EP3414355B1 - 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 Download PDF

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Publication number
EP3414355B1
EP3414355B1 EP17703386.7A EP17703386A EP3414355B1 EP 3414355 B1 EP3414355 B1 EP 3414355B1 EP 17703386 A EP17703386 A EP 17703386A EP 3414355 B1 EP3414355 B1 EP 3414355B1
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EP
European Patent Office
Prior art keywords
steel
aluminum
coating
cover layer
hot
Prior art date
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EP17703386.7A
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German (de)
English (en)
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EP3414355A1 (fr
Inventor
Thomas Koll
Marc Debeaux
Friedrich Luther
Matthias Graul
Jan-Frederik LASS
Haucke-Frederik Hartmann
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Volkswagen AG
Salzgitter Flachstahl GmbH
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Volkswagen AG
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
    • 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 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
    • C21D8/0278—Modifying the physical properties 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 a process for producing press-hardened components from steel sheets or steel strips with an aluminum-based coating for steel sheets or steel strips, the coating comprising an aluminum-based coating applied by hot-dip coating and an aluminum oxide and / or hydroxide-containing cover layer being arranged on the coating .
  • 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 high-strength components to be produced that are mainly used in the area of the body.
  • Press hardening can in principle 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 take place separately from one another, in direct processes they take place together in one tool. However, only the direct method is considered below.
  • a steel sheet blank is heated to the so-called austenitizing temperature (Ac3), then the blank heated in this way is transferred to a molding tool and formed into the finished component in a one-step forming step, and at the same time by the cooled molding tool at a speed that is above the critical cooling rate of the steel is cooled, so that a hardened component is produced.
  • Ac3 austenitizing temperature
  • Known hot-formable steels for this area of application are, for example, the manganese-boron steel "22MnB5" and more recently also air-hardenable steels according to the European patent EP 2 449 138 B1 .
  • a steel strip coated with aluminum by a hot-dip process is known that after the hot-dip process, which is carried out in a hot-dip bath with a low Si content of 1.5% by weight to at most 6% by weight, a heat treatment at 300 to 460 ° C. is subjected, which promotes the diffusion of Si in the coating. It is believed that a native oxide layer is formed during this treatment.
  • the steel strip produced in this way is said to have excellent total reflection properties and improved corrosion resistance. It is also an object that the appearance of the steel strip, despite an anodizing treatment, is comparable to the appearance of an ordinary aluminum-coated steel strip.
  • the European patent application EP 0 575 926 A1 describes an aluminum-based coating for metallic products, especially for metal sheets.
  • the aluminum-based coating is applied by means of a hot-dip process, the aluminum bath containing Si: ⁇ 10%, Fe: ⁇ 1%, Mn: 0.5-2% and the rest Al.
  • the coated products are cooled in air to 300 ° C and with water to about 40 ° C. It can be assumed that a native oxide layer is formed during this treatment.
  • the coating ensures that the products are more resistant to hot oxidation and wet corrosion.
  • European patent application EP 0 204 423 A2 discloses a process for the production of aluminum-coated, iron-based foils, wherein a steel strip is provided with an aluminum coating by the hot-dip process and the coated steel strip is subsequently reduced to foil thickness.
  • the film coated in this way is then subjected to a heat treatment at 600 ° C. to 1200 ° C. under an oxidation atmosphere. This promotes the diffusion of aluminum into the base steel layer and creates a porous one Aluminum oxide layer, which has a matt, gray appearance.
  • the following (alloy) coatings applied by hot-dip coating are currently known for press hardening: aluminum-silicon (AS), zinc-aluminum (Z), zinc-aluminum-iron (ZF / galvannealed), zinc-magnesium-aluminum-iron (ZM), as well as electrodeposited coatings made 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 made of zinc-nickel or zinc the latter being converted into an iron-zinc alloy layer before hot forming.
  • German published 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 covering material made of a non-ferrous metal.
  • Aluminum or an aluminum alloy are proposed as the covering material.
  • the overlay material is also subjected to nitriding or anodic oxidation in order to increase the wear resistance and the corrosion resistance of the surface of the overlay material.
  • a sheet metal plate previously heated above the austenitizing temperature to 800 - 1200 ° C and possibly provided with a metallic coating of zinc or based on zinc is formed into a component in a tool that is occasionally cooled by hot forming, during the forming by rapid heat removal
  • Sheet metal or component in the forming tool undergoes quench hardening (press hardening) and the required martensitic hardness structure achieves the required strength properties.
