EP3925713A1 - Skin pass rolled and coated steel sheet and method for producing the same - Google Patents

Skin pass rolled and coated steel sheet and method for producing the same Download PDF

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Publication number
EP3925713A1
EP3925713A1 EP21178807.0A EP21178807A EP3925713A1 EP 3925713 A1 EP3925713 A1 EP 3925713A1 EP 21178807 A EP21178807 A EP 21178807A EP 3925713 A1 EP3925713 A1 EP 3925713A1
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EP
European Patent Office
Prior art keywords
steel sheet
coating
metallic coating
skin
surface structure
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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
EP21178807.0A
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German (de)
French (fr)
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EP3925713B1 (en
Inventor
Burak William Cetinkaya
Dr. Fabian Junge
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ThyssenKrupp Steel Europe AG
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ThyssenKrupp Steel Europe AG
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Publication of EP3925713A1 publication Critical patent/EP3925713A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B1/227—Surface roughening or texturing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B2001/228—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length skin pass rolling or temper rolling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
    • B21B2001/383—Cladded or coated products

Definitions

  • the invention relates to a steel sheet dressed with a deterministic surface structure and coated with a metallic coating, as well as a method for its production.
  • gas phase deposition for example in physical gas phase deposition
  • a starting material is converted into the gas phase with the aid of physical processes (laser, temperature, ion bombardment) and then made to condense on a surface.
  • laser, temperature, ion bombardment the aid of physical processes
  • many materials and material combinations in the form of a wide variety of layer structures can be applied to a surface in an advantageous manner.
  • zinc-, aluminum-based layers and high-melting layers for example for hot forming, are of particular interest.
  • a disadvantage of these layers is the directional application, i.e. the material always comes from a fixed angle as long as the material is not rotated.
  • Gas phase deposition is economical for the steel industry when a high throughput can take place as quickly as possible, so that the material (sheet steel) is fed and coated in the form of a strip or sheet, so that the layers are applied depending on the direction.
  • the surface structure can form areas of undercuts and / or depressions in which irregular deposition can occur, since the coating material cannot get into the "blind" areas.
  • Electrolytically and hot-dip coated surfaces are no problem with corresponding surface structures, since both the aqueous electrolyte and the liquid melt can reach all corresponding areas.
  • the skin pass leads to push-ups, undercuts, steep flanks, breaks and / or roughening on the surface of the sheet steel. Since the step of skin pass is usually a necessary step before coating, in order to preferably set the mechanical parameters in the steel sheet and to ensure a sufficiently large surface for the coating but also for the downstream processes (oiling, etc.), irregular surfaces can be used Many points and undercuts can hardly be avoided, which in turn can have a negative effect on coating by vapor deposition. It is therefore a great challenge to design dressed surfaces in such a way that optimal and homogeneous coating by means of gas phase deposition, in particular in a direction-independent manner, is possible.
  • the task is therefore to provide a steel sheet coated with a deterministic surface structure, which enables an optimal and homogeneous coating by gas phase deposition.
  • the object is achieved in relation to a steel sheet with the features of claim 1 and in relation to a method with the features of claim 5.
  • the provision of a defined surface structure on a dressed steel sheet is essential for the coating by gas phase deposition and an application of a metallic coating that is as homogeneous as possible on the dressed steel sheet.
  • the inventors have found that it is advantageous if the surface structure is embossed into the steel sheet starting from a surface of the steel sheet, the surface structure having a flank area which extends from the surface to a valley area, the flank area being perpendicular to the Steel sheet is formed with an angle, and the steel sheet is coated with a metallic coating that, according to the invention, the angle is formed between 20 ° and 85 ° and the coating is applied by a gas phase deposition.
  • a defined setting of the angle between the flank area and the perpendicular of the steel sheet can be used to influence a homogeneous deposition in a targeted manner, in particular by consciously modeling the flank area.
  • the technology described and the possibility of laser structuring of defined structures on a skin-pass roller it is possible to design the shape of the skin-pass mark in such a way that a positive impression on the skin-pass roller is generated by acting on the surface of a steel sheet to form a negative impression and thus the deterministic surface structure on the steel sheet that a surface structure is provided which is optimally suited for coating by vapor deposition.
  • the skin pass roller is designed in such a way that flank areas that are as flat and slow as possible and, in particular, no steep or no vertical flank areas, in particular relating to all directions, are impressed on the surface of the steel sheet.
  • bulges and / or undercuts in the (negative) skin-pass impression are essentially avoided, so that the deposit can be distributed without obstacles on the surface and in the skin-pass impression.
  • a deterministic surface structure is understood to mean recurring surface structures which have a defined shape and / or configuration, cf. EP 2 892 663 B1 .
  • this also includes surfaces with a (quasi-) stochastic appearance, which, however, are applied using a deterministic texturing process and are thus composed of deterministic form elements.
  • Sheet steel is generally to be understood as a flat steel product which can be provided in sheet form or in blank form or in strip form.
  • the metallic coating can be based on zinc or aluminum.
  • base means that more than 50% by weight of the coating consists of zinc or aluminum.
  • the coating can also consist only of zinc together with unavoidable impurities or only of aluminum together with unavoidable impurities.
  • Further chemical elements such as magnesium, iron, silicon, manganese, nickel, chromium and / or zirconium can be added individually or in combination in order to improve the properties of the coating.
  • zinc-aluminum combination (along with unavoidable impurities) with or without further chemical elements conceivable.
  • high-melting coatings in particular iron-based coatings, can also be applied.
  • Coating by vapor deposition takes place in a conventional manner and is familiar to the person skilled in the art.
  • the surface structure has a flank area which, starting from the surface, extends to a valley area and is formed at an angle between 30 ° and 85 ° to the perpendicular of the steel sheet.
  • the angle can particularly preferably be formed between 35 ° and 85 °.
  • the valley and flank area (negative shape) of the surface structure essentially corresponds to the surface (positive shape) on a skin pass roller, which forms or impresses the surface structure by corresponding action on the steel sheet.
  • the flank area surrounding and forming the surface structure, together with the valley area connected in one piece to the flank area defines a closed volume of the surface structure embossed in the steel sheet by means of skin-passaging.
  • the closed volume the so-called empty volume, can contain a process medium to be applied, for example oil, for later processing by means of a forming process.
  • the geometric design (size and depth) of a deterministic surface structure (negative shape) on a tempered steel sheet depends in particular on how the corresponding geometric structure (positive shape) is designed on a skin-pass roller.
  • Laser texturing processes are preferably used in order to be able to set specific structures (positive shape) on the surface of a skin-pass roller by removing material.
  • targeted control of the energy, the pulse duration and the selection of a suitable wavelength of a laser beam acting on the surface of the skin-pass roller can have a positive influence on the design of the structure (s). With high or higher pulse duration increases the interaction time of the laser beam and skin-pass roller surface and more material can be removed from the surface of the skin-pass roller.
  • a pulse leaves an essentially circular crater on the skin-pass roller surface, which, in the case of several craters, after the skin-pass process, maps the surface or the area of the elevations on the steel sheet and thus the contact area between the steel sheet and the shaping skin-pass roller.
  • a reduction in the pulse duration has an influence on the formation of a crater; in particular, the diameter of the crater can be reduced.
  • any inclines (angles) of the flank area can be set in a targeted manner in the flank area.
  • the steel sheet can be coated with a further metallic coating, which is arranged below the metallic coating applied by gas phase deposition, thus being applied directly to the steel sheet.
  • the further metallic coating is applied by hot-dip coating.
  • the further metallic coating is a zinc-based coating.
  • the further metallic coating can preferably contain additional elements such as aluminum with a content of up to 5% by weight and / or magnesium with a content of up to 5% by weight in the further metallic coating.
  • Steel sheets with a zinc-based coating have very good cathodic corrosion protection, which has been used in automotive engineering for years.
  • the coating also has magnesium with a content of at least 0.3% by weight, in particular at least 0.6% by weight, preferably at least 0.9% by weight.
  • magnesium can be present with a content of at least 0.3 wt essentially to prevent coated steel sheet so that the positive corrosion properties are retained.
  • a thickness of the further metallic coating can be between 1 and 15 ⁇ m, in particular between 2 and 12 ⁇ m, preferably between 3 and 10 ⁇ m.
  • hot-melt exchange coating the steel sheets are first coated with a corresponding additional metallic coating and then passed on to skin-pass molding. The skin pass takes place after the hot dip coating of the steel sheet.
  • the steel sheet can be coated with a further metallic coating, which is arranged below the metallic coating applied by vapor deposition, and thus applied directly to the steel sheet.
  • the further metallic coating is applied by electrolytic coating.
  • a thickness of the further metallic coating can be between 1 and 10 ⁇ m, in particular between 1.5 and 8 ⁇ m, preferably between 2 and 5 ⁇ m.
  • the steel sheet can first be skin-passed and then electrolytically coated.
  • the angle in the flank area can essentially also be retained after the electrolytic coating.
  • an electrolytic coating with subsequent skin-passing is also conceivable.
  • the further metallic coating can be applied subsequently to the metallic coating that has already been applied by gas phase deposition, so that, for example, the metallic coating applied to the steel sheet by gas phase deposition can function as a quasi "adhesion promoter" or "interface" for further metallic coatings in order to In particular, to make steel sheet surfaces that are poorly wettable, for example hot-dip-coatable, capable of applying the further metallic coating. Poorly wettable steel sheets are, for example, high-alloy steel materials that are familiar to the person skilled in the art.
  • the further metallic coating, which is applied to the metallic coating by vapor deposition is preferably applied by hot-dip coating.
  • the further metallic coating can also be applied by electrolytic coating.
  • the surface (positive shape) of the skin pass roller forms a surface structure through the action of force on the surface of the steel sheet, which defines a valley and flank area (negative shape) and essentially corresponds to the surface (positive shape) of the skin pass roller.
  • the skin pass roller for the formation of a deterministic surface structure can be processed with suitable means, for example with a laser, see also EP 2 892 663 B1 .
  • removal methods can also be used to adjust a surface on a skin-pass roller, for example cutting production methods with geometrically defined or indefinite cutting edges, chemical or electrochemical, optical or plasma-induced methods which are suitable for converting a steel sheet to be skin-dressed with a surface structure , which at least in the flank area has an angle to the perpendicular of the surface of the steel sheet between 20 ° and 85 °.
  • FIGs 1a) and 2a Sketched steel sheets (1) with a deterministic surface structure (2) are shown in schematic partial sectional views.
  • the steel sheets (1) which are provided in sheet form or preferably in the form of a strip, are coated with a metallic coating (1.2), the application of the metallic coating (1.2) taking place by vapor deposition in a suitable device.
  • the example shown shows schematically a physical vapor phase deposition (4), with corresponding coating material such as zinc, aluminum and the like being converted into the gas phase (4.1) and being in the form of a metallic coating (1.2) on the surface (1.1) of the steel sheet ( 1) separates, in particular condenses.
  • the difference between the versions in Figure 1a) and Figure 2a ) is that the sheet steel (1) in the Figure 2a ) with an angle ( ⁇ ) between 20 ° and 85 ° between the flank area (2.3) and the vertical (O) of the steel sheet (1) has been set according to the invention.
  • the surface structure (2) is embossed into the steel sheet (1) starting from a surface (1.1) of the steel sheet (1), the surface structure (2) having a flank area (2.3) which, starting from the surface (1.1) up to a Valley area (2.2) runs.
  • the flank area (2.3) and the valley area (2.2) through the corresponding area (positive shape) on the not shown Skin pass roller set.
  • the flank area (2.3) surrounding and forming the surface structure (2) defines, together with the valley area (2.2) integrally connected to the flank area (2.3), a closed volume of the surface structure (2) embossed in the sheet steel (1) by means of skin-passaging.
  • coating defects can occur in the areas or flanks in the surface structure (2) which, in relation to the transport direction (T), are at an unfavorable angle to the gas phase deposition (4) during the deposition, cf. Figure 1a ).
  • the angle ( ⁇ ) is specifically formed between 20 ° and 85 °.
  • the angle ( ⁇ ) was set at approx. 50 ° and it is easy to see that there are no coating defects and that a dressed steel sheet (1) can be coated with a homogeneous metallic coating (1.2) by vapor deposition, with an essentially flat transition between the valley area (2.2) and the surface (1.1) surrounding the valley areas (2.2) can be set essentially without undercuts and other disruptive obstacles, cf. Figure 2b ).
  • the specific setting of the deterministic surface structure (2) can promote a direction-independent deposition.
  • a further metallic coating is symbolically indicated, which can optionally be applied, for example, by hot-dip coating or by electrolytic coating before coating by gas phase deposition or, alternatively, optionally applied after coating by gas phase deposition.

