EP3947754B1 - Procédé de production d'une tôle d'acier avec une adhérence améliorée de revêtements métalliques à chaud - Google Patents

Procédé de production d'une tôle d'acier avec une adhérence améliorée de revêtements métalliques à chaud Download PDF

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Publication number
EP3947754B1
EP3947754B1 EP20715830.4A EP20715830A EP3947754B1 EP 3947754 B1 EP3947754 B1 EP 3947754B1 EP 20715830 A EP20715830 A EP 20715830A EP 3947754 B1 EP3947754 B1 EP 3947754B1
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EP
European Patent Office
Prior art keywords
iron
steel strip
layer
oxygen
zinc
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EP20715830.4A
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German (de)
English (en)
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EP3947754A1 (fr
Inventor
Dr. Kai KÖHLER
Dr. Nils KÖPPER
Dr.-Ing. Friedrich LUTHER
Dr. Marc DEBEAUX
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Salzgitter Flachstahl GmbH
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Salzgitter Flachstahl GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • C23C2/02—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
    • 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
    • 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
    • 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
    • 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
    • C23C28/028—Including graded layers in composition or in physical properties, e.g. density, porosity, grain size
    • 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
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/20—Electroplating: Baths therefor from solutions of iron

Definitions

  • the invention relates to a method for producing a cold- or hot-rolled steel strip with a metallic coating, the steel strip having iron as the main component and, in addition to carbon, an Mn content of 4.1 to 8.0% by weight and optionally one or more of the alloying elements Al , Si, Cr, B, Ti, V, Nb and/or Mo, wherein the surface of the uncoated steel strip is cleaned, a layer of pure iron with an average iron content of more than 96% by weight is applied to the cleaned surface an oxygen-containing, iron-based layer is applied to the layer of pure iron, which contains more than 5 percent by mass of oxygen, after which the steel strip is annealed with the oxygen-containing, iron-based layer and is reduction-treated in the course of the annealing treatment in a reducing furnace atmosphere, and then the treated and annealed in this way Steel strip is hot dip coated with the metallic coating. Furthermore, the invention relates to a steel strip with a metallic coating applied by hot dipping and the use of such a steel strip.
  • the cited publication discloses, among other things, a method in which, during annealing under oxidizing conditions, the steel strip is pre-oxidized in a first step, with which a specifically covering FeO layer is produced, which prevents selective external oxidation of the alloying elements. In a second step, this layer is then reduced back to metallic iron.
  • the patent specification DE 10 2013 105 378 B3 discloses a method for producing a flat steel product which, in addition to iron and unavoidable impurities, contains up to 35 Mn, up to 10 Al, up to 10 Si and up to 5 Cr by weight. After heating in a preheating furnace, in which the flat steel product is exposed to an oxidizing atmosphere, and recrystallizing annealing in the annealing furnace, in which an annealing atmosphere that has a reducing effect on FeO prevails, the flat steel product is coated in a hot-dip bath.
  • the disclosure document DE 10 2010 037 254 A1 discloses a method for hot-dip coating a flat steel product, the flat steel product being produced from a stainless steel which, in addition to iron and unavoidable impurities, contains in % by weight: 5 to 30 Cr, ⁇ 6 Mn, ⁇ 2 Si and ⁇ 0.2 Al.
  • the steel flat product is first heated under an oxidizing pre-oxidation atmosphere, held under a reducing holding atmosphere, and then passed through a molten bath.
  • the Disclosures U.S. 2016 010 23 79 A1 and U.S. 2013 030 49 82 A1 each disclose a method for producing a coated steel strip containing in weight %: 0.5 to 2 Si, 1 to 3 Mn, 0.01 to 0.8 Cr and 0.01 to 0.1 Al. After an oxidation treatment of the steel strip in an oxidative atmosphere, the steel strip is subjected to reduction annealing and then hot-dip coated.
  • a method for producing a coated steel sheet with reduced surface defects in which a coating of zinc or a zinc alloy is applied to at least one surface of a steel strip.
  • a layer of Fe is provided immediately below the coating of zinc or a zinc alloy, and a layer in which elements of the steel with an affinity for oxygen are concentrated is provided directly below the layer of Fe.
