US20170321314A1 - Method for producing an anti-corrosion coating for hardenable sheet steels and an anti-corrosion coating for hardenable sheet steels - Google Patents

Method for producing an anti-corrosion coating for hardenable sheet steels and an anti-corrosion coating for hardenable sheet steels Download PDF

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US20170321314A1
US20170321314A1 US15/524,552 US201515524552A US2017321314A1 US 20170321314 A1 US20170321314 A1 US 20170321314A1 US 201515524552 A US201515524552 A US 201515524552A US 2017321314 A1 US2017321314 A1 US 2017321314A1
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layer
zinc
nickel
manganese
corrosion
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Siegfried Kolnberger
Ernst Commenda
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Voestalpine Stahl GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/0478—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular surface treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
    • 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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/625—Discontinuous layers, e.g. microcracked layers
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/62—Quenching devices
    • C21D1/673—Quenching devices for die quenching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment

Definitions

  • the invention relates to a method for producing an anti-corrosion coating for hardenable sheet steels and to an anti-corrosion coating for hardenable sheet steels.
  • the two methods share the fact that a steel band is produced from a steel material by means of hot rolling, usually also followed by cold rolling and the steel band is then continuously galvanized.
  • the usual galvanizing method in this case is hot-dip galvanizing in which the steel band is conveyed through a vat of molten zinc; the molten zinc adheres to the steel, the galvanized steel band is usually conveyed vertically from the vat after which the excess zinc is stripped by means of stripping jets, and then the band undergoes a heat treatment as needed.
  • the resulting galvanized steel band is then usually shipped in coils, i.e. in wound form.
  • blanks of a desired size are stamped from the steel band and these blanks are then processed further in two different ways.
  • the blanks are shaped in an intrinsically conventional manner in a multi-stage process and in particular, are deep drawn, until the component has been shaped into its final form.
  • the component is usually about 2% smaller in all three spatial directions in order to take into account a subsequent thermal expansion.
  • this sheet metal component is heated to an austenitization temperature, i.e. a temperature above Ac 3 , and possibly kept there until the steel material is in the austenitic phase.
  • the heated sheet steel component is transferred to a form-hardening die and in the form-hardening die, into which the heated sheet steel component can usually be inserted in a form-fitting manner, is held in a pressed way—without being appreciably shaped—by a female die and a male die.
  • the steel component is cooled at a speed that is greater than the critical hardening speed, which results in a conversion of the austenite essentially to martensite and yields a high hardness of the component.
  • the blank is directly heated to a temperature above Ac 3 that is necessary for hardening and if need be, is kept there and then shaped in a one-step stroke in a tool composed of a female die and male die, and, by means of the contact of the tool with the work piece, is simultaneously cooled quickly enough so that the hardening outlined above occurs.
  • This method is referred to as press-hardening.
  • Form-hardening is superior to press-hardening when it comes to the possible geometries of a component because more complicated or complex three-dimensional forms can be achieved in a multi-step shaping process, whereas during the one-step shaping press-hardening, only comparatively simple geometries can be achieved.
  • Usual materials for these sheet steel components are so-called boron-manganese steels, in particular the most commonly used 22MnB5.
  • DE 10 2010 030 465 A1 has disclosed a method for producing a shaped sheet metal component provided with an anti-corrosion coating and composed of a higher-strength sheet steel material.
  • This method includes the steps of shaping a prepared initial sheet metal material into a shaped sheet metal component and producing the anti-corrosion coating by electrolytically depositing a zinc-nickel coating onto the shaped sheet metal component; at the beginning of the coating process, first a thin nickel layer is deposited, which in the succeeding steps, prevents a hydrogen embrittlement of the sheet steel material.
  • It also discloses a hot-formed and in particular press-hardened shaped sheet metal component composed of a higher-strength sheet steel material with an electrolytically deposited zinc-nickel coating. The point of this is to provide the nickel layer as a barrier against hydrogen that is typically introduced into the sheet steel material during the electrolytic coating process.
  • a method for producing a steel component provided with a metallic coating that protects against corrosion and the steel component itself are known from EP 2 290 133 B1.
  • the aim is to create a method that is simple to carry out in practice, which makes it possible—with a comparatively small amount of effort—to produce a steel component provided with a favorably adhering metallic coating that reliably protects against corrosion since, as is explained, zinc coatings do not adhere well to the sheet steel types used for hot press-hardening.