Abstract

Die Erfindung betrifft ein mit einer deterministischen Oberflächenstruktur (2) dressiertes und mit einem metallischen Überzug (1.2) beschichtetes Stahlblech (1) sowie ein Verfahren zu seiner Herstellung.The invention relates to a steel sheet (1) tempered with a deterministic surface structure (2) and coated with a metallic coating (1.2) and to a method for its production.

Description

Die Erfindung betrifft ein mit einer deterministischen Oberflächenstruktur dressiertes und mit einem metallischen Überzug beschichtetes Stahlblech sowie ein Verfahren zu seiner Herstellung.The invention relates to a steel sheet dressed with a deterministic surface structure and coated with a metallic coating, as well as a method for its production.

Aus dem Stand der Technik sind gattungsgemäße mit einer deterministischen Oberflächenstruktur dressierte Stahlbleche bekannt, s. zum Beispiel Patentschrift EP 2 892 663 B1 . Des Weiteren sind gattungsgemäße dressierte Stahlbleche auch in den Offenlegungsschiften DE 10 2019 214 133 A1 , DE 10 2019 214 135 A1 , DE 10 2019 214 136 A1 und DE 10 2019 215 580 A1 der Anmelderin beschrieben. Aus der Offenlegungsschrift DE 10 2012 112 109 A1 ist ferner ein mit einem Muster texturiertes und mit einer PVD-Beschichtung beschichtetes Stahlblech bekannt.From the prior art, generic steel sheets dressed with a deterministic surface structure are known, see for example patent specification EP 2 892 663 B1 . Furthermore, generic shelled steel sheets are also in the laid-open documents DE 10 2019 214 133 A1 , DE 10 2019 214 135 A1 , DE 10 2019 214 136 A1 and DE 10 2019 215 580 A1 described by the applicant. From the published patent application DE 10 2012 112 109 A1 a steel sheet textured with a pattern and coated with a PVD coating is also known.

Bei der Gasphasenabscheidung (CVD, PVD), beispielsweise bei der physikalischen Gasphasenabscheidung wird ein Ausgangsmaterial mit Hilfe physikalischer Verfahren (Laser, Temperatur, lonenbeschuss) in die Gasphase überführt und anschließend auf einer Oberfläche zum Kondensieren gebracht. Dadurch können in vorteilhafter Weise viele Materialien und Materialkombinationen in Form unterschiedlichster Schichtaufbauten auf eine Oberfläche appliziert werden. Für die Stahlindustrie mit dem Fokus Automobilbau sind vor allem zink-, aluminiumbasierte Schichten und hochschmelzende Schichten beispielsweise für die Warmumformung interessant. Ein Nachteil dieser Schichten ist die richtungsbedingte Applikation, d.h. das Material kommt immer aus einem festgelegten Winkel, solange das Material nicht rotiert wird. Wirtschaftlich für die Stahlindustrie ist die Gasphasenabscheidung dann, wenn ein hoher Durchsatz schnellstmöglich erfolgen kann, so dass das Material (Stahlblech) band- oder blechförmig zugeführt und beschichtet wird, somit die Applikation der Schichten richtungsbedingt durchgeführt wird.In gas phase deposition (CVD, PVD), for example in physical gas phase deposition, a starting material is converted into the gas phase with the aid of physical processes (laser, temperature, ion bombardment) and then made to condense on a surface. As a result, many materials and material combinations in the form of a wide variety of layer structures can be applied to a surface in an advantageous manner. For the steel industry with a focus on automotive engineering, zinc-, aluminum-based layers and high-melting layers, for example for hot forming, are of particular interest. A disadvantage of these layers is the directional application, i.e. the material always comes from a fixed angle as long as the material is not rotated. Gas phase deposition is economical for the steel industry when a high throughput can take place as quickly as possible, so that the material (sheet steel) is fed and coated in the form of a strip or sheet, so that the layers are applied depending on the direction.

