EP4073288A1 - Tôle métallique comportant un revêtement promoteur d'adhérence en tant que produit semi-fini pour la fabrication de composants composites métal-thermoplastique, et procédé de production d'une tôle métallique de ce type - Google Patents

Tôle métallique comportant un revêtement promoteur d'adhérence en tant que produit semi-fini pour la fabrication de composants composites métal-thermoplastique, et procédé de production d'une tôle métallique de ce type

Info

Publication number
EP4073288A1
EP4073288A1 EP20838369.5A EP20838369A EP4073288A1 EP 4073288 A1 EP4073288 A1 EP 4073288A1 EP 20838369 A EP20838369 A EP 20838369A EP 4073288 A1 EP4073288 A1 EP 4073288A1
Authority
EP
European Patent Office
Prior art keywords
sheet
adhesion promoter
zirconium
titanium
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20838369.5A
Other languages
German (de)
English (en)
Inventor
Christian Vree
Benjamin Poller
Andreas WEDEMEIER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Salzgitter Flachstahl GmbH
Original Assignee
Salzgitter Flachstahl GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102020117925.1A external-priority patent/DE102020117925A1/de
Application filed by Salzgitter Flachstahl GmbH filed Critical Salzgitter Flachstahl GmbH
Publication of EP4073288A1 publication Critical patent/EP4073288A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • 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
    • C23C28/021—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 including at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/16—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes

Definitions

  • Sheet metal with an adhesion promoter coating as a semi-finished product for the production of metal-thermoplastic composite components and a method for producing such a sheet
  • the present invention relates to a metal-containing, preferably a steel-containing or steel-containing sheet with an adhesion promoter coating as a semi-finished product for the production of steel-thermoplastic composite components, a method for its production and the use of a sheet with an adhesion promoter coating as a semi-finished product for the production of metal-thermoplastic composite components.
  • composite materials made of metal preferably steel and thermoplastics, are used, such.
  • metal components preferably steel and thermoplastics
  • plastic in which plastic is injected.
  • thermoplastics made of metal and thermoplastics can only be produced in a materially bonded manner with the aid of adhesion promoters or adhesion-promoting surface treatments, since the thermoplastic itself is not chemically reactive.
  • the composite is particularly at risk at the interface between the sheet metal and the plastic, since two different materials are joined here, which can result in increased thermal stresses due to different thermal expansion coefficients between the joining partners.
  • the diffusion of moisture, other media, salts, etc. into this interface can have a detrimental effect on the strength of the material composite. This aging in the joining area is referred to as corrosive degradation and can ultimately lead to the destruction of the bond.
  • thermoplastic In addition to an activation or chemical modification of the thermoplastic, it is also known and customary, in the production of metal-thermoplastic composite components, to apply the adhesion promoter directly to a metal sheet, e.g. B. on a galvanized sheet steel to apply.
  • a metal sheet e.g. B. on a galvanized sheet steel
  • the corrosion resistance of the sheet with the adhesion promoter applied to it is not optimal, especially in areas with a damaged adhesion promoter layer. If the adhesion promoter layer is damaged, infiltration corrosion can intensify in the affected areas. Examples of damage are cracks, Cut edges, punchings as well as scratches and holes in the coating. This also applies to damage in the hybrid component that is designed in such a way that the sheet metal / thermoplastic interface with the adhesion promoter is accessible to diffusing salts and moisture.
  • the object of the present invention is to provide an alternative sheet metal with an adhesion promoter coating and a method for its production which overcomes the aforementioned disadvantages known from the prior art and is characterized in particular by good adhesion and high corrosion resistance of the sheet with an applied adhesion promoter coating.
  • the invention solves this problem with the features of the claims and in particular by providing a sheet with an adhesion promoter coating as a semi-finished product for the production of metal-thermoplastic composite components, comprising a metal-containing sheet and an adhesion promoter coating, with a titanium-containing and / or zirconium-containing conversion layer between the metal-containing sheet and the adhesion promoter coating is arranged.
  • the metal-containing sheet is preferably a steel-containing or steel sheet.
