sulfuric acid, thereby causing displacement precipitation of the metal.
  • the plated steel material 1 according to this embodiment has a plated layer 12 on a steel material 11.
  • the plated layer 12 of the plated steel material 1 according to this embodiment is mainly composed of a Zn-Al-Mg alloy layer due to the chemical composition described below.
  • the plated layer 12 of the plated steel material 1 according to this embodiment may include an Fe-Al-based interface alloy layer between the steel material 11 and the Zn-Al-Mg alloy layer.
  • the plated layer 12 may be a single-layer structure of a Zn-Al-Mg alloy layer, or may be a laminated structure including a Zn-Al-Mg alloy layer and an Fe-Al-based interface alloy layer.
  • the Fe-Al-based interface alloy layer may contain Ni.
  • the chemical composition of the plating layer according to this embodiment is composed of Zn and other alloying elements.
  • the chemical composition of the plating layer is described in detail below. Note that elements with a lower limit of 0% concentration are not essential for solving the problems of the plated steel according to this embodiment, but are optional elements that are permitted to be included in the plating layer for the purpose of improving characteristics, etc.
  • Al forms an ⁇ -phase solid solution with Zn, and contributes to improving the corrosion resistance of flat surfaces, corrosion resistance in acidic environments, and sacrificial corrosion resistance. Therefore, the Al concentration is set to 6.0% or more. It may be 0% or more, 12.0% or more, or 15.0% or more. On the other hand, if Al is excessive, the Mg concentration and Zn concentration are relatively decreased, and the sacrificial corrosion protection property is deteriorated. Therefore, The Al concentration is set to 30.0% or less. The Al concentration may be set to 28.0% or less, 25.0% or less, 22.0% or less, or 20.0% or less.
  • Mg is an essential element for ensuring flat surface corrosion resistance, acidic environment corrosion resistance, and sacrificial corrosion resistance. Therefore, the Mg concentration is set to 3.0% or more.
  • the Mg content may be 5% or more or 6.0% or more.
  • the Mg concentration is The Mg concentration may be 12.0% or less, 10.0% or less, or 8.0% or less.
  • the plating layer may contain 0.01% or more of Fe. It has been confirmed that the performance of the plating layer is not adversely affected if the Fe concentration is 15.00% or less. %, 0.10% or more, 0.50% or more, or 1.00% or more.
  • the Fe concentration may be 10.00% or less, 5.00% or less, 2.00% or less, or 1.00% or more. % or less. Since Fe may be mixed in from the steel material, the Fe concentration may be 0.05% or more.
  • the Si concentration may be 0%.
  • Si contributes to improving the corrosion resistance of the flat surface and the corrosion resistance in an acidic environment. Therefore, the Si concentration is set to 0.05% or more, 0.1% or more, 0.2% or more.
  • the Si concentration may be 0.5% or more, or 0.5% or more.
  • the Si concentration is set to 2.0% or less.
  • the Si concentration may be 1.5% or less, 1.0% or less, or 0.5% or less.
  • the Ca concentration may be 0%.
  • Ca is an element that can adjust the amount of Mg elution that is optimal for imparting flat surface corrosion resistance and acidic environment corrosion resistance. Therefore, the Ca concentration is 0. However, if the Ca concentration is excessive, the corrosion resistance and workability of the flat portion are deteriorated. Therefore, the Ca concentration is preferably 2.00% or more.
  • the Ca concentration may be 1.00% or less, 0.50% or less, or 0.10% or less.
  • the plating layer according to this embodiment contains Sb: 0-0.50%, Pb: 0-0.50%, Cu: 0-1.00%, Sn: 0-1.00%, Ti: 0-1.00%, Cr: 0-1.00%, Nb: 0-1.00%, Zr: 0-1.00%, Ni: 0-1.000%, Mn: 0-1.00%, Mo: 0-1.00%, Ag: 0-1.00%, Li: 0
  • the alloy may contain one or more elements selected from the group consisting of: Cr: 0-1.00%, La: 0-1.000%, Ce: 0-1.000%, B: 0-0.500%, Y: 0-0.50%, P: 0-0.50%, Sr: 0-0.50%, Co: 0-0.500%, Bi: 0-0.500%, In: 0-0.50%, V: 0-0.500%, and W: 0-0.50%.
