EP3250727A1 - Component made of press-form-hardened, aluminum-based coated steel sheet, and method for producing such a component - Google Patents

Component made of press-form-hardened, aluminum-based coated steel sheet, and method for producing such a component

Info

Publication number
EP3250727A1
EP3250727A1 EP17721056.4A EP17721056A EP3250727A1 EP 3250727 A1 EP3250727 A1 EP 3250727A1 EP 17721056 A EP17721056 A EP 17721056A EP 3250727 A1 EP3250727 A1 EP 3250727A1
Authority
EP
European Patent Office
Prior art keywords
coating
thickness
aluminum
layer
steel sheet
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
EP17721056.4A
Other languages
German (de)
French (fr)
Other versions
EP3250727B1 (en
EP3250727B2 (en
Inventor
Thomas Koll
Marc Debeaux
Friedrich Luther
Christian Fritzsche
Stefan MÜTZE
Frank Beier
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
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
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Application filed by Salzgitter Flachstahl GmbH filed Critical Salzgitter Flachstahl GmbH
Publication of EP3250727A1 publication Critical patent/EP3250727A1/en
Publication of EP3250727B1 publication Critical patent/EP3250727B1/en
Application granted granted Critical
Publication of EP3250727B2 publication Critical patent/EP3250727B2/en
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
    • 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-hardened aluminum-coated steel sheet, the coating having a hot-dip coating containing 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 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 the indirect process, the process steps of forming and hardening run separately, they take place together in a direct process in a tool. In the following, only the direct method will be considered. In the direct process, a steel sheet is over the so-called
  • thermoformable steels for this 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.
  • Scaling protection for press hardening eg for automotive body construction
  • 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 (ZM ), as well as electrodeposited zinc-nickel or zinc coatings, the latter being converted to an iron-zinc alloy layer prior to hot working.
  • AS aluminum-silicon
  • Z zinc-aluminum
  • ZF / Galvannealed zinc-magnesium-aluminum
  • ZM zinc-magnesium-aluminum
  • 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
  • the publication US 201 1/0300407 A1 discloses a process for the production a press-formed hardened steel sheet for use in the automotive industry.
  • the steel sheet is provided with an aluminum-silicon (AS) coating with a layer coverage of 20 to 80 g / m 2 , heated to temperatures above 820 ° C and held the temperature for some time (about 3 minutes).
  • AS aluminum-silicon
  • different intermetallic phases are formed in the coating, for example Fe 3 Al, FeAl or Fe-Al 2 O 3 .
  • European Patent Application EP 2 312 01 1 A1 also describes a process for the production of metallic coatings on moldings for use in the automotive industry. For this purpose, the casting is provided in a molten bath with an aluminum alloy and then to produce a
  • anodic oxidation is also provided.
  • German patent DE 198 53 285 C1 presents a method for producing a protective layer on martensitic steel. Under a protective gas atmosphere (argon with 5% H2), the steel to be coated is immersed in a melt of aluminum or an aluminum alloy, cooled and then at
  • Austenitizing temperature hot isostatically pressed The aluminum protective layer produced in this way is between 100 and 200 .mu.m thick and should contain on its surface an approximately 1 .mu.m thick alumina layer, for the formation or receipt of which no further details are given.
  • Aluminum oxide layer is above the temperature of the aluminum and the
  • Oxygen concentration adjusted during the coating it is between 4 and 30 nm.
  • the advantage of the aluminum-based coatings compared to the zinc-based coatings is that in addition to a larger process window (eg with regard to the heating parameters), the finished components before further processing is not must be blasted. In addition, there is no risk of molten metal embrittlement in the case of aluminum-based coatings and no microcracks in the near-surface substrate region can form on the former austenite grain boundaries, which can have a negative effect on the fatigue strength at depths above 10 ⁇ m.
  • AS Aluminum-silicon
  • KTL automotive-typical cathodic dip coating
  • the surface has a too low roughness, so that no sufficient paint adhesion is achieved.
  • aluminum-based coatings can not or only insufficiently phosphating and thus can not be achieved by the phosphating step improvement in paint adhesion.
  • the alloying of the coating with iron and the formation of a paintable surface topography require a correspondingly long residence time in the roller hearth furnace commonly used, which significantly prolongs the cycle times and reduces the economy of the press-forming.
  • the minimum residence time is thus determined by the coating and not by the base material, for which only the achievement of the necessary Austenitmaschinestemperatur would be necessary.
  • the corrosion resistance is reduced by the stronger alloying with iron, since the aluminum content in the alloy layer with the
  • the object of the invention is therefore to provide a component of a press-form-hardened based on aluminum-coated sheet steel, which is inexpensive to produce and excellent paintability and weldability, in particular resistance point weldability, has. Furthermore, a method for producing such a component is to be specified.
  • the teaching of the invention comprises a component made of press-hardened, based on aluminum coated steel sheet, wherein the coating has a in
  • Hot-dip method applied coating containing aluminum and silicon which is characterized in that the press-form hardened component in the transition region between steel sheet and coating has an interdiffusion zone I, wherein depending on the coating layer of the coating before heating and press curing, the thickness of the interdiffusion zone I following formula
  • a zone with different intermetallic phases is formed with an average total thickness between 8 and 50 .mu.m, on which in turn a cover layer containing alumina and / or hydroxide in an average thickness of at least 0.05 .mu.m to at most 5 .mu.m is arranged.
  • 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, e.g. Magnesium, transition metals such as manganese, titanium and rare earths.
  • An inventive coating of the steel sheet 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, balance aluminum.
  • cover layers containing aluminum oxide and / or hydroxide act on the component formed by press-forming hardening as ideal adhesion promoters for a subsequent painting, in particular the
  • Oven temperatures between 900 and 950 ° C should also be observed here. Oven temperatures between 930 and 950 ° C are advantageous for high cycle times.
  • cover layer of aluminum oxides and / or hydroxides according to the invention has an advantageous effect on the resistance spot weldability with short furnace times, since the contact resistance is increased and thus a good
  • cover layers having an average thickness of between 0.15 and 1 ⁇ m are particularly advantageous.
  • the invention also relates to a method for producing a component, in particular according to claim 1, from press-hardened, based on aluminum coated steel sheet with particular suitability for painting and resistance spot welding, wherein as an aluminum-based coating
  • Coating is applied to the steel sheet in the hot-dip method, which is characterized
  • Hot water treatment and / or treatment in an atmosphere which is at least variable proportions of oxygen, water vapor is subjected to the hot water treatment or treatment under water vapor at temperatures of at least 90 ° C, preferably at least 95 ° C, carried out in the course of treatment on the Surface of the coating to form oxides or hydroxides an alumina and / or - hydroxide contained cover layer is formed with a thickness of at least 0.05 .mu.m to a maximum of 5 ⁇
  • the steel sheet or steel strip is at least partially heated to a temperature above the Austenitmaschinestemperatur that the heated steel sheet or steel strip is then formed and then cooled at a rate that at least
  • the term is at least partially in the Understand the meaning of local sections of the treated steel sheet or steel strip, so that a steel sheet or steel strip with targeted spatially divergent structures and properties arise.
  • the cover layer is applied to the surface of the coating in a continuous process.
  • the treatment 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 cover layer can advantageously be obtained by anodic oxidation (thin-film anodization), plasma oxidation and a hydroxide-containing topcoat by means of a hot water treatment of the aluminum-based coating at temperatures of at least 90 ° C, preferably at least 95 ° C and / or a treatment in water vapor at temperatures of at least 90 ° C, advantageously at least 95 ° C are prepared.
  • gas phase treatment of the AS surface also leads to the same target.
  • the AS surface is treated with an atmosphere which may contain at least variable proportions of oxygen, water vapor, optionally also fractions of basic components, in particular ammonia, primary, secondary or tertiary aliphatic amines.
  • This treatment leads to a time- or temperature-controlled growth of a cover 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.
  • Treatment is carried out at a temperature of 40 ° C to 100 ° C, preferably 90 C to 100 ° C. Lower treatment temperatures extend the
  • treatment temperatures above 100 ° C may require
  • Both anodization and gas phase treatment lead to a cover layer containing aluminum oxide and / or hydroxide, which has net or needle-like structures on its surface.
  • the associated surface enlargement improves the adhesion of a subsequent KT coating. Since longer heating times are no longer required to form a coatable surface topography, the corrosion protection of the coating is also increased. This can be explained by the fact that less diffusion of aluminum and iron takes place with only a short required annealing time in the roller hearth furnace. Among other things, this leads to a relatively low level of education
  • Interdiffusion zone By way of example, this is for an AS support of the starting material of 150 g / m 2 (AS150) below 7 ⁇ m.