  • titanium and / or zirconium-containing means that the conversion layer contains at least a layer weight of 1 to 30 mg / m 2 titanium and / or 1 to 30 mg / m 2 zirconium.
  • the surface of such a sheet is optionally galvanized, the galvanizing being applied electrolytically or by means of hot-dip dipping. As a result, the corrosion protection of the later composite component is once again significantly improved.
  • an adhesion promoter coating is understood to mean a layer consisting of or comprising an adhesion promoter, regardless of the thickness of this layer.
  • the layer thickness of the adhesion promoter coating is also different over its length and width and / or the layer consists of several separate sub-layers, as they are e.g. B. arise with an only punctiform or partial area instead of a full-area application of the adhesion promoter.
  • a further conversion layer which contains iron and optionally further metal ions such as cobalt and / or nickel, is arranged between the metal-containing and preferably steel-containing or made of steel sheet with an optionally galvanized surface and the titanium-containing and / or zirconium-containing conversion layer.
  • the further conversion layer containing iron and optionally further metal ions such as cobalt and / or nickel preferably has a layer weight of 1 to 80 mg / m 2 iron, and layer weights of 1 to 30 mg / m 2 each for the optionally contained metal ions.
  • the sheet metal according to the invention with an adhesion promoter coating is produced in a process which, after an optional cleaning and before the application of the adhesion promoter, includes a one or two-stage pretreatment of the sheet metal surface.
  • a pretreatment of the sheet metal surface is understood to mean, in particular, the application of a conversion layer.
  • a medium is applied to the optionally previously cleaned sheet metal surface, which reacts chemically with the sheet metal surface to form the conversion layer.
  • the optional cleaning of the sheet metal surface can in particular include alkaline cleaning and / or degreasing of the sheet metal surface.
  • the process for producing the sheet metal with an adhesion promoter coating includes the following steps:
  • the method for producing the sheet with an adhesion promoter coating also includes a step of pretreating the sheet with an acidic or basic iron or cobalt before the step of pretreating the metal-containing sheet with the acidic or basic titanium and / or zirconium-containing conversion solution - and / or nickel-containing conversion solution, whereby an iron, cobalt and / or nickel-containing conversion layer is obtained on the sheet metal.
  • Both the one-stage and the two-stage pretreatment of the sheet metal surface improves the corrosion protection at the interface between the sheet metal surface and the adhesion promoter coating.
  • the sheet metal surface is treated with at least one acidic (pH ⁇ 6) or basic (pH> 8) conversion solution. Due to the high or low pH value of the conversion solution, the thin oxide layers on the sheet metal surface are pickled, so that the reactivity of the sheet metal surface is increased.
  • the ions or complexes contained in the conversion solution then react with the metal sheet surface to form a conversion layer, whereby in the case of the one-stage pretreatment a conversion layer is created between the sheet metal and the adhesion promoter and in the case of the two-stage pretreatment two conversion layers are created between the sheet metal and the adhesion promoter become.
  • the acidic or basic conversion solution which is used to produce a titanium and / or zirconium-containing conversion layer on the sheet metal contains at least one titanium and / or one zirconium compound.
  • the titanium and / or the zirconium compound is or are preferably present in the form of one or more complex compounds which contain a titanium ion or a zirconium ion as the central ion.
  • the step of pretreating the sheet or the sheet provided with the iron, cobalt and / or nickel-containing conversion layer with the acidic or basic titanium and / or zirconium-containing conversion solution in a previous pretreatment therefore comprises a pretreatment with an acidic or basic conversion solution that contains a titanium and / or zirconium-containing complex compound.
  • a typical conversion solution contains a titanium and / or zirconium-containing complex compound with fluoride ions as ligands and / or manganese ions as counterions.
  • the titanium and / or zirconium-containing conversion layer produced in this way therefore contains, for example, hexafluorotitanates and / or hexafluorozirconates.
  • a single-stage pretreatment with the titanium and / or zirconium-containing conversion solution can produce a sheet with an adhesion promoter coating which has a significantly improved corrosion resistance compared to conventional sheets with an adhesion promoter coating.