  • the total of these elements is 0-5.0%. If the total exceeds 5.0%, the flat corrosion resistance, red rust resistance, and base steel corrosion resistance may decrease. In addition,
  • the concentrations of Sb and Pb may be 0%.
  • Sb and Pb contribute to improving sacrificial corrosion protection. Therefore, the concentrations of Sb and Pb may be 0.05% or more, 0.10% or more, or 0.15% or more.
  • concentrations of Sb and Pb are 0.50% or less.
  • concentrations of Sb and Pb may be 0.40% or less, 0.30% or less, or 0.25% or less.
  • ⁇ Cu, Ti, Cr, Nb, Zr, Mn, Mo, Ag and Li 0 to 1.00% each>
  • the concentrations of Cu, Ti, Cr, Nb, Zr, Mn, Mo, Ag and Li may each be 0%.
  • these contribute to improving sacrificial corrosion resistance. Therefore, the concentrations of Cu, Ti, Cr, Nb, Zr, Mn, Mo, Ag and Li may each be 0.05% or more, 0.08% or more, or 0.10% or more.
  • the concentrations of Cu, Ti, Cr, Nb, Zr, Mn, Mo, Ag and Li are excessive, the corrosion resistance of the flat surface portion deteriorates.
  • the concentrations of Cu, Ti, Cr, Nb, Zr, Mn, Mo, Ag and Li are each 1.00% or less.
  • the concentrations of Cu, Ti, Cr, Nb, Zr, Mn, Mo, Ag and Li may each be 0.80% or less, 0.70% or less, or 0.60% or less.
  • Ni concentration may be 0%. However, these elements contribute to improving sacrificial corrosion protection. Therefore, the Ni concentration may be 0.050% or more, 0.080% or more, or 0.100% or more. On the other hand, if the Ni concentration is excessive, the corrosion resistance of the flat portion is deteriorated. Therefore, the Ni concentration is set to 1.000% or less. It may be 0.600% or less.
  • the Sn concentration may be 0%.
  • Sn is an element that forms an intermetallic compound with Mg and improves the sacrificial corrosion resistance of the plating layer. Therefore, the Sn concentration is set to 0.01% or more and 0.01% or less. It may be 0.05% or more, or 0.10% or more. However, if the Sn concentration is excessive, the flat surface corrosion resistance deteriorates. Therefore, the Sn concentration is 1.00% or less.
  • the Sn concentration is 0.50% or less. It may be set to 0.30% or less, or 0.20% or less.
  • the concentrations of La and Ce may each be 0%.
  • La and Ce contribute to improving sacrificial corrosion protection. Therefore, the concentrations of La and Ce may each be 0.100% or more, 0.150% or more, or 0.200% or more.
  • the concentrations of La and Ce are each set to 1.000% or less.
  • the concentrations of La and Ce may each be set to 0.500% or less.
  • the total of one or two of La and Ce may be set to 0.010 to 0.500%.
  • the concentration of B may be 0%.
  • B contributes to improving sacrificial corrosion protection. Therefore, the concentration of B may be 0.100% or more, 0.150% or more, or 0.200% or more.
  • the concentration of B is set to 0.500% or less.
  • the concentration of B is set to 0.400% or less, 0.300% or less. Good too.
  • ⁇ Y, P and Sr 0 to 0.50% each>
  • the concentrations of Y, P and Sr may be 0%.
  • Y, P and Sr contribute to improving sacrificial corrosion resistance. Therefore, the concentrations of Y, P and Sr may be 0.10% or more, 0.15% or more, or 0.20% or more.
  • the concentrations of Y, P and Sr are 0.50% or less.
  • the concentrations of Y, P and Sr may be 0.40% or less, 0.30% or less.