  • the low-carbon or very low-carbon steel strip to which the Fe plating is applied contains at least one component selected from the group of Si, Mn, P, Ti, Nb, Al, Ni, Cu, Mo, V, Cr and B in one Amount of at least 0.1% by weight for Si, Ti, Ni, Cu, Mo, Cr and V and at least 0.5% by weight for Mn, at least 0.05% by weight for P, Al and Nb and at least 0.001% by weight for B.
  • the layer of Fe has an application weight of 0.1 to 10 g/m 2 , an oxygen content of 0.1 to 10% by weight and a carbon content of 0.01% by weight. % to less than 10% by weight.
  • the aim here is to create a layer at the interface between the oxygen-containing Fe layer and the steel strip during annealing prior to hot-dip coating, in which the elements with an affinity for oxygen contained in the steel are concentrated. This is intended to prevent further diffusion of the oxygen-affinity elements contained in the steel in the direction of the Fe plating surface and to achieve good galvanizability.
  • EP 2 798 094 A1 discloses a method for producing a cold-rolled steel strip with an Mn content between 1 and 6% by weight and a C content of less than 0.3% by weight and with a metallic coating.
  • the steel strip is electroplated with a layer of pure iron, then the iron layer is oxidized to an iron oxide layer and then reduced at a temperature between 750 °C and 900 °C in an atmosphere with 1 to 20% by volume of hydrogen.
  • a zinc coating is then applied by hot dip coating.
  • U.S. 2004/0 121 162 A1 already described a cold- or hot-rolled steel strip with up to 0.5% by weight of C and with up to 15% by weight of Mn and with a coating.
  • the coating comprises an iron plating and a metallic zinc coating.
  • the disclosure discloses CN 109 477 191 A another cold or hot rolled coated steel strip with a coating.
  • the steel strip has 0.08 to 0.3% by weight of C, 3.1 to 8.0% by weight of Mn, 0.01 to 2.0% by weight of Si, 0.001 to 0.5% by weight of Al.
  • the coating consists of a layer based on elemental iron and a metallic coating applied to it by means of hot-dip coating.
  • the metallic coating is zinc, zinc-iron, zinc-aluminum or zinc-aluminum-magnesium.
  • EP 2 918 696 A1 is another steel strip composed of 0.05 to 0.50% by weight of C, 0.5 to 5.0% by weight of Mn, 0.2 to 3.0% by weight of Si and 0.001 to 1.0% by weight of Al described, which is hot-dip coated with a Zn-Fe alloy. At its interface with the Zn-Fe coating, the steel strip has a layer with at least 50% by volume ferrite and at least 90% unoxidized iron.
  • the object of the invention is therefore to specify a method for producing a cold- or hot-rolled steel strip with a metallic coating which, in addition to carbon, iron as the main component, has an Mn content of 4.1 to 8.0% by weight and optionally other oxygen-affine Contains elements such as Al, Si, Cr, B, which provides uniform and reproducible adhesion conditions for the coating on the steel strip surface, regardless of the current alloy composition of the steel strip.
  • the teaching of the invention includes a method for producing a cold- or hot-rolled steel strip with a metallic coating with improved adhesion, the steel strip has iron as the main component and, in addition to carbon, an Mn content of 4.1 to 8.0% by weight and optionally one or several of the alloying elements Al, Si, Cr, B, Ti, V, Nb and/or Mo, whereby the surface of the uncoated steel strip is cleaned, a layer of pure iron with an average iron content of more than 96% by weight is applied to the cleaned surface % is applied, an oxygen-containing, iron-based layer is applied to the layer of pure iron, which contains more than 5% by mass of oxygen, after which the steel strip is annealed with the oxygen-containing, iron-based layer and is reduction-treated in the course of the annealing treatment in a reducing furnace atmosphere, and then the steel strip thus treated and annealed with the metallic coating is hot-dip coated, which is characterized in that a layer of pure iron is applied after cleaning and before the application of the oxygen-containing, iron
  • the teaching of the invention includes a steel strip, which, in addition to carbon, has iron as the main component, an Mn content of 4.1 to 8.0% by weight and optionally one or more of the alloying elements Al, Si, Cr, B, Ti, V, Nb and/or Mo with a metallic coating applied to the surface of the steel strip by means of hot dipping, which is characterized in that a predominantly ferritic edge zone with more than 60% by volume ferrite is formed in the transition area between the metallic coating and the surface of the steel strip, which has a thickness from 0.15 to 1.1 ⁇ m and, viewed from the steel strip surface, consists of a pure iron layer with an average iron content of more than 96% by weight and on top of that an oxygen-containing, iron-based layer that has more than 5 Percentage by mass contains oxygen.
