WO2019054483A1 - Plaque à damier plaquée par immersion à chaud et procédé de fabrication associé - Google Patents

Plaque à damier plaquée par immersion à chaud et procédé de fabrication associé Download PDF

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Publication number
WO2019054483A1
WO2019054483A1 PCT/JP2018/034188 JP2018034188W WO2019054483A1 WO 2019054483 A1 WO2019054483 A1 WO 2019054483A1 JP 2018034188 W JP2018034188 W JP 2018034188W WO 2019054483 A1 WO2019054483 A1 WO 2019054483A1
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hot
plating
dip
plating layer
steel plate
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PCT/JP2018/034188
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English (en)
Japanese (ja)
Inventor
完 齊藤
高橋　武寛
石塚　清和
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新日鐵住金株式会社
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Priority to JP2019542309A priority Critical patent/JP6669316B2/ja
Priority to CN201880059381.7A priority patent/CN111094613B/zh
Priority to KR1020207009277A priority patent/KR102346426B1/ko
Priority to SG11202002217XA priority patent/SG11202002217XA/en
Priority to BR112020004763-5A priority patent/BR112020004763A2/pt
Publication of WO2019054483A1 publication Critical patent/WO2019054483A1/fr
Priority to PH12020500490A priority patent/PH12020500490A1/en

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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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection
    • 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
    • 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
    • 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
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • 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
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0224—Two or more thermal pretreatments
    • 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
    • C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces

Definitions

  • the present invention relates to a hot-dip galvanized steel sheet and a method of manufacturing the same.
  • Priority is claimed on Japanese Patent Application No. 2017-178011, filed September 15, 2017, the content of which is incorporated herein by reference.
  • the striped steel plate is a steel plate having a non-slip projection (convex portion) continuous on the surface by rolling.
  • projections of a constant width, a constant length and a constant height are provided at a constant angle and a constant pitch with respect to the rolling direction.
  • a striped steel plate is manufactured by hot rolling. And it is used for floor boards and steps such as buses and trucks, floor boards for factories, decks of ships, temporary scaffolds for construction sites, stairs and the like.
  • striped steel plates are often used as they are hot-rolled or painted.
  • the cut sheet of the striped steel plate is galvanized by going through a batch-type hot dip galvanization process by a flux method.
  • batch-type hot-dip galvanizing process has low productivity, and the Fe-Zn alloy layer generated in the hot-dip plating process is enlarged, so that the processability of the plating layer is impaired, and the plating cracking and peeling of the plating layer occur. It may occur and cause problems in corrosion resistance.
  • Continuous galvanization is more productive than batch galvanization.
  • Continuous galvanization is generally performed by passing a steel sheet heated to a predetermined temperature in a reducing or non-oxidizing atmosphere to a hot dip galvanizing bath.
  • at least about 0.05% of Al is contained in the molten zinc bath, it is possible to suppress the growth of the Fe—Zn alloy layer which impairs the processability of the plating film.
  • batch hot dip galvanization by a general flux method, when Al is contained in a Zn bath, Al decomposes a flux, so that non-plating occurs frequently and plating can not be performed well.
  • Patent Document 1 teaches a continuous hot-dip galvanizing method for strip-shaped striped steel plates, in particular, tension in a plating line and appropriate conditions for gas wiping after hot-dip plating.
  • continuous hot-dip galvanized striped steel plates are commercialized.
  • hot-dip zinc-based alloy coated steel sheets such as Zn-Al, Zn-Al-Mg and Zn-Al-Mg-Si have been developed from the demand for excellent corrosion resistance over zinc plating. It is commercialized. In response to this, attempts have also been made to apply hot-dip zinc-based alloy plating to striped steel plates.
  • Patent Document 2 has a Ni-Al-Zn-Fe quaternary alloy layer having a thickness of 2 ⁇ m or less as a first layer on the surface of a striped steel plate, and 0.1 to 1% in weight conversion as a second layer.
  • a striped steel plate excellent in workability and corrosion resistance characterized by having a hot-dip plating layer of a Zn-based alloy containing Al.
  • Patent Document 2 performs Ni plating of 0.5 to 2.0 g / m 2 on a striped steel plate, and then heats the striped steel plate, and subsequently 0.1 to 1% in weight conversion.
  • the method of producing a striped steel plate is provided, which comprises the steps of immersing in a molten zinc bath to which Al is added for an immersion time of 1 to 30 seconds.
  • Patent Document 3 uses a plating bath considered to be substantially the same as Patent Document 2, but specifies the structure of a hot-dip plating film obtained by the Sendzimir method.
  • Each of Patent Documents 2 and 3 is essentially characterized by using a molten zinc-based alloy having an Al concentration of 1% or less.
  • the Al concentration in the plating layer is 1% or less, it is difficult to obtain the barrier anticorrosion effect caused by Al, and a preferable improvement in the remarkable corrosion resistance of the plating film itself can not be expected.
  • Patent Document 4 is, by mass%, Al: 4.0-20.0%, Mg: 1.0-4.0%, and optionally, Ti: 0.002-0.1% and B: 0.
  • a hot-dip galvanized steel sheet excellent in scratch resistance, wear resistance and corrosion resistance characterized in that it is covered with a hot-dip plating layer containing 001 to 0.045% and the balance being Zn and unavoidable impurities.
  • This plated layer has a large proportion of ternary eutectic structure of Al / Zn / ZnMg intermetallic compound, and since this ternary eutectic is hard, the Vickers hardness becomes 120 to 180 Hv, and in addition to corrosion resistance, It is considered to be excellent in scratch resistance and abrasion resistance.
  • the present inventors also initially attempted to apply zinc base alloy plating with an Al concentration of more than 1.0% to a striped steel plate for the purpose of further improving the corrosion resistance of the striped steel plate.