  • the concentrations of Co, Bi, and V may be 0%.
  • Co, Bi, and V contribute to improving sacrificial corrosion resistance. Therefore, the concentrations of Co, Bi, and V may be 0.100% or more, 0.150% or more, or 0.200% or more.
  • the concentrations of Co, Bi, and V are 0.500% or less.
  • the concentrations of Co, Bi, and V may be 0.400% or less, or 0.300% or less.
  • the respective concentrations of In and W may be 0%.
  • In and W contribute to improving sacrificial corrosion protection. Therefore, the respective concentrations of In and W may be 0.10% or more, 0.15% or more, or 0.20% or more.
  • the respective concentrations of In and W are set to 0.50% or less.
  • the respective concentrations of In and W may be set to 0.40% or less, or 0.30% or less.
  • Zn and impurities The remainder of the components of the plating layer according to this embodiment are Zn and impurities.
  • Zn is an element that provides the plating layer with flat corrosion resistance, acidic environment corrosion resistance, and sacrificial corrosion protection.
  • impurities refer to those that are mixed in from the manufacturing environment, etc., and those that are acceptable within a range that does not adversely affect the properties of the plated steel material according to this embodiment.
  • trace amounts of components other than Fe may be mixed in as impurities into the plating layer due to mutual atomic diffusion between the base steel material and the plating bath.
  • the chemical composition of the plating layer is measured by the following method.
  • the plated steel is cut to a size of 30 mm x 30 mm to obtain a measurement sample.
  • an acid solution is obtained by peeling and dissolving the plating layer of the measurement sample using a 10% hydrochloric acid solution containing 0.06 mass% of an inhibitor (Ibit 710K, manufactured by Asahi Chemical Industry Co., Ltd.) that suppresses corrosion of steel.
  • the obtained acid solution is then subjected to ICP analysis. This allows the chemical composition of the plating layer to be obtained. Note that when cutting the plated steel, it is preferable to avoid the ends and welds of the plated steel.
  • the plating layer contains an ⁇ phase and an MgZn 2 phase.
  • the ⁇ phase is a phase containing a fine Al phase and a fine Zn phase.
  • the ⁇ phase and the MgZn 2 phase may partially form a lamellar binary eutectic structure ( ⁇ phase/MgZn 2 eutectic structure).
  • ⁇ phase/MgZn 2 eutectic structure When the ⁇ phase/MgZn 2 eutectic structure is included, the corrosion resistance of the flat surface of the plating layer is further improved.
  • the ⁇ phase/MgZn 2 eutectic structure is preferably in the range of 70% or less, more preferably in the range of 5 to 70%, and may be 10 to 70% in terms of area ratio.
  • the eutectic structure of [ ⁇ phase/MgZn2 ] may be 0% or more than 0%.
  • the plating layer of the present embodiment contains an ⁇ -Zn phase in addition to the ⁇ -phase and the MgZn 2 -phase. At least a part of the ⁇ -Zn phase forms a ternary eutectic structure together with the ⁇ -phase and the MgZn 2 -phase.
  • the ⁇ -Zn phase may be contained in the plating layer as a massive ⁇ -Zn phase.
  • the plating layer when the plating layer contains 0.05 to 0.5% Sn, the plating layer definitely contains the Mg 2 Sn phase.
  • the Mg 2 Sn phase may be contained even when the Sn content is 0.05% or less. Since the amount of the Mg 2 Sn phase is small, its presence can be confirmed by X-ray diffraction measurement.
  • the inclusion of the Mg 2 Sn phase in the plating layer further improves the sacrificial corrosion protection of the plated steel material.
  • X-ray diffraction measurements are performed using K ⁇ radiation from a Cu tube, and if a peak is detected at 23.4 ⁇ 0.3°, it is determined that the Mg2Sn phase is present.