  • Heating time in the oven even lower thicknesses of the diffusion layers of less than 3 microns, and even be achieved below 2 microns on the finished component.
  • the thicknesses of the interdiffusion layers I according to the invention for a layer overlay of the starting material resulting from the linear relationship according to the following formulas for various sheet thickness-dependent heating times:
  • the necessary heating time in the oven depends, according to the invention, only on the sheet thickness, since the coating according to the invention does not have a holding time in the oven
  • Table 1 shows short (220 seconds), very short (180 seconds) and extremely short (150 seconds) heating times in comparison to the usual heating times (360 seconds) in the roller hearth furnace.
  • Another positive effect of the short heating time is a significantly reduced pore content in the alloy layer and in the diffusion zone. Pores are formed at longer annealing times, e.g. through the Kirkendall effect. Experiments have shown that short-term annealing reduces the total pore fraction to values of less than 6% and even to values below 4% and 2%, respectively. What is e.g. can have an advantageous effect on the weldability.
  • Forming press fed, reshaped and quenched As a result, also advantageously shorter roller hearth furnaces than those used so far can be used.
  • the use of other types of furnaces, for example for inductive or conductive rapid heating is possible without the heated boards to form a paintable Surface topography must be kept at temperature.
  • Figure 1 shows schematically the layer structure of the coating on a
  • a steel sheet with a coating of AS150, ie with a coating layer of the coating of 150 g / m 2 was used.
  • an interdiffusion zone Fe (Al, Si) is formed with a thickness of 7 to 14 microns, on which a zone with different intermetallic phases (eg Fe2SiAl 2 and FeAl 2 ) has formed, with the individual phases in this zone can occur cell-shaped or cluster-shaped distributed. Due to the oxidation in the oven as well as the transfer to the press, a very thin aluminum oxide layer with a thickness of less than 0.05 ⁇ m has formed. Also visible are pores that have formed in the different zones.
  • FIG. 2 shows, by comparison, the layer structure of an inventive device
  • Cover layer of at least 0.05 microns is formed and which has been produced with shortened compared to the prior art heating times.
  • an interdiffusion zone is formed, in which aluminum and silicon are diffused into the steel Fe (Al, Si). Due to the only very short necessary heating time in the oven
  • this layer for example, for AS150 has a thickness of less than 7 microns on average.
  • a further layer with different intermetallic phases eg Fe 2 SiAl 2 and FeAl 2 ) forms on this layer, wherein the individual phases in this zone can occur in a cell-shaped or cluster-shaped manner and on which an aluminum oxide and / or Hydroxide-containing topcoat in an average thickness of at least 0.05 microns to is arranged at most 5 microns.
  • FIG. 3 shows graphically the thickness I of the interdiffusion zone according to the invention for a layer coverage of the starting material between 50 g / m 2 and 180 g / m 2 according to the following relationship:
  • an inventive cover layer containing aluminum oxide and / or hydroxide is present.
  • short heating times of 220 s and less resulted in interdiffusion layers of less than 7 ⁇ m on the press-hardened component.
  • long heating times of 360 s according to the prior art on the other hand due to the alloying of the coating with iron, a good paint adhesion and weldability is also provided in the samples without the cover layer containing the aluminum oxide and / or hydroxide according to the invention.
  • the thickness of the interdiffusion layers is significantly above 7 ⁇ m after a heating time of 360 s.

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Abstract

The invention relates to a component made of press-form-hardened, aluminium-based coated steel sheet, the coating having a covering which contains aluminum and silicon applied in the hot-dip process, characterized in that the press-form-hardened component in the transition region between steel sheet and covering has an inter-diffusion zone I, wherein, depending on the layer application of the covering before heating and press hardening, the thickness of the inter-diffusion zone I obeys the following formula: I [µm] < (1/35) x application on both sides [g/m2] + (19/7), on the inter-diffusion zone I there is formed a zone having various intermetallic phases having an average total thickness between 8 and 50 µm, on which zone there is in turn arranged a covering layer containing aluminum oxide and/or hydroxide having an average thickness of at least 0.05 µm to at most 5 µm. The invention further relates to a method for producing the aforementioned component.

Description

Bauteil aus pressformgehärtetem, auf Basis von Aluminium beschichtetem Stahlblech und Verfahren zur Herstellung eines solchen Bauteils  Component of press-hardened aluminum-coated steel sheet and method for producing such a component
Die Erfindung betrifft ein Bauteil aus pressformgehärtetem, auf Basis von Aluminium beschichtetem Stahlblech, wobei die Beschichtung einen im Schmelztauchverfahren aufgebrachten Überzug aufweist, der Aluminium und Silizium enthält. Auch betrifft die Erfindung ein Verfahren zur Herstellung eines solchen Bauteils. Insbesondere betrifft die Beschichtung einen Aluminium-Silizium-Überzug. Es ist bekannt, dass warmumgeformte Stahlbleche insbesondere im Automobilbau immer häufiger Verwendung finden. Durch den auch als Presshärten bezeichneten Prozess können hochfeste Bauteile erzeugt werden, die vorwiegend im Bereich der Karosserie eingesetzt werden. Das Presshärten kann grundsätzlich mittels zwei verschiedener Verfahrensvarianten durchgeführt werden, nämlich mittels des direkten oder indirekten Verfahrens. Während beim indirekten Verfahren die Prozessschritte des Umformens und Härtens getrennt voneinander ablaufen, finden sie beim direkten Verfahren in einem Werkzeug gemeinsam statt. Im Folgenden wird nur das direkte Verfahren betrachtet. Beim direkten Verfahren wird ein Stahlblech über die sogenannte The invention relates to a component made of press-hardened aluminum-coated steel sheet, the coating having a hot-dip coating containing aluminum and silicon. The invention also relates to a method for producing such a component. In particular, the coating relates to an aluminum-silicon coating. It is known that hot-formed steel sheets are used more and more frequently, especially in the automotive industry. The process, also known as 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 the indirect process, the process steps of forming and hardening run separately, they take place together in a direct process in a tool. In the following, only the direct method will be considered. In the direct process, a steel sheet is over the so-called
Austenitisierungstemperatur (Ac3) aufgeheizt. Anschließend wird das so erhitzte Stahlblech in ein Formwerkzeug überführt und in einem einstufigen Umformschritt zum fertigen Bauteil umgeformt und hierbei durch das gekühlte Formwerkzeug gleichzeitig mit einer Geschwindigkeit, die über der kritischen Abkühlgeschwindigkeit des Stahls liegt, abgekühlt, so dass ein gehärtetes Bauteil erzeugt wird. Das  Austenitizing temperature (Ac3) heated. Subsequently, the thus heated steel sheet is transferred to a mold and formed in a one-step forming step to the finished component and thereby cooled by the cooled mold simultaneously with a speed which is above the critical cooling rate of the steel, so that a hardened component is produced. The
Stahlblech selbst wird dabei üblicherweise aus einem meist als Coil aufgewickelten Stahlband herausgeschnitten und anschließend weiterverarbeitet. Das umzuformende Stahlblech wird häufig auch als Platine bezeichnet. Bekannte warmumformbare Stähle für diesen Einsatzbereich sind zum Beispiel der Mangan-Bor-Stahl„22MnB5" und neuerdings auch luftvergütbare Stähle gemäß des europäischen Patentes EP 2 449 138 B1.  Steel sheet itself is usually cut out of a usually wound as a coil steel strip and then further processed. The reshaped steel sheet is often referred to as a board. Known thermoformable steels for this 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.
Neben unbeschichteten Stahlblechen werden auch Stahlbleche mit einem In addition to uncoated steel sheets are also steel sheets with a
Verzunderungsschutz für das Presshärten (z.B. für den automobilen Karosseriebau) eingesetzt. Die Vorteile liegen hier neben der erhöhten Korrosionsbeständigkeit des fertigen Bauteils darin, dass die Platinen oder Bauteile im Ofen nicht verzundern, wodurch der Verschleiß der Pressenwerkzeuge durch abgeplatzten Zunder reduziert wird und die Bauteile vor der Weiterverarbeitung oft nicht aufwendig gestrahlt werden müssen. Scaling protection for press hardening (eg for automotive body construction) used. 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.
