EP4538420A1 - Stahlblech mit guter plattierungsqualität und herstellungsverfahren dafür - Google Patents

Stahlblech mit guter plattierungsqualität und herstellungsverfahren dafür Download PDF

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Publication number
EP4538420A1
EP4538420A1 EP23820147.9A EP23820147A EP4538420A1 EP 4538420 A1 EP4538420 A1 EP 4538420A1 EP 23820147 A EP23820147 A EP 23820147A EP 4538420 A1 EP4538420 A1 EP 4538420A1
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EP
European Patent Office
Prior art keywords
steel sheet
plating
concentration
less
plating layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23820147.9A
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English (en)
French (fr)
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EP4538420A4 (de
Inventor
Jin-Ho Jung
Won-Hwi LEE
Seong-Choon KWON
Ki-Cheol KANG
Seong-Ho Han
Jae-Hoon Lee
Yong-Hoon Choi
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Posco Holdings Inc
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Posco Co Ltd
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Publication date
Application filed by Posco Co Ltd filed Critical Posco Co Ltd
Publication of EP4538420A1 publication Critical patent/EP4538420A1/de
Publication of EP4538420A4 publication Critical patent/EP4538420A4/de
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • 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
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • 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
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    • 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
    • C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C23C2/0224—Two or more thermal pretreatments
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
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    • 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
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    • 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
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    • 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
    • C23C28/023—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 only coatings of metal elements only
    • C23C28/025—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 only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/20—Electroplating: Baths therefor from solutions of iron
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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
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    • C25D7/0614—Strips or foils
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25D9/00—Electrolytic coating other than with metals
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes

Definitions

  • plating quality of hot-dip galvanizing is determined by a surface condition of an annealed steel sheet immediately before plating, and plating properties may deteriorate due to the formation of surface oxides during annealing caused by elements such as Mn, Si, Al, Cr, and B added to secure physical properties of the steel sheet. That is, during the annealing process, the elements may diffuse to surfaces thereof and react with a trace amount of oxygen or water vapor present in an annealing furnace to form single or complex oxides of the elements on the surface of the steel sheet, thereby reducing reactivity of the surface.
  • elements such as Mn, Si, Al, Cr, and B added to secure physical properties of the steel sheet. That is, during the annealing process, the elements may diffuse to surfaces thereof and react with a trace amount of oxygen or water vapor present in an annealing furnace to form single or complex oxides of the elements on the surface of the steel sheet, thereby reducing reactivity of the surface.
  • Patent Document 1 discloses a technology providing a hot-dip galvanized steel sheet or a galvannealed steel sheet having excellent plating quality, by controlling an air-fuel ratio of air and fuel to 0.08 to 0.95, during the annealing process, oxidizing the steel sheet in a direct flame furnace in an oxidizing atmosphere to form an iron oxide including Si, Mn or Al alone or complex oxides to a certain depth inside the steel sheet, and then reducing and annealing the iron oxide in a reducing atmosphere and then performing hot-dip galvanizing.
  • Si is concentrated directly below the iron oxide during the reduction process, thereby forming a band-shaped Si oxide, so that peeling occurs in a surface layer portion including a plating layer, that is, peeling occurs at an interface between the reduced iron and a base steel sheet therebelow, causing a problem in that it is difficult to secure adhesion of the plating layer.
  • Another aspect of the present disclosure is to provide a steel sheet for plating that can be manufactured to form a hot-dip galvanized steel sheet having excellent plating quality, and a method for manufacturing the same.
  • a steel sheet for plating having a composition including, by wt%: 0.1 to 1.0% of Mn, 0.1% or less (excluding 0%) of Si, 0.0005 to 0.03% of C, 0.005 to 3.0% of Al, 0.04% or less of P, 0.015% or less of S, 1.5% or less of Cr, 0.005% or less of B, with a balance of Fe and inevitable impurities, wherein each of a GDS profile of an Mn component and a GDS profile of an Si component, observed from a surface thereof in a depth direction, sequentially includes a maximum point and a minimum point, wherein a difference between a value obtained by dividing a Mn concentration at the maximum point in the GDS profile of the Mn component by a Mn concentration of a base material and a value obtained by dividing a Mn concentration at the minimum point in the GDS profile of the Mn component by the Mn concentration of the base material, a difference of converted
  • a hot-dip galvanized steel sheet may include the steel sheet for plating described above and a hot-dip galvanizing layer formed on the steel sheet for plating.