  • X-ray diffraction measurements are performed using an X-ray diffraction device (Rigaku Corporation, model number RINT-TTR III) with an X-ray output of 50 kV, 300 mA, copper target, goniometer TTR (horizontal goniometer), K ⁇ filter slit width of 0.05 mm, longitudinal limiting slit width of 2 mm, receiving slit width of 8 mm, receiving slit 2 open, and measurement conditions of scan speed 5 deg./min, step width 0.01 deg, and scan axis 2 ⁇ (5 to 90°).
  • the plating layer may contain other phases as the remainder, other than those mentioned above.
  • it may contain an Al-Ca-Si phase.
  • the X-ray diffraction intensity obtained from the X-ray diffraction measurement of the plating layer needs to satisfy the relationship of the following formula (1).
  • the (002) plane of the ⁇ -Zn phase is oriented so as to be parallel to the surface of the plating layer, and the corrosion resistance in an acidic environment is improved. More preferably, the following formula (2) is satisfied.
  • I(002) Zn / ⁇ I(100) Zn +I(101) Zn ⁇ is less than 0.5
  • the orientation of the (002) plane of the ⁇ -Zn phase is insufficient, and the corrosion resistance in an acidic environment is insufficient.
  • I(002) Zn / ⁇ I(100) Zn +I(101) Zn ⁇ exceeds 25.0, the sacrificial corrosion protection may be reduced.
  • I(002) Zn is the diffraction intensity of (002) in the ⁇ -Zn phase
  • I(100) Zn is the diffraction intensity of (100) in the ⁇ -Zn phase
  • I(101) Zn is the diffraction intensity of (101) in the ⁇ -Zn phase.
  • the method for measuring the area ratio of the [ ⁇ -phase/ MgZn2 eutectic structure] is as follows. First, the surface of the plating layer is adjusted to be flat by mechanical polishing. Next, the surface of the plating layer is chemically polished by colloidal polishing until the surface becomes a mirror surface. The surface of the plated layer after polishing is observed by SEM. Specifically, an element distribution image is taken using SEM-EDS at a magnification of 5000 times (area of 200 ⁇ m vertical and 200 ⁇ m horizontal). In this element distribution image, the phase in which Mg and Zn coexist is identified as MgZn 2 phase. Also, the phase containing Al and Zn is identified as ⁇ phase. Most of the ⁇ phase shows a dendritic form.
  • the area ratio of the [ ⁇ phase/MgZn 2 eutectic structure] contained in the field of view is calculated by binarization using image analysis software.
  • the method for measuring I(002) Zn / ⁇ I(100) Zn +I(101) Zn ⁇ in formulas (1) and (2) is as follows. First, the surface of the plating layer is mechanically polished, and if necessary, chemically polished to make the surface of the plating layer mirror-finished. Next, for example, an X-ray diffraction apparatus (manufactured by Rigaku Corporation (model number RINT-TTR) III), X-ray output 50 kV, 300 mA, copper target, goniometer TTR (horizontal goniometer), K ⁇ filter slit width 0.05 mm, longitudinal limiting slit width 2 mm, receiving slit width 8 mm, receiving slit 2 open, measurement conditions of scan speed 5 deg.
  • X-ray diffraction apparatus manufactured by Rigaku Corporation (model number RINT-TTR) III
  • copper target copper target
  • goniometer TTR horizontal goniometer
  • the diffraction intensity of the (100) plane of the ⁇ -Zn phase (maximum intensity in the range of 38.993 ⁇ 0.2°)
  • the diffraction intensity of the (002) plane (maximum intensity in the range of 36.297 ⁇ 0.2°)
  • the diffraction intensity of the (101) plane (maximum intensity in the range of 43.232 ⁇ 0.2°) are measured.
  • the diffraction intensity is the intensity excluding the background intensity. From the obtained diffraction intensity, I(002) Zn / ⁇ I(100) Zn +I(101) Zn ⁇ is calculated.
  • Whether or not the plating layer contains an Mg 2 Sn phase is determined by whether or not a diffraction peak specific to Mg 2 Sn appears when the above-mentioned X-ray diffraction measurement is performed.
