Classifications

• • 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
  • C23C2/04—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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C18/00—Alloys based on zinc
  • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
• • 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
  • 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
  • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
  • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
  • C23C2/36—Elongated material
  • C23C2/40—Plates; Strips
• • 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
  • C23C2/50—Controlling or regulating the coating processes

Definitions

• the present disclosure relates to a plated steel material and a method for manufacturing the plated steel material.
• the first highly corrosion-resistant plated steel material for building materials was Zn-5% Al-plated steel material (Galfan plated steel material), which had Al added to the Zn-based plating layer to improve corrosion resistance. It is a well-known fact that corrosion resistance is improved by adding Al to the plating layer, and when 5% Al is added, Al crystals are formed in the plating layer (specifically, the Zn phase) and the corrosion resistance is improved.
• Zn-55%Al-1.6%Si plated steel (galvalume steel) is basically a plated steel with improved corrosion resistance for the same reason.
• the appeal of Zn-based plated steel is its sacrificial corrosion protection effect on base steel.
• the surrounding plating layer is eluted before the base steel corrodes, and the eluted components of the plating are protected. Forms a film. Thereby, it is possible to prevent red rust from the base steel material to some extent.
• a plated steel material disclosed in Patent Document 1 has been developed as a plated steel material containing a certain amount of Al and Mg.
• Patent Document 1 states, ⁇ On the surface of the steel material, Al: 5 to 18% by mass, Mg: 1 to 10% by mass, Si: 0.01 to 2% by mass, the balance being Zn and unavoidable impurities.
• Patent Document 2 describes "a plated steel material having a steel material and a plating layer including a Zn-Al-Mg alloy layer disposed on the surface of the steel material, the plating layer having Zn: 65.0%. It has a chemical composition containing super, Al: more than 5.0% to less than 25.0%, Mg: more than 3.0% to less than 12.5%, and Sn: 0.1% to 20.0%. , in a backscattered electron image of the Zn-Al-Mg alloy layer obtained when the surface of the Zn-Al-Mg alloy layer was polished to 1/2 of the layer thickness and then observed with a scanning electron microscope at 100x magnification. , a plated steel material in which Al crystals are present and the average value of the cumulative circumferential length of the Al crystals is 88 to 195 mm/mm 2 ” is disclosed.
• Patent Document 1 JP2001-355053
• Patent Document 2 WO2019/221193
• Zn-Al-Mg alloy-plated steel materials with high Al and Mg concentrations have superior corrosion resistance than Zn-based plated steel materials in heavy salt-damaged areas with high levels of airborne salt and severe corrosive environments, but they still develop white rust early after construction. tends to occur. Furthermore, plating with a high Mg concentration is susceptible to oxidative discoloration, and the plating is hard, which may result in poor workability.
• an object of the present disclosure is to provide a plated steel material that has excellent corrosion resistance even in areas affected by heavy salt damage, and that can achieve both workability and discoloration resistance, and a method for manufacturing the same.
• a plated steel material comprising a base steel material, a Zn-Al-Mg alloy layer disposed on the surface of the base steel material, and a plating layer including an Mg enriched layer disposed on the surface of the Zn-Al-Mg alloy layer.
• the plating layer is in mass%, Zn: more than 65.00%, Al: more than 5.00% to less than 25.00%, Mg: more than 3.00% to less than 12.50%, Sn: 0% to 3.0%, Bi: 0% to less than 5.00%, In: 0% to less than 2.00%, Ca: 0% to 3.00%, Y: 0% to 0.50%, La: 0% to less than 0.50%, Ce: 0% to less than 0.50%, Si: 0% to less than 2.5%, Cr: 0% to less than 0.25%, Ti: 0% to less than 0.25%, Zr: 0% to less than 0.25%, Mo: 0% to less than 0.25%, W: 0% to less than 0.25%, Ag: 0% to less than 0.25%, P: 0% to less than 0.25%, Ni: 0% to less than 0.25%, Co: 0% to less than 0.25%, V: 0% to less than 0.25%, Nb: 0% to less than 0.25%,
• ⁇ 2> The plated steel material according to ⁇ 1>, wherein the plating layer includes an Al-Fe alloy layer between the base steel material and the Zn-Al-Mg alloy layer.
• the method for producing a plated steel material according to ⁇ 1> or ⁇ 2> wherein skin pass rolling is performed under the conditions that the surface roughness Ra of the skin pass roll is 1 to 5 ⁇ m and the skin pass rolling force is 100 to 500 tons.
• a plated steel material that has excellent corrosion resistance even in areas affected by heavy salt damage, and that can achieve both workability and discoloration resistance, and a method for manufacturing the same.
• FIG. 1 is a graph for explaining a method for measuring the thickness of an Mg-enriched layer.
• the content of each element in the chemical composition is expressed as “%”, meaning “mass %”.
• a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ ” as lower and upper limits.
• a numerical range in which "more than” or “less than” is attached to the numerical value written before and after “ ⁇ ” means a range that does not include these numerical values as the lower limit or upper limit.
• the content of elements in a chemical composition is sometimes expressed as element concentration (for example, Zn concentration, Mg concentration, etc.).