  • the teaching of the invention also includes the use of a steel strip according to the invention for the production of parts for motor vehicles.
  • the core of the invention consists in a combination of a pure iron coating applied to the steel strip surface with an oxygen-containing iron coating deposited over it with subsequent annealing and hot-dip finishing.
  • a layer with an average iron content of more than 96% by weight is understood as a pure iron layer.
  • the oxygen-containing, iron-based layer is understood to mean a layer with an iron content in % by weight of at least 50%, which contains more than 5% by weight of oxygen in the form of oxides and/or hydroxides.
  • the oxides and/or hydroxides can be present in the oxygen-containing, iron-based layer in the form of crystalline, amorphous or also as mixtures of crystalline, such as magnetite (Fe 3 O 4 ), and amorphous compounds.
  • magnetite Fe 3 O 4
  • amorphous compounds such as magnetite (Fe 3 O 4 )
  • the distribution of the amorphous and/or crystalline compounds is also not restricted.
  • the layer is thus characterized in that it contains oxygen-containing, reducible iron species.
  • the pure iron layer can preferably be deposited electrolytically or by deposition from the gas phase (e.g. by means of PVD, CVD).
  • sulphate or chloride electrolytes and combinations thereof are typically used, the pH of which is less than or equal to 5.5. At higher pH values, ferrous species precipitate as hydroxides. Iron with a purity in % by weight of greater than 99.5 is preferably used as the anode material. Electrolytic cells with separate anode and cathode compartments can also be used, which makes it possible to use oxygen-generating or insoluble anodes. To reduce the cell resistance, a conductive salt can optionally be added to the electrolyte. It is also possible to use other additives, such as surfactants to improve wetting and/or defoamers.
  • Electrolytic deposition takes place at current densities that result in a deposition thickness that is homogeneous over the length of the strip, regardless of the respective strip speed. Furthermore, the current density depends on the length of the anode in the direction of travel of the strip. Typical values are between 1 and 150 A/dm 2 per strip side. Below 1 A/dm 2 too long treatment lengths are required, which means that the process cannot be operated economically. At current densities above 150 A/dm 2 , homogeneous deposition is made significantly more difficult by burning or dendrite formation. The duration of the electrolytic deposition depends on the treatment length, the current density, the current yield and the desired layer coverage and is typically between 1 s and 30 s per side.
  • Example compositions of aqueous electrolytes and deposition conditions are shown in Table 1.
  • Table 1 electrolyte system composition conditions sulfate FeSO 4 .7H 2 O: 220 g/l pH 2.2; 35°C NaSO 4 : 90 g/l chloride FeCl 2 ⁇ 4H 2 O: 280 g/l pH 1.4; 48oC KCI: 210 g/l sulfate chloride FeSO 4 .7H 2 O: 400 g/l pH 1.6; 85oC FeCl 2 ⁇ 4H 2 O: 400 g/l CaCl 2 : 180 g/l sulfamate Fe(SO 3 NH 2 ) 2 : 220 g/l pH 3.2; 60°C NH 4 (SO 3 NH 2 ): 30 g/l fluoroborate Fe(BF 4 ) 2 : 240 g/l pH 2.1; 58oC NaCl: 8 g/l
  • the pure iron layer is deposited at an electrolyte temperature of 60 °C with a current density of 30 A/dm 2 using an iron anode with a purity in % by weight of greater than 99.5 in an aqueous sulfuric acid electrolyte with the following composition: 60 g/l iron(II), 20 g/l sodium, pH 1.8.
  • the preferred deposition of the oxygen-containing, iron-based layer takes place electrolytically from an electrolyte containing Fe(II) and/or Fe(III). Sulfate or chloride electrolytes and combinations thereof are typically used for this purpose, the pH of which is generally less than or equal to 5.5.
  • Electrolytic deposition takes place at current densities that result in a deposition thickness that is homogeneous over the length of the strip, regardless of the respective strip speed. Furthermore, the current density depends on the length of the anode in the direction of travel of the strip. Typical values are between 1 and 150 A/dm 2 per strip side. Below 1 A/dm 2 too long treatment lengths are required, which means that the process cannot be operated economically. At current densities above 150 A/dm 2 , homogeneous deposition is made significantly more difficult by burning or dendrite formation.