  • a method for manufacturing a steel sheet for plating including: preparing a base steel sheet having a composition including, by wt%: 0.1 to 1.0% of Mn, 0.1% or less (excluding 0%) of Si, 0.0005 to 0.03% of C, 0.005 to 3.0% of Al, 0.04% or less of P, 0.015% or less of S, 1.5% or less of Cr, 0.005% or less of B, with a balance of Fe and inevitable impurities; performing electroplating on the base steel sheet to form an Fe plating layer including 5 to 50 wt% of oxygen; and annealing the base steel sheet on which the Fe plating layer is formed by maintaining the same at a temperature within a range of 600 to 950°C for 5 to 120 seconds in an annealing furnace with 1 to 70% H 2 -remaining N 2 gas atmosphere, controlled to have a dew point temperature of -15 to +30°C.
  • a method for manufacturing a hot-dip galvanized steel sheet including: preparing a base steel sheet having a composition including, by wt%: 0.1 to 1.0% of Mn, 0.1% or less (excluding 0%) of Si, 0.0005 to 0.03% of C, 0.005 to 3.0% of Al, 0.04% or less of P, 0.015% or less of S, 1.5% or less of Cr, 0.005% or less of B, with a balance of Fe and inevitable impurities; performing electroplating on the base steel sheet to form an Fe plating layer including 5 to 50 wt% of oxygen; and obtaining a steel sheet for plating by annealing the base steel sheet on which the Fe plating layer is formed by maintaining the same at a temperature within a range of 600 to 950°C for 5 to 120 seconds in an annealing furnace with 1 to 70% H 2 -remaining N 2 gas atmosphere, controlled to have a dew point temperature of -15 to +30°C; and
  • a hot-dip galvanized steel sheet in which a phenomenon in which non-plating occurs during hot-dip galvanizing is significantly improved and plating adhesion is improved by forming a pre-plating layer and controlling concentration profiles of Mn and Si components therein, may be provided.
  • an Fe electroplating amount is a plating amount measured as a total amount of Fe included in a plating layer per unit area, and oxygen and inevitable impurities in the plating layer were not included in the plating amount.
  • FIG. 1 is a graph schematically illustrating a typical GDS profile of an Mn component that may appear from a surface portion after a galvanizing layer is removed from a hot-dip galvanized steel sheet including the steel sheet of the present disclosure.
  • a vertical axis represents a concentration of alloying elements such as Mn, Si, and the like
  • a horizontal axis represents a depth.
  • the steel sheet for plating of the present disclosure may have a form in which maximum points and minimum points appear sequentially when a concentration profile of a Mn or Si component moves from a surface (an interface with a plating layer when hot-dip galvanized) toward the inside.
  • the maximum point may be formed at a depth of 0.05 to 1.0 ⁇ m from a surface of the steel sheet. If the maximum point appears in a region deeper than the region described above, it may not be determined to be a maximum point due to the effect of the present disclosure.
  • the minimum point can be formed at a location within 5 ⁇ m of depth of the surface of the steel sheet. As described above, if the minimum point is not formed at the point within 5 ⁇ m of depth, the 5 ⁇ m of depth may be determined to be a point at which the minimum point is formed. Since the concentration at the depth of 5 ⁇ m is substantially the same as the concentration of a base material, it can be considered to be a point at which the concentration no longer decreases.
  • a value of the converted concentration of Mn at the maximum point - a value of the converted concentration of Mn at the minimum point may be 80% or more, and a value of the converted concentration of Si at the maximum point-a value of the converted concentration value of Si at the minimum point may be 50% or more.
  • a hot-dip galvanized steel sheet is cut to a size of 30 to 50 mm in length, immersed in a 5 to 10 wt% hydrochloric acid solution at room temperature of 20 to 25°C, to remove a galvanizing layer.