• the plated steel material of the present disclosure includes a base steel material, a plating layer including a Zn-Al-Mg alloy layer disposed on the surface of the base steel material, and an Mg enriched layer disposed on the surface of the Zn-Al-Mg alloy layer; has. And, in the Zn-Al-Mg alloy layer, Al crystal, MgZn 2 crystal, Zn/Al/M The total area ratio of the gZn two- component eutectic is 90% or more. Further, the thickness of the Mg enriched layer is 0.8 ⁇ m or more (thickness of the plating layer x 1/2) or less.
• the plated steel material of the present disclosure has an Mg-enriched layer of the Zn-Al-Mg alloy layer on the surface of the Zn-Al-Mg alloy layer, a dense corrosion product film containing Mg is formed early in the initial stage of corrosion. be done.
• the dense corrosion product film reduces the corrosion rate. Therefore, it has excellent corrosion resistance even in areas affected by heavy salt damage, which is a severe corrosive environment with a lot of airborne salt.
• the presence of the Zn-Al-Mg alloy layer with the above-mentioned structure under the Mg-concentrated layer allows Mg ions and Al ions to enter the corrosive environment from the middle to late stages of corrosion while ensuring workability. Supplied. This maintains a dense corrosion product film, improving corrosion resistance.
• base steel material There are no particular restrictions on the shape of the base steel material.
• base steel materials include steel pipes, civil engineering construction materials (fence culverts, corrugated pipes, drain covers, sand prevention boards, bolts, wire mesh, guardrails, water-stop walls, etc.), and home appliance parts (air conditioner outdoor unit casings). Examples include molded base steel materials such as body parts, etc.) and automobile parts (suspension parts, etc.). Various plastic working methods such as press working, roll forming, and bending can be used for the forming process.
• base steel There are no particular restrictions on the material of the base steel.
• base steel materials include general steel, pre-plated steel, Al-killed steel, ultra-low carbon steel, high carbon steel, various high-strength steels, and some high-alloy steels (such as steels containing strengthening elements such as Ni and Cr).
• Various types of base steel materials are applicable.
• the base steel material is not particularly limited in terms of conditions such as the manufacturing method of the base steel material and the manufacturing method of the base steel plate (hot rolling method, pickling method, cold rolling method, etc.). Note that as the base steel material, hot rolled steel plates, hot rolled steel strips, cold rolled steel plates, and cold rolled steel strips described in JIS G 3302 (2010) can also be applied.
• the base steel material may be a pre-plated steel material.
• the pre-plated steel material is obtained, for example, by an electrolytic treatment method or a displacement plating method.
• a pre-plated steel material is obtained by immersing a base steel material in a sulfuric acid bath or a chloride bath containing metal ions of various pre-plating components and subjecting it to electrolytic treatment.
• a pre-plated steel material is obtained by immersing a base steel material in an aqueous solution containing metal ions of various pre-plating components and having its pH adjusted with sulfuric acid to cause displacement precipitation of metals.
• a representative example of the pre-plated steel material is pre-Ni plated steel material.
• the plating layer includes a Zn--Al--Mg alloy layer and an Mg-enriched layer disposed on the surface of the Zn--Al--Mg alloy layer.
• the plating layer may include an Al-Fe alloy layer in addition to the Zn-Al-Mg alloy layer and the Mg enriched layer.
• the Al--Fe alloy layer is arranged between the base steel material and the Zn--Al--Mg alloy layer.
• the plating layer may have a laminated structure including a Zn--Al--Mg alloy layer, a Mg-enriched layer, and an Al--Fe alloy layer.
• an oxide film of the elements constituting the plating layer may be formed on the surface of the plating layer to a thickness of about 50 nm, it is thin compared to the overall thickness of the plating layer (about 8 to 60 ⁇ m) and is the main part of the plating layer. It is assumed that there is no such thing.
• the amount of plating layer deposited is preferably 40 to 300 g/m 2 per side.
• the coating weight of the plating layer is 40 g/m 2 or more, corrosion resistance can be ensured more reliably.
• the amount of the plating layer is 300 g/m 2 or less, appearance defects such as sagging patterns of the plating layer can be suppressed.
• the chemical composition of the plating layer is in mass%, Zn: more than 65.00%, Al: more than 5.00% to less than 25.00%, Mg: more than 3.00% to less than 12.50%, Sn: 0% to 3.00%, Bi: 0% to less than 5.00%, In: 0% to less than 2.00%, Ca: 0% to 3.00%, Y: 0% to 0.50%, La: 0% to less than 0.50%, Ce: 0% to less than 0.50%, Si: 0% to less than 2.5%, Cr: 0% to less than 0.25%, Ti: 0% to less than 0.25%, Zr: 0% to less than 0.25%, Mo: 0% to less than 0.25%, W: 0% to less than 0.25%, Ag: 0% to less than 0.25%, P: 0% to less than 0.25%, Ni: 0% to less than 0.25%, Co: 0% to less than 0.25%, V: 0% to less than less than less than 0.25%,
• the chemical composition of the plating layer is the average chemical composition of the entire plating layer (the total average chemical composition of the Zn-Al-Mg alloy layer and the Mg concentrated layer, or the average chemical composition of the Al-Fe alloy layer, Zn-Al-Mg alloy average chemical composition of the sum of the Mg-enriched layer and the Mg-enriched layer.