  • the corrosion resistance can, however, be increased significantly if, instead of the single-stage pretreatment, a two-stage pretreatment of the sheet metal surface takes place before the adhesion promoter is applied.
  • the optionally galvanized sheet metal surface is treated in a first step with an acidic or basic conversion solution that contains iron, cobalt and / or nickel.
  • the conversion solution particularly preferably contains iron (II) or iron (III) ions, e.g. B. in the form of iron (II) - or iron (III) nitrate or sulfate.
  • iron (II) or iron (III) ions e.g. B. in the form of iron (II) - or iron (III) nitrate or sulfate.
  • a chemical reaction takes place between the preferably galvanized sheet metal surface and the iron, cobalt and / or nickel ions from the conversion solution.
  • Metallic zinc is oxidized and the more noble iron, cobalt and / or nickel ions are reduced, so that a very thin iron, cobalt and / or nickel-containing layer is deposited on the sheet metal surface.
  • the sheet metal surface with the conversion layer created in the first step is treated with an acidic or basic titanium and / or zirconium-containing conversion solution, creating a titanium and / or zirconium-containing conversion layer on the iron, cobalt and / or nickel-containing conversion layer is produced.
  • the titanium and / or zirconium-containing conversion solution is preferably of the same nature as described with reference to the single-stage pretreatment, i.e. H.
  • the titanium and / or zirconium-containing conversion solution preferably contains one or more complex compounds with a titanium and / or zirconium ion as the central ion and particularly preferably with fluoride ions as ligands and / or manganese ions as counter ions.
  • rinsing with fully demineralized water and / or drying can be carried out in order to remove residues of the respective conversion solution from the sheet metal surface .
  • the inventive method after the step of pretreating the metal-containing and preferably steel-containing or steel sheet with the acidic or basic iron, cobalt and / or nickel-containing conversion solution, which is used to form an iron, cobalt and / or nickel-containing conversion layer leads on the sheet, and / or after the step of pretreating the sheet or the sheet provided with the iron, cobalt and / or nickel-containing conversion layer with the acidic or basic titanium and / or zirconium-containing conversion solution, which is used to form a titanium and / or zirconium-containing conversion layer performs a step of rinsing and / or drying the sheet provided with the iron, cobalt and / or nickel-containing conversion layer and / or the sheet metal provided with the titanium and / or zirconium-containing conversion layer.
  • the sheet metal produced as an intermediate product in the process according to the invention with the titanium and / or zirconium-containing conversion layer arranged thereon and the optional iron, cobalt and / or nickel-containing conversion layer arranged between these is then heated to temperatures above 200 ° C, in particular to temperatures between 220 ° C and 270 ° C heated e.g. B. in a continuous furnace.
  • the aforementioned temperatures relate to the sheet metal temperature, the so-called “peak metal temperature”.
  • the adhesion promoter coating is laminated onto the still hot sheet metal surface, ie onto the titanium and / or zirconium-containing conversion layer.
  • the method according to the invention is preferably carried out as a coil coating method and comprises, in particular after the adhesion promoter has been laminated onto the titanium and / or zirconium-containing conversion layer with the optionally underlying iron, cobalt and / or nickel-containing conversion layer, a further step of winding on the coated and with the adhesion promoter provided sheet, which takes place after an optional step of cooling, in particular by water.
  • a preferably steel-containing sheet metal with an adhesion promoter coating and improved corrosion properties is obtained as a semi-finished product for the production of metal-thermoplastic composite components.
  • a thickness of the adhesion promoter layer of 15 ⁇ m to 500 ⁇ m has proven to be particularly favorable for the adhesion properties of the thermoplastic on the sheet metal. Within this range, the layer thickness range from 50 ⁇ m to 200 ⁇ m has proven to be particularly preferred.
  • coil coating can also be applied to the rear side, ie to the one facing away from the adhesion promoter coating Side of the sheet.
  • This has the advantage that process steps can be saved in the further processing of the sheet metal, and forming steps can be improved and / or lubricant-free forming can be implemented.