  • an acid solution was removed within 10 seconds when bubble generation due to a reaction between the galvanizing layer and the acid solution is stopped, and the base steel sheet was washed using pure water and dried. If it is a steel sheet for plating that has not yet been hot-dip galvanized, it may be analyzed without removing the plating layer.
  • the steel sheet for plating targeted in the present disclosure may include a base steel sheet and an Fe plating layer formed on the base steel sheet.
  • the composition of the base steel sheet is not particularly limited.
  • a hot-dip galvanized steel sheet including the steel sheet for plating may be provided, and the hot-dip galvanized steel sheet may include a steel sheet for plating and a hot-dip galvanizing layer formed on a surface of the steel sheet for plating.
  • any commercially available hot-dip galvanized steel sheet can be used, and there are no specific restrictions on the type thereof.
  • the steel sheet for plating may be manufactured by processes including: preparing a base steel sheet; performing electroplating on the base steel sheet to form an Fe plating layer including 5 to 50 wt% of oxygen; and annealing the base steel sheet on which the Fe plating layer is formed to obtain a steel sheet for plating.
  • the steel sheet annealed at a dew point of +5°C on which Fe plating was not performed had fine Mn and Si oxides observed on the surface layer, and thick grain boundary oxides were formed inside the base steel sheet. This is because grain boundary oxides begin to form from a stage in which a cold-rolled structure is recovered and recrystallized into fine grains during a temperature-increase process, and as an annealing temperature increases and an annealing time increases, oxygen flows into the coarsened base steel sheet, thereby generating oxides centered on grain boundaries.
  • the Fe plating layer (surface layer portion) contains small amounts of Mn and Si components, and not only a maximum point may be shown at the interface, but also a depletion layer in which the contents of Mn and Si in the region deeper than the maximum value are greatly reduced may be shown.
  • the Fe plating layer may be formed through a continuous plating process, and the Fe plating amount herein may be 0.5 to 3.0 g/m 2 based on the Fe adhesion amount. If the Fe plating amount is less than 0.5 g/m 2 , a diffusion suppression effect of alloying elements by the Fe plating layer may be insufficient in a common continuous annealing process.
  • the Fe plating layer having the above-described high oxygen concentration may have maximum and minimum points in the GDS concentration profile of Mn and Si elements formed inside the steel sheet for plating by controlling the temperature, dew point temperature, and atmosphere in a subsequent annealing process, and is configured so that the converted concentration at the maximum point and the converted concentration at the minimum point may satisfy a numerical range limited in an embodiment of the present disclosure.
  • the concentration of oxygen in the Fe plating layer may be 5 to 50 wt%, and in another embodiment, the concentration of oxygen in the Fe plating layer may be 10 to 40 wt%. In order to obtain the surface oxide suppression effect, the amount of oxygen in the Fe plating layer should be sufficient.
  • a dew point temperature inside the annealing furnace may be -15°C to +30°C. If the dew point temperature is lower than -15°C, an amount of oxygen flowing into the steel decreases, so that only surface oxidation aggravates and internal oxidation does not occur, so a large amount of oxides exist on the surface, thereby deteriorating the quality of hot-dip galvanizing.
  • FIG. 2 schematically illustrates a phenomenon which occurs inside a steel sheet as a temperature of the steel sheet increases according to the conditions of the present disclosure.
  • FIG. 2 (a) illustrates a schematic cross-sectional view of a base steel sheet on which an Fe plating layer containing a large amount of oxygen is formed.
  • the base steel sheet includes alloying elements such as Mn, Si, and the like, and the Fe plating layer includes 5 to 50 wt% of oxygen and impurities which are inevitably incorporated during electroplating, and the remainder is comprised of Fe.
  • the control conditions by temperature have been explained, but the most critical operation in the annealing process is an operation of maintaining the temperature of the steel sheet at a temperature within a range of 600 to 950°C. Only controlling the dew point to the atmosphere in this temperature range can effectively control the distribution of oxides inside the steel sheet for plating. Even if such dew point control is performed in all processes prior to the holding operation, which is not particularly problematic.
  • the above-described process is merely an example of an embodiment of the present disclosure, and that the reaction mechanism of the present disclosure is not always interpreted to be bound by the above-described description.