  • zinc base alloy plating having an Al concentration of more than 1.0% to the striped steel sheet. That is, as in Patent Documents 2 and 3, if the Al concentration in zinc-based alloy plating is 1.0% or less, occurrence of non-plating does not become a problem, but as in Patent Document 4, zinc-based alloy plating is It became clear that the occurrence of non-plating becomes a problem if the Al concentration of Al exceeds 1.0%.
  • the present inventors initially intended to impart excellent corrosion resistance to a striped steel plate, and generally said that the corrosion resistance is generally superior to Zn plating. It was studied to apply a Zn-based alloy plating containing a slight amount of Mg to a striped steel plate. And in that process, when the Zn-Al-Mg alloy with Al concentration over 1.0% is electroplated on the striped steel sheet by Sendzimir method that is usually adopted as the hot dip plating method, non-plating occurs frequently. Found out.
  • the inventors of the present invention have found that the non-plating tends to occur in the process of hot-dip plating a Zn-based alloy containing Al: more than 1.0% and a certain amount of Mg onto the striped steel sheet. It is considered that the wettability between the steel plate and the molten metal is reduced as it is performed, and that a specific cause resulting from the hot rolling history of the striped steel plate is also related.
  • the present inventors tried to adopt Ni pre-plating, which is also adopted in Patent Document 2.
  • the present inventors can suppress the occurrence of non-plating to some extent by performing zinc-based alloy plating after Ni pre-plating, but a zinc-based alloy having an Al concentration of more than 1.0% with respect to a striped steel plate It has been found that in the case of plating, it is necessary to relatively increase the amount of Ni attached in Ni pre-plating.
  • Non-plating occurs frequently only by applying zinc-based alloy plating having an Al concentration of more than 1.0% to a striped steel plate.
  • the present inventors considered the above phenomenon as follows. For example, when a hot-dip galvanized steel sheet is used as a floor plate or the like, wear and wear of the hot-dip plating layer may be large at the convex portions, and the Ni plating layer may be exposed.
  • Ni pre-plated steel plates are plated with molten Zn or molten Zn-Al etc., some Ni will move into the plating layer or melt due to the reaction with the molten metal, but some Ni will move It remains on the surface of a steel plate as a Ni plating layer. Therefore, when the Ni adhesion amount of Ni pre-plating is large, the Ni plating layer remaining on the surface of the steel sheet after hot-dip plating becomes thick.
  • the natural immersion potential is higher in the order of Ni, Fe and plated layer, but the natural immersion potential of a relatively thin Ni plated layer is a hybrid potential of Ni and Fe.
  • the galvanized layer of the upper Zn-based alloy is worn away, and when the Ni-plated layer is exposed, Galvanic corrosion occurs between the exposed portion and the vicinity of the exposed portion.
  • Galvanic corrosion occurs between the Ni plating layer exposed at the convex portion and the hot-dip plating layer near the exposed portion.
  • the hot-dip plating layer is susceptible to corrosion and wear.
  • Ni plating layer to indicate a plating layer
  • Ni plating Ni coating remaining after hot-dip plating
  • Ni pre-plating layer Ni pre-plating shall mean the Ni coating layer which exists before a hot dip plating process.
  • the present invention is a striped steel plate on which a Zn-Al-Mg-based alloy containing 1.0% or more of Al has been subjected to hot-dip plating, which has almost no non-plating and a Zn-based alloy at the convex portion of the striped steel plate. It is an object of the present invention to provide a hot-dip galvanized steel sheet which exhibits excellent corrosion resistance even when hot-dip plating is worn out (corrosion or wear) and a method for producing the same. In the present invention, after satisfying the plating appearance and processability, etc., which are general characteristics required for hot-dip galvanized striped steel sheets, the hot-dip plating can achieve both the suppression of the non-plating and the corrosion resistance after wear. It aims at providing a striped steel plate and its manufacturing method.
  • the present inventors attempted to carry out the hot-dip plating of a Zn-Al-Mg-based alloy containing 1.0% or more of Al on a Ni pre-plated striped steel plate, the relatively large Ni adhesion from the viewpoint of preventing non-plating. Although the amount is required, it was considered that at least the amount of Ni adhesion at the convex portion needs to be suppressed to a certain value or less from the viewpoint of securing the corrosion resistance at the convex portion of the striped steel plate.
  • electroplating is usually employed. Although it is possible to deposit Ni on a steel strip by the electroless method, it is not preferable because the productivity is inferior and, in addition, a large amount of elements other than Ni are mixed into the deposited film.
  • electroplating is performed on a general steel strip, usually, the anode is disposed to face the steel strip surface which is a cathode, and electrolysis is performed by minimizing the distance between the steel strip and the anode as much as possible. The power cost can be reduced while ensuring the uniformity of the current distribution.
  • the distance between the electrode and the anode is closer to the convex portion of the striped steel plate than to the flat portion of the striped steel plate, so the amount of Ni attached becomes large at the convex portion of the striped steel plate. That is, in the case of performing Ni pre-plating by electroplating a striped steel plate in a conventional electrolytic cell under conventional conditions, the amount of Ni attached on the convex portion becomes very large, and as a result, the hot-dip galvanized steel layer There is a concern that significant Galvanic corrosion will occur at the ridges when the.
  • the present inventors regarding hot-dip galvanized steel sheets of Zn-Al-Mg-based alloy containing 1.0% or more of Al, have a lower limit value of the thickness of Ni pre-plating layer required for preventing non-plating and By determining the upper limit value of the thickness of the Ni plating layer to be limited in order to secure the corrosion resistance in the convex portion, and defining the thickness ratio of the Ni plating layer in the convex portion and the flat portion, I found that I could overcome the problem.