  • the coating weight per side of the plating layer may be, for example, within the range of 20 to 300 g/ m2 .
  • the coating weight per side may be, for example, within the range of 20 to 300 g/ m2 .
  • the planar corrosion resistance, acidic environment corrosion resistance, and sacrificial corrosion protection of the plated steel material can be further improved.
  • the coating weight per side by setting the coating weight per side to 300 g/ m2 or less, the workability of the plated steel material can be further improved.
  • the method for producing the plated steel material of this embodiment is not particularly limited.
  • the plated steel material of this embodiment can be obtained according to the production conditions described below.
  • a steel material is annealed in a reducing atmosphere, the temperature of the annealed steel material is reduced to (plating bath temperature - 20) ° C. or less, the steel material is then immersed in a hot-dip plating bath, and the steel material is pulled out of the hot-dip plating bath to form a plating layer on the surface of the steel material.
  • the steel material is cooled at an average cooling rate of 15 ° C./sec or more while spraying a cooling gas at a flux of 5000 (L/min/m 2 ) or less in the range from the bath temperature to 320 ° C., and then cooled at an average cooling rate of 5 ° C./sec or less in the range from 320 to 260 ° C. while spraying a cooling gas at a flux of 25000 (L/min/m 2 ) or more.
  • Annealing of the steel material to be plated is carried out in a reducing atmosphere. There are no particular restrictions on the reducing atmosphere and annealing conditions. This annealing removes as much oxide as possible from the steel surface.
  • the steel is cooled with a cooling gas such as nitrogen until its temperature drops to (the plating bath temperature - 20)°C or below, and then immersed in a hot-dip plating bath.
  • a cooling gas such as nitrogen
  • the temperature of the steel is lowered to at least 20°C lower than the plating bath temperature, the surface roughness of the Fe-Al interfacial alloy layer (surface roughness on the Zn-Al-Mg alloy layer side) that forms at the interface between the steel and the plating layer is reduced.
  • the chemical composition of the plating bath may be adjusted as appropriate so as to obtain the chemical composition of the plating layer described above.
  • the temperature of the plating bath is not particularly limited, and any temperature at which hot-dip plating can be performed may be selected as appropriate.
  • the plating bath temperature may be set to a value approximately 20°C or more higher than the melting point of the plating bath.
  • the amount of the plating layer attached can be controlled by controlling the pulling speed of the steel material. If necessary, the steel material to which the plating layer is attached may be wiped to control the amount of the plating layer attached.
  • the amount of the plating layer attached is not particularly limited, and can be within the above-mentioned range, for example.
  • the plating layer is cooled.
  • the plating layer is first cooled at an average cooling rate of 15°C/sec or more until the temperature of the plating layer is reduced from the bath temperature to 320°C.
  • the average cooling rate until the temperature of the plating layer is reduced from the bath temperature to 320°C may be 30°C/sec or less.
  • the cooling is performed, for example, by spraying a cooling gas, and the flux of the cooling gas is set to 5000 (L/min/ m2 ) or less to minimize vibration of the steel material.
  • the flux of the cooling gas may be set to 100 (L/min/ m2 ) or more.
  • a plurality of spray nozzles for the cooling gas may be arranged along the transport path of the steel material, and the cooling gas may be sprayed from the nozzles.
  • the ⁇ -phase and MgZn2 phase are crystallized, and further, the eutectic reaction between the ⁇ -phase and MgZn2 phase proceeds, promoting the generation of a binary eutectic structure of the ⁇ -phase and MgZn2 phase ( ⁇ -phase/ MgZn2 eutectic structure).
  • the crystallization of the ternary eutectic structure originating from the surface of the coating layer becomes less likely to proceed.
  • cooling is performed at an average cooling rate of 5°C/sec or less while blowing cooling gas at a flux of 25000 (L/min/m 2 ) or more in the range of 320 to 260°C.
  • multiple blowing nozzles for cooling gas are arranged along the steel material transport path.