Nachteilig können beim Beschichten durch Gasphasenabscheidung auf der Oberfläche der Stahlbleche, insbesondere auf mit einer Oberflächenstruktur dressierte Stahlbleche, durch ungünstige Ausgestaltung der Oberflächenstruktur Beschichtungsfehler entstehen. Die Oberflächenstruktur kann Bereiche von Hinterschneidungen und/oder Vertiefungen ausbilden, in welchen es zu einem unregelmäßigen Abscheiden kommen kann, da das Beschichtungsmaterial nicht in die "blinden" Bereiche gelangen kann. Im Fall von herkömmlichen elektrolytisch- und schmelztauch-beschichteten Oberflächen sind entsprechende Oberflächenstrukturen kein Problem, da sowohl der wässrige Elektrolyt, als auch die flüssige Schmelze alle entsprechenden Bereiche erreichen kann.When coating by gas phase deposition on the surface of the steel sheets, in particular on steel sheets coated with a surface structure, coating defects can disadvantageously arise due to an unfavorable design of the surface structure. The surface structure can form areas of undercuts and / or depressions in which irregular deposition can occur, since the coating material cannot get into the "blind" areas. In the case of conventional Electrolytically and hot-dip coated surfaces are no problem with corresponding surface structures, since both the aqueous electrolyte and the liquid melt can reach all corresponding areas.

Durch das Dressieren kommt es auf der Oberfläche des Stahlblechs zu Aufschiebungen, Hinterschneidungen, steilen Flanken, Brüchen und/oder Aufrauhungen. Da der Schritt des Dressierens in der Regel vor dem Beschichten ein notwendiger Schritt ist, um vorzugsweise die mechanischen Kennwerte im Stahlblech einzustellen und eine ausreichend große Oberfläche für den Überzug aber auch die nachgelagerten Prozesse (Beölen etc.) zu gewährleisten, lassen sich unregelmäßige Oberflächen mit vielen Spitzen und Hinterschneidungen kaum vermeiden, was sich wiederum negativ auf das Beschichten durch Gasphasenabscheidung ausüben kann. Daher ist es eine große Herausforderung, dressierte Oberflächen so zu gestalten, dass ein optimales und homogenes Beschichten durch Gasphasenabscheidung, insbesondere richtungsunabhängig, möglich wird.The skin pass leads to push-ups, undercuts, steep flanks, breaks and / or roughening on the surface of the sheet steel. Since the step of skin pass is usually a necessary step before coating, in order to preferably set the mechanical parameters in the steel sheet and to ensure a sufficiently large surface for the coating but also for the downstream processes (oiling, etc.), irregular surfaces can be used Many points and undercuts can hardly be avoided, which in turn can have a negative effect on coating by vapor deposition. It is therefore a great challenge to design dressed surfaces in such a way that optimal and homogeneous coating by means of gas phase deposition, in particular in a direction-independent manner, is possible.

Die Aufgabe ist daher, ein mit einer deterministischen Oberflächenstruktur dressiertes Stahlblech zur Verfügung zu stellen, welches ein optimales und homogenes Beschichten durch Gasphasenabscheidung ermöglicht.The task is therefore to provide a steel sheet coated with a deterministic surface structure, which enables an optimal and homogeneous coating by gas phase deposition.

Die Aufgabe wird in Bezug auf ein Stahlblech mit den Merkmalen des Patentanspruchs 1 und in Bezug auf ein Verfahren mit den Merkmalen des Patentanspruchs 5 gelöst.The object is achieved in relation to a steel sheet with the features of claim 1 and in relation to a method with the features of claim 5.

Die Bereitstellung einer definierten Oberflächenstruktur auf einem dressierten Stahlblech ist wesentlich für das Beschichten durch Gasphasenabscheidung und einem Applizieren eines möglichst homogenen metallischen Überzugs auf dem dressierten Stahlblech. Die Erfinder haben festgestellt, dass es von Vorteil ist, wenn die Oberflächenstruktur ausgehend von einer Oberfläche des Stahlblechs in das Stahlblech eingeprägt ist, wobei die Oberflächenstruktur einen Flankenbereich aufweist, welcher ausgehend von der Oberfläche bis zu einem Talbereich verläuft, wobei der Flankenbereich zur Senkrechten des Stahlblechs mit einem Winkel ausgebildet ist, und das Stahlblech mit einem metallischen Überzug beschichtet ist, dass erfindungsgemäß der Winkel zwischen 20° und 85° ausgebildet ist und der Überzug durch eine Gasphasenabscheidung aufgebracht ist.The provision of a defined surface structure on a dressed steel sheet is essential for the coating by gas phase deposition and an application of a metallic coating that is as homogeneous as possible on the dressed steel sheet. The inventors have found that it is advantageous if the surface structure is embossed into the steel sheet starting from a surface of the steel sheet, the surface structure having a flank area which extends from the surface to a valley area, the flank area being perpendicular to the Steel sheet is formed with an angle, and the steel sheet is coated with a metallic coating that, according to the invention, the angle is formed between 20 ° and 85 ° and the coating is applied by a gas phase deposition.

Durch eine definierte Einstellung des Winkels zwischen Flankenbereich und Senkrechten des Stahlblechs kann gezielt Einfluss auf eine homogene Abscheidung genommen werden, insbesondere durch bewusste Modellierung des Flankenbereichs.A defined setting of the angle between the flank area and the perpendicular of the steel sheet can be used to influence a homogeneous deposition in a targeted manner, in particular by consciously modeling the flank area.

Mit der in der EP 2 892 663 B1 beschriebenen Technologie und Möglichkeit zum Laserstrukturieren von definierten Strukturen auf einer Dressierwalze ist es möglich, die Form des Dressierabdrucks so zu gestalten, dass ein Positivabdruck auf der Dressierwalze durch Einwirken auf die Oberfläche eines Stahlblechs zu einem Negativabdruck und somit die deterministische Oberflächenstruktur auf dem Stahlblech erzeugt wird, dass eine Oberflächenstruktur bereitgestellt wird, welche sich optimal für das Beschichten durch Gasphasenabscheidung eignet. Hierfür wird die Dressierwalze so gestaltet, dass sich möglichst flache und langsam auslaufende und insbesondere keine steilen respektive keine senkrechten Flankenbereiche, insbesondere alle Richtungen betreffend, auf der Oberfläche des Stahlblechs eindrücken. Dementsprechend werden Aufwürfe und/oder Hinterschneidungen im (negativen) Dressierabdruck im Wesentlichen vermieden, sodass das Abscheiden ohne Hindernisse auf der Oberfläche und sich im Dressierabdruck verteilen kann.With the in the EP 2 892 663 B1 The technology described and the possibility of laser structuring of defined structures on a skin-pass roller, it is possible to design the shape of the skin-pass mark in such a way that a positive impression on the skin-pass roller is generated by acting on the surface of a steel sheet to form a negative impression and thus the deterministic surface structure on the steel sheet that a surface structure is provided which is optimally suited for coating by vapor deposition. For this purpose, the skin pass roller is designed in such a way that flank areas that are as flat and slow as possible and, in particular, no steep or no vertical flank areas, in particular relating to all directions, are impressed on the surface of the steel sheet. Correspondingly, bulges and / or undercuts in the (negative) skin-pass impression are essentially avoided, so that the deposit can be distributed without obstacles on the surface and in the skin-pass impression.