  • the method is also extremely advantageous in terms of process economy, since the application of the Conversion layer (s), the lamination of the adhesion promoter and the optional backside coating can be carried out in one pass.
  • the process is particularly economical when the adhesion promoter coating is applied as a film.
  • Figures 2a and 2b show pictures of samples without pretreatment, with one-stage pretreatment and with two-stage pretreatment after various exposure times in the alternating corrosion test
  • FIG. 1 shows the schematic layer structure of a fourth variant in FIG.
  • FIG. 1 shows schematically the structure of the sheet metal samples shown in FIGS. 2a and 2b and used in the alternating corrosion test.
  • a zinc scratch 5 approximately 120 mm long was made in the center of the side coated with the adhesion promoter.
  • the opposite longitudinal edges of the samples were provided with cutting burrs 6, specifically the right edge with a cutting burr to the front 6a and the left edge with a cutting burr to the rear 6b.
  • two punch holes 7 with a diameter of 8 mm were made in each test piece, one of the punch holes 7a being punched out from the front to the back and the other punch hole 7b being punched out from the back to the front.
  • Example 1 Influence of infiltration corrosion in the alternating corrosion test The results of the infiltration corrosion of samples in the cyclic alternating corrosion test VDA 233-102 after various exposure times are shown in FIGS. 2a and 2b.
  • Electrolytically galvanized sheet steel was used for all of the samples shown in FIGS. 2a and 2b. However, the tests were carried out in the same way with hot-dip galvanized sheet metal and led to comparable results.
  • Some of the samples were then subjected to a one-step pretreatment with titanium and / or zirconium-containing conversion solution.
  • the conversion solution corrosion protection agent for metals
  • the conversion solution was applied with a so-called chemcoater (applied layer weight of titanium: 4.8 mg / m 2 ).
  • the sheets were then dried in a continuous oven.
  • Another part of the samples was subjected to a two-stage pretreatment, which included a pretreatment with a conversion solution containing iron, cobalt and / or nickel in the first step and a pretreatment with a conversion solution containing titanium and / or zirconium in the second step.
  • the bath preparation for the iron, cobalt and / or nickel-containing conversion solution in deionized water contained a conversion solution (4.3% by volume) + 50% NaOH (2.3% by volume).
  • the metal sheets were immersed in the approx. 50 ° C warm bath for a period of 9 to 11 seconds, then rinsed twice with deionized water and dried. This was followed by the application of the titanium and / or zirconium-containing conversion solution (corrosion protection agent for metals with a chemcoater) (applied layer weight of titanium: 4.8 mg / m 2 ) and the sheets were dried in a continuous oven.
  • thermoplastic adhesion promoter film was then laminated onto the hot sheet metal surface in a heatable lamination unit and the sheets were cooled to room temperature by means of water cooling.
  • FIGS. 2a and 2b Exemplary photos of electrolytically galvanized samples are shown in FIGS. 2a and 2b.
  • Figure 2a line a) shows three test pieces, each with an adhesion promoter film which, before the start of the alternating corrosion test, namely on the left (i) without chemical pretreatment, in the middle (ii) with one-stage pretreatment (corrosion protection agent for metals) and on the right (iii) with two-stage pretreatment ( Conversion solution and anti-corrosion agent for metals).
  • FIG. 2a, line b) shows three test pieces, each with an adhesion promoter film, after one week of aging in the alternating corrosion test, namely on the left (i) without chemical pretreatment, in the middle (ii) with one-stage pretreatment
  • Figure 2b, line c) shows three test pieces, each with an adhesion promoter film, after three weeks of aging in the alternating corrosion test, namely on the left (i) without chemical pretreatment, in the middle (ii) with one-stage pretreatment (corrosion protection agent for metals) and right (iii) with two-stage pretreatment (Conversion solution and anti-corrosion agent for metals).
  • FIG. 1 shows three test pieces, each with an adhesion promoter film, after three weeks of aging in the alternating corrosion test, namely on the left (i) without chemical pretreatment, in the middle (ii) with one-stage pretreatment (corrosion protection agent for metals) and right (iii) with two-stage pretreatment (Conversion solution and anti-corrosion agent for metals).