  • the hot-dip galvanized striped steel sheet according to one aspect of the present invention comprises a base steel plate, a Ni-plated layer disposed on the surface of the base steel plate, and a hot-dip plated layer disposed on the surface of the Ni-plated layer.
  • a Ni-plated layer in the convex portion having a thickness of 0.07 to 0.4 ⁇ m per side, and the Ni plated layer in the flat portion is The film thickness is 0.05 to 0.35 ⁇ m per one side, and the film thickness of the Ni plating layer in the convex portion is more than 100% and 400% or less of the film thickness of the Ni plating layer in the flat portion.
  • the adhesion amount of the layer is 60 to 400 g / m 2 per one side, and the hot-dip plating layer has a chemical composition of Al: more than 1.0% and 26% or less, Mg: 0.05 to 10%, Si: Containing 0 to 1.0%, Sn: 0 to 3.0%, Ca: 0 to 1.0%, the balance being Zn and impurities It consists of things.
  • the thickness of the Ni plating layer in the convex portion is more than 100% and 300% or less of the thickness of the Ni plating layer in the flat portion. Good.
  • the film thickness of the Ni plating layer in the convex portion may be 0.07 to 0.3 ⁇ m per one surface.
  • the hot-dip plated layer has a chemical composition of, by mass%, Al: 4.0 to 25.0%, Mg May contain 1.5 to 8.0%.
  • the hot-dip plated layer has a chemical composition represented by mass: Si: 0.05 to 1.0%, Sn It may contain at least one of 0.1 to 3.0% and Ca: 0.01 to 1.0%.
  • the coverage of the hot-dip plating layer is 99 to 99% in area% with respect to the plate surface. It may be 100%.
  • the method of manufacturing a hot-dip galvanized striped steel sheet according to an aspect of the present invention is a method of producing the striped steel sheet according to any one of the above (1) to (6)
  • the pre-plating process includes a rolling process for providing a convex portion and a flat surface, a pre-plating process for applying Ni pre-plating to a steel plate subjected to the rolling process, and a hot-dip plating process for hot dip plating on a steel plate subjected to the pre-plating process.
  • the rolling surface and the anode surface of the steel plate are arranged to face each other, the distance between the projections of the rolling surface and the anode is controlled to 40 to 100 mm, and the plating adhesion amount per one side is 0.5 on average.
  • the hot dipping step heating the steel sheet contains, by mass%, Al: 1.0 super 26% or less, Mg: 0.05 ⁇ 10%, Si: Contains 0 to 1.0%, Sn: 0 to 3.0%, Ca: 0 to 1.0%
  • the steel plate is immersed in a hot-dip plating bath containing the remainder of Zn and impurities, and continuous hot-dip plating is performed under the condition that the plating adhesion amount per one side is 60 to 400 g / m 2 on average.
  • the distance between the electrodes may be controlled to 45 to 100 mm in the pre-plating step.
  • the hot-dip plating layer contains Al of more than 1.0%, excellent corrosion resistance is obtained, and additionally, the film thickness of the Ni plating layer is controlled. The occurrence can be suppressed, and the corrosion when the hot-dip plating layer is worn out and the Ni plating layer is exposed can also be suppressed. As a result, it is possible to suppress floor plates, base plates, structures, and other life cycle costs as hot-dip galvanized steel sheets.
  • the hot-dip galvanized striped steel sheet comprises a base steel plate, a Ni plating layer disposed on the surface of the base steel plate, and a Zn-based (Zn-Al-Mg-based) alloy disposed on the surface of the Ni plating layer. And a convex portion and a flat portion on the plate surface.
  • the film thickness of the Ni plating layer in the convex portion is 0.07 to 0.4 ⁇ m per one surface
  • the film thickness of the Ni plating layer in the flat portion is 0.05 to 0.35 ⁇ m per one surface
  • the film thickness of the Ni plating layer is more than 100% and 400% or less of the film thickness of the Ni plating layer in the flat portion.
  • the adhesion amount of the hot-dip plating layer is 60 to 400 g / m 2 per one side, and the hot-dip plating layer has a chemical composition of Al: more than 1.0% and 26% or less, Mg: 0.05 to 10%, Si: 0 to 1.0%, Sn: 0 to 3.0%, Ca: 0 to 1.0%, the balance being Zn and impurities.
  • a thin intermetallic compound layer may be formed on the Ni plating layer side of the hot-dip plating layer based on the reaction between a molten metal (hot-dip plating bath of Zn-based alloy) and a steel plate preplated with Ni. Varies with the composition of the Zn-based alloy hot-dip plating bath.
  • the “hot-dip plating layer of a Zn-based alloy” is used in the meaning including the intermetallic compound layer.
  • the hot-dip plating layer is a Zn-based alloy and contains, as a chemical composition, by mass, Al: more than 1.0% and not more than 26%, and Mg: 0.05 to 10%.
  • the Al concentration of the hot-dip plating layer exceeds 1.0%.
  • the Al concentration in the plating bath increases, the melting point rises, so it is necessary to raise the temperature of the molten metal.
  • the Al concentration exceeds 26% it is difficult to secure the beauty of the surface properties of the plating layer It is easy to cause the deterioration of processability. Therefore, the Al concentration of the hot-dip plating layer is 26% or less.
  • the Al concentration of the hot-dip plating layer is preferably 4.0% or more.
  • the Al concentration of the hot-dip plating layer is preferably 25.0% or less, more preferably 21.0% or less.
  • Mg manganesium
  • the preferable lower limit of the Mg concentration is 0.5%, more preferably 1%, still more preferably 1.5%, and still more preferably 2.0%.
  • the upper limit of the Mg concentration is preferably 8.5%, more preferably 8.0%, and still more preferably 6.0%.
  • the hot-dip plated layer of the hot-dip galvanized striped steel sheet according to the present embodiment contains Al and Mg which are the above-described basic elements as a chemical composition, and the balance is made of Zn and impurities.