• Zn more than 65.00% Zn is an element necessary to obtain corrosion resistance.
• the plating layer is composed of low specific gravity elements such as Al and Mg, so it is necessary that the atomic composition ratio also be Zn-based. Therefore, the Zn concentration is set to exceed 65.00%.
• the Zn concentration is preferably 70.00% or more. Note that the upper limit of the Zn concentration is the concentration of elements other than Zn and the remainder other than impurities.
• Al more than 5.00% to less than 25.00%
• Al is an essential element for forming Al crystals and ensuring corrosion resistance. Further, Al is an essential element in order to improve the adhesion of the plating layer and ensure workability. Therefore, the lower limit of the Al concentration is set to exceed 5.00% (preferably 10.00% or more). On the other hand, if the Al concentration increases too much, corrosion resistance tends to deteriorate. Therefore, the upper limit of the Al concentration is less than 25.00% (preferably 23.00% or less).
• Mg More than 3.00% to less than 12.50% Mg is an essential element to ensure corrosion resistance. Therefore, the lower limit of the Mg concentration is set to exceed 3.00% (preferably exceed 4.00%). On the other hand, if the Mg concentration increases too much, processability tends to deteriorate. Therefore, the upper limit of the Mg concentration is less than 12.50% (preferably 10.00% or less).
• Sn 0-3.00%
• Sn is an element that contributes to corrosion resistance and initial discoloration resistance. Therefore, the lower limit of the Sn concentration is preferably more than 0.00% (preferably 0.05% or more, more preferably 0.10% or more). On the other hand, if the Sn concentration increases too much, corrosion resistance and initial discoloration resistance tend to deteriorate. Therefore, the upper limit of the Sn concentration is set to 3.00% or less.
• Bi 0% to less than 5.00% Bi is an element that contributes to corrosion resistance. Therefore, the lower limit of the Bi concentration is preferably more than 0.00% (preferably 0.10% or more, more preferably 3.00% or more). On the other hand, if the Bi concentration increases too much, corrosion resistance tends to deteriorate. Therefore, the upper limit of the Bi concentration is less than 5.00% (preferably 4.80% or less).
• In 0% to less than 2.00% In is an element that contributes to corrosion resistance. Therefore, the lower limit of the In concentration is preferably more than 0.00% (preferably 0.10% or more, more preferably 1.00% or more). On the other hand, if the In concentration increases too much, corrosion resistance tends to deteriorate. Therefore, the upper limit of the In concentration is less than 2.00% (preferably 1.80% or less).
• Ca 0% to 3.00% Ca is an element that can adjust the optimal amount of Mg elution to impart corrosion resistance. Therefore, the lower limit of the Ca concentration is preferably more than 0.00% (preferably 0.05% or more). On the other hand, if the Ca concentration increases too much, corrosion resistance and workability tend to deteriorate. Therefore, the upper limit of the Ca concentration is set to 3.00% or less (preferably 1.00% or less).
• Y 0% to 0.50% Y is an element that contributes to corrosion resistance. Therefore, the lower limit of the Y concentration is preferably more than 0.00% (preferably 0.10% or more). On the other hand, if the Y concentration increases too much, corrosion resistance tends to deteriorate. Therefore, the upper limit of the Y concentration is set to 0.50% or less (preferably 0.30% or less).
• La and Ce 0% to less than 0.50%
• La and Ce are elements that contribute to corrosion resistance. Therefore, the lower limits of the La concentration and the Ce concentration are each preferably greater than 0.00% (preferably 0.10% or more). On the other hand, if the La concentration and Ce concentration increase too much, corrosion resistance tends to deteriorate. Therefore, the upper limits of the La concentration and Ce concentration are each less than 0.50% (preferably 0.40% or less).
• Si 0% to less than 2.50% Si is an element that suppresses the growth of the Al--Fe alloy layer and contributes to improving corrosion resistance. Therefore, the Si concentration is preferably more than 0.00% (preferably 0.05% or more, more preferably 0.10% or more). In particular, when Sn is not included (that is, when the Sn concentration is 0%), the Si concentration is preferably 0.10% or more (preferably 0.20% or more) from the viewpoint of ensuring corrosion resistance. On the other hand, if the Si concentration increases too much, corrosion resistance and workability tend to deteriorate. Therefore, the upper limit of the Si concentration is set to be less than 2.50%. In particular, from the viewpoint of corrosion resistance, the Si concentration is preferably 2.40% or less, more preferably 1.80% or less, and still more preferably 1.20% or less.
• the concentrations of Cr, Ti, Zr, Mo, W, Ag, P, Ni, Co, V, Nb, Cu, Mn, Li, Na, and K increase too much, corrosion resistance tends to deteriorate. Therefore, the upper limit values of the concentrations of Cr, Ti, Zr, Mo, W, Ag, P, Ni, Co, V, Nb, Cu, Mn, Li, Na, and K are each less than 0.25%. .
• the upper limit of the concentration of Cr, Ti, Zr, Mo, W, Ag, P, Ni, Co, V, Nb, Cu, Mn, Li, Na, and K is preferably 0.22% or less.