Unter deterministischer Oberflächenstruktur sind wiederkehrende Oberflächenstrukturen zu verstehen, welche eine definierte Form und/oder Ausgestaltung aufweisen, vgl. EP 2 892 663 B1 . Insbesondere gehören hierzu zudem Oberflächen mit einer (quasi-)stochastischen Anmutung, die jedoch mittels eines deterministischen Texturierungsverfahrens aufgebracht werden und sich somit aus deterministischen Formelementen zusammensetzen.A deterministic surface structure is understood to mean recurring surface structures which have a defined shape and / or configuration, cf. EP 2 892 663 B1 . In particular, this also includes surfaces with a (quasi-) stochastic appearance, which, however, are applied using a deterministic texturing process and are thus composed of deterministic form elements.

Unter Stahlblech ist allgemein ein Stahlflachprodukt zu verstehen, welches in Blechform bzw. in Platinenform oder in Bandform bereitgestellt werden kann.Sheet steel is generally to be understood as a flat steel product which can be provided in sheet form or in blank form or in strip form.

Der metallische Überzug kann auf Zink- oder Aluminiumbasis bestehen. Basis bedeutet in diesem Zusammenhang, dass mehr als 50 Gew.-% des Überzugs aus Zink oder Aluminium bestehen. Der Überzug kann auch nur aus Zink nebst unvermeidbaren Verunreinigungen oder auch nur aus Aluminium nebst unvermeidbaren Verunreinigungen bestehen. Weitere chemische Elemente wie zum Beispiel Magnesium, Eisen, Silizium, Mangan, Nickel, Chrom und/oder Zirkon können jeweils einzeln oder in Kombination zusätzlich eingebracht werden, um den Überzug in seiner Eigenschaft zu verbessern. Auch eine Zink-Aluminium-Kombination (nebst unvermeidbaren Verunreinigungen) mit oder ohne weitere chemische Elemente ist denkbar. Des Weiteren können auch hochschmelzende Überzüge, insbesondere auf Eisenbasis appliziert werden.The metallic coating can be based on zinc or aluminum. In this context, base means that more than 50% by weight of the coating consists of zinc or aluminum. The coating can also consist only of zinc together with unavoidable impurities or only of aluminum together with unavoidable impurities. Further chemical elements such as magnesium, iron, silicon, manganese, nickel, chromium and / or zirconium can be added individually or in combination in order to improve the properties of the coating. There is also a zinc-aluminum combination (along with unavoidable impurities) with or without further chemical elements conceivable. Furthermore, high-melting coatings, in particular iron-based coatings, can also be applied.

Das Beschichten durch Gasphasenabscheidung erfolgt in konventioneller Art und Weise und ist für den Fachmann geläufig.Coating by vapor deposition takes place in a conventional manner and is familiar to the person skilled in the art.

Weitere vorteilhafte Ausgestaltungen und Weiterbildungen gehen aus der nachfolgenden Beschreibung hervor. Ein oder mehrere Merkmale aus den Ansprüchen, der Beschreibung wie auch der Zeichnung können mit einem oder mehreren anderen Merkmalen daraus zu weiteren Ausgestaltungen der Erfindung verknüpft werden. Es können auch ein oder mehrere Merkmale aus den unabhängigen Ansprüchen durch ein oder mehrere andere Merkmale verknüpft werden.Further advantageous configurations and developments emerge from the following description. One or more features from the claims, the description and also the drawing can be linked with one or more other features from them to form further developments of the invention. One or more features from the independent claims can also be linked by one or more other features.

Gemäß einer Ausgestaltung des erfindungsgemäßen Stahlblechs weist die Oberflächenstruktur einen Flankenbereich auf, welcher ausgehend von der Oberfläche bis zu einem Talbereich verläuft und zur Senkrechten des Stahlblechs mit einem Winkel zwischen 30° und 85° ausgebildet ist. Der Winkel kann besonders bevorzugt zwischen 35° und 85° ausgebildet sein. Der Tal- und Flankenbereich (negative Form) der Oberflächenstruktur entspricht im Wesentlichen der Oberfläche (positive Form) an einer Dressierwalze, welche durch entsprechende Einwirkung auf das Stahlblech die Oberflächenstruktur ausbildet respektive einprägt. Der die Oberflächenstruktur umlaufende und ausbildende Flankenbereich definiert zusammen mit dem einstückig an den Flankenbereich angeschlossenen Talbereich ein geschlossenes Volumen der in das Stahlblech mittels Dressieren eingeprägten Oberflächenstruktur. Das geschlossene Volumen, das sogenannte Leervolumen, kann für die spätere Verarbeitung mittels Umformverfahren ein zu applizierendes Prozessmedium, beispielsweise Öl, enthalten.According to one embodiment of the steel sheet according to the invention, the surface structure has a flank area which, starting from the surface, extends to a valley area and is formed at an angle between 30 ° and 85 ° to the perpendicular of the steel sheet. The angle can particularly preferably be formed between 35 ° and 85 °. The valley and flank area (negative shape) of the surface structure essentially corresponds to the surface (positive shape) on a skin pass roller, which forms or impresses the surface structure by corresponding action on the steel sheet. The flank area surrounding and forming the surface structure, together with the valley area connected in one piece to the flank area, defines a closed volume of the surface structure embossed in the steel sheet by means of skin-passaging. The closed volume, the so-called empty volume, can contain a process medium to be applied, for example oil, for later processing by means of a forming process.

Die geometrische Ausgestaltung (Größe und Tiefe) einer deterministischen Oberflächenstruktur (negative Form) auf einem dressierten Stahlblech hängt insbesondere davon ab, wie die entsprechende geometrische Struktur (positive Form) auf einer Dressierwalze gestaltet ist/wird. Vorzugsweise kommen Laser-Texturierverfahren zur Anwendung, um gezielte Strukturen (positive Form) auf der Oberfläche einer Dressierwalze durch Materialabtrag einstellen zu können. Insbesondere kann durch gezielte Ansteuerung der Energie, der Pulsdauer und Wahl einer geeigneten Wellenlänge eines auf die Oberfläche der Dressierwalze einwirkenden Laserstrahls positiv Einfluss auf die Gestaltung der Struktur(en) genommen werden. Mit hoher bzw. höherer Pulsdauer steigt die Wechselwirkungszeit von Laserstrahl und Dressierwalzenoberfläche und es kann mehr Material auf der Oberfläche der Dressierwalze abgetragen werden. Ein Puls hinterlässt auf der Dressierwalzenoberfläche einen im Wesentlichen kreisrunden Krater, der bzw. die, bei mehreren Kratern, nach dem Dressiervorgang die Oberfläche respektive die Fläche der Erhebungen auf dem Stahlblech und somit die Kontaktfläche zwischen Stahlblech und formgebender Dressierwalze abbildet. Eine Reduktion der Pulsdauer hat Einfluss auf die Ausbildung eines Kraters, insbesondere kann der Durchmesser des Kraters verringert werden. Durch die Reduktion der Pulsdauer, insbesondere bei der Verwendung von Kurz- bzw. Ultrakurzpulslasern, ist es möglich, die geometrische Struktur (positive Form) auf der Oberfläche einer Dressierwalze derart gezielt einzustellen, um damit eine Stahlblechoberfläche derart zu texturieren, dass im Flankenbereich der Oberflächenstruktur des dressierten Stahlblechs ein Winkel zwischen 20° und 85° erzeugt werden kann. Dies wird beispielsweise erreicht, wenn die Pulsdauer des Lasers, mit dem die Oberfläche der Dressierwalze texturiert wird, verringert wird und so die geometrische Struktur auf der Walze mit höherer Auflösung erzeugt werden kann. Insbesondere durch die hohe Auflösung bzw. geringe Kraterfläche, die durch die kürzere Wechselwirkung von Laser und Dressierwalze entsteht, können am Flankenbereich gezielt beliebige Steigungen (Winkel) des Flankenbereichs eingestellt werden.The geometric design (size and depth) of a deterministic surface structure (negative shape) on a tempered steel sheet depends in particular on how the corresponding geometric structure (positive shape) is designed on a skin-pass roller. Laser texturing processes are preferably used in order to be able to set specific structures (positive shape) on the surface of a skin-pass roller by removing material. In particular, targeted control of the energy, the pulse duration and the selection of a suitable wavelength of a laser beam acting on the surface of the skin-pass roller can have a positive influence on the design of the structure (s). With high or higher pulse duration increases the interaction time of the laser beam and skin-pass roller surface and more material can be removed from the surface of the skin-pass roller. A pulse leaves an essentially circular crater on the skin-pass roller surface, which, in the case of several craters, after the skin-pass process, maps the surface or the area of the elevations on the steel sheet and thus the contact area between the steel sheet and the shaping skin-pass roller. A reduction in the pulse duration has an influence on the formation of a crater; in particular, the diameter of the crater can be reduced. By reducing the pulse duration, especially when using short or ultra-short pulse lasers, it is possible to adjust the geometric structure (positive shape) on the surface of a skin-pass roller in such a way that a sheet steel surface can be textured in such a way that in the flank area of the surface structure of the tempered steel sheet an angle between 20 ° and 85 ° can be generated. This is achieved, for example, if the pulse duration of the laser with which the surface of the skin-pass roller is textured is reduced and the geometric structure on the roller can be generated with a higher resolution. In particular, due to the high resolution or small crater area, which results from the shorter interaction between laser and skin-pass roller, any inclines (angles) of the flank area can be set in a targeted manner in the flank area.