  • the flux of the cooling gas in the range of 320 to 260°C may be 80000 (L/min/m 2 ) or less.
  • cooling gas sprayed When cooling to the range from the bath temperature to 320°C and the range from 320°C to 260°C, there are no particular restrictions on the cooling gas sprayed, and it may be a non-oxidizing gas such as nitrogen, an inert gas such as argon, or air, or a mixture of these gases.
  • a non-oxidizing gas such as nitrogen, an inert gas such as argon, or air, or a mixture of these gases.
  • the shape of the gas nozzle from which the cooling gas is ejected is, for example, in the range of 1 to 50 mm in diameter.
  • the angle between the tip of the gas nozzle and the steel plate is, for example, in the range of 70 to 110°, and more preferably 90° (right angle).
  • the distance between the tip of the gas nozzle and the steel plate is in the range of 30 to 1000 mm. Note that the shape, angle, and distance of the gas nozzle are merely examples and are not limited to the above ranges.
  • the surface roughness of the Fe-Al-based interface alloy layer is reduced by lowering the temperature of the steel material by 20° C. or more than the temperature of the plating bath when the steel material is immersed in the plating bath, and the nucleation sites of the ternary eutectic structure are reduced.
  • the temperature difference between the temperature of the steel material and the plating bath temperature when the steel material is immersed in the plating bath is 40° C. or less. If the temperature difference between the temperature of the steel material and the plating bath temperature when the steel material is immersed in the plating bath exceeds 40° C., the plating appearance is poor.
  • the steel material immersed in the plating bath is pulled up, the steel material is quenched in the range from the bath temperature to 320° C. while suppressing vibration of the steel material, thereby crystallizing ⁇ -phase and MgZn 2- phase in the plating layer, while suppressing crystallization of the ternary eutectic structure, and the eutectic reaction start temperature is set to a temperature lower than the eutectic start temperature predicted from the plating composition.
  • the temperature is cooled in the range of 320°C to 260°C under the above-mentioned conditions to initiate crystallization of the ternary eutectic structure.
  • the conditions in the embodiment are merely one example of conditions adopted to confirm the feasibility and effects of the present invention.
  • the present invention is not limited to this one example of conditions.
  • Various conditions may be adopted in the present invention as long as they do not deviate from the gist of the present invention and the object of the present invention is achieved.
  • a hot-rolled steel sheet with a thickness of 1.6 mm was used as the plated original sheet.
  • This plated original sheet was annealed.
  • the annealing conditions were a N 2 -4% H 2 atmosphere, a soaking temperature of 800°C, and a soaking time of 2 minutes.
  • the plated original sheet after annealing was air-cooled with N 2 gas to adjust the temperature at the time of immersion in the plating bath to (plating bath temperature - 20) °C or less, and then immersed in various hot-dip plating baths and pulled up at a pulling speed of 20 to 200 mm/sec. During pulling, the plating adhesion amount was controlled by N 2 wiping gas. After the steel material was pulled out of the plating bath, cooling was performed under the conditions shown in Table 2.
  • N2 gas was used as the cooling gas, and the gas flux was controlled as shown in the table.
  • the shape of the gas nozzle from which the cooling gas was ejected was 6 mm in diameter, the angle between the tip of the gas nozzle and the steel plate was a right angle, and the distance between the tip of the gas nozzle and the steel plate was 35 mm. In this manner, plated steel products No. 1 to 50 were produced.
  • the chemical composition of the plating layer is as shown in Table 1.
  • the metal structure of the plating layer was also evaluated, and the results are shown in Table 3.
  • the corrosion resistance in acidic environments and sacrificial corrosion protection of the plated steel were evaluated, and the results are shown in Table 3.
  • the chemical composition of the plating layer was measured by immersing samples cut to a size of 30 mm x 30 mm in a 10% HCl aqueous solution containing an inhibitor to remove the plating layer by pickling, and then performing ICP analysis of the elements dissolved in the aqueous solution.