  • the Zn concentration is 64 to 98.95% in mass%.
  • the hot-dip plating layer contains 1.0% or less of Si, 3.0% or less of Sn, and 1.0% or less of Ca in mass%, as a selective element, instead of part of Zn that is the above-mentioned remaining portion. You may
  • the Si suppresses the growth of the interfacial alloy phase formed at the interface with the base steel plate, contributes to the improvement of the workability, suppresses the oxidation of Mg, and forms Mg and Mg 2 Si. Contributes to the improvement of corrosion resistance. Therefore, the Si concentration of the hot-dip plating layer may be 0 to 1.0%. In order to preferably obtain the above-mentioned effect of Si, Si is contained in an amount of 0.05% or more, preferably 0.1% or more. On the other hand, the above effect is saturated even if the Si concentration exceeds 1.0%. The preferred upper limit of the Si concentration is 0.6%.
  • the Sn concentration of the hot-dip plating layer may be 0 to 3.0%. In order to preferably obtain the above effect of Sn, 0.1% or more, preferably 0.3% or more of Sn is contained. On the other hand, when the Sn concentration exceeds 3.0%, the corrosion resistance, particularly the corrosion resistance of the flat portion tends to be reduced.
  • the preferred upper limit of the Sn concentration is 2.4%.
  • Ca (calcium) is effective in preventing oxidation of the plating bath surface.
  • the molten metal of the Zn-Al-Mg-based alloy tends to be easily oxidized as compared with the case where it does not contain Mg.
  • the Ca concentration of the hot-dip plating layer may be 0 to 1.0%.
  • the Ca concentration is preferably 0.01% or more, more preferably 0.1% or more.
  • the Ca concentration exceeds 1.0%, precipitation of Ca-based intermetallic compounds is increased, which may lower the corrosion resistance, particularly the corrosion resistance of the flat portion.
  • the preferred upper limit of the Ca concentration is 0.7%.
  • the balance of the above-mentioned basic element and selective element consists of Zn and impurities.
  • an "impurity" refers to the thing mixed from a raw material or a manufacturing environment etc.
  • the hot-dip plated layer of the hot-dip galvanized striped steel sheet according to the present embodiment Ni, Fe and the like dissolve from the surface of the steel plate into the plating bath to become impurities of the Zn-based alloy.
  • the hot-dip plating layer may contain Ni derived from the Ni pre-plating layer, and the Ni concentration may be 0.01 to 0.3% by mass%.
  • impurities are allowed to be contained as long as the target characteristics are not impaired.
  • a Ni-Al based intermetallic compound layer may be formed at the interface between the hot-dip plating layer and the Ni plating layer.
  • this intermetallic compound layer is considered to be part of the hot-dip plating layer.
  • the average adhesion amount of the hot-dip plating layer is 60 g / m 2 or more per one side.
  • the average amount of adhesion means the average amount of adhesion including the convex portion and the flat portion of the hot-dip galvanized steel sheet. That is, it means the amount of adhesion per projected area ignoring the unevenness of the convex part of the hot-dip galvanized steel sheet.
  • the corrosion resistance is insufficient.
  • the upper limit of the average adhesion amount of the hot-dip plating layer is not necessarily limited, but excessive adhesion of the hot-dip plating layer makes the plating sagging remarkable and impairs the appearance, so the average adhesion amount of the hot-dip plating layer is 400 g / m 2 or less per side. It is preferable to do.
  • the coverage of the hot-dip plating layer is preferably 99 to 100% in area% with respect to the plate surface. If the coverage of the hot-dip plating layer is 99% or more in area%, it can be judged that the occurrence of non-plating can be preferably suppressed.
  • Ni pre-plating layer previously formed on the surface of the base steel plate in order to prevent non-plating in the hot-dip plating process remains between the base steel plate and the hot-dip plating layer even after hot dipping. It is.
  • the Ni-plated layer is, for example, a light-colored contrast area observed between the base steel plate and the hot-dip plating layer when the cross section of the hot-dip streaked steel plate is observed by a reflection electron image of SEM (Scanning Electron Microscope) It is the range displayed white).
  • an intermetallic compound layer containing Ni that may be formed at the interface between the Ni plating layer and the base steel plate, and Ni that may be formed at the interface between the Ni plating layer and the hot-dip plating layer The intermetallic compound layer is not included in the Ni plating layer.
  • the Ni plating layer contains Ni as a chemical composition, and the balance consists of impurities.
  • the Ni concentration of the Ni plating layer is preferably 50 to 100% by mass.
  • an "impurity" refers to the thing mixed from a raw material or a manufacturing environment etc.
  • the Ni plating layer of the hot-dip galvanized striped steel sheet according to the present embodiment contains impurities due to diffusion of Fe from the base steel sheet, and the like.
  • the thickness of the Ni plating layer on the convex part of the hot-dip galvanized steel sheet is 0.4 ⁇ m or less on average per one side when viewed in a cut surface in which the thickness direction and the cutting direction are parallel. is necessary.
  • the film thickness of the Ni plating layer of this convex part is 0.3 micrometer or less.
  • the lower limit of the film thickness of the Ni plating layer of the convex portion is set to 0.07 ⁇ m or more per one surface on average. When the film thickness is less than 0.07 ⁇ m, non-plating occurs in the convex portion. It is preferable that the film thickness of the Ni plating layer of this convex part is 0.1 micrometer or more.
  • the thickness of the Ni plating layer in the flat portion of the hot-dip galvanized steel sheet is 0.05 ⁇ m or more per one surface on the cut surface in which the thickness direction and the cutting direction are parallel. It is necessary. If this film thickness is less than 0.05 ⁇ m, non-plating occurs on the flat portion. On the other hand, the upper limit of the film thickness of the Ni plating layer in the flat portion is 0.35 ⁇ m or less on an average per one side. If the film thickness exceeds 0.35 ⁇ m, the effect of improving the plating adhesion on the flat portion is saturated, which is not economical.