  • known coatings have a poor paint adhesion due to oxidation of the surface.
  • the applied anti-corrosion layer should be an electrolytically deposited ⁇ -ZnNi phase, which should favorably withstand subsequently performed heating operations for purposes of austenitization.
  • EP 0 364 596 B1 relates to a method for producing zinc-nickel alloy-coated thin sheets with good press-deformation properties, the purpose being to improve the shaping capacity of such sheets by means of a zinc-nickel alloy coating.
  • the layer in this case is to be deposited with approx. 30 g/m 2 and a nickel content of 12.5%.
  • the object of the invention is to create a method for producing hardened sheet steel components.
  • Another object of the invention is to create an anti-corrosion coating for hardenable sheet steels, which, while having good cathodic corrosion protection, reduces or even prevents liquid metal embrittlement.
  • an at least two-layered anti-corrosion layer is produced on a steel sheet; in this case, either a very thin 1 ⁇ m nickel layer is electrolytically deposited onto the steel and then a zinc layer is likewise electrolytically deposited onto the nickel layer, or the thin nickel layer is formed by means of an electrolytic deposition onto the steel sheet and then a zinc layer is applied by means of hot-dip galvanization.
  • a nickel-containing layer onto a normal hot-dip galvanized sheet steel band by means of a corresponding aftertreatment (coater).
  • the nickel layer is approx. 1 ⁇ m thick if it is applied as a first layer by means of electrolytic deposition.
  • the outer nickel-containing layer is approx. 250 nm to 700 nm thick.
  • the nickel does not in any way constitute a barrier against the ability of the molten zinc to come into contact with the steel; instead, the nickel appears to react very quickly with the zinc and also iron so that the melting point of the entire anti-corrosion layer increases abruptly since instead of zinc-iron ⁇ phases, an increased amount of zinc-nickel-iron phases are formed, which have a significantly higher melting point.
  • an outer applied nickel layer yields a comparable effect; the nickel, which is deposited onto the outermost surface, diffuses into the anti-corrosion layer so quickly that it assures the increase in the melting point.
  • nickel or nickel-based layers instead of nickel or nickel-based layers, other elements, which form baser intermetallic phases with Zn or Fe and have a higher oxidation potential than Zn, for example Cu, Co, Mn, or Mo, can be used since the same effects are achieved by manganese, molybdenum, cobalt, and copper.
  • x-based where x is an element, means that these elements make up the majority (>50 wt %), but other elements are present as alloying elements.
  • Nickel and cobalt as well as manganese or copper do not act as physical barriers against the diffusion between zinc and iron, but are dissolved in and incorporated into the molten zinc and zinc-iron phases. With a previously applied nickel layer and a subsequent hot-dip galvanization, the molten zinc at least begins to dissolve the nickel during the galvanization process.
  • phase structure of the layer forms, which is similar to that of pure hot-dip galvanized layers (phs-ultraform); this phase structure, however, is richer in zinc and has a higher percentage of ⁇ phases.
  • the fact that these phases are richer in zinc is advantageous for the cathodic corrosion protection capacity of the layer.
  • FIG. 1 shows a light microscopically etched micrograph of a steel sheet with the coating according to the invention in which a hot-dip galvanized layer has been applied onto a 1 ⁇ m-thick intermediate nickel layer;
  • FIG. 2 shows an enlarged depiction of the layer according to FIG. 1 ;
  • FIG. 3 shows a layer according to FIG. 1 in which EDX element mapping has been used to depict the distribution of the elements iron, zinc, nickel, and aluminum in an intermediate nickel layer that has been applied 1 ⁇ m thick;
  • FIG. 4 shows a micrograph of the coating with a 0.5 ⁇ m-thick nickel layer and a 10 ⁇ m-thick zinc layer that has been annealed at 800° C.;
  • FIG. 5 shows the layer according to FIG. 4 with a 1 ⁇ m-thick nickel layer
  • FIG. 6 shows a coating according to the invention after the annealing, a holding time, a transfer time, and a subsequent cooling for press-hardening purposes;
  • FIG. 7 shows an X-ray microscopic micrograph of an anti-corrosion layer according to the invention, after an austenitic annealing at 870° C.;
  • FIG. 8 shows the layer according to FIG. 7 with the distribution of the iron
  • FIG. 9 shows the layer according to FIG. 7 with the distribution of the zinc
  • FIG. 10 shows the layer according to FIG. 7 with the distribution of the nickel in which a nickel support layer has been applied to the surface as a preparation aid;
  • FIG. 11 shows the layer according to FIG. 7 with the distribution of the aluminum
  • FIG. 12 shows the layer according to FIG. 7 with the distribution of the manganese
  • FIG. 13 shows a coating according to the invention after the austenitization and quenching, with an EDX scan line indicated;
  • FIG. 14 shows the coating according to FIG. 13 , with the scan profile for the elements iron, nickel, and zinc;
  • FIG. 15 shows four V samples with a bending radius of 1.5 mm.
  • the method according to the invention for producing sheet steel components can either be a press-hardening method or a form-hardening method, i.e. a method in which a sheet steel component is heated and then quench-hardened in a tool (form-hardening) or a method in which a blank is shaped and quench-hardened in a single step (press-hardening).
