EP3414355A1 - Revêtement à base d'aluminium pour tôles d'acier ou bandes d'acier et procédé pour leur fabrication - Google Patents

Revêtement à base d'aluminium pour tôles d'acier ou bandes d'acier et procédé pour leur fabrication

Info

Publication number
EP3414355A1
EP3414355A1 EP17703386.7A EP17703386A EP3414355A1 EP 3414355 A1 EP3414355 A1 EP 3414355A1 EP 17703386 A EP17703386 A EP 17703386A EP 3414355 A1 EP3414355 A1 EP 3414355A1
Authority
EP
European Patent Office
Prior art keywords
aluminum
coating
steel
based coating
hot
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.)
Granted
Application number
EP17703386.7A
Other languages
German (de)
English (en)
Other versions
EP3414355B1 (fr
Inventor
Thomas Koll
Marc Debeaux
Friedrich Luther
Matthias Graul
Jan-Frederik LASS
Haucke-Frederik Hartmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Volkswagen AG
Salzgitter Flachstahl GmbH
Original Assignee
Volkswagen AG
Salzgitter Flachstahl GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Volkswagen AG, Salzgitter Flachstahl GmbH filed Critical Volkswagen AG
Publication of EP3414355A1 publication Critical patent/EP3414355A1/fr
Application granted granted Critical
Publication of EP3414355B1 publication Critical patent/EP3414355B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—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
    • C23C2/12—Aluminium or alloys based thereon
    • 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
    • C21D1/62—Quenching devices
    • C21D1/673—Quenching devices for die 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment 
    • C21D8/0284—Application of a separating or insulating coating
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C28/30—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
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy 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
    • C23C28/30—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
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y10T428/1275—Next to Group VIII or IB metal-base component
    • Y10T428/12757—Fe