Für das Presshärten sind derzeit die folgenden, durch Schmelztauchen aufgebrachten (Legierungs-) Beschichtungen bekannt: Aluminium-Silizium (AS), Zink-Aluminium (Z), Zink-Aluminium-Eisen (ZF/ Galvannealed), Zink-Magnesium-Aluminium (ZM), sowie elektrolytisch abgeschiedene Beschichtungen aus Zink-Nickel oder Zink, wobei die letztere vor der Warmumformung in eine Eisen-Zink-Legierungsschicht umgewandelt wird. Diese Korrosionsschutzbeschichtungen werden üblicherweise in kontinuierlichen Durchlaufverfahren auf das Warm- oder Kaltband aufgebracht. Die Herstellung von Bauteilen mittels Abschrecken von Vorprodukten aus For press hardening, the following hot-dip (alloy) coatings are currently known: aluminum-silicon (AS), zinc-aluminum (Z), zinc-aluminum-iron (ZF / Galvannealed), zinc-magnesium-aluminum (ZM ), as well as electrodeposited zinc-nickel or zinc coatings, the latter being converted to an iron-zinc alloy layer prior to hot working. These anticorrosion coatings are usually applied to the hot or cold strip in continuous flow processes. The manufacture of components by quenching precursors
presshärtbaren Stählen durch Warmumformen in einem Umformwerkzeug ist aus dem deutschen Patent DE 601 19 826 T2 bekannt. Hier wird eine zuvor oberhalb der Austenitisierungstemperatur auf 800 - 1200 °C erwärmte und ggf. mit einem metallischen Überzug aus Zink oder auf Basis von Zink versehene Blechplatine in einem fallweise gekühlten Werkzeug durch Warmumformung zu einem Bauteil umgeformt, wobei während des Umformens durch schnellen Wärmeentzug das Blech bzw. Bauteil im Umformwerkzeug eine Abschreckhärtung (Presshärtung) erfährt und durch das entstehende martensitische Härtegefüge die geforderten Press-hardenable steels by hot forming in a forming tool is known from German patent DE 601 19 826 T2. Here is a previously heated above the Austenitisierungstemperatur to 800 - 1200 ° C and possibly provided with a metallic coating of zinc or based on zinc sheet metal blank formed in a case by case cooled tool by hot forming into a component, during the forming by rapid heat removal the Sheet metal or component undergoes a quench hardening (press hardening) in the forming tool and the required martensitic hardness structure
Festigkeitseigenschaften erreicht. Strength properties achieved.
Die Herstellung von Bauteilen mittels Abschrecken von mit einer Aluminiumlegierung beschichteten Vorprodukten aus presshärtbaren Stählen durch Warmumformen in einem Umformwerkzeug ist aus dem deutschen Patent DE 699 33 751 T2 bekannt. Hier wird ein mit einer Aluminiumlegierung beschichtetes Blech vor einem Umformen auf über 700 °C erwärmt, wobei eine intermetallisch legierte Verbindung auf Basis von Eisen, Aluminium und Silizium auf der Oberfläche entsteht und nachfolgend das Blech umgeformt und mit einer Geschwindigkeit oberhalb der kritischen 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. Here, 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
Abkühlgeschwindigkeit abkühlt. Aus der Offenlegungsschrift US 201 1/0300407 A1 ist ein Verfahren zur Herstellung eines pressformgehärteten Stahlblechs zur Verwendung in der Automobilbranche bekannt. Im Schmelztauchverfahren wird das Stahlblech mit einem Aluminium- Silizium (AS)-Überzug mit einer Schichtauflage von 20 bis 80 g/m2 versehen, auf Temperaturen über 820°C erwärmt und die Temperatur für einige Zeit (ca. 3 Minuten) gehalten. Dabei werden im Überzug unterschiedliche intermetallische Phasen ausgebildet, beispielsweise Fe3AI, FeAl oder Fe-Al2O3. Nach dem Warmumformen mittels einer Presse wird das Produkt noch in der Presse abgekühlt. Cooling rate cools down. The publication US 201 1/0300407 A1 discloses a process for the production a press-formed hardened steel sheet for use in the automotive industry. In the hot-dip process, the steel sheet is provided with an aluminum-silicon (AS) coating with a layer coverage of 20 to 80 g / m 2 , heated to temperatures above 820 ° C and held the temperature for some time (about 3 minutes). In this case, different intermetallic phases are formed in the coating, for example Fe 3 Al, FeAl or Fe-Al 2 O 3 . After hot forming by means of a press, the product is still cooled in the press.
Auch die europäische Patentanmeldung EP 2 312 01 1 A1 beschreibt ein Verfahren zur Herstellung von metallischen Beschichtungen auf Gussformteilen für den Einsatz im Automobilbau. Dazu wird das Gussformteil in einem Schmelzbad mit einer Aluminiumlegierung versehen und anschließend zur Herstellung einer European Patent Application EP 2 312 01 1 A1 also describes a process for the production of metallic coatings on moldings for use in the automotive industry. For this purpose, the casting is provided in a molten bath with an aluminum alloy and then to produce a
hochtemperaturbeständigen Aluminiumoxidschicht einer Wärmebehandlung in einer oxidierenden Atmosphäre unterzogen. Nach der Wärmebehandlung ist auch eine anodische Oxidation vorgesehen. subjected to a heat treatment in an oxidizing atmosphere. After the heat treatment, anodic oxidation is also provided.
Die deutsche Patentschrift DE 198 53 285 C1 stellt ein Verfahren zur Herstellung einer Schutzschicht auf martensitischem Stahl vor. Unter Schutzgasatmosphäre (Argon mit 5% H2) wird der zu beschichtende Stahl in eine Schmelze aus Aluminium oder einer Aluminiumlegierung getaucht, abgekühlt und dann bei The German patent DE 198 53 285 C1 presents a method for producing a protective layer on martensitic steel. Under a protective gas atmosphere (argon with 5% H2), the steel to be coated is immersed in a melt of aluminum or an aluminum alloy, cooled and then at
Austenitisierungstemperatur heißisostatisch gepresst. Die derart erzeugte Aluminium- Schutzschicht ist zwischen 100 und 200 μm dick und soll an ihrer Oberfläche eine ca. 1 μηη dicke Aluminiumoxid-Schicht enthalten, zu deren Entstehung oder Erhalt keine weiteren Angaben gemacht werden.  Austenitizing temperature hot isostatically pressed. The aluminum protective layer produced in this way is between 100 and 200 .mu.m thick and should contain on its surface an approximately 1 .mu.m thick alumina layer, for the formation or receipt of which no further details are given.
Aus der europäischen Patentanmeldung EP 2 017 074 A2 ist eine From the European patent application EP 2 017 074 A2 is a
Kraftfahrzeugrohrleitung aus einem Stahlrohr mit einer Aluminiumschicht bekannt, die mittels Schmelztauchbeschichten aufgebracht wird. Eine Dicke einer Motor vehicle pipeline made of a steel pipe with an aluminum layer known, which is applied by hot dip coating. A thickness of one
Aluminiumoxidschicht wird über die Temperatur des Aluminiums und der Aluminum oxide layer is above the temperature of the aluminum and the
Sauerstoffkonzentration während der Beschichtung eingestellt; sie liegt zwischen 4 und 30 nm. Oxygen concentration adjusted during the coating; it is between 4 and 30 nm.
Der Vorteil bei den aluminiumbasierten Überzügen gegenüber den zinkbasierten Überzügen liegt darin, dass neben einem größeren Prozessfenster (z.B. hinsichtlich der Erwärmungsparameter) die fertigen Bauteile vor der Weiterverarbeitung nicht gestrahlt werden müssen. Darüber hinaus besteht bei aluminiumbasierten Überzügen nicht die Gefahr von Flüssigmetallversprödung und es können sich keine Mikrorisse im oberflächennahen Substratbereich an den ehemaligen Austenitkorngrenzen ausbilden, die bei Tiefen über 10 μm einen negativen Effekt auf die Dauerfestigkeit haben können. The advantage of the aluminum-based coatings compared to the zinc-based coatings is that in addition to a larger process window (eg with regard to the heating parameters), the finished components before further processing is not must be blasted. In addition, there is no risk of molten metal embrittlement in the case of aluminum-based coatings and no microcracks in the near-surface substrate region can form on the former austenite grain boundaries, which can have a negative effect on the fatigue strength at depths above 10 μm.
Nachteilig bei der Verwendung von aluminiumbasierten Überzügen, z.B. aus A disadvantage of using aluminum-based coatings, e.g. out
Aluminium-Silizium (AS), ist jedoch die mangelhafte Lackhaftung des umgeformten Bauteils bei der automobiltypischen kathodischen Tauchlackierung (KTL), wenn eine zu kurze Erwärmungszeit beim Presshärten verwendet wurde. Bei kurzen Aluminum-silicon (AS), however, is the defective paint adhesion of the formed component in the automotive-typical cathodic dip coating (KTL), if too short heating time was used in press hardening. In short
Erwärmungszeiten weist die Oberfläche eine zu geringe Rauheit auf, so dass keine ausreichende Lackhaftung erreicht wird.  Heating times, the surface has a too low roughness, so that no sufficient paint adhesion is achieved.