  • a boron-manganese steel is used as the steel material for the press-hardening or form-hardening and with regard to the transformation of the austenite into other phases, the transformation can be shifted to lower ranges and martensite is formed.
  • alloying elements boron, manganese, carbon, and optionally chromium and molybdenum are present in steels of this kind as transformation delayers, i.e. as an element that shifts the phase transformation of austenite into martensite to lower temperatures.
  • the conventional steels 22MnB5 and 20MnB8 are thus particularly also suitable.
  • a quench-hardening i.e. the rapid cooling at a cooling speed that is greater than the critical hardening speed, is still reliably achieved below 780° C.
  • processing is carried out below the peritectic temperature of the zinc-iron system, i.e. mechanical stresses are only exerted below the peritectic temperature. This also means that at the moment in which mechanical stresses are exerted, there are no longer any molten zinc phases that can come into contact with austenite.
  • An anti-corrosion layer according to the invention is an anti-corrosion layer that is applied in at least two layers, with at least one nickel layer and one zinc layer being applied to a substrate composed of a hardenable steel material. Instead of a nickel layer, it is also possible to apply a manganese or copper layer.
  • the nickel, copper, or manganese layer is preferably deposited electrolytically.
  • the zinc layer can be electrolytically deposited or deposited by means of a hot-dip method.
  • Another possibility lies in depositing the zinc layer electrolytically or by means of a hot-dip method as a first layer and then applying a nickel layer on the outermost layer thereof, in particular by means of electrolytic deposition.
  • nickel is used here, this is also meant to include other elements that form baser intermetallic phases with Zn or Fe and that have a higher oxidation potential than Zn, for example Cu, Co, Mn, or Mo.
  • the element nickel in this case is also used as a proxy for copper and manganese.
  • FIG. 1 shows a light microscopically etched micrograph of the layer according to the invention on a steel substrate.
  • FIG. 2 shows it again, enlarged even further.
  • a 1 ⁇ m-thick intermediate nickel layer is applied to the steel substrate and then hot-dip galvanized, with the intermediate nickel layer having been dissolved in the zinc bath in the hot-dip galvanization.
  • FIG. 3 clearly shows that a homogeneous distribution of iron is present in the region of the steel, with the iron content decreasing at the boundary layer with the layer applied on top of it. It is clear from the distribution of zinc that the zinc content increases in the boundary zone with the higher layers.
  • FIGS. 4 and 5 both compare respective layers, in one of which, the intermediate nickel layer had a thickness of 0.5 ⁇ m ( FIG. 4 ) and in the other of which, it had a layer thickness of 1 ⁇ m ( FIG. 5 ).
  • a hot-dip galvanized layer 10 ⁇ m thick was then deposited onto this. Both layer samples were then heated to 800° C.
  • the uppermost, light-colored layer is not part of the anti-corrosion layers; it is a preparation aid layer composed of nickel, which was applied before the sample preparation, i.e. after the heating and cooling.
  • a structure that has two phases in the micrograph forms on the surface of the steel substrate, with a light-colored phase, which is interspersed with dark areas ( FIG. 6 ).
  • annealing was performed at 870° C., followed by a waiting period of 45 s, then a transfer time of 5 s, and then a cooling in a press.
  • a layer according to FIG. 6 was measured with an EDX element mapping; here, too, a preparation aid in the form of a nickel support layer is present on the sample.
  • the layer section that was measured is shown in FIG. 7 .
  • the nickel ( FIG. 10 ) is still not very visible in the light-colored zinc matrix, but is clearly not present in the iron-rich nodules, whereas aluminum ( FIG. 11 ) is distributed in a relatively homogeneous fashion throughout the entire layer, even though there are concentrations in the iron-rich phases.
  • Manganese which is present in the base steel material, is hardly present at all in the entire layer and is detectable only in the substrate.
  • the distribution of elements in the depth direction was determined using a so-called EDX line scan ( FIG. 13 ).
  • the scan begins already in the nickel support layer and extends deep into the steel base material.
  • An originally present nickel layer is no longer detectable in the phase structure.
  • the positive effect of the nickel in the layer is clear from bending samples with a radius of 1.5 mm ( FIG. 15 ).
  • the thickness of the nickel layer only influences the quantity of the nickel in the layer.
  • the invention thus makes it possible, by means of an additional nickel layer, to exert influence on the zinc-based anti-corrosion layer such that during the cooling, this layer clearly forms solid phases more quickly, which then do not react with the austenite of the steel substrate during shaping.
  • the invention has the advantage that it enables a mixed deposition using both an electrolytic method and a hot-dip coating method.
  • the nickel layer can be easily applied to conventional sheets that have already been hot-dip galvanized; this can be done with both an electrolytic coating method and other coating methods, e.g. roller application, i.e. a method that uses rollers for application, for example a coil-coating method in which a nickel-containing layer with a thickness of 250 nm to 700 nm is applied.