Definitions

  • the invention relates to an aluminum-based coating for steel sheets or steel strips, wherein the coating in a hot dip method
  • coated, aluminum-based coating comprises and wherein on the coating, an alumina and / or hydroxide contained cover layer is arranged. Also, the invention relates to a method for producing a steel sheet or
  • the invention relates to a method for producing press-hardened components from steel sheets or steel strips with an aluminum-based coating, which are produced by the aforementioned method.
  • the invention relates to a press-hardened component made of steel sheets or steel strips with an aluminum-based coating, which is produced by the aforementioned method.
  • press hardening enables the production of high-strength components, which are mainly used in the bodywork area.
  • the press-hardening can basically be carried out by means of two different process variants, namely by means of the direct or indirect process. While in indirect processes, the process steps of forming and hardening run separately from each other, they take place together in direct process in a tool. In the following, however, only the direct method is considered.
  • thermoformable steels for this application are, for example, the Manganese-boron steel "22MnB5" and recently also air-temperable steels according to the European patent EP 2 449 138 B1.
  • Scaling protection for press hardening used by the automotive industry.
  • the advantages here are in addition to the increased corrosion resistance of the finished component in that the boards or components do not scale in the oven, whereby the wear of the press tools is reduced by chipped scale and the components often have to be blasted before further processing.
  • hot-dip (alloy) coatings are currently known: aluminum-silicon (AS), zinc-aluminum (Z), zinc-aluminum-iron (ZF / galvannealed), zinc-magnesium-aluminum-iron (ZM), as well as electrodeposited coatings of zinc-nickel or zinc, the latter being converted into an iron-zinc alloy layer before hot-forming.
  • AS aluminum-silicon
  • Z zinc-aluminum
  • ZF / galvannealed zinc-magnesium-aluminum-iron
  • ZM zinc-magnesium-aluminum-iron
  • electrodeposited coatings of zinc-nickel or zinc the latter being converted into an iron-zinc alloy layer before hot-forming.
  • German patent application DE 197 26 363 A1 describes a clad metal strip with a base body made of a carbon-containing steel, which is provided on one or both sides with a support material made of a non-ferrous metal.
  • a support material aluminum or an aluminum alloy are proposed.
  • the overlay material is subjected to nitriding or anodic oxidation to increase the wear resistance and corrosion resistance of the surface of the overlay material.
  • This molten coating bath contains in addition to AI and unavoidable
  • Impurities Mn and / or Mg, Fe, Ti and / or Zr This should increase the corrosion resistance compared to AlSi alloys.
  • Corrosion protection coating can also be anodized.
  • Press-hardenable steels by hot forming in a forming tool is known from German patent DE 601 19 826 T2.
  • German Patent DE 699 33 751 T2 The production of components by quenching of aluminum alloy-coated precursors of press-hardenable steels by hot forming in a forming tool is known from German Patent DE 699 33 751 T2.
  • a coated aluminum alloy sheet is heated to above 700 ° C prior to forming, resulting in an intermetallic alloy based on iron, aluminum and silicon on the surface and subsequently formed the sheet and at a speed above the critical
  • Cooling rate cools down.
  • the advantage of the aluminum-based coatings is that in addition to a larger process window (for example with regard to the heating parameters), the finished components do not have to be blasted prior to further processing. In addition, there is no risk of aluminum-based coatings
  • Liquid metal embrittlement and it can form no microcracks in the near-surface substrate area at the former Austenitkorngrenzen, which may have a negative effect on the fatigue strength at depths over 10 ⁇ .
  • a difficulty with the use of aluminum-based coatings is that the coating can react with the ceramic transport rollers when heating a steel plate in the roller hearth furnace prior to hot working, which significantly reduces the life of the furnace rolls.
  • the wear of the tools during press hardening is very high due to the iron-alloyed aluminum-silicon coating during heating.
  • Automotive often used resistance spot welding, due to locally varying electrical resistances on the component surface. But even when cold-forming aluminum-based coatings problems occur. For example, the abrasion when forming in the tool opposite
  • the object of the invention is therefore to provide an aluminum-based coating for a steel or steel strip, which has an excellent suitability for hot and cold forming. Furthermore, a method for producing such a coating is to be specified as well as a method for producing press-hardened components from such steel sheets or steel strips and a press-hardened component from such steel sheets or steel strips.
  • the teaching of the invention comprises an aluminum-based coating for
  • a coating which comprises aluminum oxide and / or hydroxide is disposed on the coating, which plasma oxidation and / or hot water treatment at temperatures of at least 90 ° C, preferably at least 95 ° C and / / or a treatment in steam at temperatures of at least 90 ° C, preferably at least 95 ° C was prepared.
  • the coating in a molten bath with a Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, balance aluminum are produced.
  • aluminum-based coatings are hereinafter understood metallic coatings in which aluminum is the main component in mass.
  • Examples of possible aluminum-based coatings are aluminum, aluminum-silicon (AS), aluminum-zinc-silicon (AZ), as well as the same coatings with
  • the teaching of the invention comprises an aluminum-based coating for steel sheets or steel strips, wherein the coating has a in the
  • the coating comprises an aluminum oxide and / or hydroxide
  • Cover layer is arranged, which was prepared by anodization, characterized in that the coating in a molten bath with a Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, balance aluminum was prepared.