Im Gegensatz zu den zinkbasierten Überzügen lassen sich aluminiumbasierte Überzüge nicht oder nur unzureichend Phosphatieren und somit kann durch den Phosphatierschritt keine Verbesserung der Lackhaftung erzielt werden. Aus diesen Gründen müssen bisher bei der Verarbeitung von Platinen mit aluminiumbasierten Überzügen Mindesterwärmzeiten eingehalten werden, wodurch der Überzug mit Eisen durchlegiert und sich eine raue Oberflächentopografie ausbildet, die eine ausreichende Lackhaftung beim Lackieren des umgeformten Bauteils bewirkt. In contrast to the zinc-based coatings, aluminum-based coatings can not or only insufficiently phosphating and thus can not be achieved by the phosphating step improvement in paint adhesion. For these reasons, so far in the processing of boards with aluminum-based coatings Mindesterwärmzeiten must be complied with, whereby the coating ironed through and forms a rough surface topography, which causes a sufficient paint adhesion when painting the formed part.
Das Durchlegieren des Überzugs mit Eisen und die Ausbildung einer lackierfähigen Oberflächentopografie erfordern allerdings eine entsprechend lange Verweildauer im üblicherweise verwendeten Rollenherdofen, was die Taktzeiten deutlich verlängert und die Wirtschaftlichkeit des Pressformhärtens reduziert. Die Mindestverweildauer wird somit durch den Überzug bestimmt und nicht durch das Grundmaterial, für das lediglich die Erreichung der notwendigen Austenitisierungstemperatur notwendig wäre. Zudem wird die Korrosionsbeständigkeit durch das stärkere Auflegieren mit Eisen verringert, da der Aluminiumgehalt in der Legierungsschicht mit der However, the alloying of the coating with iron and the formation of a paintable surface topography require a correspondingly long residence time in the roller hearth furnace commonly used, which significantly prolongs the cycle times and reduces the economy of the press-forming. The minimum residence time is thus determined by the coating and not by the base material, for which only the achievement of the necessary Austenitisierungstemperatur would be necessary. In addition, the corrosion resistance is reduced by the stronger alloying with iron, since the aluminum content in the alloy layer with the
Ofenverweilzeit abnimmt und der Eisengehalt ansteigt. Für AS-Platinen werden üblicherweise angepasste, längere Öfen eingesetzt, um trotz der notwendigen Ofenverweilzeit hohe Taktraten zu erzielen. Diese sind jedoch teurer in der Oven dwell time decreases and the iron content increases. For AS boards usually adapted, longer furnaces are used to achieve high clock rates despite the necessary Ofenverweilzeit. These are however more expensive in the
Anschaffung und im Betrieb und haben zudem einen sehr großen Platzbedarf. Acquisition and operation and also have a very large footprint.
Ein weiterer Nachteil von AS-Überzügen besteht darin, dass bei sehr kurzen Another disadvantage of AS coatings is that when very short
Glühzeiten die Schweißbarkeit im Punktschweißverfahren äußerst schlecht ist. Dies drückt sich z.B. in einem nur sehr kleinen Schweißbereich aus. Ursächlich hierfür ist unter anderem ein sehr geringer Übergangswiderstand bei kurzen Glühzeiten. Glowing times the weldability in the spot welding process is extremely poor. This expresses itself eg in a very small welding area. One of the reasons for this is a very low contact resistance with short annealing times.
Aufgabe der Erfindung ist es deshalb, ein Bauteil aus einem pressformgeharteten auf Basis von Aluminium beschichteten Stahlblech anzugeben, welches kostengünstig herstellbar ist und eine hervorragende Lackierbarkeit und Schweißbarkeit, insbesondere Widerstandspunktschweißbarkeit, aufweist. Des Weiteren soll ein Verfahren zur Herstellung eines solchen Bauteils angegeben werden. Die Lehre der Erfindung umfasst ein Bauteil aus pressformgehärtetem, auf Basis von Aluminium beschichtetem Stahlblech, wobei die Beschichtung einen im The object of the invention is therefore to provide a component of a press-form-hardened based on aluminum-coated sheet steel, which is inexpensive to produce and excellent paintability and weldability, in particular resistance point weldability, has. Furthermore, a method for producing such a component is to be specified. The teaching of the invention comprises a component made of press-hardened, based on aluminum coated steel sheet, wherein the coating has a in
Schmelztauchverfahren aufgebrachten Überzug aufweist, der Aluminium und Silizium enthält, welches dadurch gekennzeichnet ist, dass das pressformgehärtete Bauteil im Übergangsbereich zwischen Stahlblech und Überzug eine Interdiffusionszone I aufweist, wobei abhängig von der Schichtauflage des Überzugs vor Erwärmung und Presshärtung die Dicke der Interdiffusionszone I folgender Formel Hot-dip method applied coating containing aluminum and silicon, which is characterized in that the press-form hardened component in the transition region between steel sheet and coating has an interdiffusion zone I, wherein depending on the coating layer of the coating before heating and press curing, the thickness of the interdiffusion zone I following formula
gehorcht, auf der Interdiffusionszone I eine Zone mit verschiedenen intermetallischen Phasen mit einer mittleren Gesamtdicke zwischen 8 und 50 μm ausgebildet ist, auf der wiederum eine Aluminiumoxid und/oder -hydroxid enthaltende Deckschicht in einer mittleren Dicke von mindestens 0,05 μm bis höchstens 5 μm angeordnet ist.  obeys, on the interdiffusion zone I, a zone with different intermetallic phases is formed with an average total thickness between 8 and 50 .mu.m, on which in turn a cover layer containing alumina and / or hydroxide in an average thickness of at least 0.05 .mu.m to at most 5 .mu.m is arranged.
Als aluminiumbasierte Überzüge werden nachfolgend metallische Überzüge verstanden, bei denen Aluminium der Hauptbestandteil (in Massenprozent) ist. As aluminum-based coatings are hereinafter understood metallic coatings in which aluminum is the main component (in mass percent).
Beispiele für mögliche aluminiumbasierte Überzüge sind Aluminium-Silizium (AS), Aluminium-Zink-Silizium (AZ), sowie dieselben Überzüge mit Beimischungen zusätzlicher Elemente, wie z.B. Magnesium, Übergangsmetallen wie Mangan, Titan und seltenen Erden. Ein erfindungsgemäßer Überzug des Stahlbleches wird beispielsweise in einem Schmelzbad mit einem Si-Gehalt von 8 bis 12 Gewichts-%, einem Fe-Gehalt von 1 bis 4 Gewichts-%, Rest Aluminium erzeugt.  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, e.g. Magnesium, transition metals such as manganese, titanium and rare earths. An inventive coating of the steel sheet 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, balance aluminum.
Durch die Ausbildung einer definierten Aluminiumoxid und/oder -hydroxid By training a defined alumina and / or hydroxide
enthaltenden Deckschicht auf der aluminiumbasierten Beschichtung des Stahlbleches oder des Stahlbandes, können die vorgenannten negativen Aspekte von containing cover layer on the aluminum-based coating of the steel sheet or the steel strip, the aforementioned negative aspects of
aluminiumbasierten Beschichtungen deutlich reduziert oder sogar ganz verhindert werden. Die Aluminiumoxid und/oder -hydroxid enthaltenen Deckschichten wirken auf dem durch Pressformhärten umgeformten Bauteil auf Grund ihrer netzartigen Struktur als ideale Haftvermittler für eine anschließende Lackierung, insbesondere der aluminum-based coatings significantly reduced or even completely prevented. Due to their net-like structure, the cover layers containing aluminum oxide and / or hydroxide act on the component formed by press-forming hardening as ideal adhesion promoters for a subsequent painting, in particular the
kathodischen Tauchlackierung (KTL). Ein langwieriges Durchlegieren der cathodic dip painting (KTL). A lengthy breakdown of the
aluminiumbasierten Beschichtung im Ofen mit Eisen ist damit nicht mehr erforderlich, so dass sich die Durchlaufzeiten im Ofen zum Aufheizen des Stahlblechs auf Aluminum-based coating in the furnace with iron is therefore no longer necessary, so that the throughput times in the furnace for heating the steel sheet up
Umformtemperatur drastisch verkürzen lassen. Während bislang beispielsweise bei Blechdicken von 1 ,5 mm Glühzeiten im Rollenherdofen von mindestens 4 Minuten bei 950 °C Ofentemperatur für das Durchlegieren der Beschichtung mit Eisen und die Ausbildung einer lackierfähigen Oberflächentopografie erforderlich sind, werden beim erfindungsgemäßen Verfahren bei einer Blechdicke von 1 ,5 mm Glühzeiten von nur noch 2 - 3 Minuten benötigt, die Glühzeit wird somit signifikant reduziert. Die maximal möglichen Ofenzeiten ändern sich durch die Aluminiumoxid und/oder -hydroxid enthaltene Deckschicht nicht. Somit wird das Prozessfenster der Erwärmung hin zu kürzeren Ofenzeiten stark erweitert.  Shorten the forming temperature drastically. While hitherto, for example, with sheet thicknesses of 1, 5 mm annealing times in the roller hearth furnace of at least 4 minutes at 950 ° C oven temperature for the alloying of the coating with iron and the formation of a paintable surface topography are required in the inventive method at a sheet thickness of 1, 5 mm Annealing times of only 2 - 3 minutes required, the annealing time is thus significantly reduced. The maximum possible furnace times do not change due to the cover layer containing aluminum oxide and / or hydroxide. Thus, the process window of heating towards shorter oven times is greatly expanded.