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US15/524,552 2014-11-04 2015-11-04 Method for producing an anti-corrosion coating for hardenable sheet steels and an anti-corrosion coating for hardenable sheet steels Abandoned US20170321314A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102014116085 2014-11-04
DE102014116085.1 2014-11-04
PCT/EP2015/075702 WO2016071399A1 (fr) 2014-11-04 2015-11-04 Procédé de production d'un revêtement anti-corrosion pour tôles d'acier trempables et revêtement anti-corrosion pour tôles d'acier trempables

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US20170321314A1 true US20170321314A1 (en) 2017-11-09

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111434402A (zh) * 2019-07-30 2020-07-21 苏州普热斯勒先进成型技术有限公司 表面具有含锰涂层的热冲压件的制造方法
JP2021517204A (ja) * 2018-03-09 2021-07-15 アルセロールミタル 高い生産性でのプレス硬化部品の製造方法
CN114072541A (zh) * 2019-05-17 2022-02-18 奥钢联艾弗勒涂层有限公司 制造用于高强度和超高强度钢的改进的冷成型工具的方法和冷成型工具
DE102020130543A1 (de) 2020-11-19 2022-05-19 Voestalpine Stahl Gmbh Stahlmaterial und Verfahren zu seiner Herstellung
CN114555838A (zh) * 2019-10-30 2022-05-27 安赛乐米塔尔公司 模压淬火方法
US12043902B2 (en) 2020-01-24 2024-07-23 Thyssenkrupp Steel Europe Ag Steel component comprising an anti-corrosion layer containing manganese

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016218688A1 (de) 2016-09-28 2018-03-29 Bayerische Motoren Werke Aktiengesellschaft Verfahren zur Herstellung eines wasserstoffführenden Stahlbauteils zum Einsatz bei Kraftfahrzeugen, wasserstoffführendes Stahlbauteil und Kraftfahrzeug mit einem wasserstoffführenden Stahlbauteil
JP6880690B2 (ja) * 2016-12-07 2021-06-02 日本製鉄株式会社 溶融Ｚｎ−Ａｌ−Ｍｇ系めっき鋼板および溶融Ｚｎ−Ａｌ−Ｍｇ系めっき鋼板の製造方法
DE102018128131A1 (de) 2018-11-09 2020-05-14 Thyssenkrupp Ag Gehärtetes Bauteil umfassend ein Stahlsubstrat und eine Korrosionsschutzbeschichtung, entsprechendes Bauteil zur Herstellung des gehärteten Bauteils sowie Herstellverfahren und Verwendung
DE102018009745A1 (de) 2018-12-14 2020-06-18 Salzgitter Flachstahl Gmbh Blechplatine zur Hertstellung eines warmumgeformten und pressgehärteten Stahlblechbauteils sowie Warmumformverfahren
EP3712292B1 (fr) 2019-03-19 2023-08-02 ThyssenKrupp Steel Europe AG Composant comprenant un substrat en acier, une couche de revêtement intermédiaire et une couche protection contre la corrosion, leur procédé de fabrication
DE102020203421A1 (de) 2020-03-17 2021-09-23 Thyssenkrupp Steel Europe Ag Stahlflachprodukt mit einem ZnCu-Schichtsystem
DE102021105131A1 (de) 2021-03-03 2022-09-08 Salzgitter Flachstahl Gmbh Verfahren zur Herstellung eines warmumgeformten und pressgehärteten Stahlblechbauteils