  • the advantage of aluminum-based coatings is that, in addition to a larger process window (e.g. with regard to the heating parameters), the finished components do not have to be blasted before further processing.
  • a difficulty with the use of aluminum-based coatings is that when a steel plate is heated in the roller hearth furnace, the coating can react with the ceramic transport rollers before the hot forming, which significantly reduces the life of the furnace rollers.
  • the wear of the tools during press hardening is caused by the heating with iron alloyed aluminum-silicon coating very high.
  • an uneven formation of the surface structure or the thickness of the coating leads to welding problems in the course of the heating, in particular in the case of resistance spot welding, which is frequently used in the automotive industry, due to locally varying electrical resistances on the component surface.
  • the object of the invention is therefore to provide a method for producing press-hardened components from steel sheets or steel strips and a press-hardened component from such steel plates or steel strips.
  • a method for the press hardening of components according to the invention from the steel sheets or steel strips provided with an aluminum-based coating, a method is provided, characterized in that the steel sheets or steel strips are at least partially heated to a temperature above Ac3 with the aim of hardening, then reshaped at this temperature and thereafter cooled at a rate that is at least in regions above the critical cooling rate, the aluminum-based coating being a hot-dip coating, the coating after the hot-dip process and before heating to the forming temperature of a treatment under anodizing conditions and / or plasma oxidation and / or or is subjected to a hot water treatment and / or a treatment in steam, in which the coating on the surface is oxidized to form oxides or hydroxides and the practice in a molten bath with an Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, the remainder being aluminum.
  • the teaching of the invention includes an aluminum-based coating for steel sheets or steel strips, the coating being an Melt-dip applied coating comprises, on the coating an aluminum oxide and / or hydroxide-containing cover layer is arranged, which by plasma oxidation and / or hot water treatment at temperatures of at least 90 ° C, advantageously at least 95 ° C and / or a treatment in water vapor Temperatures of at least 90 ° C, advantageously at least 95 ° C was produced.
  • the coating can advantageously be produced in a molten bath with an Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, the rest being aluminum.
  • aluminum-based coatings are understood to mean metallic coatings in which aluminum is the main component in mass percent.
  • examples of possible aluminum-based coatings are aluminum, aluminum-silicon (AS), aluminum-zinc-silicon (AZ), as well as the same coatings with admixtures of additional elements, such as magnesium, manganese, titanium and rare earths.
  • the teaching of the invention comprises an aluminum-based coating for steel sheets or steel strips, the coating comprising an aluminum-based coating which has been applied by hot-dip coating and wherein an aluminum oxide and / or hydroxide-containing cover layer, which has been produced by anodic oxidation, is arranged on the coating characterized in that the coating was produced in a molten bath with an Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, the balance aluminum.
  • an aluminum oxide and / or hydroxide-containing cover layer which has been produced by anodic oxidation
  • cover layers containing aluminum oxide and / or hydroxide act during hot forming as a separating layer between the coating and the ceramic furnace rollers. This effectively prevents metallic material from being transferred to the furnace rollers. Furthermore, the cover layer containing aluminum oxide and / or hydroxide separates the iron-based, aluminum-based coating of the steel strip from the metal tool surface of the forming tool and thus serves as a separating aid. This reduces welding and abrasion and thus tool wear and maintenance, since the layers are changed significantly less by press hardening and thus become significantly less abrasive than in the prior art. This is shown in the Figures 1 a) to d) .
  • a comparison is shown of exemplary scanning electron microscopic surface images of an AS coating a) untreated initial state without press hardening, b) anodized state without press hardening, c) untreated state after press hardening, d) anodized state after press hardening.
  • An alkaline pretreatment preceding the generation of the cover layer with occasional subsequent acidic removal for example with sulfuric acid or nitric acid and subsequent rinsing of the steel sheet or steel strip provided with an aluminum-based coating, advantageously removes the arbitrarily formed layer already created by atmospheric oxidation and thereby creates a layer defined initial state for the cover layer subsequently generated.
  • the production of defined cover layers containing aluminum oxide and / or hydroxide on a steel strip with an aluminum-based coating is a challenge for large-scale production.
  • the cover layer containing aluminum oxide and / or hydroxide is therefore generated by means of plasma oxidation.