  • the deposition time depends on the length of treatment, the current density, the current yield and the desired layer coverage and is typically between 1 s and 30 s per side.
  • Example compositions of aqueous electrolytes and deposition conditions are shown in Table 2.
  • Table 2 complexing agent composition conditions citrate FeSO 4 .7H 2 O: 350 g/l pH 2.3; 45°C Fe 2 (SO 4 ) 3 : 10 g/l Na 2 SO 4 : 110 g/l Sodium citrate: 20 g/l triethanolamine Fe 2 (SO 4 ) 3 : 170 g/l pH 13; 80°C NaOH: 12 g/l C6 H15 NO3 : 15 g/l
  • a complexing agent for the iron ions is also required in the acidic electrolyte to produce oxygen-containing, iron-based layers.
  • This is typically a compound with one or more carbonyl functionalities, such as citric acid, acetic acid or else nitrilotriacetic acid (NTA) or ethanolamine.
  • Iron with a purity in % by weight of greater than 99.5 is preferably used as the anode material.
  • Electrolytic cells with separate anode and cathode compartments can also be used, which makes it possible to use oxygen-generating or insoluble anodes.
  • a conductive salt can optionally be added to the electrolyte. It is also possible to use other additives, such as surfactants to improve wetting and/or defoamers.
  • the oxygen-containing iron layer is deposited at 60° C. with a current density of 30 A/dm 2 using an iron anode with a purity in % by weight greater than 99.5 in an aqueous sulfuric acid electrolyte with the following composition: 60 g /l iron(II), 3 g/l iron(III), 25 g/l sodium, 11 g/l citrate, pH 1.8.
  • the surface of the steel strip is preferably activated by cleaning in a typically alkaline, aqueous medium and subsequent optional desmutting in an acidic, aqueous medium prior to deposition with the pure iron layer.
  • a sulfuric acid bath with an acid content of 20 to 70 g/l at temperatures of 30 to 70 °C is preferably used for desmutting.
  • the subsequent coating with the Oxygen-containing, iron-based layer on the previously deposited pure iron layer is preferably carried out wet on wet or after drying the steel strip surface.
  • the steel strip surface is preferably dried in order to prevent an undefined entry of water into the annealing furnace atmosphere.
  • a rinsing can optionally be used after each process step.
  • the layers can be deposited within one electrolytic cell or in a plurality of electrolytic cells arranged one after the other, the design of which is preferably horizontal or vertical.
  • the oxygen-containing, iron-based layer is deposited in particularly fine-crystalline form and leads to better adhesion of the hot-dip coating than if the oxygen-containing, iron-based layer is applied directly to the steel surface.
  • the nucleation conditions for the subsequent oxygen-containing, iron-based layer are significantly improved by the pre-coating with pure iron, whereby the nucleation rate increases and the crystallite size therefore decreases compared to a single-layer system.
  • the pure iron layer is formed with an average thickness of 0.05 to 0.5 ⁇ m and the oxygen-containing, iron-based layer is formed with an average thickness of 0.1 to 0.6 ⁇ m.
  • the pure iron layer has an average thickness of 0.1 to 0.4 ⁇ m and the oxygen-containing, iron-based layer has an average thickness of 0.2 to 0.5 ⁇ m.
  • the mean thickness of the oxygen-containing, iron-based layer is greater than the mean thickness of the pure iron layer.
  • the oxygen-containing, iron-based layer has an oxygen content of more than 5 to 40% by weight, advantageously of more than 10 to 30% by weight. In a particularly advantageous embodiment of the invention, this layer has an oxygen content of more than 12 to 25% by weight.
  • oxygen content is more than 5 to 40% by weight, advantageously of more than 10 to 30% by weight.
  • this layer has an oxygen content of more than 12 to 25% by weight.
  • the pure iron layer itself can be applied either electrolytically or by deposition from the gas phase, while the oxygen-containing, iron-based layer is advantageously deposited electrolytically.
  • a pure iron layer is a layer with an average iron content of more than 96% by weight.
  • the method according to the invention also includes an annealing treatment of the steel strip provided with a pure iron and an oxygen-containing, iron-based layer applied thereto in a continuous annealing furnace.