  • the area ratio of the [ ⁇ -phase/MgZn 2 eutectic structure] was evaluated as follows. First, the surface of the plating layer was polished to a mirror state by mechanical polishing and colloidal polishing. Next, the plating layer surface was observed at a magnification of 5000 times (area of 200 ⁇ m vertical and 200 ⁇ m horizontal) using a field emission scanning electron microscope (FE-SEM) equipped with an energy dispersive elemental analyzer (EDS), and an element distribution image was taken using the EDS.
  • FE-SEM field emission scanning electron microscope
  • EDS energy dispersive elemental analyzer
  • the phase in which Mg and Zn coexist was identified as the MgZn 2 phase, and the phase containing Al and Zn was identified as the ⁇ phase, and the [ ⁇ -phase/MgZn 2 eutectic structure] in which these are in a lamellar form was identified. Then, the area ratio of the [ ⁇ -phase/MgZn 2 eutectic structure] contained in the field of view was calculated by binarization using image analysis software.
  • the measurement method of I(002) Zn / ⁇ I(100) Zn +I(101) Zn ⁇ in formula (1) was as follows. First, the surface of the plating layer was mirror-finished in the same manner as above. Next, an X-ray diffraction measurement was performed using an X-ray diffractometer (Rigaku Corporation, model number RINT-TTR III) with an X-ray output of 50 kV, 300 mA, copper target, goniometer TTR (horizontal goniometer), K ⁇ filter slit width of 0.05 mm, longitudinal limiting slit width of 2 mm, receiving slit width of 8 mm, and receiving slit 2 open, with a scan speed of 5 deg./min, a step width of 0.01 deg, and a scan axis 2 ⁇ (5 to 90°).
  • X-ray diffractometer Raku Corporation, model number RINT-TTR III
  • K ⁇ filter slit width of 0.05 mm longitudinal limiting slit width of 2
  • the diffraction intensity of the (100) plane of the ⁇ -Zn phase (maximum intensity in the range of 38.993 ⁇ 0.2°)
  • the diffraction intensity of the (002) plane maximum intensity in the range of 36.297 ⁇ 0.2°
  • the diffraction intensity of the (101) plane maximum intensity in the range of 43.232 ⁇ 0.2°
  • the diffraction intensity was the intensity excluding the background intensity. From the obtained diffraction intensities, I(002) Zn / ⁇ I(100) Zn +I(101) Zn ⁇ was calculated.
  • the plating layer contained an Mg 2 Sn phase was judged based on whether or not a diffraction peak specific to Mg 2 Sn appeared when the above-mentioned X-ray diffraction measurement was performed.
  • Corrosion resistance in acidic environments was evaluated as follows. Plated steel was cut into pieces measuring 150 mm x 50 mm to prepare test pieces. To prevent the edges of the test pieces from being exposed, the edges were protected with polyester tape manufactured by Nitto Denko, and the area of the flat portion to be used for corrosion evaluation was then measured.
  • the test specimens whose end faces were protected with tape, were subjected to an artificial acid rain cycle test as specified in JIS H8502:1999.
  • the artificial acid rain cycle test consisted of a cycle of spraying the acid test liquid (spraying time: 2 h, temperature: 35°C, pH: 3.5), drying (drying time: 4 h, temperature: 60°C, humidity: 20-30% RH), and wetting (wetting time: 2 h, temperature: 50°C, humidity: 95% RH ), and this cycle was repeated.
  • the acid test liquid used was 5% NaCl to which HNO3.H2SO4 was added, and the pH was adjusted to 3.5 by adding NaOH.
  • the tape protecting the end faces of the test pieces was peeled off and the samples were immersed in a 30% chromic acid (VI) solution at 25°C for 10 minutes to remove the corrosion products that had formed on the sample surface.
  • the weight of the test pieces after immersion in the chromic acid (VI) solution was measured, and the difference from the weight before the test was calculated. This was then divided by the area of the evaluation surface to convert it into corrosion weight loss and evaluate corrosion resistance.