Für dickere Bleche verlängert sich die Ofenzeit bedingt durch die geringere For thicker sheets, the oven time is extended due to the lower
Aufheizgeschwindigkeit des Stahl Werkstoff es entsprechend. Die typischen Heating rate of the steel material accordingly. The typical
Ofentemperaturen zwischen 900 und 950 °C sollten auch hier eingehalten werden. Für hohe Taktzeiten sind Ofentemperaturen zwischen 930 und 950 °C vorteilhaft. Oven temperatures between 900 and 950 ° C should also be observed here. Oven temperatures between 930 and 950 ° C are advantageous for high cycle times.
Zudem wirkt sich die erfindungsgemäße Deckschicht aus Aluminiumoxiden und/oder - hydroxiden vorteilhaft auf die Widerstandpunktschweißbarkeit bei kurzen Ofenzeiten aus, da der Übergangswiderstand erhöht wird und so eine gute In addition, the cover layer of aluminum oxides and / or hydroxides according to the invention has an advantageous effect on the resistance spot weldability with short furnace times, since the contact resistance is increased and thus a good
Widerstandserwärmung erreicht wird. Für eine gute Schweißbarkeit nach kurzen Erwärmzeiten hat sich daher eine Dicke dieser Deckschicht von mindestens 0,05 μm als positiv herausgestellt. Resistance heating is achieved. For a good weldability after short heating times, therefore, a thickness of this cover layer of at least 0.05 microns has been found to be positive.
Bei Versuchen wurde festgestellt, dass die Lackhaftung besser bzw. die In tests, it was found that the paint adhesion better or
Unterwanderung infolge eines korrosiven Angriffs umso geringer wird, je dicker die Aluminiumoxid und/oder -hydroxid enthaltende Deckschicht ist. Andererseits ist bei zu großer Dicke dieser Deckschicht der Übergangswiderstand beim Infiltration due to a corrosive attack is the lower, the thicker the alumina and / or hydroxide-containing topcoat is. On the other hand, too large thickness of this cover layer of the contact resistance
Widerstandspunktschweißen zu hoch, wodurch sich die Schweißbarkeit wiederum verschlechtern würde. Daher sollte eine maximale Dicke der Deckschicht von 5 μm nicht überschritten werden.  Resistance spot welding too high, which in turn would worsen the weldability. Therefore, a maximum thickness of the top layer of 5 microns should not be exceeded.
Als guter Kompromiss zwischen Schweißeignung und Lackhaftung wurde für die Deckschicht eine Dicke zwischen 0,10 und 3 μm gefunden. As a good compromise between weldability and paint adhesion, a thickness of between 0.10 and 3 μm was found for the cover layer.
Für eine hervorragende Schweißeignung bei guter Lackhaftung sind Deckschichten mit einer mittleren Dicke zwischen 0,15 und 1 μm besonders vorteilhaft. For excellent weldability with good paint adhesion, cover layers having an average thickness of between 0.15 and 1 μm are particularly advantageous.
Erfindungsgemäß umfasst die Erfindung ebenfalls ein Verfahren zur Herstellung eines Bauteils, insbesondere nach Anspruch 1 , aus pressformgehärtetem, auf Basis von Aluminium beschichtetem Stahlblech mit besonderer Eignung zum Lackieren und Widerstandspunktschweißen, wobei als Beschichtung ein aluminiumbasierterAccording to the invention, the invention also relates to a method for producing a component, in particular according to claim 1, from press-hardened, based on aluminum coated steel sheet with particular suitability for painting and resistance spot welding, wherein as an aluminum-based coating
Überzug im Schmelztauchverfahren auf das Stahlblech aufgebracht wird, welches dadurch gekennzeichnet ist, Coating is applied to the steel sheet in the hot-dip method, which is characterized
dass das Stahlblech oder Stahlband mit dem Überzug nach dem  that the steel sheet or steel strip with the coating after the
Schmelztauchprozess und vor dem Umformprozess einer Behandlung durch anodische Oxidation und/oder einer Plasmaoxidation und/oder einer  Hot dip process and before the forming process of anodic oxidation treatment and / or plasma oxidation and / or a
Heißwasserbehandlung und/oder einer Behandlung in einer Atmosphäre, die mindestens variable Anteile von Sauerstoff, Wasserdampf unterzogen wird dass die Heißwasserbehandlung oder die Behandlung unter Wasserdampf bei Temperaturen von wenigstens 90 °C, vorteilhaft wenigstens 95 °C, erfolgt dass im Zuge der Behandlung auf der Oberfläche des Überzugs unter Ausbildung von Oxiden oder Hydroxiden eine Aluminiumoxid und/oder - hydroxid enthaltene Deckschicht mit einer Dicke von mindestens 0,05 μm bis höchstens 5μηι ausgebildet wird  Hot water treatment and / or treatment in an atmosphere which is at least variable proportions of oxygen, water vapor is subjected to the hot water treatment or treatment under water vapor at temperatures of at least 90 ° C, preferably at least 95 ° C, carried out in the course of treatment on the Surface of the coating to form oxides or hydroxides an alumina and / or - hydroxide contained cover layer is formed with a thickness of at least 0.05 .mu.m to a maximum of 5μηι
dass das Stahlblech oder Stahlband zumindest bereichsweise auf eine Temperatur oberhalb der Austenitisierungstemperatur erwärmt wird dass das erwärmte Stahlblech oder Stahlband anschließend umgeformt und danach mit einer Geschwindigkeit abgekühlt wird, die zumindest that the steel sheet or steel strip is at least partially heated to a temperature above the Austenitisierungstemperatur that the heated steel sheet or steel strip is then formed and then cooled at a rate that at least
bereichsweise oberhalb der kritischen Abkühlgeschwindigkeit liegt. Im Zusammenhang mit der Erfindung ist der Begriff zumindest bereichsweise im Sinne von örtlichen Abschnitten des behandelten Stahlblechs oder Stahlbandes zu verstehen, so dass ein Stahlblech oder Stahlband mit gezielt örtlich voneinander abweichenden Gefügen und Eigenschaften entstehen. Bevorzugt wird die Deckschicht in einem kontinuierlichen Prozess auf die Oberfläche des Überzugs aufgebracht. in some areas above the critical cooling rate. In the context of the invention, the term is at least partially in the Understand the meaning of local sections of the treated steel sheet or steel strip, so that a steel sheet or steel strip with targeted spatially divergent structures and properties arise. Preferably, the cover layer is applied to the surface of the coating in a continuous process.
Vorteilhafter Weise findet die Behandlung in einer Atmosphäre statt, die auch Anteile basischer Komponenten, vorzugsweise Ammoniak (NH3), primäre, sekundäre oder tertiäre aliphatische Amine (NH2R, NHR2), NR3) enthält. Advantageously, the treatment 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 ).
Verfahrenstechnisch kann eine dünne oxidische Deckschicht vorteilhaft durch anodische Oxidation (Dünnschichteloxieren), Plasmaoxidation und eine Hydroxid enthaltene Deckschicht mittels einer Heißwasserbehandlung der aluminiumbasierten Beschichtung bei Temperaturen von mindestens 90 °C, vorteilhaft mindestens 95 °C und/oder einer Behandlung in Wasserdampf bei Temperaturen von mindestens 90 °C, vorteilhaft mindestens 95 °C hergestellt werden. In terms of process technology, a thin oxidic cover layer can advantageously be obtained by anodic oxidation (thin-film anodization), plasma oxidation and a hydroxide-containing topcoat by means of a hot water treatment of the aluminum-based coating at temperatures of at least 90 ° C, preferably at least 95 ° C and / or a treatment in water vapor at temperatures of at least 90 ° C, advantageously at least 95 ° C are prepared.