  • cover layers contained in the aluminum oxide and / or hydroxide act during hot working as a release layer between the coating and the ceramic
  • Furnace rollers Thus, a transfer of metallic material is effectively avoided on the furnace rollers. Furthermore, the cover layer containing aluminum oxide and / or hydroxide separates the iron-alloyed, aluminum-based coating of the
  • An alkaline pre-treatment prior to the formation of the cover layer with subsequent acid pickling for example with sulfuric acid or nitric acid and subsequent rinsing of the aluminum-based coated steel sheet or strip, advantageously removes the randomly formed layer already formed by atmospheric oxidation and thereby creates one defined initial state for the subsequently produced cover layer.
  • the production of defined cover layers containing aluminum oxide and / or hydroxide on a steel strip with an aluminum-based coating is, however, a challenge in terms of mass production technology.
  • the cover layer containing aluminum oxide and / or hydroxide is therefore produced according to the invention by means of plasma oxidation.
  • the cover layer containing alumina and / or hydroxide is produced in an anodic process.
  • the coating is prepared in a molten bath with an Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, balance aluminum.
  • the anodic process is considerably more versatile compared to a chemical oxidation process. It is particularly advantageous for this process in a continuous process on a coated
  • the anodic oxidation of an aluminum (alloy) layer can occur in both
  • the negatively charged sulfate anions of the sulfuric acid and the OH ions of the water migrate to the anode in the forming electric field. At the anode, these react with Al 3 + ions to form alumina.
  • the layer thickness is dependent on the amount of charge flowed according to Faraday's laws. This will allow the thickness of the
  • oxide layer defined so as to tailor it tailored to the particular application.
  • Citric acid sulfuric acid, oxalic acid, chromic acid, alkylsulfonic acids,
  • typical current densities for the process range from 1 to 50 A / dm 2 . Since the process uses a constant current, a voltage sets in. This is typically in a range of 10-120 V.
  • the electrolyte temperature is indeed between 0-65 ° C according to the electrolyte system.
  • the hardness of the layer can be influenced by the choice of the electrolyte temperature. In electrolytes based on sulfuric acid or oxalic acid, particularly hard coatings are obtained at low electrolyte temperatures (eg 0-10 ° C.).
  • a nanoporous oxide layer covering the entire surface forms from densely assembled oxide cells with hexagonal cross-sections. These pores are open to the electrolyte side. The pore diameter depends on the type of electrolyte used.
  • the oxidic layer can form locally in different phases (see FIG. Experiments have shown in a sulfuric acid DC process that the phases contained in an AS alloy coating behave differently at the microscopic level during the anodic treatment with respect to oxide layer thickness and pore size. This forms a different from the original, metallic surface microstructure. At the macroscopic level, the film formation is very homogeneous.
  • FIG. 2 shows, by way of example, a scanning electron micrograph of the nanoporous surface structure of an anodized AS coating.
  • dyes organic or inorganic
  • functional pigments eg conductive, metallic particles, fullerenes, nanostructured particles
  • coloring and properties of the layer such as the electrical conductivity, hardness, corrosion protection , antibacterial properties, can be customized.
  • the advantageously subsequent compaction step also called sealing, closes the pore structure by taking up water of crystallization and prevents e.g. another shot of dyes or functional pigments.
  • the compression can be achieved by a steam or a hot water treatment.
  • temperatures of at least 90 ° C., more preferably at least 95 ° C. have proved to be advantageous for this purpose.
  • the compression time depends on the
  • additives such as e.g. Metal salts during compaction improve the corrosion resistance and color fastness.
  • the aluminum-based coating is particularly suitable for hot or cold forming.
  • the inventive method comprises the production of a steel sheet or steel strip with an aluminum-based coating, wherein as coating an aluminum-based coating in the hot dip method is applied to the steel sheet or steel strip, characterized in that the coated
  • Steel sheet or steel strip is subjected to the coating after the hot dip process and before the forming process of hot or cold forming a plasma oxidation and / or a hot water treatment and / or a treatment in water vapor, wherein on the surface of the coating to form oxides or hydroxides an alumina and / or hydroxide contained cover layer is formed.
  • the coating in a molten bath with a Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, balance aluminum are produced.
  • the optional hot water treatment or the treatment under steam at temperatures of at least 90 ° C, more preferably at least 95 ° C.
  • Another method according to the invention comprises the production of a
  • Steel sheet or steel strip with an aluminum-based coating wherein an aluminum-based hot dip coating is applied to the steel sheet or steel strip as coating, wherein the steel sheet or steel strip is subjected to anodic oxidation with the coating after the hot dip process and prior to the forming process, on the surface of the Coating to form oxides or hydroxides a cover layer containing aluminum oxide and / or hydroxide is formed, characterized in that the coating in a molten bath with a Si content of 8 to 12% by weight, an Fe content of 1 to 4 weight -%, rest aluminum is produced.
  • the cover layer is applied to the surface of the coating in a continuous process.
  • the anodic oxidation according to the invention is advantageously carried out in a medium based on boric acid, citric acid, sulfuric acid, oxalic acid, chromic acid,
  • Alkylsulfonic acids carboxylic acids, alkali metal carbonates, alkali phosphates, phosphoric acid or hydrofluoric acid.
  • the aluminum-based coating produced by the method according to the invention is particularly suitable for hot or cold forming.
  • the aluminum-based coating is a hot-dip coating, wherein the coating after the hot dipping process and before the Heating to forming temperature of a treatment under anodizing