  • This furnace can be a combination of a furnace part with open combustion (DFF, Direct Fired Furnace / NOF, Non-Oxidizing Furnace) and a radiant tube furnace (RTF, Radiation Tube Furnace) arranged after it, or in an all radiant tube furnace (All Radiant Tube Furnace). take place.
  • DFF Direct Fired Furnace / NOF, Non-Oxidizing Furnace
  • RTF Radiation Tube Furnace
  • the steel strip is annealed at an annealing temperature of 550 °C to 880 °C and an average heating rate of 1 K/s to 100 K/s, as well as a holding time of the steel strip at the annealing temperature of between 30 s and 650 s.
  • a reducing annealing atmosphere consisting of 2% to 40% H 2 and 98 to 60% N 2 and a dew point between +15 °C and -70 °C is used in the radiant tube furnace, so that a surface consisting essentially of metallic iron is obtained .
  • the strip is then cooled to a temperature above the melt bath temperature of the coating and then coated with the metallic coating.
  • the strip can be cooled to a so-called overaging temperature between 200° C. and 600° C. and kept at this temperature for up to 500 s. If an overaging temperature below the melting bath temperature of the coating is chosen, for example to influence the structure and the resulting technological characteristics of the steel, the strip can be heated before it enters the melting bath, for example by inductive heating to a temperature above the melting bath temperature of between 400 °C and 750 °C so that the cold steel strip does not draw heat from the weld pool.
  • the use of the precoatings according to the invention makes an additional introduction of water vapor to increase the dew point, as is customary in the previously known processes, unnecessary. It has therefore been found to be sufficient for the annealing atmosphere in the furnace if the ratio of the partial pressures of water vapor and hydrogen during annealing in the radiant tube furnace is in the range 0.00077 > pH 2 O/pH 2 > 0.00021, advantageously between 0.00254 > pH 2 O/pH 2 > 0.00021.
  • An exemplary advantageous process sequence for the production of a steel strip according to the invention with improved adhesion of hot-dip galvanizing provides that first a hot-rolled steel strip (hot strip) is pickled, then cold-rolled and then galvanized in a hot-dip galvanizing line. Within the hot-dip galvanizing line, the strip goes through a pre-cleaning section, after pre-cleaning the strip goes through further strip activation (pickling/pickling) and then 6 electrolytic cells. An iron layer is deposited in the first 3 cells, and an oxygen-containing, iron-based layer in the next 3 cells. The coated strip then runs through rinsing and drying. The strip then enters the furnace section of the galvanizing line, where it is annealed and galvanized.
  • Aluminum-silicon AS, AISi
  • zinc Z
  • zinc-aluminum ZA, Galfan
  • zinc-aluminum-iron ZF, galvannealed
  • zinc-magnesium-aluminum ZM, ZAM
  • aluminium-zinc AZ, Galvalume
  • the metallic coating is based on zinc and the zinc coating contains 0.1 to 1% by weight Al or 0.1 to 6% by weight Al and 0.1 to 6% by weight Mg or 5 to 15% by weight Fe .
  • a steel strip according to the invention is further characterized in that a predominantly ferritic surface zone with more than 60% by volume ferrite is formed in the transition area between the metallic coating and the surface of the steel strip, which has a thickness of 0.15 to 1.1 ⁇ m and advantageously a thickness between 0 .3 and 0.9 ⁇ m.
  • the thickness of this edge zone results directly from the deposited pre-coatings, which, even after annealing and hot-dip coating, have a microstructure that differs from the steel substrate and thus has the desired positive effects.
  • Table 3 shows the results of galvanizing tests that were carried out on a hot-dip galvanizing simulator with test sheets made of medium manganese steel (6 percent by mass Mn and 2 percent by mass Si+Al).
  • the pre-coatings were deposited electrolytically with a current density of 75 A/dm 2 per side.
  • the tests were carried out at two different heat treatments (800°C for 200 seconds and 700°C for 120 seconds). Samples with complete zinc wetting and good adhesion could only be achieved by means of a pre-coating of pure iron and a pre-coating of an oxygen-containing, iron-based layer on top.
  • Coating adhesion is tested in two different test geometries to ensure adhesion in the different uses of the steels.
  • the coating adhesion in the forming process is tested using a ball impact test in accordance with SEP1931.
  • a hemispherical stamp is hit with high impact energy on a test panel.