• Fe 0% to 5.00%
• a certain Fe concentration is contained in the Zn-Al-Mg alloy layer and the Al-Fe alloy layer. It has been confirmed that up to a Fe concentration of 5.00%, there is no adverse effect on performance even if it is included in the plating layer (particularly in the Zn--Al--Mg alloy layer). Since much of Fe is often contained in the Al--Fe alloy layer, the Fe concentration generally increases as the thickness of this layer increases.
• Sr, Sb, Pb and B 0% to less than 0.50% Sr, Sb, Pb and B are elements that contribute to corrosion resistance. Therefore, the lower limit values of the concentrations of Sr, Sb, Pb, and B are each preferably greater than 0% (preferably 0.05% or more, more preferably 0.10% or more). On the other hand, if the concentrations of Sr, Sb, Pb, and B increase too much, corrosion resistance tends to deteriorate. Therefore, the upper limit values of the concentrations of Sr, Sb, Pb, and B are each less than 0.50%.
• Impurities refer to components contained in raw materials or components mixed in during the manufacturing process, but not intentionally included. For example, trace amounts of components other than Fe may be mixed into the plating layer as impurities due to mutual atomic diffusion between the base steel material and the plating bath.
• the chemical components of the plating layer are measured by the following method. First, an acid solution is obtained by removing and dissolving the plating layer with an acid containing an inhibitor that suppresses corrosion of the base steel material. Next, the chemical composition of the plating layer can be obtained by measuring the obtained acid solution by ICP analysis.
• the acid species is not particularly limited as long as it can dissolve the plating layer. Note that the chemical composition is measured as an average chemical composition.
• the components of the pre-plating are also detected.
• ICP analysis detects not only Ni in the plating layer but also Ni in the pre-Ni plating. Specifically, for example, if the amount of Ni attached is 1 g/ When pre-plated steel with a thickness of m 2 to 3 g/m 2 (thickness approximately 0.1 to 0.3 ⁇ m) is used as a base steel material, even if the Ni concentration in the plating layer is 0%, it will not be possible in ICP analysis. When measured, the Ni concentration is detected as 0.1 to 15%.
• the method for determining whether the base steel material is a pre-Ni plated steel material is as follows.
• a sample is taken from the steel material to be measured, with the cross section cut along the thickness direction of the plating layer serving as the measurement surface.
• a line analysis is performed on the measurement surface of the sample near the interface between the plating layer and the base steel material in the steel material using an electron probe microanalyzer (FE-EPMA) to measure the Ni concentration.
• the measurement conditions were an acceleration voltage of 15 kV, a beam diameter of about 100 nm, an irradiation time of 1000 ms per point, and a measurement pitch of 60 nm.
• the measurement distance may be any distance that allows confirmation of whether the Ni concentration is concentrated at the interface between the plating layer and the base steel material in the steel material. If the Ni concentration is concentrated at the interface between the plating layer and the base steel in the steel material, the base steel is determined to be pre-Ni plated steel.
• the Ni concentration of the plating layer is defined as a value measured as follows. First, using a high-frequency glow discharge luminescence surface analyzer (GDS: manufactured by Horiba, model number: GD-Profiler2), three or more types of standard samples (Zn alloy standard samples manufactured by BAS, IMN ZH1, ZH2, and ZH4) with different Ni concentrations were analyzed. The luminescence intensity of Ni is measured. A calibration curve is created from the relationship between the obtained Ni luminescence intensity and the Ni concentration of the standard sample. Next, the surface of the plating layer of the sample is polished in the thickness direction of the plating layer (hereinafter also referred to as "Z-axis direction").
• GDS glow discharge luminescence surface analyzer
• Zn alloy standard samples manufactured by BAS IMN ZH1, ZH2, and ZH4
• a finishing solution containing alumina with an average particle size of 3 ⁇ m, a finishing solution containing alumina with an average particle size of 1 ⁇ m, and a finish containing colloidal silica were applied. Final polishing is performed using each solution in this order.
• the Zn intensity on the surface of the plating layer was measured by XRF (fluorescent X-ray analysis) before and after polishing, and when the Zn intensity after polishing became 1/2 of the Zn intensity before polishing, the layer of the plating layer was determined. The thickness should be 1/2.
• the luminescence intensity of Ni at a position of 1/2 the thickness of the plating layer of the plated steel material to be measured is measured using a high frequency glow discharge luminescence surface analyzer (GDS: manufactured by Horiba, model number: GD-Profiler 2).
• GDS glow discharge luminescence surface analyzer
• the Ni concentration at the 1/2 position of the plating layer is determined from the obtained Ni emission intensity and the prepared calibration curve.
• the Zn concentration of the plating layer is defined as the Zn concentration calculated from the following formula.
• Formula: Zn concentration 100 - (element concentration other than Zn and Ni determined by ICP analysis + Ni concentration determined by GDS)
• the measurement conditions of the high frequency glow discharge luminescent surface analyzer are as follows. ⁇ H. V. :630V ⁇ Anode diameter: ⁇ 4mm ⁇ Gas: Ar ⁇ Gas pressure: 600Pa ⁇ Output: 35W
• the total area ratio of Al crystal, MgZn 2 crystal, and Zn/Al/MgZn 2 ternary eutectic in the Zn--Al--Mg alloy layer is 90% or more. From the viewpoint of improving corrosion resistance, the lower limit of the area ratio is preferably 92%, 95%, or 98%. Ideally, the area ratio is particularly preferably 100%. Further, like the Zn crystal, the area ratio of the structure excluding the above-mentioned Al crystal, MgZn 2 crystal, and Zn/Al/MgZn 2 ternary eutectic is preferably 0 to 10%, 0 to 8%, 0 to 5%. , more preferably 0 to 2%. Ideally, the area ratio of Zn crystal is particularly preferably 0% (that is, it is particularly preferable that Zn crystal is not included).