  • line d) shows three test pieces, each with an adhesion promoter film, after six Weeks exposure time in the alternating corrosion test, namely on the left (i) without chemical pretreatment, in the middle (ii) with one-stage pretreatment (corrosion protection agent for metals) and right (iii) with two-stage pretreatment (conversion solution and corrosion protection agent for metals).
  • Example 2 Influence of the pretreatment of the sheet metal surface on the adhesive strength
  • strips measuring 12.5 mm x 25 mm were cut from polyamide 6 thermoplastic films (PA6 with 60% unidirectional carbon fibers). The unidirectional long fibers lay parallel to the 12.5 mm edge.
  • the strips were stored in a drying cabinet at 60 ° C.
  • Strips with dimensions of 25 mm ⁇ 100 mm were cut from the sheet metal substrates, these were deburred, degreased with heptane (mixture of isomers) and dried in an upright position. Then tensile shear tests were created from the sheet metal and thermoplastic strips.
  • thermoplastic strip 10 (PA6 strip) is fixed by two clamps between a sheet metal strip, the top 8 of which is coated with adhesion promoter, and a sheet metal strip, the underside 9 of which is coated with an adhesion promoter.
  • the bonding layer thickness for the carbon fiber reinforced thermoplastic strips was realized through the fiber thickness.
  • the lap shear samples were placed in an oven preheated to 260 ° C. and joined by melting the thermoplastic matrix at 260 ° C. for 30 minutes. The temperature was controlled via the thermocouple of the furnace used and the time between reaching the joining temperature and removal from the furnace was defined as the dwell time.
  • test specimens were stored for at least 24 h in the room climate so that tensions in the thermoplastic could be relieved and it could change to the "normal state" by absorbing air humidity.
  • Some of the hybrid samples were then phosphated in the typical automotive style and coated with cathodic dip painting (KTL). The KTL was then cured at 175 ° C for 25 minutes.
  • the tensile shear test was carried out in a standard tensile testing machine based on DIN EN 1465 and the average tensile shear strengths obtained and shown in FIG. 4 are mean values from five parallel samples in each case.
  • a comparison of the results of samples a) to d) shows, on the one hand, that the influence of phosphating and cathodic dip painting on the bond strength in the composite is comparatively small and, on the other hand, that the bond strength remains almost unchanged due to the one or two-stage pretreatment.
  • the diagonally hatched bars represent the results for the electrolytically galvanized steel sheet
  • the horizontally hatched bars represent the results for the electrolytically galvanized steel sheet pretreated in one stage
  • the checkered bars represent the results for the two-stage pretreated electrolytically galvanized steel sheet
  • the unhatched bars represent the results for the operating material.
  • the adhesive strength of the sheet metal pretreated in one and two stages decreases less sharply as a result of aging in the alternating corrosion test than that of the untreated sheet metal and the operating material.
  • the sheets according to the invention with one or two conversion layers and the adhesion promoter coating in the composite are therefore also characterized by a reduced decrease in adhesion after aging in the alternating corrosion test.
  • Another advantage of the sheets according to the invention is that the adhesive strength after aging in the alternating corrosion test is significantly more homogeneous than in the case of the untreated sheets.
  • FIGS. 6 to 9 once again summarize the schematic layer structure of the various coating variants of the sheet according to the invention with an adhesion promoter coating.
  • the thermoplastic 10 applied to the adhesion promoter coating is not shown here.
  • FIG. 6 shows a first variant with a metal-containing sheet 1, a conversion layer 3 applied to it and an adhesion promoter 2 as a top coating.
  • FIG. 7 shows an additional metallic coating 1 1 on the sheet 1 and the conversion layer 3 and the adhesion promoter coating 2 applied to it.
  • FIG. 9 shows a layer structure corresponding to FIG. 8, but here the metal-containing sheet 1 again has an additional metallic coating 1 'as corrosion protection on.