Gemäß einer Ausgestaltung des erfindungsgemäßen Stahlblechs kann das Stahlblech mit einem weiteren metallischen Überzug beschichtet sein, welcher unterhalb dem durch Gasphasenabscheidung applizierten metallischen Überzug angeordnet ist, somit direkt auf dem Stahlblech aufgebracht sein. Beispielsweise ist der weitere metallische Überzug durch Schmelztauchbeschichten aufgebracht. Insbesondere ist der weitere metallische Überzug ein zinkbasierter Überzug. Vorzugsweise kann der weitere metallische Überzug neben Zink und unvermeidbaren Verunreinigungen zusätzliche Elemente wie Aluminium mit einem Gehalt von bis zu 5 Gew.-% und/oder Magnesium mit einem Gehalt von bis zu 5 Gew.-% in dem weiteren metallischen Überzug enthalten. Stahlbleche mit zinkbasiertem Überzug weisen einen sehr guten kathodischen Korrosionsschutz auf, welche seit Jahren im Automobilbau eingesetzt werden. Ist ein verbesserter Korrosionsschutz vorgesehen, weist der Überzug zusätzlich Magnesium mit einem Gehalt von mindestens 0,3 Gew.-%, insbesondere von mindestens 0,6 Gew.-%, vorzugsweise von mindestens 0,9 Gew.-% auf. Aluminium kann alternativ oder zusätzlich zu Magnesium mit einem Gehalt von mindestens 0,3 Gew.-% vorhanden sein, um insbesondere eine Anbindung des Überzugs an das Stahlblech zu verbessern und insbesondere eine Diffusion von Eisen aus dem Stahlblech in den Überzug bei einer Wärmebehandlung des beschichteten Stahlblechs im Wesentlichen zu verhindern, damit die positiven Korrosionseigenschaften weiterhin erhalten bleiben. Dabei kann eine Dicke des weiteren metallischen Überzugs zwischen 1 und 15 µm, insbesondere zwischen 2 und 12 µm, vorzugsweise zwischen 3 und 10 µm betragen. Beim Schmelztauschbeschichten werden zunächst die Stahlbleche mit einem entsprechenden weiteren metallischen Überzug beschichtet und anschließend dem Dressieren zugeführt. Das Dressieren erfolgt nach dem Schmelztauchbeschichten des Stahlblechs.According to one embodiment of the steel sheet according to the invention, the steel sheet can be coated with a further metallic coating, which is arranged below the metallic coating applied by gas phase deposition, thus being applied directly to the steel sheet. For example, the further metallic coating is applied by hot-dip coating. In particular, the further metallic coating is a zinc-based coating. In addition to zinc and unavoidable impurities, the further metallic coating can preferably contain additional elements such as aluminum with a content of up to 5% by weight and / or magnesium with a content of up to 5% by weight in the further metallic coating. Steel sheets with a zinc-based coating have very good cathodic corrosion protection, which has been used in automotive engineering for years. If improved corrosion protection is provided, the coating also has magnesium with a content of at least 0.3% by weight, in particular at least 0.6% by weight, preferably at least 0.9% by weight. As an alternative or in addition to magnesium, aluminum can be present with a content of at least 0.3 wt essentially to prevent coated steel sheet so that the positive corrosion properties are retained. A thickness of the further metallic coating can be between 1 and 15 μm, in particular between 2 and 12 μm, preferably between 3 and 10 μm. In hot-melt exchange coating, the steel sheets are first coated with a corresponding additional metallic coating and then passed on to skin-pass molding. The skin pass takes place after the hot dip coating of the steel sheet.

Gemäß einer alternativen Ausgestaltung des erfindungsgemäßen Stahlblechs kann das Stahlblech mit einem weiteren metallischen Überzug beschichtet sein, welcher unterhalb dem durch Gasphasenabscheidung applizierten metallischen Überzug angeordnet ist, somit direkt auf dem Stahlblech aufgebracht sein. Beispielsweise ist der weitere metallische Überzug durch elektrolytisches Beschichten aufgebracht. Dabei kann eine Dicke des weiteren metallischen Überzugs zwischen 1 und 10 µm, insbesondere zwischen 1,5 und 8 µm, vorzugsweise zwischen 2 und 5 µm betragen. Im Vergleich zum Schmelztauchbeschichten kann das Stahlblech zunächst dressiert und anschließend elektrolytisch beschichtet werden. Je nach Dicke des weiteren metallischen Überzugs kann der Winkel im Flankenbereich im Wesentlichen auch nach dem elektrolytischen Beschichten beibehalten werden. Alternativ ist auch zunächst ein elektrolytisches Beschichten mit anschließendem Dressieren denkbar.According to an alternative embodiment of the steel sheet according to the invention, the steel sheet can be coated with a further metallic coating, which is arranged below the metallic coating applied by vapor deposition, and thus applied directly to the steel sheet. For example, the further metallic coating is applied by electrolytic coating. A thickness of the further metallic coating can be between 1 and 10 μm, in particular between 1.5 and 8 μm, preferably between 2 and 5 μm. In comparison to hot-dip coating, the steel sheet can first be skin-passed and then electrolytically coated. Depending on the thickness of the further metallic coating, the angle in the flank area can essentially also be retained after the electrolytic coating. Alternatively, an electrolytic coating with subsequent skin-passing is also conceivable.

Alternativ kann der weitere metallische Überzug nachträglich auf dem bereits durch Gasphasenabscheidung applizierten metallischen Überzug aufgebracht werden/sein, so dass dadurch beispielsweise der auf dem Stahlblech durch Gasphasenabscheidung applizierte metallische Überzug als quasi "Haftvermittler" oder "Interface" für weitere metallische Überzüge fungieren kann, um insbesondere schlecht benetzbare, beispielsweise schmelztauchbeschichtbare Stahlblechoberflächen für das Aufbringen des weiteren metallischen Überzugs zu ertüchtigen. Schlecht benetzbare Stahlbleche sind beispielsweise hochlegierte Stahlwerkstoffe, die dem Fachmann geläufig sind. Der weitere metallische Überzug, welcher auf dem durch Gasphasenabscheidung metallischen Überzug appliziert wird, ist vorzugsweise durch Schmelztauchbeschichten aufgebracht. Alternativ kann auch der weitere metallische Überzug durch elektrolytisches Beschichten aufgebracht werden.Alternatively, the further metallic coating can be applied subsequently to the metallic coating that has already been applied by gas phase deposition, so that, for example, the metallic coating applied to the steel sheet by gas phase deposition can function as a quasi "adhesion promoter" or "interface" for further metallic coatings in order to In particular, to make steel sheet surfaces that are poorly wettable, for example hot-dip-coatable, capable of applying the further metallic coating. Poorly wettable steel sheets are, for example, high-alloy steel materials that are familiar to the person skilled in the art. The further metallic coating, which is applied to the metallic coating by vapor deposition, is preferably applied by hot-dip coating. Alternatively, the further metallic coating can also be applied by electrolytic coating.