Alternativ zur Anodisierung führt auch eine Gasphasenbehandlung der AS-Oberfläche zum gleichen Ziel. Hierzu wird die AS-Oberfläche mit einer Atmosphäre behandelt, die mindestens variable Anteile von Sauerstoff, Wasserdampf, optional auch Anteile basischer Komponenten, insbesondere Ammoniak, primären, sekundären oder tertiären aliphatischen Aminen enthalten kann. Diese Behandlung führt zu einem zeit- bzw. temperaturgesteuerten Wachstum einer Aluminiumoxid und/oder -hydroxid enthaltenen Deckschicht. Weiterhin lässt sich die Zusammensetzung der Gasphase zur Steuerung des Schichtdickenwachstums dieser Deckschicht nutzen. Die As an alternative to anodization, gas phase treatment of the AS surface also leads to the same target. For this purpose, the AS surface is treated with an atmosphere which may contain at least variable proportions of oxygen, water vapor, optionally also fractions of basic components, in particular ammonia, primary, secondary or tertiary aliphatic amines. This treatment leads to a time- or temperature-controlled growth of a cover layer containing aluminum oxide and / or hydroxide. Furthermore, the composition of the gas phase can be used to control the layer thickness growth of this cover layer. The
Behandlung wird bei einer Temperatur von 40 °C bis 100 °C, vorzugsweise 90 C bis 100 °C durchgeführt. Niedrigere Behandlungstemperaturen verlängern die Treatment is carried out at a temperature of 40 ° C to 100 ° C, preferably 90 C to 100 ° C. Lower treatment temperatures extend the
Behandlungsdauer, Behandlungstemperaturen über 100 °C erfordern ggf. Duration of treatment, treatment temperatures above 100 ° C may require
Druckbehälter. Pressure vessel.
Sowohl Anodisierung als auch Gasphasenbehandlung führen zu einer Aluminiumoxid und/oder -hydroxid enthaltenen Deckschicht, die an ihrer Oberfläche netz- oder nadelartige Strukturen aufweist. Die damit verbundene Oberflächenvergrößerung verbessert die Haftung einer nachfolgenden KT-Lackierung. Da längere Erwärmungszeiten zur Ausbildung einer lackierfähigen Oberflächentopografie nicht mehr erforderlich sind, wird zudem der Korrosionsschutz der Beschichtung erhöht. Dies ist damit zu erklären, dass bei einer nur kurzen erforderlichen Glühzeit im Rollenherdofen weniger Diffusion von Aluminium und Eisen stattfindet. Dies führt unter anderem auch zu einer relativ gering ausgebildetenBoth anodization and gas phase treatment lead to a cover layer containing aluminum oxide and / or hydroxide, which has net or needle-like structures on its surface. The associated surface enlargement improves the adhesion of a subsequent KT coating. Since longer heating times are no longer required to form a coatable surface topography, the corrosion protection of the coating is also increased. This can be explained by the fact that less diffusion of aluminum and iron takes place with only a short required annealing time in the roller hearth furnace. Among other things, this leads to a relatively low level of education
Interdiffusionszone. Beispielhaft ist diese für eine AS-Auflage des Ausgangsmaterials von 150 g/m2 (AS150) unterhalb von 7 μm. Interdiffusion zone. By way of example, this is for an AS support of the starting material of 150 g / m 2 (AS150) below 7 μm.
In Versuchen wurden je nach Ofenverweildauer bei Verwendung von Platinen mit einer AS-Auflage von 150 g/m2 auch Dicken der Diffusionszone von unterhalb 5 μm, und sogar unterhalb 4 μm am fertigen Bauteil erzielt. In experiments, depending on the furnace residence time when using boards with an AS coating of 150 g / m 2 and thicknesses of the diffusion zone of below 5 microns, and even below 4 microns achieved on the finished component.
Bei Verwendung von Platinen mit einer AS-Auflage von 80 g/m2 (AS80) ist bekannt, dass sich hier die Ofenzeit auch bei nicht erfindungsgemäßem Überzug geringfügig reduzieren lässt und auch dadurch dünnere Diffusionsschichten von z.B. 5 μm resultieren. Versuche haben gezeigt, dass sich mit der erfindungsgemäßen Lösung die Ofenzeiten auch in diesem Fall noch weiter reduzieren lassen und hierdurch Dicken der Diffusionsschichten von unterhalb 5 μm am fertigen Bauteil erzielt werden können. In weiteren Versuchen konnten durch eine weitere Verkürzung der When using circuit boards with an AS support of 80 g / m 2 (AS80) it is known that the furnace time can be slightly reduced even if the coating is not according to the invention and also result in thinner diffusion layers of eg 5 .mu.m. Experiments have shown that with the solution according to the invention, the furnace times can be reduced even further in this case and, as a result, thicknesses of the diffusion layers of less than 5 μm can be achieved on the finished component. In further experiments could by a further shortening of the
Erwärmzeit im Ofen auch noch geringere Dicken der Diffusionsschichten von unterhalb 3 μm, und sogar unterhalb von 2 μm am fertigen Bauteil erzielt werden. Heating time in the oven even lower thicknesses of the diffusion layers of less than 3 microns, and even be achieved below 2 microns on the finished component.
Bei Einsatz von Platinen mit einer Schichtauflage zwischen AS80 und AS150 und bei Schichtauflagen die kleiner als AS80 sind oder größer als AS150 ergeben sich nach dem Presshärten die Dicken der erfindungsgemäßen Interdiffusionschichten I für eine Schichtauflage des Ausgangsmaterials aus dem linearen Zusammenhang gemäß den folgenden Formeln für verschiedene blechdickenabhängige Erwärmzeiten: When using blanks with a layer overlay between AS80 and AS150 and with layer overlays which are smaller than AS80 or greater than AS150, the thicknesses of the interdiffusion layers I according to the invention for a layer overlay of the starting material resulting from the linear relationship according to the following formulas for various sheet thickness-dependent heating times:
Die notwendige Erwärmzeit im Ofen richtet sich erfindungsgemäß nur nach der Blechdicke, da der erfindungsgemäße Überzug keine Haltezeit im Ofen zur The necessary heating time in the oven depends, according to the invention, only on the sheet thickness, since the coating according to the invention does not have a holding time in the oven
Erzeugung einer lackierfähigen Oberfläche erfordert. Dickere Bleche erfordern für die Erwärmung daher längere Erwärmzeiten als dünnere Bleche.  Creation of a paintable surface required. Thicker sheets therefore require longer heating times for heating than thinner sheets.
Beispielhaft für Bleche mit 1 ,5 mm Dicke sind in Tabelle 1 kurze (220 Sekunden), sehr kurze (180 Sekunden) und äußerst kurze (150 Sekunden) Erwärmzeiten im Vergleich zu üblichen Erwärmzeiten (360 Sekunden) im Rollenherdofen aufgeführt. As an example for sheets with a thickness of 1, 5 mm, Table 1 shows short (220 seconds), very short (180 seconds) and extremely short (150 seconds) heating times in comparison to the usual heating times (360 seconds) in the roller hearth furnace.
Ein weiterer positiver Effekt der kurzen Erwärmzeit ist ein deutlich verringerter Porenanteil in der Legierungsschicht sowie in der Diffusionszone. Poren entstehen bei längeren Glühzeiten z.B. durch den Kirkendall-Effekt. Bei Versuchen wurde festgestellt, dass sich durch die Kurzzeitglühung der Gesamtporenanteil auf werte von weniger als 6 % und sogar auf Werte von unter 4 % bzw. 2 % reduzieren lässt. Was sich z.B. vorteilhaft auf die Schweißeignung auswirken kann. Another positive effect of the short heating time is a significantly reduced pore content in the alloy layer and in the diffusion zone. Pores are formed at longer annealing times, e.g. through the Kirkendall effect. Experiments have shown that short-term annealing reduces the total pore fraction to values of less than 6% and even to values below 4% and 2%, respectively. What is e.g. can have an advantageous effect on the weldability.
Für das Pressformhärten von Platinen mit einer Aluminium-Silizium Beschichtung ist es nun nicht mehr erforderlich, lange Verweilzeiten des Stahlbleches im Ofen einzuhalten. Das Stahlblech muss nur noch auf die erforderliche Umformtemperatur aufgeheizt werden und kann bei Erreichen der Umformtemperatur sofort der For the press-form hardening of boards with an aluminum-silicon coating, it is no longer necessary to maintain long residence times of the steel sheet in the furnace. The steel sheet only has to be heated to the required forming temperature and can reach the forming temperature immediately
Umformpresse zugeführt, umgeformt und abgeschreckt werden. Dadurch können auch vorteilhaft kürzere Rollenherdöfen als die bislang eingesetzten verwendet werden. Darüber hinaus ist die Verwendung von anderen Ofentypen beispielsweise zur induktiven oder konduktiven Schnellerwärmung möglich, ohne dass die erwärmten Platinen zur Ausbildung einer lackierfähigen Oberflächentopografie auf Temperatur gehalten werden müssen. Forming press fed, reshaped and quenched. As a result, also advantageously shorter roller hearth furnaces than those used so far can be used. In addition, the use of other types of furnaces, for example for inductive or conductive rapid heating is possible without the heated boards to form a paintable Surface topography must be kept at temperature.