• Al crystal and Zn crystal each mean independently crystallized crystals.
• the structure of the Zn-Al-Mg alloy layer is measured as follows. First, a sample is taken from the plated steel material to be measured. However, the sample is taken from a location other than the vicinity of the punched end face of the plated steel material (2 mm from the end face) and from a location where there are no defects in the plating layer.
• the surface of the plating layer of the sample is polished in the thickness direction of the plating layer (hereinafter also referred to as "Z-axis direction"). Specifically, after dry polishing the surface of the plating layer with a #1200 polishing sheet, a finishing solution containing alumina with an average particle size of 3 ⁇ m, a finishing solution containing alumina with an average particle size of 1 ⁇ m, and a finish containing colloidal silica were applied. Final polishing is performed using each solution in this order.
• the Zn intensity on the surface of the plating layer was measured by XRF (X-ray fluorescence analysis) before and after polishing, and when the Zn intensity after polishing became 1/2 of the Zn intensity before polishing, the plating layer was The thickness should be 1/2. Since the Zn-Al-Mg alloy layer occupies 1/2 or more of the thickness of the plating layer, the polished surface of the surface of the plating layer polished to 1/2 of the layer thickness is similar to the polished surface of the Zn-Al-Mg alloy layer. Become. Therefore, by analyzing the polished surface, it is possible to understand the metal structure contained in the Zn--Al--Mg alloy layer.
• SEM backscattered electron image a backscattered electron image (hereinafter also referred to as "SEM backscattered electron image”).
• the SEM observation conditions are acceleration voltage: 15 kV, irradiation current: 10 nA, and field of view size: 244 ⁇ m ⁇ 198 ⁇ m.
• mapping was performed at a magnification of 500 times with an accelerating voltage of 15 kV, an irradiation current of 30 nA, a beam diameter of about 100 nm, an irradiation time of 5 ms per point, and a measurement pitch of 300 nm.
• Conduct analysis Then, it can be roughly divided into a region where the detection points of Mg and Zn overlap, a region where the detection points of Al and Zn overlap, and a region where Zn is detected alone.
• a region where Mg and Zn detection locations overlap is defined as MgZn 2
• a region where Al and Zn detection locations overlap is defined as Al crystal.
• FE-EPMA line analysis is performed at a magnification of 2000 times over a length of 10 ⁇ m.
• a region in which 1% or more of Mg or Al is detected in the measurement region can be determined as Zn/Al/MgZn binary ternary eutectic, and a region in which less than 1% of either Mg or Al is detected can be determined as Zn crystal.
• the Mg-enriched layer is a layer in which an Mg-containing phase such as a Zn/Al/ MgZn binary ternary eutectic existing on the surface layer of the Zn--Al--Mg alloy layer is densified and the Mg concentration is increased. If the Mg concentration layer is thin, corrosion resistance will be inferior. On the other hand, if the Mg concentrated layer is too thick, the discoloration resistance will deteriorate. Therefore, the thickness of the Mg enriched layer is set to 0.8 ⁇ m or more (plating layer thickness x 1/2) or less.
• the thickness of the Mg concentrated layer is preferably 0.9 ⁇ m or more and 25 ⁇ m or less, more preferably 1.0 ⁇ m or more and 22.5 ⁇ m or less.
• the thickness of the plating layer is preferably 5 ⁇ m or more and 50 ⁇ m or less, more preferably 10 ⁇ m or more and 45 ⁇ m or less.
• the Mg enriched layer is a layer defined as follows.
• sputtering is performed from the surface side of the plating layer in the depth direction using glow discharge optical emission spectrometry (quantitative GDS), and the depth distribution of the intensity of elements (Zn, Al, Mg, Fe, etc.) contained in each plating layer is determined.
• Measure see FIG. 1 (measuring equipment: manufactured by Horiba, model number: GD-Profiler 2, measurement conditions: DC mode, voltage 900 V, current 20 mA).
• the element that is the main component of the film for example, carbon (C) in the case of an organic film, the element that is the main component in the case of an inorganic film).
• the depth distribution of intensity is also measured.
• the main component element is, for example, zirconium (Zr) in the case of a zirconium oxide film, and silicon (Si) in the case of a film containing a silane coupling agent.
• Measurements are carried out to a depth where the plating layer disappears and the base metal is sufficiently exposed.
• the depth [ ⁇ m] of the hole after measurement is measured, and the sputtering speed [ ⁇ m/s] is determined by dividing the GDS measurement time [s] from the measured value. By multiplying this sputtering speed by the elapsed time from the start of measurement at the target measurement position, the depth [ ⁇ m] from the surface of the target measurement position can be determined.
• the point where the increase in Fe intensity per 0.1 ⁇ m exceeds 0.003 is defined as (A).
