EP3250727B1 - Pièce constituée de tôle d'acier revêtue à base d'aluminium durcie par moulage par compression et procédé de fabrication d'une telle pièce - Google Patents

Pièce constituée de tôle d'acier revêtue à base d'aluminium durcie par moulage par compression et procédé de fabrication d'une telle pièce Download PDF

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Publication number
EP3250727B1
EP3250727B1 EP17721056.4A EP17721056A EP3250727B1 EP 3250727 B1 EP3250727 B1 EP 3250727B1 EP 17721056 A EP17721056 A EP 17721056A EP 3250727 B1 EP3250727 B1 EP 3250727B1
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European Patent Office
Prior art keywords
thickness
steel sheet
overcoat
press
component
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EP17721056.4A
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German (de)
English (en)
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EP3250727A1 (fr
EP3250727B2 (fr
Inventor
Thomas Koll
Marc Debeaux
Friedrich Luther
Christian Fritzsche
Stefan MÜTZE
Frank Beier
Matthias Graul
Haucke-Frederik Hartmann
Jan-Frederik LASS
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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
    • 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
    • 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
    • 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
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • 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
    • C23C2/261—After-treatment in a gas atmosphere, e.g. inert 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
    • C23C2/26—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
    • C23C28/324—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 matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
    • 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
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • 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
    • C23C8/80—After-treatment
    • 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 component made of press-form-hardened sheet steel coated on the basis of aluminum, the coating having a coating which is applied in the hot-dip process and which contains aluminum and silicon.
  • the invention also relates to a method for producing such a component.
  • the coating relates to an aluminum-silicon coating.
  • press hardening can be used to produce high-strength components that are primarily used in the bodywork area.
  • Press hardening can in principle be carried out using two different method variants, namely using the direct or indirect method. While the process steps of forming and hardening run separately in the indirect process, they take place together in one tool in the direct process. In the following only the direct method is considered.
  • a steel sheet is heated above the so-called austenitizing temperature (Ac3).
  • the steel sheet heated in this way is then transferred to a forming tool and formed into the finished component in a single-stage forming step and cooled by the cooled forming tool at a speed that is above the critical cooling rate of the steel, so that a hardened component is produced.
  • the steel sheet itself is usually cut out of a steel strip, usually wound up as a coil, and then processed further.
  • the sheet steel to be formed is often referred to as a blank.
  • Known hot-formable steels for this area of application are, for example, the manganese-boron steel "22MnB5" and recently also air-hardenable steels according to the European patent EP 2 449 138 B1 .
  • steel sheets with anti-scaling protection are also used for press hardening (e.g. for automotive body construction) used.
  • press hardening e.g. for automotive body construction
  • the advantages here are that the blanks or components do not scale in the furnace, which reduces wear on the press tools due to flaked scale and the components often do not have to be blasted before further processing.
  • the following (alloy) coatings applied by hot dipping are currently known: aluminum-silicon (AS), zinc-aluminum (Z), zinc-aluminum-iron (ZF / Galvannealed), zinc-magnesium-aluminum (ZM ), as well as electrolytically deposited 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
  • ZM zinc-magnesium-aluminum
  • EP 2 312 011 A1 describes a process for the production of metallic coatings on molded parts for use in automobile construction.
  • the molded part is provided with an aluminum alloy in a molten bath and then subjected to a heat treatment in an oxidizing atmosphere to produce a high-temperature-resistant aluminum oxide layer.
  • Anodic oxidation is also planned after the heat treatment.
  • the German patent DE 198 53 285 C1 presents a method for producing a protective layer on martensitic steel.
  • a protective gas atmosphere argon with 5% H 2
  • the steel to be coated is immersed in a melt of aluminum or an aluminum alloy, cooled and then hot isostatically pressed at the austenitizing temperature.
  • the aluminum protective layer produced in this way is between 100 and 200 ⁇ m thick and should contain an approximately 1 ⁇ m thick aluminum oxide layer on its surface, no further information is given on its formation or preservation.
  • the advantage of the aluminum-based coatings compared to the zinc-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 processed further need to be blasted. In addition, there is no risk of liquid metal embrittlement with aluminum-based coatings and no microcracks can form in the near-surface substrate area at the former austenite grain boundaries, which can have a negative effect on fatigue strength at depths of more than 10 ⁇ m.
  • the alloying of the coating with iron and the formation of a paintable surface topography require a correspondingly long dwell time in the roller hearth furnace that is usually used, which significantly increases the cycle times and reduces the profitability of the press mold hardening.
  • the minimum dwell time is thus determined by the coating and not by the base material, for which only the required austenitizing temperature would be required.
  • the corrosion resistance is reduced by the stronger alloying with iron, since the aluminum content in the alloy layer decreases with the dwell time in the furnace and the iron content increases.