Weiter ist es nun möglich, Platinen nur partiell zu erwärmen und zu härten, wodurch auch in den Bereichen mit geringem Wärmeeinfluss eine gute Punktschweißbarkeit und KT-Lackhaftung gegeben ist. Furthermore, it is now possible to heat and harden boards only partially, which is also in the areas with low heat influence a good Punktschweißbarkeit and KT paint adhesion is given.
Nachfolgend wird anhand der dargestellten Figuren die Erfindung näher beschrieben. The invention will be described in more detail with reference to the illustrated figures.
Figur 1 zeigt schematisch den Schichtaufbau der Beschichtung an einem Figure 1 shows schematically the layer structure of the coating on a
pressformgehärteten Bauteil mit einer Beschichtung aus AS und üblicher, zurPress-hardened component with a coating of AS and conventional, for
Erzielung einer Durchlegierung des Überzugs mit Eisen, langer Erwärmungszeit nach dem Stand der Technik. Für das Bauteil wurde ein Stahlblech mit einem Überzug aus AS150, also mit einer Schichtauflage des Überzugs von 150 g/m2 verwendet. Auf dem martensitischen Stahlgrundwerkstoff ist eine Interdiffusionszone Fe(AI,Si) mit einer Dicke von 7 bis 14 μm ausgebildet, auf der sich eine Zone mit verschiedenen intermetallischen Phasen (z.B. Fe2SiAl2 und FeAl2) gebildet hat, wobei die einzelnen Phasen in dieser Zone zellenförmig oder auch clusterförmig verteilt auftreten können. Durch die Oxidation im Ofen sowie beim Transfer in die Presse hat sich eine nur sehr dünne Aluminiumoxidschicht mit einer Dicke von weniger als 0,05 μm gebildet. Zu erkennen sind ebenfalls Poren, die sich in den verschiedenen Zonen gebildet haben. Achieving iron-alloy galling, long-term heating time of the prior art. For the component, a steel sheet with a coating of AS150, ie with a coating layer of the coating of 150 g / m 2 was used. On the martensitic steel base material an interdiffusion zone Fe (Al, Si) is formed with a thickness of 7 to 14 microns, on which a zone with different intermetallic phases (eg Fe2SiAl 2 and FeAl 2 ) has formed, with the individual phases in this zone can occur cell-shaped or cluster-shaped distributed. Due to the oxidation in the oven as well as the transfer to the press, a very thin aluminum oxide layer with a thickness of less than 0.05 μm has formed. Also visible are pores that have formed in the different zones.
Figur 2 zeigt im Vergleich dazu den Schichtaufbau einer erfindungsgemäßen FIG. 2 shows, by comparison, the layer structure of an inventive device
Beschichtung an einem pressformgehärteten Bauteil mit einer AS-Beschichtung auf der eine erfindungsgemäße Aluminiumoxid und/oder -hydroxid enthaltene Coating on a press-form-hardened component with an AS coating on which an aluminum oxide and / or hydroxide according to the invention is contained
Deckschicht von mindestens 0,05 μm ausgebildet ist und die mit im Vergleich zum Stand der Technik verkürzten Erwärmzeiten erzeugt wurde. Im Übergangsbereich zwischen Stahlblech und Beschichtung ist eine Interdiffusionszone ausgebildet, in der Aluminium und Silizium in den Stahl hinein diffundiert sind Fe(AI, Si). Durch die nur noch sehr kurze notwendige Erwärmungszeit im Ofen auf Cover layer of at least 0.05 microns is formed and which has been produced with shortened compared to the prior art heating times. In the transition region between steel sheet and coating, an interdiffusion zone is formed, in which aluminum and silicon are diffused into the steel Fe (Al, Si). Due to the only very short necessary heating time in the oven
Austenitisierungstemperatur, weist diese Schicht beispielsweise für AS150 eine Dicke von weniger als 7 μm im Mittel auf. Auf dieser Schicht bildet sich im Zuge der Erwärmung eine weitere Schicht mit verschiedenen intermetallischen Phasen (z.B. Fe2SiAl2 und FeAl2), wobei die einzelnen Phasen in dieser Zone zellenförmig oder auch clusterförmig verteilt auftreten können und, auf der eine Aluminiumoxid und/oder -hydroxid enthaltene Deckschicht in einer mittleren Dicke von mindestens 0,05 μm bis höchstens 5 μm angeordnet ist. Austenitizing, this layer, for example, for AS150 has a thickness of less than 7 microns on average. In the course of the heating, a further layer with different intermetallic phases (eg Fe 2 SiAl 2 and FeAl 2 ) forms on this layer, wherein the individual phases in this zone can occur in a cell-shaped or cluster-shaped manner and on which an aluminum oxide and / or Hydroxide-containing topcoat in an average thickness of at least 0.05 microns to is arranged at most 5 microns.
Figur 3 zeigt grafisch die erfindungsgemäße Dicke I der Interdiffusionszone für eine Schichtauflage des Ausgangsmaterials zwischen 50 g/m2 und 180 g/m2 nach dem folgenden Zusammenhang: FIG. 3 shows graphically the thickness I of the interdiffusion zone according to the invention for a layer coverage of the starting material between 50 g / m 2 and 180 g / m 2 according to the following relationship:
Tabelle 1 fasst Versuche zur Lackhaftung (automobiltypische  Table 1 summarizes attempts to paint adhesion (automobiltypische
Phosphatierungsbehandlung und kathodische Tauchlackierung; Prüfung nach 72 Stunden Kondenswasser-Konstantklima gemäß DIN EN ISO 6270-2:2005 CH) und Schweißeignung (Widerstandspunktschweißen) pressgehärteter AS 150-Proben bei 940 °C Ofentemperatur und verschiedenen Erwärmzeiten zusammen. Die Blechdicke der Proben beträgt 1 ,5 mm. Zu erkennen ist, dass sich nur eine gute Lackhaftung und Schweißeignung bei Erwärmzeiten von 220 s und weniger ergibt, wenn  Phosphating treatment and cathodic dip painting; Testing after 72 hours condensate constant climate according to DIN EN ISO 6270-2: 2005 CH) and welding suitability (resistance spot welding) of press-hardened AS 150 samples at 940 ° C oven temperature and different heating times together. The sheet thickness of the samples is 1, 5 mm. It can be seen that only a good paint adhesion and weldability results in heating times of 220 s and less, if
eineerfindungsgemäße Aluminiumoxid und/oder -hydroxid enthaltene Deckschicht vorhanden ist. Bei kurzen Erwärmzeiten von 220 s und weniger ergaben sich darüber hinaus Interdiffusionsschichten von weniger als 7 μm am pressgehärteten Bauteil. Bei den nicht erfindungsgemäßen langen Erwärmzeiten von 360 s nach dem Stand der Technik, ist hingegen auf Grund der Durchlegierung des Überzugs mit Eisen auch bei den Proben ohne die erfindungsgemäße Aluminiumoxid und/oder -hydroxid enthaltene Deckschicht eine gute Lackhaftung und Schweißeignung gegeben. Die Dicke der Interdiffusionsschichten liegt nach 360 s Erwärmzeit deutlich über 7 μm. an inventive cover layer 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 μm on the press-hardened component. In contrast to the non-inventive long heating times of 360 s according to the prior art, on the other hand due to the alloying of the coating with iron, a good paint adhesion and weldability is also provided in the samples without the cover layer containing the aluminum oxide and / or hydroxide according to the invention. The thickness of the interdiffusion layers is significantly above 7 μm after a heating time of 360 s.

Claims

Patentansprüche claims
1 . Bauteil aus pressformgehärtetem, auf Basis von Aluminium beschichtetem 1 . Component of press-hardened, aluminum-coated
Stahlblech, wobei die Beschichtung einen im Schmelztauchverfahren aufgebrachten Überzug aufweist, der Aluminium und Silizium enthält, welches dadurch  Sheet steel, wherein the coating has a hot-dip coating containing aluminum and silicon, which thereby
gekennzeichnet ist, dass das pressformgehärtete Bauteil im Übergangsbereich zwischen Stahlblech und Überzug eine Interdiffusionszone I aufweist, wobei abhängig von der Schichtauflage des Überzugs vor Erwärmung und Presshärtung die Dicke der Interdiffusionszone I folgender Formel  characterized in that the press-form-hardened component has an interdiffusion zone I in the transition region between the steel sheet and the coating, the thickness of the interdiffusion zone I of the following formula being dependent on the coating layer of the coating before heating and press-hardening
gehorcht, auf der Interdiffusionszone I eine Zone mit verschiedenen intermetallischen Phasen mit einer mittleren Gesamtdicke zwischen 8 und 50 μm ausgebildet ist, auf der wiederum eine Aluminiumoxid und/oder -hydroxid enthaltende Deckschicht in einer mittleren Dicke von mindestens 0,05 μm bis höchstens 5 μm angeordnet ist.  obeys, on the interdiffusion zone I, a zone with different intermetallic phases is formed with an average total thickness between 8 and 50 .mu.m, on which in turn a cover layer containing alumina and / or hydroxide in an average thickness of at least 0.05 .mu.m to at most 5 .mu.m is arranged.