  • the evaluation criteria were as follows: "AAAA”, “AAA”, "AA” and “A” were deemed to be pass marks. "AAAA”, “AAA”, “AA” and “A” were deemed to be pass marks.
  • AAAA corrosion loss of 20 g/m2 or less at 60 cycles
  • AAA corrosion loss of more than 20 g/ m2 and less than 40 g/m2 at 60 cycles
  • AA corrosion loss of more than 40 g/ m2 and less than 60 g/ m2 at 60 cycles
  • A corrosion loss of more than 60 g/ m2 and less than 100 g/ m2 at 60 cycles
  • B corrosion loss of more than 100 g/ m2 at 60 cycles
  • Sacrificial corrosion protection (simulated end surface corrosion resistance) was evaluated as follows. Plated steel was cut into 100 mm x 100 mm test pieces. The plating layer in a 25 mm diameter area centred on the intersection of the diagonals of the test piece was removed by milling to expose the steel sheet (base steel). A neutral salt spray test as specified in JIS Z2371:2015 was carried out on the exposed 25 mm diameter area of the base steel, and evaluation was based on the occurrence of red rust in the exposed area of the base steel. The evaluation criteria for sacrificial corrosion protection are as follows. "AAA”, "AA" and "A" were deemed to be acceptable.
  • AAA Red rust area ratio 5% or less after 2200 hours AA: Red rust area ratio 5% or more and 10% or less after 1800 hours A: Red rust area ratio 10% or more and 15% or less after 1000 hours B: Red rust area ratio over 15% after 1000 hours
  • Nos. 1 to 32, 42 to 45, 47, 48, and 50 (Examples) of the present invention had appropriately controlled chemical compositions and metal structures of the plating layers, and were excellent in both acidic environment corrosion resistance and sacrificial corrosion resistance.
  • Comparative example No. 33 had an insufficient amount of Al in the plating layer. As a result, No. 33 had insufficient corrosion resistance in an acidic environment.
  • Comparative example No. 34 had an excessive amount of Al in the plating layer. As a result, in No. 34, excessive ⁇ -phase dendrites were formed, and these dendrites functioned as nucleation sites for the ⁇ -Zn phase, so the orientation of the ⁇ -Zn phase could not be secured, resulting in a lack of both acidic environment corrosion resistance and sacrificial corrosion protection.
  • Comparative example No. 35 had an insufficient amount of Mg in the plating layer. As a result, No. 35 was unable to ensure the orientation of the ⁇ -Zn phase, and both acidic environment corrosion resistance and sacrificial corrosion resistance were insufficient.
  • the plated steel material disclosed herein has excellent sacrificial corrosion resistance and corrosion resistance in acidic environments, making it highly applicable in industry.

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WO2011001662A1 (ja) 2009-06-30 2011-01-06 新日本製鐵株式会社 Ｚｎ－Ａｌ－Ｍｇ系溶融めっき鋼板とその製造方法
JP2021014605A (ja) * 2019-07-10 2021-02-12 株式会社神戸製鋼所 溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板の製造方法
JP2021085086A (ja) 2019-11-29 2021-06-03 日本製鉄株式会社 溶融めっき鋼板
JP2023064064A (ja) 2021-10-25 2023-05-10 国立大学法人信州大学 貴金属回収方法

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EP3992323A4 (en) * 2019-06-27 2022-08-24 Nippon Steel Corporation PLATED STEEL MATERIAL
MY209330A (en) * 2019-11-29 2025-07-02 Nippon Steel Corp Zn-al-mg-based hot-dip plated steel sheet
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JP2001355053A (ja) * 2000-04-11 2001-12-25 Nippon Steel Corp 表面性状に優れた溶融Ｚｎ−Ａｌ−Ｍｇ−Ｓｉめっき鋼材とその製造方法
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WO2011001662A1 (ja) 2009-06-30 2011-01-06 新日本製鐵株式会社 Ｚｎ－Ａｌ－Ｍｇ系溶融めっき鋼板とその製造方法
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