  • longer ovens are usually used for AS boards in order to achieve high cycle rates despite the necessary oven dwell time. However, these are more expensive to purchase and operate and also take up a lot of space.
  • Another disadvantage of AS coatings is that with very short annealing times, spot welding is extremely poor. This is expressed, for example, in only a very small welding area. One of the reasons for this is a very low contact resistance with short glow times.
  • the object of the invention is therefore to provide a component made of a press-hardened steel sheet coated on the basis of aluminum, which can be produced inexpensively and has excellent paintability and weldability, in particular resistance spot weldability. Furthermore, a method for producing such a component is to be specified.
  • the teaching of the invention comprises a component made of press-form-hardened sheet steel coated on the basis of aluminum, the coating having a coating applied in the hot-dip process which contains aluminum and silicon, which is characterized in that the press-form-hardened component has an interdiffusion zone in the transition area between sheet steel and coating I, the thickness of the interdiffusion zone I having the following formula, depending on the layer thickness of the coating prior to heating and press hardening I.
  • both sides G / m 2 + 19th 7th obeys, on the interdiffusion zone I a zone with different intermetallic phases with an average total thickness between 8 and 50 microns is formed, on which in turn a cover layer containing aluminum oxide and / or hydroxide with an average thickness of at least 0.05 microns to at most 5 microns is arranged.
  • aluminum-based coatings are understood to be metallic coatings in which aluminum is the main component (in percent by mass).
  • examples of possible aluminum-based coatings are aluminum-silicon (AS), aluminum-zinc-silicon (AZ), as well as the same coatings with admixtures of additional elements such as magnesium, transition metals such as manganese, titanium and rare earths.
  • a coating of the steel sheet according to the invention is produced, for example, 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.
  • top layers containing aluminum oxide and / or hydroxide act on the component formed by compression molding due to their network-like structure as ideal adhesion promoters for subsequent painting, in particular cathodic dip painting (KTL).
  • KTL cathodic dip painting
  • a lengthy alloying of the aluminum-based coating with iron in the furnace is no longer necessary, so that the throughput times in the furnace for heating the sheet steel to the forming temperature can be drastically reduced. While so far, for example, annealing times in a roller hearth furnace of at least 4 minutes at a furnace temperature of 950 ° C have been required for the alloying of the coating with iron and the formation of a paintable surface topography for sheet metal thicknesses of 1.5 mm Glowing times of only 2 - 3 minutes are required, which significantly reduces the glow time.
  • the maximum possible furnace times do not change due to the top layer containing aluminum oxide and / or hydroxide.
  • the heating process window is thus greatly expanded towards shorter furnace times.
  • furnace time is extended accordingly due to the lower heating rate of the steel material.
  • the typical oven temperatures between 900 and 950 ° C should also be adhered to here.
  • furnace temperatures between 930 and 950 ° C are advantageous.
  • the cover layer according to the invention made of aluminum oxides and / or hydroxides has an advantageous effect on resistance spot weldability in the case of short furnace times, since the contact resistance is increased and good resistance heating is thus achieved.
  • a thickness of this cover layer of at least 0.05 ⁇ m has therefore proven to be positive.
  • a thickness between 0.10 and 3 ⁇ m was found for the top layer as a good compromise between weldability and paint adhesion.
  • top layers with an average thickness between 0.15 and 1 ⁇ m are particularly advantageous.
  • the term is to be understood at least in some areas in the sense of local sections of the treated steel sheet or steel strip, so that a steel sheet or steel strip is created with structures and properties that specifically differ from one another locally.
  • the cover layer is preferably applied to the surface of the coating in a continuous process.
  • the treatment advantageously takes place in an atmosphere which also contains proportions of basic components, preferably ammonia (NH 3 ), primary, secondary or tertiary aliphatic amines (NH 2 R, NHR 2 ), NR 3 ).
  • basic components preferably ammonia (NH 3 ), primary, secondary or tertiary aliphatic amines (NH 2 R, NHR 2 ), NR 3 ).
  • a thin oxidic top layer can advantageously be achieved by anodic oxidation (thin layer anodizing), plasma oxidation and a hydroxide-containing top layer by means of a hot water treatment of the aluminum-based coating at temperatures of at least 90 ° C, advantageously at least 95 ° C and / or a treatment in steam at temperatures of at least 90 ° C, advantageously at least 95 ° C can be produced.
  • a gas phase treatment of the AS surface also leads to the same goal.
  • the AS surface is treated with an atmosphere which can contain at least variable proportions of oxygen, water vapor, and optionally also proportions of basic components, in particular ammonia, primary, secondary or tertiary aliphatic amines.