  • the annealed steel sheet may be cooled. Since the cooling conditions in the cooling operation after the annealing operation do not significantly affect the surface quality of a final product, that is, the plating quality, there is no need to specifically limit the cooling conditions in the present disclosure. However, in order to prevent oxidation of iron components during the cooling process, an atmosphere which is at least reducing for iron may be applied.
  • a steel sheet for plating obtained by the above-described process may be hot-dip galvanized to form a hot-dip galvanizing layer.
  • the hot-dip galvanizing method is not particularly limited.
  • an electroplating solution in order to form an Fe plating layer, an electroplating solution may be used, the electroplating solution including: iron ions including ferrous ions and ferric ions; a complexing agent; and inevitable impurities, wherein a concentration of the ferric ions of the iron ions is 5 to 60% by weight.
  • the concentration of ferric ions among the iron ions is 5 to 60 wt%.
  • the concentration of iron ions is preferably 1 to 80 g per 1 L of the electroplating solution, and is more preferably 10 to 50 g per 1 L.
  • concentration of iron ions is less than 1g/L, there is a problem that the plating efficiency and plating quality deteriorate rapidly.
  • concentration of iron ions exceeds 80g/L, solubility may be exceeded and precipitation may occur, and loss of a raw material due to loss of the solution in the continuous plating process increases, which is uneconomical.
  • the amino acid When an amino acid is added to an acidic electrolyte containing iron ions, the amino acid is complexed with ferrous and ferric ions, and the iron ions complexed with the amino acid maintain a cationic state even in the complexed state. Therefore, it exhibits electrically opposite properties to the common complexing agent having a plurality of carboxyl groups, having a negative charge in a weakly acidic aqueous solution.
  • an amino acid forms fewer bonds with iron ions and has a weaker bonding force, but the bonding force with ferric ions which generates sludge is sufficiently strong, so precipitation due to ferric ions may be prevented.
  • an amino acid as a complexing agent, sludge may be prevented, and not only ferrous ions but also ferric ions may be used as a plating material, and when ferrous ions and ferric ions are mixed and used, the change in pH of the solution may be slowed down, and the accumulation of ferric ions may be easily prevented, so that the electroplating efficiency and plating quality may be maintained to be constant in a continuous electroplating process.
  • the complexing agent is preferably at least one selected from amino acids or amino acid polymers.
  • the complexing agent may be at least one selected from alanine, glycine, serine, threonine, arginine, glutamine, glutamic acid, and glycylglycine.
  • the temperature of the Fe electroplating solution does not significantly affect the quality of the Fe plating layer, but when the temperature of the Fe electroplating layer exceeds 80°C, evaporation of the solution becomes severe and the concentration of the solution continuously changes, making uniform electroplating difficult.
  • the current density is less than 3A/dm 2 , a plating overvoltage of the cathode decreases and the Fe electroplating efficiency decreases, so it is not suitable for a continuous plating process. If the current density exceeds 120A/dm 2 , burning occurs on the plating surface, causing the electroplating layer to become uneven and the Fe plating layer to easily fall off.
  • the Fe plating layer As described above, in the present disclosure, 5 to 50 wt% of oxygen is preferably contained in the Fe plating layer.
  • the causes in which oxygen is incorporated into the Fe plating layer are as follows. In the process in which iron is precipitated on the surface of the steel sheet to which a cathode is applied, and at the same time, as hydrogen ions are reduced to hydrogen gas, the pH increases. Therefore, both ferrous and ferric ions are temporarily combined with OH - ions and can be incorporated together when the Fe plating layer is formed.
  • the Fe electroplating amount is less than 0.5g/m 2 , since oxygen contained in the Fe plating layer is quickly reduced and removed, Mn and Si diffuse from the base steel sheet so that the formation of surface oxides may not be effectively suppressed, so that there is a problem in that the quality of hot-dip plating deteriorates.
  • the Fe plating amount is an iron concentration contained in the plating layer, and when the Fe plating layer is completely reduced during annealing, it has a thickness of about 0.05 to 0.4 ⁇ m.

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EP23820147.9A 2022-06-10 2023-06-09 Stahlblech mit guter plattierungsqualität und herstellungsverfahren dafür Pending EP4538420A4 (de)

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