Gemäß einem zweiten Aspekt betrifft die Erfindung ein Verfahren zum Herstellen eines mit einer deterministischen Oberflächenstruktur dressierten und mit einem metallischen Überzug beschichteten Stahlblechs umfassend folgende Schritte:

  • Bereitstellen eines Stahlblechs,
  • Dressieren des Stahlblechs mit einer Dressierwalze, wobei die Oberfläche der Dressierwalze, welche auf die Oberfläche des Stahlblechs einwirkt, mit einer deterministischen Oberflächenstruktur derart eingerichtet ist, dass nach dem Dressieren die Oberflächenstruktur ausgehend von einer Oberfläche des Stahlblechs in das Stahlblech eingeprägt ist, wobei die Oberflächenstruktur einen Flankenbereich aufweist, welcher ausgehend von der Oberfläche bis zu einem Talbereich verläuft, wobei der Flankenbereich zur Senkrechten des Stahlblechs mit einem Winkel ausgebildet ist und
  • Beschichten des dressierten Stahlblechs mit einem metallischen Überzug, wobei erfindungsgemäß das Stahlblech mit einem Winkel zwischen 20° und 85° zwischen Flankenbereich und Senkrechten des Stahlblechs dressiert und anschließend durch eine Gasphasenabscheidung beschichtet wird.
According to a second aspect, the invention relates to a method for producing a steel sheet dressed with a deterministic surface structure and coated with a metallic coating, comprising the following steps:
  • Provision of a steel sheet,
  • Skin passaging of the steel sheet with a skin pass roller, the surface of the skin pass roller, which acts on the surface of the steel sheet, being set up with a deterministic surface structure in such a way that, after skin passaging, the surface structure is embossed into the steel sheet starting from a surface of the steel sheet, the surface structure has a flank area which, starting from the surface, extends to a valley area, the flank area being formed at an angle to the perpendicular of the steel sheet, and
  • Coating of the tempered steel sheet with a metallic coating, wherein according to the invention the steel sheet is skinned at an angle between 20 ° and 85 ° between the flank area and the perpendicular of the steel sheet and then coated by a vapor deposition.

Die Oberfläche (positive Form) der Dressierwalze bildet durch Krafteinwirkung auf die Oberfläche des Stahlblechs eine Oberflächenstruktur aus, welche einen Tal- und Flankenbereich (negative Form) definiert und entspricht im Wesentlichen der Oberfläche (positive Form) der Dressierwalze. Die Dressierwalze zur Ausbildung einer deterministischen Oberflächenstruktur kann mit geeigneten Mitteln bearbeitet werden, beispielsweise mittels Laser, vgl. auch EP 2 892 663 B1 . Des Weiteren können auch andere Abtragverfahren zur Einstellung einer Oberfläche an einer Dressierwalze eingesetzt werden, beispielsweise spanende Fertigungsverfahren mit geometrisch bestimmter oder unbestimmter Schneide, chemische bzw. elektrochemische, optische oder plasmainduzierte Verfahren, welche geeignet sind, ein zu dressierendes Stahlblech mit einer Oberflächenstruktur umsetzen zu können, welche zumindest im Flankenbereich einen Winkel zur Senkrechten der Oberfläche des Stahlblechs zwischen 20° und 85° aufweist.The surface (positive shape) of the skin pass roller forms a surface structure through the action of force on the surface of the steel sheet, which defines a valley and flank area (negative shape) and essentially corresponds to the surface (positive shape) of the skin pass roller. The skin pass roller for the formation of a deterministic surface structure can be processed with suitable means, for example with a laser, see also EP 2 892 663 B1 . Furthermore, other removal methods can also be used to adjust a surface on a skin-pass roller, for example cutting production methods with geometrically defined or indefinite cutting edges, chemical or electrochemical, optical or plasma-induced methods which are suitable for converting a steel sheet to be skin-dressed with a surface structure , which at least in the flank area has an angle to the perpendicular of the surface of the steel sheet between 20 ° and 85 °.

Um Wiederholungen zu vermeiden, wird jeweils auf die Ausführungen zu dem erfindungsgemäßen mit einer deterministischen Oberflächenstruktur dressierten und mit einem metallischen Überzug beschichteten Stahlblech verwiesen.In order to avoid repetition, reference is made in each case to the explanations relating to the steel sheet according to the invention which is dressed with a deterministic surface structure and coated with a metallic coating.

Im Folgenden werden konkrete Ausgestaltungen der Erfindung mit Bezugnahme auf die Zeichnung im Detail näher erläutert:
Die Zeichnung und begleitende Beschreibung der resultierenden Merkmale sind nicht beschränkend auf die jeweiligen Ausgestaltungen zu lesen, dienen jedoch der Illustration beispielhafter Ausgestaltung. Weiterhin können die jeweiligen Merkmale untereinander wie auch mit Merkmalen der obigen Beschreibung genutzt werden für mögliche weitere Entwicklungen und Verbesserungen der Erfindung, speziell bei zusätzlichen Ausgestaltungen, welche nicht dargestellt sind. Gleiche Teile sind stets mit den gleichen Bezugszeichen versehen.In the following, specific embodiments of the invention are explained in more detail with reference to the drawing:
The drawing and accompanying description of the resulting features are not to be read in a restrictive manner to the respective configurations, but serve to illustrate exemplary configurations. Furthermore, the respective features can be used with one another as well as with features of the above description for possible further developments and improvements of the invention, especially in the case of additional configurations which are not shown. The same parts are always provided with the same reference numerals.

Die Zeichnungen zeigen in

Figur 1a, b)
eine schematische Teilschnittansicht eines Ausführungsbeispiels eines mit einer deterministischen Oberflächenstruktur dressierten Stahlblechs nach dem Stand der Technik, welches mit einem metallischen Überzug durch Gasphasenabscheidung beschichtet wird a) und eine Teilschnittansicht anhand eines FIB-Schnitts eines nach konventionell dressierten und durch Gasphasenabscheidung beschichteten Stahlblechs b), und
Figur 2a, b)
eine schematische Teilschnittansicht eines erfindungsgemäßen Ausführungsbeispiels eines mit einer deterministischen Oberflächenstruktur dressierten und mit einem metallischen Überzug durch Gasphasenabscheidung beschichteten Stahlblechs a) und eine Teilschnittansicht anhand eines FIB-Schnitts an einem erfindungsgemäß dressierten und durch Gasphasenabscheidung beschichteten Stahlblechs b).
The drawings show in
Figure 1a, b)
a schematic partial sectional view of an embodiment of a steel sheet dressed with a deterministic surface structure according to the prior art, which is coated with a metallic coating by vapor deposition a) and a partial sectional view based on an FIB section of a conventionally dressed and coated by vapor deposition steel sheet b), and
Figure 2a, b)
a schematic partial sectional view of an exemplary embodiment according to the invention of a steel sheet a) dressed with a deterministic surface structure and coated with a metallic coating by vapor deposition and a partial sectional view based on an FIB section of a steel sheet b) which has been dressed according to the invention and coated by vapor deposition.