  • This treatment leads to a time- or temperature-controlled growth of a top layer containing aluminum oxide and / or hydroxide.
  • the composition of the gas phase can be used to control the layer thickness growth of this cover layer.
  • the treatment is carried out at a temperature of 40 ° C to 100 ° C, preferably 90 ° C to 100 ° C. Lower treatment temperatures lengthen the treatment time, treatment temperatures above 100 ° C may require pressure vessels.
  • Both anodization and gas phase treatment result in an aluminum oxide and / or hydroxide-containing cover layer, which has mesh-like or needle-like structures on its surface.
  • the associated increase in surface area improves the adhesion of a subsequent KT coating. Since longer heating times are no longer required to create a paintable surface topography, the corrosion protection of the coating is also increased. This can be explained by the fact that with only a short annealing time required in the roller hearth furnace, there is less diffusion of aluminum and iron. Among other things, this also leads to a relatively small interdiffusion zone. This is exemplary for an AS layer of the starting material of 150 g / m 2 (AS150) below 7 ⁇ m.
  • the thicknesses of the interdiffusion layers I according to the invention for a layer of the starting material result from the linear relationship according to the following formulas for various sheet thickness-dependent Heating times:
  • the necessary heating time in the oven depends only on the sheet metal thickness, since the coating according to the invention does not require any holding time in the oven to produce a paintable surface. Thicker sheets therefore require longer heating times for heating than thinner sheets.
  • table 1 lists short (220 seconds), very short (180 seconds) and extremely short (150 seconds) heating times compared to conventional heating times (360 seconds) in a roller hearth furnace.
  • Another positive effect of the short heating time is a significantly reduced proportion of pores in the alloy layer and in the diffusion zone. Pores arise with longer glow times, e.g. due to the Kirkendall effect. Tests have shown that the short-term annealing can reduce the total pore proportion to values of less than 6% and even to values of less than 4% or 2%. Which can, for example, have a beneficial effect on the suitability for welding.
  • Figure 1 shows schematically the layer structure of the coating on a compression-molded component with a coating of AS and the usual long heating time according to the prior art in order to achieve a through-alloying of the coating with iron.
  • a steel sheet with a coating of AS150 that is to say with a layer of 150 g / m 2 of the coating, was used for the component.
  • An interdiffusion zone Fe (Al, Si) with a thickness of 7 to 14 ⁇ m is formed on the martensitic steel base material, on which a zone with different intermetallic phases (e.g. Fe 2 SiAl 2 and FeAl 2 ) has formed, the individual phases in this zone can be distributed in rows or clusters.
  • an only very thin aluminum oxide layer with a thickness of less than 0.05 ⁇ m has formed. You can also see pores that have formed in the various zones.
  • Figure 2 shows the layer structure of a coating according to the invention on a press-hardened component with an AS coating on which a cover layer according to the invention of at least 0.05 ⁇ m containing aluminum oxide and / or hydroxide is formed and which is produced with shorter heating times compared to the prior art has been.
  • a cover layer according to the invention of at least 0.05 ⁇ m containing aluminum oxide and / or hydroxide is formed in the transition area between sheet steel and coating there is an interdiffusion zone in which aluminum and silicon have diffused into the steel Fe (Al, Si). Due to the very short heating time required in the furnace to the austenitizing temperature, this layer has an average thickness of less than 7 ⁇ m for AS150, for example.
  • Another layer with different intermetallic phases e.g. Fe 2 SiAl 2 and FeAl 2
  • the individual phases in this zone can appear in rows or in clusters and on which an aluminum oxide and / or -hydroxide-containing top layer in an average thickness of at least 0.05 ⁇ m to is
  • Figure 3 shows graphically the thickness I according to the invention of the interdiffusion zone for a layer of the starting material between 50 g / m 2 and 180 g / m 2 according to the following relationship: I. ⁇ m ⁇ 1 35 ⁇ Edition both sides G / m 2 + 19th 7th
  • Table 1 summarizes tests on paint adhesion (phosphating treatment typical for automobiles and cathodic dip painting; testing after 72 hours of constant condensation climate in accordance with DIN EN ISO 6270-2: 2005 CH) and suitability for welding (resistance spot welding) of press-hardened AS150 samples at 940 ° C oven temperature and various heating times.
  • the sheet thickness of the samples is 1.5 mm. It can be seen that there is only good paint adhesion and weldability with heating times of 220 s and less if a cover layer according to the invention containing aluminum oxide and / or hydroxide is present. In addition, short heating times of 220 s and less resulted in interdiffusion layers of less than 7 ⁇ m on the press-hardened component.