  • the impact stress creates a dome-shaped impression in the test panel.
  • This process is carried out until there is a slight crack in the test panel, several times if necessary.
  • the surface is then checked visually for delamination and delamination of the zinc-based coating in the area of the calotte. The result is evaluated with grades from 1-4 (grades 1+2 passed, grades 3+4 failed).
  • the adhesion of the coating in the event of a crash is checked using an adhesive bead test.
  • a bead of adhesive in a defined geometry, preferably 10 mm wide and 5 mm high, of a 1-component epoxy resin structural adhesive is applied to the test panel.
  • the adhesive is then cured according to the data sheet and the sample is then quickly bent through 90° within a maximum of 2 s. During this process, the adhesive bead breaks under the strong tension and suddenly pulls on the already through the Bending stressed coating.
  • the samples are then assessed visually for zinc detachment.

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Claims (15)

  1. Procédé de production d'un feuillard en acier laminé à froid ou à chaud et pourvu d'un revêtement métallique, le feuillard en acier comportant du fer comme constituant principal et en plus du carbone, une teneur en Mn de 4,1 à 8,0 % en poids et éventuellement un ou plusieurs des éléments d'alliage Al, Si, Cr, B, Ti, V, Nb et/ou Mo, la surface du feuillard en acier non revêtu étant d'abord nettoyée, une couche de fer pur d'une teneur moyenne en fer supérieure à 96 % en poids étant appliquée sur la surface nettoyée, une couche à base de fer contenant de l'oxygène étant appliquée sur la couche de fer pur et contenant plus de 5 % en masse d'oxygène, puis le feuillard en acier étant recuit avec la couche à base de fer contenant de l'oxygène- et subissant un traitement de réduction au cours du traitement de recuit dans une atmosphère de four réductrice, puis le feuillard en acier ainsi traité et recuit étant revêtu du revêtement métallique dans un bain de fusion.
  2. Procédé selon la revendication 1, caractérisé en ce que l'épaisseur moyenne de la couche de fer pur est de 0,05 à 0,5 µm, de préférence de 0,1 à 0,4 µm, et l'épaisseur moyenne de la couche à base de fer contenant de l'oxygène est de 0,1 à 0,6 µm, de préférence de 0,2 à 0,5 µm.
  3. Procédé selon l'une au moins des revendications 1 et 2, caractérisé en ce que l'épaisseur moyenne de la couche à base de fer contenant de l'oxygène est supérieure à l'épaisseur moyenne de la couche de fer pur.
  4. Procédé selon l'une au moins des revendications 1 à 3, caractérisé en ce que la couche à base de fer contenant du fer est appliquée sur la couche de fer pur avec une teneur en oxygène de plus de 5 à 40 % en poids, de préférence de plus de 10 à 30 % en poids, de manière particulièrement avantageuse de plus de 12 à 25 % en poids.
  5. Procédé selon l'une au moins des revendications 1 à 4, caractérisé en ce que la couche de fer pur est déposée par voie électrolytique ou par dépôt en phase gazeuse et la couche à base de fer contenant de l'oxygène est déposée par voie électrolytique.
  6. Procédé selon l'une au moins des revendications 1 à 5, caractérisé en ce que le feuillard en acier a la composition suivante en % en poids :
    C: 0,03 % à 0,35 %,
    Mn: 4,1 % à 8,0 %,
    Si: 0,008 % à 2,5 %,
    Al: 0,001 % à 2,0 %,
    en option
    Cr: 0,01 % à 0,7 %,
    B: 0,001 % à 0,08 %,
    Ti: 0,005 % à 0,3 %,
    V: 0,005 % à 0,3 %,
    Nb: 0,005 % à 0,2 %,
    Mo: 0,005 % à 0,7 %,
    P: ≤ 0,10 %,
    S: ≤ 0,010 %,
    le reste étant du fer et des impuretés inévitables.
  7. Procédé selon l'une au moins des revendications 1 à 6, caractérisé en ce que le traitement de recuit est effectué dans un four tubulaire radiant utilisé comme four de recuit continu avec une température de recuit de 550°C à 880°C et une vitesse de chauffe moyenne de 1 K/s à 100 K/s, avec une atmosphère de recuit réductrice comprenant 2 à 40 % de H2 et 98 à 60 % de N2 et un point de rosée dans le four de recuit compris entre +15 et -70°C et un temps de séjour du feuillard en acier à une température de recuit compris entre 30 s et 650 s avec refroidissement ultérieur facultatif à une température de séjour comprise entre 200°C et 600°C pendant 500 s maximum avec chauffage inductif facultatif ultérieur à une température supérieure à la température du bain de fusion du revêtement métallique de 400°C à 750°C puis le revêtement du feuillard en acier dans le bain de fusion étant effectué avec le revêtement métallique.