2. Bauteil nach Anspruch 1 , dadurch gekennzeichnet, dass abhängig von der aktuellen Schichtauflage des Ausgangsmaterials die Dicke der Interdiffusionszone I gemäß folgender Formel 2. Component according to claim 1, characterized in that, depending on the current layer layer of the starting material, the thickness of the interdiffusion zone I according to the following formula
ausgebildet ist. is trained.
3. Bauteil nach Anspruch 1 , dadurch gekennzeichnet, dass abhängig von der aktuellen Schichtauflage des Ausgangsmaterials die Dicke der Interdiffusionszone I gemäß folgender Formel 3. Component according to claim 1, characterized in that, depending on the current layer layer of the starting material, the thickness of the interdiffusion zone I according to the following formula
ausgebildet ist. is trained.
4. Bauteil nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die mittlere Schichtdicke der Deckschicht mindestens 0,10 μm und höchstens 3,0 μm beträgt. 4. Component according to at least one of claims 1 to 3, characterized in that the average layer thickness of the cover layer is at least 0.10 microns and at most 3.0 microns.
5. Bauteil nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die mittlere Schichtdicke der Deckschicht mindestens 0,15 μm und höchstens 1 ,0 μm beträgt. 5. Component according to at least one of claims 1 to 3, characterized in that the average layer thickness of the cover layer is at least 0.15 microns and at most 1, 0 microns.
6. Bauteil nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Überzug eine Gesamtporosität von weniger als 6 %, vorteilhaft weniger als6. Component according to at least one of claims 1 to 5, characterized in that the coating has a total porosity of less than 6%, advantageously less than
4 % und optimal weniger als 2 % aufweist. 4% and optimally less than 2%.
7. Bauteil nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Überzug des Stahlbleches in einem Schmelzbad mit einem Si-Gehalt von 8 bis 12 Gewichts-%, einem Fe-Gehalt von 1 bis 4 Gewichts-%, Rest Aluminium und nicht vermeidbare Verunreinigungen hergestellt wurde. 7. Component according to at least one of claims 1 to 6, characterized in that the coating of the steel sheet 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 and unavoidable impurities were produced.
8. Verfahren zur Herstellung eines Bauteils aus pressformgehärtetem, auf Basis von Aluminium beschichtetem Stahlblech oder Stahlband mit besonderer Eignung zum Lackieren und Widerstandspunktschweißen, wobei als Beschichtung ein 8. A method for producing a component from press-hardened, based on aluminum coated steel sheet or steel strip with particular suitability for painting and resistance spot welding, wherein as a coating
aluminiumbasierter Überzug im Schmelztauchverfahren auf das Stahlblech oder Stahlband aufgebracht wird, dadurch gekennzeichnet,  aluminum-based coating is applied to the steel sheet or steel strip in the hot-dip method, characterized in that
dass das Stahlblech oder Stahlband mit dem Überzug nach dem  that the steel sheet or steel strip with the coating after the
Schmelztauchprozess und vor dem Umformprozess einer Behandlung durch anodische Oxidation und/oder einer Plasmaoxidation und/oder einer Hot dip process and before the forming process of anodic oxidation treatment and / or plasma oxidation and / or a
Heißwasserbehandlung und/oder einer Behandlung in einer Atmosphäre, die mindestens variable Anteile von Sauerstoff, Wasserdampf enthält, unterzogen wird Hot water treatment and / or treatment in an atmosphere containing at least variable amounts of oxygen, water vapor is subjected
dass die Heißwasserbehandlung oder die Behandlung unter Wasserdampf bei Temperaturen von wenigstens 90 °C, vorteilhaft wenigstens 95 °C, erfolgt dass im Zuge der Behandlung auf der Oberfläche des Überzugs unter Ausbildung von Oxiden oder Hydroxiden eine Aluminiumoxid und/oder - hydroxid enthaltene Deckschicht mit einer Dicke von mindestens 0,05 μm bis höchstens 5μηι ausgebildet wird  in that the hot water treatment or the treatment under steam at temperatures of at least 90 ° C., advantageously at least 95 ° C., takes place in the course of the treatment on the surface of the coating to form oxides or hydroxides an aluminum oxide and / or hydroxide containing top layer with a Thickness of at least 0.05 microns to a maximum of 5μηι is formed
dass das Stahlblech oder Stahlband zumindest bereichsweise auf eine Temperatur oberhalb der Austenitisierungstemperatur erwärmt wird dass das erwärmte Stahlblech oder Stahlband anschließend umgeformt und danach mit einer Geschwindigkeit abgekühlt wird, die zumindest bereichsweise oberhalb der kritischen Abkühlgeschwindigkeit liegt. that the steel sheet or steel strip at least partially on one Temperature is heated above the Austenitisierungstemperatur that the heated steel sheet or steel strip is then formed and then cooled at a rate that is at least partially above the critical cooling rate.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass die Deckschicht in einem kontinuierlichen Prozess auf die Oberfläche des Überzugs aufgebracht wird. 9. The method according to claim 8, characterized in that the cover layer is applied in a continuous process on the surface of the coating.
10. Verfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass abhängig von der aktuellen Schichtauflage des Ausgangsmaterials die Dicke der Interdiffusionszone10. The method according to claim 8 or 9, characterized in that depending on the current layer of the starting material, the thickness of the interdiffusion zone
I gemäß folgender Formel I according to the following formula
ausgebildet ist, darauf eine Zone mit verschiedenen intermetallischen Phasen mit einer Dicke zwischen 8 und 50 μm ausgebildet wird.  is formed on a zone with different intermetallic phases is formed with a thickness between 8 and 50 microns.
1 1. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass abhängig von der aktuellen Schichtauflage des Ausgangsmaterials die Dicke der Interdiffusionszone I gemäß folgender Formel 35 1 1. A method according to claim 10, characterized in that depending on the current coating layer of the starting material, the thickness of the interdiffusion zone I according to the following formula 35
ausgebildet wird.  is trained.
12. Verfahren nach Anspruch 1 1 , dadurch gekennzeichnet, dass abhängig von der aktuellen Schichtauflage des Ausgangsmaterials die Dicke der Interdiffusionszone I gemäß folgender Formel 12. The method according to claim 1 1, characterized in that depending on the current layer of the starting material, the thickness of the interdiffusion zone I according to the following formula
ausgebildet wird.  is trained.
13. Verfahren nach einem der Ansprüche 8 bis 12, dadurch gekennzeichnet, dass die Behandlung in einer Atmosphäre stattfindet, die auch Anteile basischer 13. The method according to any one of claims 8 to 12, characterized in that the treatment takes place in an atmosphere which also shares basic
Komponenten, vorzugsweise Ammoniak (NH3), primäre, sekundäre oder tertiäre aliphatische Amine (NH2R, NHR2) enthält. Components, preferably ammonia (NH3), primary, secondary or tertiary aliphatic amines (NH 2 R, NHR 2 ) contains.
14. Verwendung eines Bauteils nach den Ansprüchen 1 bis 7 zur Herstellung von Kraftfahrzeugen. 14. Use of a component according to claims 1 to 7 for the production of motor vehicles.
EP17721056.4A 2016-04-18 2017-04-13 Method for producing such a component made of press-form-hardened, aluminum-based coated steel sheet Active EP3250727B2 (en)

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DE102016107152.8A DE102016107152B4 (en) 2016-04-18 2016-04-18 Component of press-hardened aluminum-coated steel sheet and method for producing such a component and its use
PCT/EP2017/058918 WO2017182382A1 (en) 2016-04-18 2017-04-13 Component made of press-form-hardened, aluminum-based coated steel sheet, and method for producing such a component

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CN109477197B (en) 2021-10-26
WO2017182382A1 (en) 2017-10-26
EP3250727B1 (en) 2021-07-07
KR20190003502A (en) 2019-01-09
EP3250727B2 (en) 2024-01-17
US20200308708A1 (en) 2020-10-01
US11339479B2 (en) 2022-05-24
KR102189424B1 (en) 2020-12-11
DE102016107152B4 (en) 2017-11-09
DE102016107152A1 (en) 2017-10-19
CN109477197A (en) 2019-03-15

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