  • the thickness of the Ni plating layer in the convex portion is 100 as compared to the thickness of the Ni plating layer in the flat portion when viewed in a cut surface in which the thickness direction and the cutting direction are parallel. It is necessary to be more than% and not more than 400%.
  • the thickness of the Ni plating layer of the projections is the thickness of the Ni plating layer of the flat portion. In contrast, it was confirmed that it might be 2000% or more.
  • the present inventors do not thicken the film thickness of the Ni plating layer of the convex part so as to enhance the corrosion resistance after the wear in the convex part, while suppressing the non-plating in the flat part It has been found that in order to achieve this, it is necessary to secure a film thickness of the Ni plating layer in the flat portion to a certain extent. That is, in this embodiment, the film thickness ratio of the Ni plating layer of the convex portion to the flat portion (film thickness of convex portion / film thickness of flat portion ⁇ 100) is smaller than that of the conventional hot-dip galvanized steel sheet.
  • the film thickness ratio of the Ni plating layer of the convex portion to the flat portion exceeds 400%, suppression of non-plating in the flat portion and corrosion resistance after wear at the convex portion
  • the film thickness ratio of the Ni plating layer of the convex portion to the flat portion is 400% or less.
  • the film thickness ratio of the Ni plating layer of the convex portion to the flat portion is preferably 350% or less, more preferably 300% or less, and most preferably 250% or less.
  • the film thickness ratio of the Ni plating layer of the convex portion to the flat portion is set to be more than 100%.
  • the film thickness ratio of the Ni plating layer of the convex portion to the flat portion within the above range, the effect of being able to achieve both the non-plating suppression in the flat portion and the corrosion resistance after wear at the convex portion can be obtained.
  • the base steel plate (original plate to be plated) is a striped steel plate.
  • the striped steel sheet is usually given the shape of the convex portion by hot rolling.
  • the steel type of the base steel plate is not particularly limited, but generally, a steel type corresponding to the general structural rolled steel defined in JIS G3101 is used.
  • the convex shape of the striped steel sheet can be imparted, for example, by transferring the concave shape formed on the work roll to the steel sheet surface at the finishing stage of hot rolling.
  • the stripe height (height of the convex portion) and the occupancy ratio of the stripe portion (convex portion) are not necessarily limited, but in particular, in view of slip prevention as a floor plate and usability.
  • the stripe height is 0.5 to 3.5 mm, and the area occupancy of the stripe portion is 15 to 60%.
  • FIGS. 1A to 1C show the shape of a striped steel plate to be a base steel plate.
  • FIG. 1A is a schematic view when a base steel plate of a hot-dip galvanized striped steel plate according to an embodiment of the present invention is viewed from the thickness direction.
  • FIG. 1B is a schematic cross-sectional view of the base steel plate of the hot-dip galvanized striped steel plate according to the embodiment as viewed from a cut surface in which the thickness direction and the cutting direction are parallel.
  • FIG. FIG. 1C is a schematic cross-sectional view of the base steel plate of the hot-dip galvanized striped steel plate according to the embodiment as viewed from a cut surface in which the thickness direction and the cutting direction are parallel.
  • FIG. 1A is a schematic view when a base steel plate of a hot-dip galvanized striped steel plate according to an embodiment of the present invention is viewed from the thickness direction.
  • FIG. 1B is a schematic cross-sectional view of the base steel plate of the
  • A, B, C, D, E and H in these figures are as follows, respectively.
  • H Height of convex portion.
  • the convex portion and the flat portion of the hot-dip galvanized steel sheet may be observed in the appearance and the cross section of the hot-dip galvanized steel sheet.
  • the appearance of the hot-dip galvanized striped steel sheet is observed from the thickness direction, it can be determined that a convex portion and a flat portion exist in the hot-dip galvanized striped steel sheet if the appearance is equivalent to that of the striped steel plate shown in FIG.
  • the hot-dip galvanized striped steel sheet is a cross section corresponding to the GG cross section of FIG. 1A, that is, a cutting plane in which the cutting direction is parallel to the thickness direction and the center point (center of gravity) of the convex portion It may be observed on a cut surface including the major axis of the and the convex portion to determine whether or not the convex portion and the flat portion exist.
  • a reference line is determined on the basis of the region corresponding to the flat portion of the hot-dip galvanized steel sheet. If the distance is 0.5 mm or more, it may be determined that the peaks on the contour curve are convex.
  • the steel plate is a hot-dip galvanized steel plate.
  • Whether or not the base steel plate, the Ni plating layer, and the hot-dip plating layer are present in the hot-dip galvanized steel sheet may be observed by a field emission scanning electron microscope (FE-SEM) or a transmission electron microscope (TEM).
  • FE-SEM field emission scanning electron microscope
  • TEM transmission electron microscope
  • the test piece may be cut out so that the cutting direction is parallel to the thickness direction, and the cross-sectional structure of the cut surface may be observed by FE-SEM or TEM at a magnification at which each layer is included in the observation field of view.
  • FIG. 2 shows a schematic view of the cross-sectional structure of the hot-dip galvanized steel sheet according to the present embodiment.
  • the acceleration voltage is 15kV
  • the irradiation current is 10nA
  • the beam diameter is 10kA along the thickness direction at 20000 magnification using EDS (Energy Dispersive X-ray Spectroscopy).
  • Linear analysis may be performed with about 100 nm less, a measurement pitch of 0.025 ⁇ m, and an aperture diameter of the objective lens of 30 ⁇ m ⁇ , and quantitative analysis of the chemical composition of each layer may be performed with a total of 100% by mass of Ni, Fe and Zn.