  • a hot water treatment at temperatures of at least 90 ° C, advantageously at least 95 ° C or a treatment in steam at temperatures of at least 90 ° C, advantageously at least 95 ° C can be carried out.
  • This type of treatment of the coating or the top layer is also called compaction.
  • the cover layer containing aluminum oxide and / or hydroxide is produced in an anodic process.
  • the coating is produced in a molten bath with an Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, the rest being aluminum.
  • the anodic process is significantly more versatile than a chemical oxidation process. It is particularly advantageous to carry out this method in a continuous process on a coated steel strip.
  • the anodic oxidation of an aluminum (alloy) layer can be carried out using both direct current and alternating current methods.
  • the negatively charged sulfate anions of sulfuric acid and the OH ions of the water migrate to the anode in the electrical field that forms. At the anode they react with Al 3 + ions to form aluminum oxide.
  • the layer thickness depends on the amount of charge that has flowed. This makes it possible to set the thickness of the oxide layer in a defined manner so that it can be tailored to the respective purpose.
  • a layer thickness of approximately 20 ⁇ m is formed in the literature with a current passage of 1 Ah / dm 2 .
  • Different electrolyte systems can be used for the anodic oxidation of aluminum and aluminum alloys (e.g. based on boric acid, citric acid, sulfuric acid, oxalic acid, chromic acid, alkylsulfonic acids, carboxylic acids, alkali carbonates, alkali phosphates, phosphoric acid, hydrofluoric acid).
  • Typical current densities for the process are between 1-50 A / dm 2 depending on the electrolyte system. Since the process works with constant current, a voltage arises. This is typically in a range of 10-120 V.
  • the electrolyte temperature is between 0-65 ° C.
  • the hardness of the layer can be influenced, for example, by choosing the electrolyte temperature. In electrolytes based on sulfuric acid or oxalic acid obtain particularly hard layers at low electrolyte temperatures (e.g. 0-10 ° C).
  • a nanoporous oxide layer covering the entire surface is formed from densely assembled oxide cells with hexagonal cross sections. These pores are open towards the electrolyte side. The pore diameter depends on the type of electrolyte used.
  • the oxide layer can form locally in different phases (see Figure 1b ). Tests have shown in a sulfuric acid direct current process that the phases contained in an AS alloy coating behave differently during the anodic treatment in terms of oxide layer thickness and pore size at the microscopic level. This creates a microstructure that is different from the original, metallic surface. At the macroscopic level, the layer formation takes place very homogeneously.
  • Figure 2 shows an example of a scanning electron micrograph of the nanoporous surface structure of an anodized AS coating.
  • dyes organic or inorganic
  • functional pigments e.g. conductive, metallic particles, fullerenes, nanostructured particles
  • the coloring and properties of the layer such as the electrical conductivity, hardness, corrosion protection , antibacterial properties, can be tailored.
  • the advantageously subsequent compression step also called sealen, closes the pore structure by absorbing water of crystallization and prevents e.g. a further absorption of dyes or functional pigments.
  • the compression can be achieved by steam or hot water treatment. Temperatures of at least 90 ° C., particularly advantageously at least 95 ° C., have proven to be advantageous for this.
  • the compression time depends on the oxide layer thickness. Here, the compression time is increased as the oxide layer thickness increases. Additives such as Metal salts improve the corrosion resistance and color stability during compression.
  • the aluminum-based coating is particularly well suited for hot or cold forming.
  • the method according to the invention comprises the production of a steel sheet or steel strip with an aluminum-based coating, an aluminum-based coating being applied to the steel sheet or steel strip as a coating, characterized in that the coated steel sheet or steel strip with the coating after the hot-dip process and before the forming process the hot or cold forming is subjected to a plasma oxidation and / or a hot water treatment and / or a treatment in water vapor, an aluminum oxide and / or hydroxide covering layer being formed on the surface of the coating with the formation of oxides or hydroxides.
  • the coating can advantageously be produced in a molten bath with an Si content of 8 to 12% by weight, an Fe content of 1 to 4% by weight, the rest being aluminum.