• the Mg strength at the above point (A) is assumed to be 1, and the point (B) where the relative strength of Mg is 1.03 when looking at the Mg strength from the base steel (that is, the base steel material) side to the plating layer surface side is Mg. It is defined as the interface between the concentrated layer and the Zn-Al-Mg alloy layer.
• the point (C) where the strength of Mg and the strength of carbon (C) become the same is defined as the upper end of the Mg concentrated layer.
• the strength of carbon (C) that determines point (C) is derived from dust or oil attached to the surface of the plating layer. This is the strength of carbon (C).
• point (C) if a chemical conversion coating or the like is present on the plating layer, the point where the intensity is the same as that of the element that is the main component of the coating is defined as point (C) and the upper end of the Mg-enriched layer.
• the Mg enriched layer is defined as the layer between points (B) and (C), and the thickness of the Mg enriched layer is the depth of the points (B) and (C) measured at three locations. is defined as the average value of the differences between
• the Al-Fe alloy layer may be formed on the surface of the base steel material (specifically, between the base steel material and the Zn-Al-Mg alloy layer), and is a layer whose main phase is Al 5 Fe phase as a structure. be.
• the Al--Fe alloy layer is formed by mutual atomic diffusion between the base steel material and the plating bath. Since the steel material of the present disclosure forms a plating layer by a hot-dip plating method, an Al--Fe alloy layer is likely to be formed in the plating layer containing the Al element. Since the plating bath contains Al at a certain concentration or more, the Al 5 Fe phase is formed in the largest amount.
• the Al--Fe alloy layer may partially contain a small amount of AlFe phase, Al 3 Fe phase, Al 5 Fe 2 phase, etc. Furthermore, since Zn is also included at a certain concentration in the plating bath, the Al--Fe alloy layer also contains a small amount of Zn.
• Corrosion resistance here refers to corrosion resistance in areas not affected by welding.
• Si when Si is contained in the plating layer, Si is particularly easily incorporated into the Al--Fe alloy layer and may become an Al--Fe--Si intermetallic compound phase.
• the intermetallic compound phase identified is the AlFeSi phase, and the isomers include ⁇ , ⁇ , q1, q2-AlFeSi phases, etc. Therefore, these AlFeSi phases may be detected in the Al--Fe alloy layer.
• the Al--Fe alloy layer containing these AlFeSi phases is also referred to as an Al--Fe--Si alloy layer. Note that since the Al--Fe--Si alloy layer is also thinner than the Zn--Al--Mg alloy layer, its influence on the corrosion resistance of the entire plating layer is small.
• the structure of the Al--Fe alloy layer may change depending on the amount of pre-plating applied. Specifically, if the pure metal layer used for pre-plating remains around the Al-Fe alloy layer, an intermetallic compound phase (for example, (Al 3 Ni phase, etc.) to form an alloy layer, to form an Al-Fe alloy layer in which some of the Al atoms and Fe atoms have been substituted, or to form an Al-Fe alloy layer in which some of the Al atoms, Fe atoms, and Si atoms have been substituted. In some cases, an Al--Fe--Si alloy layer is formed.
• an intermetallic compound phase for example, (Al 3 Ni phase, etc.
• the Al--Fe alloy layer is a layer that includes alloy layers of the various embodiments described above in addition to the alloy layer mainly composed of the Al 5 Fe phase.
• an Al-Ni-Fe alloy layer will be formed as an Al-Fe alloy layer.
• the thickness of the Al--Fe alloy layer is, for example, 0 ⁇ m or more and 7 ⁇ m or less.
• the thickness of the Al--Fe alloy layer is preferably 0.05 ⁇ m or more and 5 ⁇ m or less from the viewpoint of improving the adhesion of the plating layer (specifically, the Zn-Al-Mg alloy layer) and ensuring corrosion resistance and workability.
• the Zn-Al-Mg alloy layer is thicker than the Al-Fe alloy layer, so the contribution of the Al-Fe alloy layer to the corrosion resistance of the plated steel is greater than that of the Zn-Al-Mg alloy layer. Then it's small.
• the Al--Fe alloy layer contains Al and Zn, which are corrosion-resistant elements, at a certain concentration or more, as estimated from the results of component analysis. Therefore, the Al--Fe alloy layer has a certain degree of corrosion resistance with respect to the base steel material.
• an Al-Fe alloy layer of 100 nm or more is often formed between the base steel material and the Zn-Al-Mg alloy layer. .
• the thickness of the Al--Fe alloy layer is preferably 0.05 ⁇ m or more.
• the thickness of the Al--Fe alloy layer is preferably 7 ⁇ m or less.
• the thickness of the Al--Fe alloy layer is more preferably 5 ⁇ m or less, and still more preferably 2 ⁇ m or less.
• the thickness of the Al--Fe alloy layer is measured as follows. After embedding the sample in resin, it was polished and an SEM backscattered electron image of the cross section of the plating layer (cut surface along the thickness direction of the plating layer) was obtained (magnification: 10,000 times, field of view size: 50 ⁇ m in height x 200 ⁇ m in width, The thickness is measured at five arbitrary locations of the identified Al--Fe alloy layer. Then, the arithmetic average of the five locations is taken as the thickness of the Al--Fe alloy layer.