  • the area where Ni concentration becomes 50 mass% or more on the scanning line is Ni plating layer It may be determined that there is. Further, the region on the surface side may be determined as the hot-dip plating layer, and the region on the inner side may be determined as the base steel plate, with the Ni plating layer identified on the scanning line as a reference.
  • the hot-dip plating layer is a Zn-based alloy, and the base steel plate is a Fe-based alloy.
  • the film thickness of the Ni plating layer of the convex portion may be determined by identifying the Ni plating layer of the convex portion in a cross section corresponding to the GG cross section of FIG. 1A. For example, in the above cross section, line analysis is performed along the thickness direction so as to include the top of the highest peak on the contour curve of the hot-dip galvanized steel sheet, and the Ni plating layer is identified on the scanning line of the line analysis; A line segment of the Ni plating layer on the scanning line may be obtained, and this line segment may be adopted as the film thickness of the Ni plating layer of the convex portion.
  • the film thickness of the Ni plating layer in the flat portion may be measured in the same manner as described above. For example, in the cross section corresponding to the GG cross section in FIG. 1A, line analysis is performed along the thickness direction at a flat portion at a position 2 mm or more away from the end of the convex portion. The layer may be identified, a line segment of the Ni plating layer on the scanning line may be determined, and this line segment may be adopted as the film thickness of the Ni plating layer in the flat portion.
  • the film thickness of the Ni plating layer of a convex part and a plane part may be measured in at least three or more places, respectively, and the average value may be adopted.
  • the film thickness of the Ni plating layer in the convex portion and the flat portion is less than 0.3 ⁇ m, it is preferable to obtain the film thickness not by SEM but by TEM.
  • the film thickness ratio of the Ni plating layer of the convex part to the flat part (film thickness of convex part ⁇ film thickness of flat part ⁇ 100) You can calculate
  • the chemical composition and the adhesion amount of the hot-dip plating layer may be measured using ICP (Inductive Coupled Plasma) emission spectroscopy.
  • ICP Inductive Coupled Plasma
  • a sample of 30 mm ⁇ 30 mm in size is taken from any part of a hot-dip galvanized steel sheet, and an inhibitor (eg, Asahi Chemical Industries Ibit, model number: Ibit 710-K, concentration: 300 ppm, ppm is Only the plating layer is pickled and peeled off using 10% hydrochloric acid added with mg / kg), ICP quantitative analysis is performed to determine the concentration of each element, and the chemical composition and adhesion amount of the hot-dip plating layer from the concentration of each element You just need to ask.
  • what is necessary is to carry out said measurement with respect to the sample extract
  • the coverage with respect to the plate surface of the hot-dip plating layer may be determined by observing the hot-dip galvanized steel sheet from the thickness direction. For example, a sample of 100 mm ⁇ 100 mm may be taken from any part of the hot-dip galvanized steel sheet, and this sample may be observed from the thickness direction to determine the area ratio of the unplated area in the sample area. The area ratio may be determined using image analysis software (for example, WinROOF manufactured by Mitani Corporation). More specifically, the 100 mm ⁇ 100 mm sample is divided into sizes that can be measured by EDS or EPMA (Electron Probe Micro-Analyzer), and surface analysis is performed on each of the divided samples using EDS or EPMA.
  • EDS or EPMA Electro Probe Micro-Analyzer
  • the Fe distribution map may be obtained, and the area ratio of the non-plating area (the area where the Fe concentration is 20 mass% or more) in the sample area may be obtained from these Fe distribution maps.
  • the coverage of the hot-dip plating layer may be determined based on the area ratio of the non-plating area.
  • the rolling surface and the anode surface of the steel plate are arranged to face each other, the distance between the projections of the rolling surface and the anode is controlled to 40 to 100 mm, and the plating adhesion amount per one side is 0 on average.
  • Electro Ni plating is performed under conditions of 5 to 3 g / m 2 . Further, in the hot-dip plating process, the steel plate is heated, and Al: 1.0 to 26% or less, Mg: 0.05 to 10%, Si: 0 to 1.0%, Sn: 0 to 3% by mass. The steel sheet is immersed in a hot-dip plating bath containing 0%, Ca: 0 to 1.0%, the balance being Zn and impurities, and the plating adhesion amount per one side is 60 to 400 g / m 2 on average. Conduct continuous hot-dip plating.
  • a convex portion and a flat portion are provided on the rolling surface of the steel plate.
  • the rolling conditions are not particularly limited, but the convex portion and the flat portion may be provided on the rolled surface of the steel sheet by transferring the concave shape formed on the working roll to the steel sheet surface at the finishing stage of hot rolling.
  • the striped steel plate shaped by hot rolling is subjected to pretreatment such as pickling to remove scale and the like. Brush grinding or the like may be performed on the surface of the steel plate as necessary.
  • the pre-treated striped steel plate is subjected to Ni pre-plating. It is desirable to use electroplating from the viewpoint of productivity and the viewpoint of suppression of mixing of an impurity element in Ni pre-plating.
  • the electroplating is exemplified by a method using a watt bath, a sulfamic acid bath or the like.
  • the preferred Ni plating bath composition is NiSO 4 .6H 2 O: 250 to 350 g / L, Na 2 SO 4 : 50 to 150 g / L, H 3 BO 3 : 30 to 50 g / L PH: 2 to 3.5, preferred bath temperature is 50 to 70 ° C., preferred cathodic current density is 5 to 30 A / dm 2 .
  • cathodic current density 20 A / dm 2 can be mentioned.
  • the Ni adhesion amount in Ni pre-plating is increased as compared to the conventional method.
  • the hot-dip plating layer is worn out and the Ni plating layer is exposed at the convex portion, excessive Ni precipitation at the convex portion is avoided so that the corrosion of the steel plate is suppressed.