  8. Procédé selon l'une au moins des revendications 1 à 7, caractérisé en ce que le rapport des pressions partielles de vapeur d'eau et d'hydrogène lors du recuit dans le four tubulaire radiant est situé dans la gamme 0,00077 > pH2O/pH2 > 0,00021, avantageusement 0,00254 > pH2O/pH2 > 0,00021.
  9. Procédé selon l'une au moins des revendications 1 à 8, caractérisé en ce que l'aluminium-silicium (AS, AISi), le zinc (Z), le zinc-aluminium (ZA, Galfan), le zinc-fer (ZF, trempé après zincage), le zinc-aluminium-magnésium (ZM, ZAM) ou l'aluminium-zinc (AZ, aluzinc) sont utilisés comme revêtements métalliques.
  10. Feuillard en acier comportant en plus du carbone, du fer comme constituant principal, une teneur en Mn de 4,1 à 8,0 % en poids et éventuellement un ou plusieurs des éléments d'alliage Al, Si, Cr, B, Ti, V, Nb et/ou Mo avec un revêtement métallique appliqué dans un bain de fusion, caractérisé en ce qu'une zone de bord essentiellement ferritique comprenant plus de 60 % en volume de ferrite est formée dans la zone de transition entre le revêtement métallique et la surface du feuillard en acier, la zone de bord essentiellement ferritique ayant une épaisseur de 0,15 à 1,1 µm et comprenant une couche de fer pur d'une teneur moyenne en fer de plus de 96 % en poids et sur celle-ci une couche à base de fer contenant de l'oxygène qui contient plus de 5 % en masse d'oxygène, dans une vue depuis la surface du feuillard en acier.
  11. Feuillard en acier selon la revendication 10, caractérisé en ce que la zone de bord essentiellement ferritique a une épaisseur comprise entre 0,3 et 0,9 µm.
  12. Feuillard en acier selon l'une au moins des revendications 10 et 11, caractérisée par la composition suivante en % en poids :
    C: 0,03 % à 0,35 %,
    Mn: 4,1 % à 8,0 %,
    Si: 0,008 % à 2,5 %,
    Al: 0,001 % à 2,0 %,
    en option
    Cr: 0,01 % à 0,7 %,
    B: 0,001 % à 0,08 %,
    Ti: 0,005 % à 0,3 %,
    V: 0,005 % à 0,3 %,
    Nb: 0,005 % à 0,2 %,
    Mo: 0,005 % à 0,7 %,
    P: ≤ 0,10 %,
    S: ≤ 0,010 %,
    le reste étant du fer et es impuretés inévitables.
  13. Feuillard en acier selon l'une au moins des revendications 10 à 12, caractérisé par un revêtement métallique en aluminium-silicium (AS, AISi), zinc (Z), zinc-aluminium (ZA), zinc-aluminium-fer (ZF/trempé après zincage), zinc-magnésium-aluminium (ZM, ZAM) ou aluminium-zinc (AZ).
  14. Feuillard en acier selon la revendication 13, caractérisé en ce que, dans le cas d'un revêtement métallique à base de zinc, le revêtement de zinc contient
    0,1 à 1 % en poids d'AI ou
    0,1 à 6 % en poids d'AI et 0,1 à 6 % en poids de Mg ou
    5 à 15 % en poids de Fe.
  15. Utilisation d'un feuillard en acier produit selon l'une au moins des revendications 1 à 9 ou d'un feuillard d'acier selon l'une au moins des revendications 10 à 14 pour la réalisation de pièces de véhicules automobiles.
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US20220220598A1 (en) 2022-07-14
DE102019108457A1 (de) 2020-10-01
KR20210144804A (ko) 2021-11-30
KR102602054B1 (ko) 2023-11-13
WO2020201133A1 (fr) 2020-10-08
EP3947754A1 (fr) 2022-02-09
DE102019108457B4 (de) 2021-02-04

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