In Figuren 1a) und 2a) sind in schematischen Teilschnittansichten dressierte Stahlbleche (1) mit einer deterministischen Oberflächenstruktur (2) dargestellt. Die Stahlbleche (1), welche blech- oder bevorzugt bandförmig bereitgestellt werden, werden mit einem metallischen Überzug (1.2) beschichtet, wobei die Applikation des metallischen Überzugs (1.2) durch Gasphasenabscheidung in einer geeigneten Vorrichtung erfolgt. Das gezeigte Beispiel zeigt schematisch eine physikalische Gasphasenabscheidung (4), wobei entsprechendes Beschichtungsmaterial, wie zum Beispiel Zink, Aluminium und dergleichen in die Gasphase (4.1) überführtwird und sich in Form eines metallischen Überzugs (1.2) auf der Oberfläche (1.1) des Stahlblechs (1) abscheidet, insbesondere kondensiert. Der Unterschied zwischen den Ausführungen in Figur 1a) und Figur 2a) ist, dass das Stahlblech (1) in der Ausführung in Figur 2a) mit einem Winkel (α) zwischen 20° und 85° zwischen Flankenbereich (2.3) und Senkrechten (O) des Stahlblechs (1) erfindungsgemäß eingestellt worden ist. Die Oberflächenstruktur (2) ist ausgehend von einer Oberfläche (1.1) des Stahlblechs (1) in das Stahlblech (1) eingeprägt, wobei die Oberflächenstruktur (2) einen Flankenbereich (2.3) aufweist, welcher ausgehend von der Oberfläche (1.1) bis zu einem Talbereich (2.2) verläuft. Abhängig von dem Abtragverfahren, mit welchem die entsprechende Dressierwalze (nicht dargestellt) zum Dressieren des Stahlblechs (1) bearbeitet worden ist, wird der Flankenbereich (2.3) und der Talbereich (2.2) durch den entsprechend korrespondierenden Bereich (positive Form) auf der nicht dargestellten Dressierwalze eingestellt. Der die Oberflächenstruktur (2) umlaufende und ausbildende Flankenbereich (2.3) definiert zusammen mit dem einstückig an den Flankenbereich (2.3) angeschlossenen bzw. angebundenen Talbereich (2.2) ein geschlossenes Volumen der in das Stahlblech (1) mittels Dressieren eingeprägten Oberflächenstruktur (2).In Figures 1a) and 2a ) Sketched steel sheets (1) with a deterministic surface structure (2) are shown in schematic partial sectional views. The steel sheets (1), which are provided in sheet form or preferably in the form of a strip, are coated with a metallic coating (1.2), the application of the metallic coating (1.2) taking place by vapor deposition in a suitable device. The example shown shows schematically a physical vapor phase deposition (4), with corresponding coating material such as zinc, aluminum and the like being converted into the gas phase (4.1) and being in the form of a metallic coating (1.2) on the surface (1.1) of the steel sheet ( 1) separates, in particular condenses. The difference between the versions in Figure 1a) and Figure 2a ) is that the sheet steel (1) in the Figure 2a ) with an angle (α) between 20 ° and 85 ° between the flank area (2.3) and the vertical (O) of the steel sheet (1) has been set according to the invention. The surface structure (2) is embossed into the steel sheet (1) starting from a surface (1.1) of the steel sheet (1), the surface structure (2) having a flank area (2.3) which, starting from the surface (1.1) up to a Valley area (2.2) runs. Depending on the removal process with which the corresponding skin-pass roller (not shown) for skin-passing the steel sheet (1) has been processed, the flank area (2.3) and the valley area (2.2) through the corresponding area (positive shape) on the not shown Skin pass roller set. The flank area (2.3) surrounding and forming the surface structure (2) defines, together with the valley area (2.2) integrally connected to the flank area (2.3), a closed volume of the surface structure (2) embossed in the sheet steel (1) by means of skin-passaging.

Der Einfluss des Winkels (α) zwischen dem Flankenbereich (2.3) und der Senkrechten (O) des Stahlblechs (1) wurde in einer Untersuchung näher untersucht. In den Figur 1b) und 2b) sind jeweils schematische Teilschnittansichten anhand von FIB-Schnitten (Focused Ion Beam = Methode zur Probenpräparation zur Herstellung kleiner Lamellen/Querschnitte) unterschiedlicher Oberflächenstrukturen (2) auf einem dressierten und durch Gasphasenabscheidung beschichteten Stahlblech (1) gezeigt. In beiden Fällen kam eine deterministische Oberflächenstruktur (2) mit einer immer wiederkehrenden napfförmigen Einprägung zur Anwendung. Andere Ausführungsformen sind ebenfalls denkbar und anwendbar und nicht auf eine napfförmige Einprägung beschränkt. Die konventionell erzeugte deterministische Oberflächenstruktur wies einen Winkel (α) kleiner als 5°, hier ca. 2° auf, so dass sich zeigte, dass sich innerhalb des metallischen Überzugs (1.2) Beschichtungsfehler, aufweiche dicke Pfeile in Figur 1b) gerichtet sind, ausgebildet hatten, so dass durch das richtungsabhängige Abscheiden (4.1) nicht alle Bereiche gleichmäßig erfasst werden können und sich somit kein homogener metallischer Überzug (1.2) auf der Oberfläche (1.1) des Stahlblechs (1) abscheiden kann. Insbesondere können Beschichtungsfehler in den Bereichen oder Flanken in der Oberflächenstruktur (2) auftreten, die zur Transportrichtung (T) während der Abscheidung im ungünstigen Winkel zur Gasphasenabscheidung (4) liegen, vgl. Figur 1a). Die Untersuchung anhand der Figur 1b) zeigt, dass sich dressierbedingte Aufwerfungen und/oder steile Flankenbereiche (2.3) auf der Oberfläche (1.1) als ungünstig für das Beschichten durch Gasphasenabscheidung erweisen, dadurch beispielsweise Hohlräume zwischen Stahlblech (1) und Überzug (1.2) entstehen und sich damit nicht nur mechanische Fehlstellen im Überzug (1.2) ausbilden, sondern auch das Eindringen von Feuchtigkeit und Prozessmedien, wie zum Beispiel alkalische Reiniger beim Automobilhersteller, und damit Korrosion begünstigen. Somit kann auch nicht ausgeschlossen werden, dass derartige Hohlräume auch im Automobilbereich bei der Benetzung von Klebstoffen auf dressierten beschichteten Blechen auftreten und so potentielle Schwachstellen im Adhäsionsverbund darstellen können.The influence of the angle (α) between the flank area (2.3) and the vertical (O) of the steel sheet (1) was examined in more detail. In the Figure 1b) and 2b ) are schematic partial sectional views based on FIB cuts (Focused Ion Beam = method for sample preparation for the production of small lamellae / cross-sections) of different surface structures (2) on a trained and coated by vapor deposition steel sheet (1). In both cases, a deterministic surface structure (2) with a recurring cup-shaped impression was used. Other embodiments are also conceivable and applicable and are not restricted to a cup-shaped impression. The conventionally produced deterministic surface structure had an angle (α) smaller than 5 °, here approx. 2 °, so that it was found that coating defects, indicated by thick arrows in Figure 1b ) are directed, so that the direction-dependent deposition (4.1) cannot cover all areas evenly and thus no homogeneous metallic coating (1.2) can be deposited on the surface (1.1) of the steel sheet (1). In particular, coating defects can occur in the areas or flanks in the surface structure (2) which, in relation to the transport direction (T), are at an unfavorable angle to the gas phase deposition (4) during the deposition, cf. Figure 1a ). The investigation based on the Figure 1b ) shows that grooving and / or steep flank areas (2.3) on the surface (1.1) prove to be unfavorable for coating by gas phase deposition, as a result, for example, voids between sheet steel (1) and coating (1.2) arise and thus not only mechanical Forming flaws in the coating (1.2), but also promoting the penetration of moisture and process media, such as alkaline cleaners at the automobile manufacturer, and thus promoting corrosion. Thus can Nor can it be ruled out that such cavities also occur in the automotive sector when adhesives are wetted on coated, coated metal sheets and can thus represent potential weak points in the adhesive bond.