  • the optional hot water treatment or the treatment under steam is advantageously carried out at temperatures of at least 90 ° C., particularly advantageously 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 coating is applied to the steel sheet or steel strip as a coating, the steel sheet or steel strip with the coating after the hot-dip process and before the forming process of anodic oxidation is subjected to, wherein on the surface of the coating with formation of oxides or hydroxides an aluminum oxide and / or hydroxide-containing top layer is formed, characterized in that the coating in a molten bath with an Si content of 8 to 12% by weight, a Fe content of 1 to 4% by weight, rest of 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 metal 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 invention comprises a press-hardened component made of the steel sheets or steel strips provided with an aluminum-based coating, produced by the previously described method.

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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)
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  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electrochemistry (AREA)
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  • Coating With Molten Metal (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (12)

  1. Procédé de fabrication de composants durcis à la presse qui sont formés à partir de tôles d'acier ou de bandes d'acier et qui sont pourvus d'un revêtement à base d'aluminium, une pellicule à base d'aluminium étant appliquée en tant que revêtement sur la tôle d'acier ou la bande d'acier dans le procédé d'immersion à chaud, la tôle d'acier ou la bande d'acier pourvue de la pellicule étant soumis à une oxydation au plasma et/ou à un traitement à l'eau chaude et/ou à un traitement à la vapeur d'eau et/ou à une oxydation anodique après le procédé d'immersion à chaud et avant le procédé de formage, une couche de recouvrement contenant de l'oxyde et/ou de l'hydroxyde d'aluminium étant formée sur la surface de la pellicule avec formation d'oxydes ou d'hydroxydes, les tôles d'acier ou les bandes d'acier étant au moins par endroits chauffées à une température supérieure à Ac3 dans le but d'effectuer une trempe, puis étant mises en forme à cette température et ensuite refroidies à une vitesse qui est au moins par endroits supérieure à la vitesse de refroidissement critique.
  2. Procédé selon la revendication 1, caractérisé en ce que la pellicule est réalisée dans un bain fondu ayant une teneur en Si de 8 à 12 % en poids, une teneur en Fe de 1 à 4 % en poids, le reste étant de l'aluminium.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le traitement à l'eau chaude ou le traitement à la vapeur d'eau est effectué à des températures d'au moins 90 °C, avantageusement d'au moins 95 °C.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la couche de recouvrement est appliquée sur la surface de la pellicule selon un procédé continu.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la couche de recouvrement est appliquée avec une épaisseur de couche moyenne inférieure à 4 µm et supérieure à 0,05 µm
  6. Procédé selon la revendication 5, caractérisé en ce que la couche de recouvrement est appliquée avec une épaisseur de couche moyenne inférieure à 1,0 µm et supérieure à 0,1 µm
  7. Procédé selon la revendication 1, caractérisé en ce que l'oxydation anodique est effectuée dans un milieu à base d'acide borique, d'acide citrique, d'acide sulfurique, d'acide oxalique, d'acide chromique, d'acides alkylsulfoniques, d'acides carboxyliques, de carbonates alcalins, de phosphates alcalins, d'acide phosphorique, d'acide fluorhydrique.
  8. Procédé selon la revendication 1 ou 7, caractérisé en ce que l'anodisation est effectuée à des densités de courant comprises entre 1 et 50 A/dm2 et à une tension de 10 à 120 V et une température d'électrolyte comprise entre 0 et 65 °C.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que des pigments de couleur et/ou des pigments influant sur la fonction de la couche de recouvrement sont introduits la couche de recouvrement après l'étape d'anodisation et/ou d'oxydation plasma de la pellicule et avant un traitement à l'eau chaude et/ou un traitement à la vapeur d'eau.
  10. Procédé selon la revendication 9, caractérisé en ce que les pigments influant sur la fonction sont des éléments influant sur la conductivité électrique et/ou les propriétés antibactériennes de la couche de recouvrement.
  11. Procédé selon la revendication 10, caractérisé en ce que les pigments influant sur la fonction sont des particules métalliques conductrices, des fullerènes, des particules nano-structurées.
  12. Composant durci à la presse qui est formé à partir de tôles d'acier ou de bandes d'acier et qui est pourvu d'un revêtement à base d'aluminium, ledit composant étant fabriqué par un procédé selon l'une au moins des revendications 1 à 11.
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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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US10876195B2 (en) 2020-12-29
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CN108699665A (zh) 2018-10-23
US20190040513A1 (en) 2019-02-07
CN108699665B (zh) 2020-04-24
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EP3414355A1 (fr) 2018-12-19
RU2704340C1 (ru) 2019-10-28

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