  • the conversion layer is also based on other elements, e.g. B. silicon is generated.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une tôle comportant un revêtement promoteur d'adhérence (2) en tant que produit semi-fini pour la fabrication de composants composites métal-thermoplastique, comprenant une tôle métallique contenant un métal (1) et un revêtement promoteur d'adhérence (2), une couche de conversion contenant du titane et/ou contenant du zirconium (3) étant agencée entre la tôle métallique (1) et le revêtement promoteur d'adhérence (2). L'invention concerne en outre un procédé de production de la tôle métallique (1) comportant un revêtement promoteur d'adhérence (2) et l'utilisation de ladite tôle métallique en tant que produit semi-fini pour la fabrication de composants composites métal-thermoplastique.
EP20838369.5A 2019-12-11 2020-12-10 Tôle métallique comportant un revêtement promoteur d'adhérence en tant que produit semi-fini pour la fabrication de composants composites métal-thermoplastique, et procédé de production d'une tôle métallique de ce type Pending EP4073288A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102019133940 2019-12-11
DE102020117925.1A DE102020117925A1 (de) 2020-07-07 2020-07-07 Blech mit Haftvermittlerbeschichtung als Halbzeug zur Fertigung von Metall-Thermoplastverbundbauteilen und Verfahren zur Herstellung eines solchen Bleches
PCT/EP2020/085599 WO2021116320A1 (fr) 2019-12-11 2020-12-10 Tôle métallique comportant un revêtement promoteur d'adhérence en tant que produit semi-fini pour la fabrication de composants composites métal-thermoplastique, et procédé de production d'une tôle métallique de ce type

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EP4073288A1 true EP4073288A1 (fr) 2022-10-19

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Publication number Priority date Publication date Assignee Title
CA1098253A (fr) * 1976-04-05 1981-03-31 Timm L. Kelly Revetement de protection comportant du zirconium et du titane pour surfaces en aluminium
US4992116A (en) * 1989-04-21 1991-02-12 Henkel Corporation Method and composition for coating aluminum
DE102009047522A1 (de) * 2009-12-04 2011-06-09 Henkel Ag & Co. Kgaa Mehrstufiges Vorbehandlungsverfahren für metallische Bauteile mit Zink- und Eisenoberflächen
CN104818474B (zh) * 2010-03-23 2018-07-10 新日铁住金株式会社 容器用钢板的制造方法
KR101431941B1 (ko) * 2010-03-25 2014-08-19 신닛테츠스미킨 카부시키카이샤 내식성이 우수한 용기용 강판
JP5754099B2 (ja) * 2010-09-15 2015-07-22 Ｊｆｅスチール株式会社 容器用鋼板の製造方法
WO2012036203A1 (fr) * 2010-09-15 2012-03-22 Ｊｆｅスチール株式会社 Tôle d'acier pour conteneurs et son procédé de fabrication
JP5845563B2 (ja) * 2010-09-15 2016-01-20 Ｊｆｅスチール株式会社 容器用鋼板の製造方法
DE102013107506A1 (de) * 2013-07-16 2015-01-22 Thyssenkrupp Rasselstein Gmbh Verfahren zur Passivierung von bandförmigem Schwarzblech
WO2016056621A1 (fr) * 2014-10-09 2016-04-14 新日鐵住金株式会社 Feuille d'acier traitée par conversion chimique, et procédé de fabrication de celle-ci
WO2016056627A1 (fr) * 2014-10-09 2016-04-14 新日鐵住金株式会社 Feuille d'acier traitée par conversion chimique, et procédé de fabrication de celle-ci
CN107735511B (zh) * 2015-04-07 2022-05-10 凯密特尔有限责任公司 无镍磷化金属表面的方法
KR20180112029A (ko) * 2016-03-22 2018-10-11 신닛테츠스미킨 카부시키카이샤 화성 처리 강판 및 화성 처리 강판의 제조 방법
JP2019526705A (ja) * 2016-09-01 2019-09-19 サン−ゴバン パフォーマンス プラスティックス コーポレイション 化成皮膜および製造方法

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