• the thickness of the plating layer is also determined by the above-mentioned cross-sectional SEM backscattered electron image (500x magnification, field of view size: 198 ⁇ m in height x 244 ⁇ m in width, with a field of view in which the entire plating layer is visible). Measure the thickness at five locations. Then, the arithmetic average of the five locations is taken as the thickness of the plating layer.
• the plated steel material of the present disclosure is obtained by forming a plating layer having the above-described predetermined chemical composition and metal structure on the surface (i.e., one or both sides) of a base steel material (base steel plate, etc.) by a hot-dip plating method.
• hot-dip plating is performed under the following conditions.
• a method for manufacturing a plated steel sheet will be described as an example of a method for manufacturing a plated steel material according to the present disclosure.
• a base steel plate as a base steel material is immersed in a plating bath, and after being pulled out of the plating bath, it is cooled in a temperature range of 450 to 395°C at an average cooling rate of 15°C/s or less.
• the temperature range of 395 to 340°C is cooled at an average cooling rate of 3°C/s or less.
• the temperature range of 340 to 280°C is cooled at an average cooling rate of 10 to 20°C/s or more.
• the plating is performed by, for example, a continuous hot-dip metal plating method such as the Sendzimir method.
• skin pass rolling is performed under the conditions that the surface roughness Ra of the skin pass roll is 1 to 5 ⁇ m and the skin pass rolling force is 100 to 500 tons.
• the plating layer solidifies in the following order: Al crystal, MgZn 2 crystal crystallized around the Al crystal, and Zn/Al/MgZn 2 ternary eutectic.
• Al crystal is grown by cooling in the temperature range of 450 to 395° C. at an average cooling rate of 15° C./s or less. Then, by cooling in the temperature range of 395 to 340° C. at an average cooling rate of 3° C./s or less, MgZn 2 crystals are reliably crystallized around the Al crystals. Thereby, the Zn/Al/MgZn two- component eutectic can be refined.
• the upper limit of the average cooling rate in the temperature range of 450 to 395°C is 15°C/s, preferably 13°C. C/s, more preferably 11 C/s.
• the lower limit is not particularly limited, but from the viewpoint of productivity, it is preferably 1°C/s or more, more preferably 2°C/s or more. Note that if the average cooling rate in the temperature range of 450 to 395° C. exceeds 15° C./s, the Al crystal will crystallize too finely, and the Zn/Al/MgZn binary eutectic will also become too fine. This makes it difficult to form an Mg-enriched layer due to skin pass rolling, which will be described later.
• the upper limit of the average cooling rate in the temperature range of 395°C to 340°C is 3°C/s, preferably 2. 5°C/s. Further, the lower limit is not particularly limited, but from the viewpoint of productivity, it is preferably 0.5°C/s, more preferably 1°C/s or more. Note that if the average cooling rate in the temperature range of 395°C to 340°C exceeds 3°C/s, the MgZn 2 crystals around the Al crystal cannot be grown sufficiently, resulting in a Zn/Al/MgZn 2 ternary eutectic. miniaturization becomes insufficient. As a result, it becomes difficult to form an Mg-enriched layer due to skin pass rolling, which will be described later.
• the Zn/Al/MgZn binary ternary eutectic is refined. This makes it easier to form a Mg-enriched layer by skin pass rolling, which will be described later.
• the average cooling rate in the temperature range of 340 to 280°C exceeds 20°C/s, the Zn/Al/MgZn binary eutectic becomes excessively fine and an Mg-enriched layer is formed due to skin pass rolling, which will be described later. It becomes difficult to be treated.
• the average cooling rate in the temperature range below 280°C is not limited.
• furnace cooling may be used, or heat retention may be achieved by adjusting the properties of the steel material.
• water cooling may be performed using mist cooling or the like.
• the average cooling rate in the method exemplified here is, for example, 50° C./second or less.
• the surface roughness Ra of the skin pass roll is 1 ⁇ m or more, and the skin pass rolling force is 1 ⁇ m or more.
• the soft Mg-containing crystals Zn/Al/MgZn binary eutectic, etc.
• the surface roughness Ra of the skin pass roll exceeds 5 ⁇ m, the surface area of the plating layer increases, so the Mg-enriched layer becomes too thick and the discoloration resistance deteriorates.
• the surface roughness Ra of the skin pass roll is less than 1 ⁇ m, the base steel sheet will slip during skin pass rolling, making it impossible to roll uniformly, making it impossible to ensure corrosion resistance and discoloration resistance. Furthermore, if the skin pass rolling force exceeds 500 tons, the soft Mg-containing crystals (Zn/Al/MgZn binary eutectic, etc.) will extend too much, making it difficult to thicken the Mg-enriched layer and deteriorating the corrosion resistance. On the other hand, if the skin pass rolling force is less than 100 tons, it is difficult to thicken the Mg-enriched layer and the corrosion resistance deteriorates. Note that when the skin pass rolling force is within an appropriate range and the surface roughness Ra of the skin pass roll increases, the point (B) in FIG. 1 tends to move to the right, and the thickness of the Mg enriched layer increases.
• the surface roughness Ra of the skin pass roll is measured as follows.
• the roughness of the surface of the skin pass roll is measured at three locations in the width direction of the roll using a stylus-type portable roughness meter, and the average value is taken.
• a film may be formed on the plating layer.
• the film can form one layer or two or more layers.