  • an electroplating bath electroplating bath
  • a steel strip is used as a cathode, and an anode is disposed to face the steel plate surface.
  • the steel strip surface and the anode are parallel and approximated by a parallel plate electrode system.
  • the distance between the poles of the convex portion of the striped steel plate and the anode is close, so that current concentration easily occurs in the convex portion.
  • the distance between the electrodes is increased in order to suppress current concentration on the convex portion of the striped steel plate.
  • the inter-electrode distance is set to less than 40 mm, but in the present embodiment, the inter-electrode distance is set to 40 to 100 mm. If the distance between the electrodes is less than 40 mm, current concentration occurs in the projections, making it difficult to control the thickness of the Ni plating layer of the projections within a predetermined range. On the other hand, if the distance between the electrodes exceeds 100 mm, an increase in power loss due to liquid resistance is caused.
  • the lower limit of the distance between the electrodes is preferably 45 mm, and more preferably 50 mm.
  • the upper limit of the distance between the electrodes is preferably 90 mm, and more preferably 85 mm.
  • the film thickness ratio of the Ni plating layer of the convex to the flat may be 2000% or more.
  • the film thickness ratio of the Ni plating layer of the convex portion to the flat portion can be easily controlled to 400% or less.
  • the thickness ratio of the Ni plating layer of the convex portion to the flat portion can be easily controlled to 300% or less when the hot-dip galvanized steel sheet is formed.
  • the average adhesion amount per side of Ni pre-plating is set to 0.5 to 3 g / m 2 . If the average adhesion amount is less than 0.5 g / m 2 , the film thickness of the Ni plating layer in the flat portion of the striped steel plate after hot-dip plating becomes less than 0.05 ⁇ m, and non-plating tends to occur. When the average adhesion amount exceeds 3 g / m 2 , the Ni plating layer remaining in the convex portions after hot-dip plating becomes excessive, and it becomes difficult to make the thickness of the Ni plating layer in the convex portions 0.4 ⁇ m or less.
  • the Ni adhesion amount of Ni pre-plating may be measured based on the following procedures a to e before hot-dip plating of a Zn-based alloy.
  • Procedure a Dissolve Ni pre-plated steel plate with 30% by mass nitric acid (dissolution solution A).
  • Procedure b A sample is taken from the vicinity of the sample used in procedure a, and after removing the pre-plated Ni layer by grinding or the like, it is dissolved in 30% by mass nitric acid (solution B).
  • solution B nitric acid
  • Procedure c The amount of Fe and the amount of Ni dissolved in the solution B are determined by ICP, and the ratio of the amount of Fe to the amount of Ni is determined.
  • Procedure d The amount of Fe dissolved in the solution A is determined by ICP, and the amount of Ni dissolved from the base steel plate is determined from the ratio calculated in the procedure c.
  • Step e The amount of Ni dissolved in the solution A is determined by ICP, and the amount of Ni derived from the base steel plate calculated in step d is subtracted to calculate the amount of Ni derived from the pre-plated Ni layer. The amount of Ni derived from the Ni pre-plated layer is converted to the amount of adhesion per unit area.
  • the hot-dip plating bath is continuously passed (continuously immersed in the hot-dip plating bath).
  • the non-oxidizing atmosphere is, for example, a mixed gas of nitrogen and hydrogen.
  • the preheating temperature is preferably in the range of [temperature of plating bath + 10 ° C.] to [temperature of plating bath + 50 ° C.]. When the preheating temperature is low, non-plating tends to occur frequently. In preheating, it is preferable to rapidly heat the steel plate so that the time for which the temperature is 350 ° C. or more is 40 seconds or less. Since the diffusion of Ni into the base steel plate can be suppressed by shortening the time during which the steel plate is 350 ° C. or more, the amount of Ni pre-plating for preventing non-plating can be sufficiently secured.
  • Al more than 1.0% and 26% or less
  • Mg 0.05 to 10%
  • Si 0 to 1.0%
  • Sn 0 to Passing (immersing in a hot-dip plating bath) a hot-dip zinc-based alloy plating bath containing 3.0%
  • Ca 0 to 1.0%.
  • the temperature of the plating bath is preferably in the range of [melting point + 20 ° C. of molten Zn-based alloy] to [melting point + 50 ° C. of molten Zn-based alloy].
  • the striped steel plate is dipped in a plating bath, preferably for 1 to 6 seconds, and then wiped, and optionally cooled by an air-water spray or the like.
  • the average adhesion amount per one side of the hot-dip plating layer is set to 60 to 400 g / m 2 . If the average adhesion amount is less than 60 g / m 2 , the corrosion resistance may be insufficient. When the average adhesion amount is more than 400 g / m 2 , excessive deposition of the hot-dip plating layer may cause significant plating sag and damage the appearance.
  • the chemical composition of the hot-dip plating bath and the adhesion amount of hot-dip plating may be measured using ICP emission spectroscopy in the same manner as described above.
  • the chemical composition of the hot-dip plating bath may be ICP measurement based on a sample collected from the hot-dip plating bath, not a sample collected from the hot-dip galvanized steel sheet.
  • a 2.3 mm thick hot-rolled steel plate was used as a plating base plate.
  • the shape of this striped steel plate was equivalent to that of FIGS. 1A to 1C.
  • A, B, C, D, E and H are as follows respectively.
  • E Arrangement pitch of convex portions.
  • H Height of convex portion.
  • the striped steel plate in which the convex portions are regularly arranged is pickled, and Ni pre-plating is performed at various distances between the electrodes to change the average adhesion amount of Ni.
  • Tables 1 and 2 show the conditions for Ni pre-plating.
  • the electrolysis efficiency was about 80%.
  • the obtained striped steel plate had a cross-sectional structure as shown in FIG.