Anders stellt sich die Situation dar, wenn gezielt der Winkel (α) zwischen 20° und 85° ausgebildet ist. In der Untersuchung ist der Winkel (α) mit ca. 50° eingestellt worden und es ist gut zu erkennen, dass keine Beschichtungsfehler vorliegen und dadurch ein dressiertes Stahlblech (1) mit einem homogenen metallischen Überzug (1.2) durch Gasphasenabscheidung beschichtet werden kann, wobei ein im Wesentlichen flacher Übergang zwischen Talbereich (2.2) und dem die Talbereiche (2.2) umgebende Oberfläche (1.1) im Wesentlichen ohne Hinterschneidungen und sonstigen störenden Hindernissen eingestellt werden kann, vgl. Figur 2b). Insbesondere kann durch die gezielte Einstellung der deterministischen Oberflächenstruktur (2) ein richtungsunabhängiges Abscheiden begünstigt werden. Mit (1.3) ist ein weiterer metallischer Überzug symbolisch angegeben, welcher beispielsweise durch Schmelztauchbeschichten oder durch elektrolytisches Beschichten vor dem Beschichten durch Gasphasenabscheidung optional appliziert oder alternativ nach dem Beschichten durch Gasphasenabscheidung optional appliziert werden kann.The situation is different if the angle (α) is specifically formed between 20 ° and 85 °. In the investigation, the angle (α) was set at approx. 50 ° and it is easy to see that there are no coating defects and that a dressed steel sheet (1) can be coated with a homogeneous metallic coating (1.2) by vapor deposition, with an essentially flat transition between the valley area (2.2) and the surface (1.1) surrounding the valley areas (2.2) can be set essentially without undercuts and other disruptive obstacles, cf. Figure 2b ). In particular, the specific setting of the deterministic surface structure (2) can promote a direction-independent deposition. With (1.3) a further metallic coating is symbolically indicated, which can optionally be applied, for example, by hot-dip coating or by electrolytic coating before coating by gas phase deposition or, alternatively, optionally applied after coating by gas phase deposition.

Die Merkmale sind, soweit technisch umsetzbar, alle miteinander kombinierbar und als miteinander kombinierbar offenbart.As far as technically feasible, the features are all combinable with one another and disclosed as being combinable with one another.

Claims (8)

Mit einer deterministischen Oberflächenstruktur (2) dressiertes Stahlblech (1), wobei die Oberflächenstruktur (2) ausgehend von einer Oberfläche (1.1) des Stahlblechs (1) in das Stahlblech (1) eingeprägt ist, wobei die Oberflächenstruktur (2) einen Flankenbereich (2.3) aufweist, welcher ausgehend von der Oberfläche (1.1) bis zu einem Talbereich (2.2) verläuft, wobei der Flankenbereich (2.3) zur Senkrechten (O) des Stahlblechs (1) mit einem Winkel (α) ausgebildet ist, und das Stahlblech (1) mit einem metallischen Überzug (1.2) beschichtet ist, wobei der Überzug (1.2) durch eine Gasphasenabscheidung aufgebracht ist, dadurch gekennzeichnet, dass der Winkel (α) zwischen 20° und 85° ausgebildet ist.Steel sheet (1) dressed with a deterministic surface structure (2), the surface structure (2) being embossed into the steel sheet (1) starting from a surface (1.1) of the steel sheet (1), the surface structure (2) having a flank area (2.3 ), which extends from the surface (1.1) to a valley area (2.2), the flank area (2.3) being formed at an angle (α) to the perpendicular (O) of the steel sheet (1), and the steel sheet (1 ) is coated with a metallic coating (1.2), the coating (1.2) being applied by a gas phase deposition, characterized in that the angle (α) is formed between 20 ° and 85 °. Stahlblech nach Anspruch 1, wobei der Winkel (α) zwischen 30° und 85° ausgebildet ist.Steel sheet according to Claim 1, the angle (α) being between 30 ° and 85 °. Stahlblech nach Anspruch 1, wobei der Winkel (α) zwischen 35° und 85° ausgebildet ist.Steel sheet according to claim 1, wherein the angle (α) is formed between 35 ° and 85 °. Stahlblech nach einem der vorhergehenden Ansprüche, wobei das Stahlblech (1) mit einem weiteren metallischen Überzug (1.3), welcher unterhalb dem metallischen Überzug (1.2) angeordnet ist, beschichtet ist und das Stahlblech (1) mindestens zwei metallische Überzüge (1.2, 1.3) umfasst, welche durch unterschiedliche Beschichtungsverfahren aufgebracht worden sind.Steel sheet according to one of the preceding claims, wherein the steel sheet (1) is coated with a further metallic coating (1.3) which is arranged below the metallic coating (1.2) and the steel sheet (1) has at least two metallic coatings (1.2, 1.3) includes, which have been applied by different coating processes. Verfahren zum Herstellen eines mit einer deterministischen Oberflächenstruktur (2) dressierten und mit einem metallischen Überzug (1.2) beschichteten Stahlblechs (1) umfassend folgende Schritte: - Bereitstellen eines Stahlblechs (1), - Dressieren des Stahlblechs (1) mit einer Dressierwalze, wobei die Oberfläche der Dressierwalze, welche auf die Oberfläche (1.1) des Stahlblechs (1.1) einwirkt, mit einer deterministischen Oberflächenstruktur derart eingerichtet ist, dass nach dem Dressieren die Oberflächenstruktur (2) ausgehend von einer Oberfläche (1.1) des Stahlblechs (1) in das Stahlblech (1) eingeprägt ist, wobei die Oberflächenstruktur (2) einen Flankenbereich (2.3) aufweist, welcher ausgehend von der Oberfläche (1.1) bis zu einem Talbereich (2.2) verläuft, wobei der Flankenbereich (2.3) zur Senkrechten (O) des Stahlblechs (1) mit einem Winkel (α) ausgebildet ist und - anschließend Beschichten des dressierten Stahlblechs (1) mit einem metallischen Überzug (1.2) durch Gasphasenabscheidung, dadurch gekennzeichnet, dass das Stahlblech (1) mit einem Winkel (α) zwischen 20° und 85° zwischen Flankenbereich (2.3) und Senkrechten (O) des Stahlblechs (1) dressiert wird.A method for producing a steel sheet (1) dressed with a deterministic surface structure (2) and coated with a metallic coating (1.2), comprising the following steps: - Provision of a steel sheet (1), Skin-passing of the steel sheet (1) with a skin-pass roller, the surface of the skin-pass roller, which acts on the surface (1.1) of the steel sheet (1.1), being set up with a deterministic surface structure in such a way that, after skin-passing, the surface structure (2) starting from a surface (1.1) of the steel sheet (1) is embossed into the steel sheet (1), the surface structure (2) having a flank area (2.3) which extends from the surface (1.1) to a valley area (2.2), wherein the flank area (2.3) is formed at an angle (α) to the perpendicular (O) of the steel sheet (1) and - then coating the dressed steel sheet (1) with a metallic coating (1.2) by gas phase deposition, characterized in that the steel sheet (1) is dressed at an angle (α) between 20 ° and 85 ° between the flank area (2.3) and the perpendicular (O) of the steel sheet (1). Verfahren nach Anspruch 5, wobei das Stahlblech (1) mit einem weiteren metallischen Überzug (1.3) bereitgestellt, wobei der weitere metallische Überzug (1.3) durch ein Schmelztauchbeschichten aufgebracht wird, und das bereitgestellte Stahlblech (1) anschließend dressiert wird.A method according to claim 5, wherein the steel sheet (1) is provided with a further metallic coating (1.3), the further metallic coating (1.3) being applied by hot-dip coating, and the steel sheet (1) provided being subsequently dressed. Verfahren nach Anspruch 5, wobei das Stahlblech (1) nach dem Dressieren mit einem weiteren metallischen Überzug (1.3) beschichtet wird, wobei der weitere metallische Überzug (1.3) durch elektrolytisches Beschichten aufgebracht wird, und anschließend der metallische Überzug (1.2) durch Gasphasenabscheidung beschichtet wird.A method according to claim 5, wherein the steel sheet (1) is coated with a further metallic coating (1.3) after the skin pass, the further metallic coating (1.3) being applied by electrolytic coating, and then the metallic coating (1.2) being coated by vapor deposition will. Verfahren nach Anspruch 5, wobei das Stahlblech (1) mit einem weiteren metallischen Überzug (1.3) beschichtet wird, wobei der weitere metallische Überzug (1.3) nach dem durch Gasphasenabscheidung applizierten metallischen Überzug (1.2) beschichtet wird.Method according to claim 5, wherein the steel sheet (1) is coated with a further metallic coating (1.3), the further metallic coating (1.3) being coated after the metallic coating (1.2) applied by vapor deposition.
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