• Examples of the type of film directly above the plating layer include a chromate film, a phosphate film, and a chromate-free film. Chromate treatment, phosphate treatment, and chromate-free treatment for forming these films can be performed by known methods.
• Chromate treatment includes electrolytic chromate treatment, which forms a chromate film through electrolysis, reactive chromate treatment, which uses a reaction with the material to form a film and then washes away the excess treatment liquid, and a process in which the treatment liquid is applied to the object.
• electrolytic chromate treatment which forms a chromate film through electrolysis
• reactive chromate treatment which uses a reaction with the material to form a film and then washes away the excess treatment liquid, and a process in which the treatment liquid is applied to the object.
• Electrolytic chromate treatment uses chromic acid, silica sol, resin (acrylic resin, vinyl ester resin, vinyl acetate acrylic emulsion, carboxylated styrene butadiene latex, diisopropanolamine-modified epoxy resin, etc.), and hard silica.
• resin acrylic resin, vinyl ester resin, vinyl acetate acrylic emulsion, carboxylated styrene butadiene latex, diisopropanolamine-modified epoxy resin, etc.
• Examples of the phosphate treatment include zinc phosphate treatment, zinc calcium phosphate treatment, and manganese phosphate treatment.
• Chromate-free treatment is particularly suitable as it does not impose any burden on the environment.
• Chromate-free treatment includes electrolytic chromate-free treatment, which forms a chromate-free film by electrolysis, reactive chromate-free treatment, which forms a film by reacting with the material and then washes away excess treatment liquid, and There is a paint-on type chromate-free treatment that is applied to the object to be coated and dries to form a film without washing with water. Either process may be adopted.
• organic resin films may be provided on the film directly above the plating layer.
• the organic resin is not limited to a specific type, and includes, for example, polyester resin, polyurethane resin, epoxy resin, acrylic resin, polyolefin resin, or modified products of these resins.
• modified products are compounds in which the reactive functional groups contained in the structure of these resins are reacted with other compounds (monomers, crosslinking agents, etc.) that contain functional groups in the structure that can react with the functional groups. Refers to resin.
• organic resin one type or a mixture of two or more types of organic resins (unmodified) may be used, or at least one type of other organic resin may be used in the presence of at least one type of organic resin.
• Organic resins obtained by modifying organic resins may be used alone or in combination of two or more.
• the organic resin film may contain any coloring pigment or antirust pigment. It is also possible to use those made into aqueous systems by dissolving or dispersing them in water.
• Example 2 After melting the ingot in a vacuum melting furnace using a predetermined amount of pure metal ingot so as to obtain a plating layer having the chemical composition shown in Tables 1 and 2, a plating bath was prepared in the atmosphere. A hot-dip plating simulator was used to fabricate the plated steel sheet. As the base steel material, a general hot-rolled steel plate (C concentration ⁇ 0.1%) with a plate thickness of 2.3 mm was used. After polishing the surface of the base steel material with a brush, degreasing and pickling were performed immediately before the plating process.
• pre-Ni-plated steel material which is a general hot-rolled steel plate with a plate thickness of 2.3 mm and pre-Ni plating, was used as the base steel material.
• the amount of Ni deposited was 1 g/m 2 to 3 g/m 2 .
• examples in which pre-Ni plated steel was used as the base steel were written as "pre-Ni" in the column of "base steel” in the table.
• a contact type K thermocouple was attached to the back side of the plated surface of the base steel material in order to monitor the temperature of the steel material during the process of producing a plated steel sheet.
• the same reduction treatment method was applied to the base steel material up to the time of immersion in the plating bath. That is, the base steel material is heated from room temperature to 800°C by electrical heating in an N 2 -H 2 (5%) environment (dew point -40°C or less, oxygen concentration less than 25ppm), held for 60 seconds, and then N 2 It was cooled to the plating bath temperature +10° C. by gas blowing, and immediately immersed in the plating bath. In addition, all the plated steel sheets were immersed in the plating bath for the time shown in the table. The N 2 gas wiping pressure was adjusted to produce a plated steel plate with a plating thickness of 30 ⁇ m ( ⁇ 1 ⁇ m).
• the plating bath temperature was 500°C.
• the immersion time in the plating bath was 2 seconds.
• a plating layer was obtained by a cooling process in which the average cooling rate of the first to third stages shown in Tables 1 to 2 was set to the conditions shown in Tables 1 to 2.
• ⁇ 1st stage average cooling rate Average cooling rate in the temperature range of 450 to 395°C
• ⁇ 2nd stage average cooling rate Average cooling rate in the 395 to 340°C temperature range
• ⁇ 3rd stage average cooling rate 340 ⁇ Average cooling rate in a temperature range of 280° C.
• the steel material was cooled by spraying N 2 gas onto the steel material after plating. At this time, cooling was performed while adjusting the amount of N 2 gas sprayed so as to achieve a predetermined cooling rate in the above temperature range.
• the examples corresponding to the plated steel materials of the present disclosure have excellent corrosion resistance compared to the comparative examples even in coastal areas where there is a lot of airborne salt and a severe corrosive environment. It can also be seen that it has excellent processability and discoloration resistance.
• test no. For No. 103 uniform rolling was not possible and the appearance varied widely, so the thicknesses of various plating layers were not measured.

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