Claims (11)

  1. Composant en tôle d'acier durcie sous presse et pourvue d'un revêtement à base d'aluminium, le revêtement comportant un enduit qui est déposé par un procédé d'immersion à chaud et qui contient de l'aluminium et du silicium, ledit composant étant caractérisé en ce que le composant durci sous presse comporte une zone d'interdiffusion I dans la région de transition entre la tôle d'acier et l'enduit, l'épaisseur de la zone d'interdiffusion I obéissant à la formule suivante I μm < 1 / 35 × couche recto verso g / m 2 + 19 / 7
    Figure imgb0012
     en fonction de la couche d'enduit avant chauffage et durcissement sous presse qui est comprise entre 50 g/m2 et 180 g/m2 pour le matériau de départ, une zone pourvue de différentes phases intermétalliques d'épaisseur totale moyenne comprise entre 8 et 50 µm étant formée sur la zone d'interdiffusion I, zone sur laquelle est disposée à son tour une couche de recouvrement contenant de l'oxyde et/ou de l'hydroxyde d'aluminium d'une épaisseur moyenne d'au moins 0,05 µm à 5 µm maximum.
  2. Composant selon la revendication 1, caractérisé en ce que l'épaisseur de la zone d'interdiffusion I est formée selon la formule suivante I μm < 1 / 35 × couche recto verso g / m 2 + 5 / 7
    Figure imgb0013
     en fonction de la couche actuelle du matériau de départ.
  3. Composant selon la revendication 1, caractérisé en ce que l'épaisseur de la zone d'interdiffusion I est formée selon la formule suivante, I μm < 1 / 35 × couche recto verso g / m 2 − 2 / 7
    Figure imgb0014
     en fonction de la couche actuelle du matériau de départ.
  4. Composant selon l'une au moins des revendications 1 à 3, caractérisé en ce que l'épaisseur moyenne de la couche de recouvrement est d'au moins 0,10 µm et de 3,0 µm maximum.
  5. Composant selon l'une au moins des revendications 1 à 3, caractérisé en ce que l'épaisseur moyenne de couche de recouvrement est d'au moins 0,15 µm et de 1,0 µm maximum.
  6. Composant selon l'une au moins des revendications 1 à 5, caractérisé en ce que l'enduit a une porosité totale inférieure à 6 %, avantageusement inférieure à 4 % et de manière optimale inférieure à 2 %.
  7. Composant selon l'une au moins des revendications 1 à 6, caractérisé en ce que l'enduit de la tôle d'acier a été produit dans un bain fondu avec 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 et des impuretés inévitables.
  8. Procédé de production d'un composant, en particulier selon la revendication 1, à partir d'une tôle d'acier ou une bande d'acier durcie sous presse et pourvue d'un revêtement à base d'aluminium, avec une aptitude particulière à la peinture et au soudage par points par résistance, un enduit à base d'aluminium étant appliqué comme revêtement sur la tôle d'acier ou la bande d'acier dans le processus d'immersion à chaud, caractérisé en ce que
    - la tôle d'acier ou la bande d'acier pourvue de l'enduit après le processus d'immersion à chaud et avant le processus de formage, est soumise à un traitement par oxydation anodique et/ou à une oxydation au plasma et/ou à un traitement à l'eau chaude et/ou à un traitement dans une atmosphère qui contient au moins des proportions variables d'oxygène, de vapeur d'eau,
    - le traitement à l'eau chaude ou le traitement sous vapeur d'eau est effectué à des températures d'au moins 90 °C, avantageusement d'au moins 95 °C,
    - un oxyde d'aluminium et/ou une couche de recouvrement contenant de l'hydroxyde et ayant une épaisseur d'au moins 0,05 µm à 5 µm maximum est formée au cours du traitement sur la surface de l'enduit avec formation d'oxydes ou d'hydroxydes,
    - la tôle d'acier ou la bande d'acier est au moins partiellement chauffée à une température supérieure à la température d'austénitisation,
    - la tôle d'acier ou la bande d'acier chauffée est ensuite remise en forme puis refroidie à une vitesse au moins par endroits supérieure à la vitesse de refroidissement critique,
    le temps de chauffage et de séjour pendant le durcissement sous presse étant choisi pour être court de sorte que l'épaisseur de la zone d'interdiffusion I obéisse à la formule qui est mentionnée dans la revendication 1.
  9. Procédé selon la revendication 8, caractérisé en ce que la couche de recouvrement est appliquée sur la surface de l'enduit selon un processus continu.
  10. Procédé selon l'une des revendications 8 et 9, caractérisé en ce que le traitement est effectué dans une atmosphère qui contient également des proportions de constituants basiques, de préférence de l'ammoniac (NH3), des amines aliphatiques primaires, secondaires ou tertiaires (NH2R, NHR2).
  11. Utilisation d'un composant selon les revendications 1 à 7 pour la production de véhicules automobiles.
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