  • Hot-dip plating of a Zn-based alloy was performed using a hot-dip plating bath of a Zn-based alloy shown in Table 2 on a Ni pre-plated steel plate.
  • Table 2 also shows the temperature of the Zn-based alloy hot-dip plating bath.
  • the steel plate is heated to a plating bath temperature of + 30 ° C. in a non-oxidizing atmosphere (N 2 -2% H 2 ) at a heating rate of 10 ° C./sec.
  • N 2 -2% H 2 non-oxidizing atmosphere
  • After cooling to a plating bath temperature of + 10 ° C. the steel sheet was immersed in the plating bath. The immersion time was 3 seconds, and the hot-dip deposition adhesion adjustment was adjusted by the hot-dip deposition adhesion adjustment device on the hot-dip plating apparatus outlet side.
  • the base steel sheet, the Ni plating layer, and the hot-dip plating layer are present in the cross-sectional structure. It confirmed that it had.
  • the film thickness of the Ni plating layer of the convex portion, the film thickness of the Ni plating layer of the flat portion, and the film thickness ratio of the Ni plating layer of the convex portion to the flat portion film thickness of the convex portion ⁇ film thickness of the flat portion ⁇ 100
  • the adhesion amount of the hot-dip plating layer, the chemical composition of the hot-dip plating layer, the coverage of the hot-dip plating layer, the Ni adhesion amount of Ni pre-plating, the chemical composition of the hot-dip plating bath, etc. were measured.
  • the obtained hot-dip galvanized steel sheet was evaluated based on the following method.
  • Corrosion test after abrasion A steel plate pasted with 5 mm thick styrene butadiene rubber is placed on a 100 mm ⁇ 50 mm sample, a 1 kg weight is placed on it, and it is reciprocated in the horizontal direction (stroke: 30 mm, reciprocation number 1000) Times) to wear the plating.
  • the exposed steel plate is exposed southward at a 45 ° inclination to the ground in the exposure frame, and the test is continued for one month with a 20 ml solution of 5% aqueous NaCl solution once a week in a rainy environment. did. After continuing for one month, the area rate of red rust generation near the convex portion was evaluated.
  • the evaluation of the area rate of occurrence of red rust was performed by using WinROOF (image analysis software) manufactured by Mitani Corporation, and the area rate was calculated by measuring the area of the red rust occurrence part.
  • the red rust generation part measured the area ratio by extracting the color of red rust by color extraction. It was judged that the corrosion resistance after abrasion was poor when the rate of occurrence of red rust was 5% or more.
  • the ratio of red rust occurrence area: less than 5% is indicated by “Good”, and the percentage of red rust generation area: 5% or more by “Bad”.
  • Plating appearance A 100 mm square sample is prepared, and the plating surface is observed from the thickness direction, and the area ratio (referred to as "dross area ratio") of the area where the plating appearance is deteriorated due to dross is made by Mitani Corporation. It measured using WinROOF (image analysis software). When the dross area ratio was 20% or more, it was determined that the plating appearance was poor. In the table, the dross area ratio: less than 20% is indicated by “Good”, and the dross area ratio: 20% or more by “Bad”.
  • Table 3 shows the manufacturing results and the evaluation results of the manufactured hot-dip galvanized steel sheet.
  • the “film thickness ratio of the Ni plating layer” shown in Table 3 means the film thickness ratio of the Ni plating layer of the convex portion to the plane portion (film thickness of the convex portion / film thickness of the plane portion ⁇ 100).
  • Comparative Example 1 since the distance between the electrodes at the time of applying Ni pre-plating is not appropriate, the thickness of the Ni plating layer in the convex portion exceeds 0.4 ⁇ m, and the thickness of the Ni plating layer in the flat portion is 0.05 ⁇ m. It did not reach. As a result, a plating failure due to non-plating occurs, and sufficient corrosion resistance can not be obtained in the corrosion test after wear. In Comparative Example 2, since the adhesion amount of Ni pre-plating was small, the film thickness of the Ni plating layer in the flat portion of the striped steel plate was insufficient. As a result, a plating failure due to non-plating occurs, and sufficient corrosion resistance can not be obtained.
  • Comparative Example 3 since the adhesion amount of Ni pre-plating was large, the film thickness of the Ni plating layer in the convex portion exceeded 0.4 ⁇ m. As a result, sufficient corrosion resistance could not be obtained in the corrosion test after abrasion. In Comparative Example 4, because the amount of Al in the hot-dip plating layer of the Zn-based alloy is small, sufficient corrosion resistance can not be obtained, and the plating appearance is also poor. In Comparative Example 5, since the amount of Al in the hot-dip plating layer of the Zn-based alloy is large, the plating appearance is poor, the processability is not sufficient, and the hot-dip galvanized steel sheet is industrially undesirable.

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Abstract

La plaque à damier plaquée par immersion à chaud selon la présente invention comporte une plaque d'acier de matériau de base, une couche de nickelage et une couche plaquée par immersion à chaud et présente, sur sa surface, une partie saillante et une partie plate. L'épaisseur de film de la couche de nickelage de la partie saillante va de 0,07 à 0,4 µm et l'épaisseur de film de la couche de nickelage de la partie plate va de 0,05 à 0,35 µm, l'épaisseur de film de la couche de nickelage de la partie saillante étant supérieure à l'épaisseur de film de la couche de nickelage de la partie plate d'un facteur allant de plus de 100% à 400%.
PCT/JP2018/034188 2017-09-15 2018-09-14 Plaque à damier plaquée par immersion à chaud et procédé de fabrication associé WO2019054483A1 (fr)

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WO2022215694A1 (fr) 2021-04-06 2022-10-13 日本製鉄株式会社 Plaque d'acier à damier plaquée de zn-al-mg

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