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013487A (en) * 1974-03-14 1977-03-22 Rederiaktiebolaget Nordstjernan Nickel and/or cobalt-coated steel with carburized interface
US20040166360A1 (en) * 2001-10-23 2004-08-26 Kazuhito Imai Hot press forming method, and a plated steel material therefor and its manufacturing method
US20070000117A1 (en) * 2003-07-29 2007-01-04 Werner Brandstatter Method for producing hardened parts from sheet steel
US20130122322A1 (en) * 2010-08-04 2013-05-16 Jfe Steel Corporation Steel sheet for hot pressing and method of manufacturing hot-pressed part using steel sheet for hot pressing

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01234592A (ja) 1988-03-16 1989-09-19 Kawasaki Steel Corp プレス成形性の優れたＺｎ−Ｎｉ合金めっき鋼板の製造方法
ATE554190T1 (de) 2009-08-25 2012-05-15 Thyssenkrupp Steel Europe Ag Verfahren zum herstellen eines mit einem metallischen, vor korrosion schützenden überzug versehenen stahlbauteils und stahlbauteil
DE102010030465B4 (de) 2010-06-24 2023-12-07 Bayerische Motoren Werke Aktiengesellschaft Verfahren zum Herstellen eines Blechformteils aus einem höherfesten Stahlblechmaterial mit einer elektrolytisch aufgebrachten Zink-Nickel-Beschichtung
DE102010056265C5 (de) * 2010-12-24 2021-11-11 Voestalpine Stahl Gmbh Verfahren zum Erzeugen gehärteter Bauteile

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013487A (en) * 1974-03-14 1977-03-22 Rederiaktiebolaget Nordstjernan Nickel and/or cobalt-coated steel with carburized interface
US20040166360A1 (en) * 2001-10-23 2004-08-26 Kazuhito Imai Hot press forming method, and a plated steel material therefor and its manufacturing method
US20070000117A1 (en) * 2003-07-29 2007-01-04 Werner Brandstatter Method for producing hardened parts from sheet steel
US20130122322A1 (en) * 2010-08-04 2013-05-16 Jfe Steel Corporation Steel sheet for hot pressing and method of manufacturing hot-pressed part using steel sheet for hot pressing

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Kalantary, M.R., Wilcox, G.D. and Gabe, D.R., 1998. Alternate layers of zinc and nickel electrodeposited to protect steel. British Corrosion Journal, 33(3), pp.197-201. (Year: 1998) *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021517204A (ja) * 2018-03-09 2021-07-15 アルセロールミタル 高い生産性でのプレス硬化部品の製造方法
JP7080333B2 (ja) 2018-03-09 2022-06-03 アルセロールミタル 高い生産性でのプレス硬化部品の製造方法
JP2022122908A (ja) * 2018-03-09 2022-08-23 アルセロールミタル 高い生産性でのプレス硬化部品の製造方法
JP7275358B2 (ja) 2018-03-09 2023-05-17 アルセロールミタル 高い生産性でのプレス硬化部品の製造方法
JP7558336B2 (ja) 2018-03-09 2024-09-30 アルセロールミタル 高い生産性でのプレス硬化部品の製造方法
US12110572B2 (en) 2018-03-09 2024-10-08 Arcelormittal Manufacturing process of press hardened parts with high productivity
CN114072541A (zh) * 2019-05-17 2022-02-18 奥钢联艾弗勒涂层有限公司 制造用于高强度和超高强度钢的改进的冷成型工具的方法和冷成型工具
CN111434402A (zh) * 2019-07-30 2020-07-21 苏州普热斯勒先进成型技术有限公司 表面具有含锰涂层的热冲压件的制造方法
CN114555838A (zh) * 2019-10-30 2022-05-27 安赛乐米塔尔公司 模压淬火方法
US12043902B2 (en) 2020-01-24 2024-07-23 Thyssenkrupp Steel Europe Ag Steel component comprising an anti-corrosion layer containing manganese
DE102020130543A1 (de) 2020-11-19 2022-05-19 Voestalpine Stahl Gmbh Stahlmaterial und Verfahren zu seiner Herstellung

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