  • Oxidized coating on the surface to form oxides or hydroxides and the coating is prepared in a molten bath with a Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, balance aluminum.
  • the invention comprises a press-hardened component of the
  • the cover layer containing aluminum oxide and / or hydroxide separates the metallic, aluminum-based coating of the steel strip from the metallic tool surface of the forming tool and serves as a separating forming aid. This reduces welds and extends the forming area by lowering the frictional resistance and avoiding the so-called stick-slip effect. This problem occurs especially at slow forming speeds and very high strength materials and can severely limit the process window.
  • the process window is opened significantly to lower speeds and higher forming forces and thus the
  • the forming process benefits from the fact that, due to the laterally heterogeneous formation of the cover layer containing aluminum oxide and / or hydroxide, there is no surface contact but a reduced contact between the workpiece and the tool. b) At the same time, the porous surface of the cover layer according to the invention containing alumina and / or hydroxide, the oil absorption capacity of
  • Steel coils that is to say steel coils wound into rolls, are already oiled by the manufacturer, on the one hand to prevent corrosion before processing Customer is guaranteed, and on the other hand a pre-oiling for subsequent forming processes is given. With a longer intermediate storage and elevated temperatures, this oil can run out of the coil windings. Thus, it lacks on the sheet surface, which leads to the need for a complex re-oiling. This can be prevented with the cover layer formed according to the invention.
  • the cover layer according to the invention containing aluminum oxide and / or hydroxide solves this problem by combining a barrier effect with a high one
  • the layers according to the invention are significantly more temperature-resistant than all known lacquers and thus enable use in corrosive environments even at elevated temperature.
  • oxide growth at high temperatures is greatly reduced, since the necessary for the growth of an oxide layer ion exchange is suppressed by the surface due to the atomically compact formation of the layer. Likewise, evaporation of the coating is effectively prevented.
  • Another advantage over a purely metallic surface is in the increased resistance to acidic and especially alkaline media.
  • the aluminum oxide and / or hydroxide according to the invention acts
  • Covering layer like a release layer that protects against the seizing effect of these media.
  • the cover layer according to the invention is very easy to paint even without previous phosphating because it is due to their inorganic nature, an ideal chemical and due to the large surface (in the absence of the
  • Compaction step) allow very good physical networking.
  • the cover layer containing aluminum oxide and / or hydroxide according to the invention increases the electrical resistance of the surface efficiently, so that, depending on
  • Covering layers are able to embed pigments before the compaction process.
  • colored aluminum surfaces are known and widely used.
  • Color information can be tailored by means of such pigments as well as other technical properties, e.g. electrical conductivity or antibacterial effect.
  • Acid pickling e.g., sulfuric acid, nitric acid .
  • Acid pickling e.g., sulfuric acid, nitric acid .
  • Acid pickling e.g., sulfuric acid, nitric acid .
  • Acid pickling e.g., sulfuric acid, nitric acid .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electrochemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating With Molten Metal (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne un revêtement à base d'aluminium pour tôles d'acier ou bandes d'acier, qui comprend un revêtement à base d'aluminium déposé au cours d'un procédé de galvanisation, selon lequel une couche de recouvrement contenant de l'oxyde et/ou de l'hydroxyde d'aluminium est disposée sur le revêtement. L'invention vise à proposer un revêtement à base d'aluminium qui présente une aptitude exceptionnelle au formage à chaud et à froid. À cet effet, la couche de recouvrement est fabriquée par oxydation plasmatique et/ou traitement à l'eau chaude à des températures d'au moins 90°C, avantageusement d'au moins 95°C, et/ou par traitement dans de la vapeur d'eau à des températures d'au moins 90°C, avantageusement d'au moins 95°C. En variante, la couche de recouvrement contenant de l'oxyde et/ou de l'hydroxyde d'aluminium est fabriquée par oxydation anodique, le revêtement ayant été fabriqué dans un bain de galvanisation possédant une teneur en Si allant de 8 à 12 % en masse, une teneur en Fe allant de 1 à 4 % en masse, le reste d'aluminium. L'invention concerne également un procédé associé et un procédé pour la fabrication d'éléments durcis sous presse ainsi que l'élément durci sous presse correspondant.
EP17703386.7A 2016-02-08 2017-02-02 Revêtement à base d'aluminium pour tôles d'acier ou bandes d'acier et procédé pour leur fabrication Active EP3414355B1 (fr)

Applications Claiming Priority (3)

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DE102016102172 2016-02-08
DE102016102504.6A DE102016102504A1 (de) 2016-02-08 2016-02-12 Aluminiumbasierte Beschichtung für Stahlbleche oder Stahlbänder und Verfahren zur Herstellung hierzu
PCT/EP2017/052266 WO2017137304A1 (fr) 2016-02-08 2017-02-02 Revêtement à base d'aluminium pour tôles d'acier ou bandes d'acier et procédé pour leur fabrication

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EP3414355A1 true EP3414355A1 (fr) 2018-12-19
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EP (1) EP3414355B1 (fr)
KR (1) KR102186771B1 (fr)
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WO (1) WO2017137304A1 (fr)

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WO2017137304A1 (fr) 2017-08-17
KR20180112799A (ko) 2018-10-12
DE102016102504A1 (de) 2017-08-10
CN108699665A (zh) 2018-10-23
RU2704340C1 (ru) 2019-10-28
KR102186771B1 (ko) 2020-12-07
EP3414355B1 (fr) 2020-04-08
US10876195B2 (en) 2020-12-29
US20190040513A1 (en) 2019-02-07
CN108699665B (zh) 2020-04-24

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