WO2020193637A1 - Procédé de modification de la surface d'une couche de protection métallique à base de zn-al-mg déposée sur un produit plat en acier et produit plat en acier - Google Patents

Procédé de modification de la surface d'une couche de protection métallique à base de zn-al-mg déposée sur un produit plat en acier et produit plat en acier Download PDF

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Publication number
WO2020193637A1
WO2020193637A1 PCT/EP2020/058375 EP2020058375W WO2020193637A1 WO 2020193637 A1 WO2020193637 A1 WO 2020193637A1 EP 2020058375 W EP2020058375 W EP 2020058375W WO 2020193637 A1 WO2020193637 A1 WO 2020193637A1
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WIPO (PCT)
Prior art keywords
protective layer
flat steel
steel product
wetting
phosphating solution
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Ceased
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PCT/EP2020/058375
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German (de)
English (en)
Inventor
Christian Altgassen
Fabian JUNGE
Jessica BRINKBÄUMER
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ThyssenKrupp Steel Europe AG
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ThyssenKrupp Steel Europe AG
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Priority to EP20715013.7A priority Critical patent/EP3947766A1/fr
Publication of WO2020193637A1 publication Critical patent/WO2020193637A1/fr
Anticipated expiration legal-status Critical
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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
    • C23C2/26—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
    • C23C2/04—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
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/07—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 aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/07—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 aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/07—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 aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/20—Orthophosphates containing aluminium cations
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/34—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/362—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/34—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

Definitions

  • the invention relates to a method for modifying the surface of a Zn-Al-Mg-based metallic protective layer which is applied to a flat steel product and covered with magnesium oxide and / or aluminum oxide
  • the invention relates to a flat steel product which is provided with a metallic protective layer based on Zn-Al-Mg and has a phosphate coating applied to the protective layer which contains Mg, Al and Zn.
  • Flat steel products are understood here to mean rolled products, the length and width of which are each substantially greater than their thickness.
  • a flat steel product or a “sheet metal product” is mentioned below, this refers to rolled products such as steel strips or sheets from which blanks or blanks are cut off for the manufacture of, for example, body parts.
  • Sheet metal parts or “sheet metal components” are made of such flat or steel
  • Phosphate crystal layer and “phosphate coating” are also to be understood synonymously in the following.
  • phosphor crystal here refers to all crystals that are made of
  • Zinc phosphate crystals Zinc phosphate crystals.
  • phosphate here includes phosphoric acid and salts of the
  • phosphate in every dissociation stage.
  • phosphate thus also includes dihydrogen phosphates and hydrogen phosphates, as well as phosphoric acid in non-dissociated form.
  • inorganic elements such as zinc, nickel, manganese or iron in the aqueous phosphating solution
  • metal cations of the corresponding salts are meant.
  • a certain proportion of zinc in the phosphating solution is described in g / l, this means in particular zinc, which is in the form of a zinc compound, in particular a zinc salt
  • ZM coatings there are different phases such as Zn, MgZn2, Al-rich Zn, each of which contributes to the protective effect of the coating.
  • the Al content of a ZM coating typically varies in the range from 1 to 3.7% by weight, while the Mg content is typically from 1 to 3% by weight.
  • Deformation degrees are formed for the respective component.
  • Flat steel products achieved an optimized anti-corrosive effect and deformability in certain applications which, compared with conventional zinc or aluminum-coated flat steel products, are less suitable for painting or gluing.
  • ZM-coated flat steel products for example, paintwork applied to them peeled off or the paintwork on them cracked
  • Substrate close cohesive failure (substrate close cohesive failure), in which the break in the adhesive takes place in the vicinity of the interface between oxide layer and adhesive.
  • Adhesive bonds on ZM-coated flat steel products can be improved by passivating the surface to be painted or bonded. This is done first by rinsing with an aggressive acid, in particular hydrochloric acid, the so-called
  • the passivation layer can form abrasion during the forming of an appropriately passivated flat steel product and thus influence the deformation behavior.
  • those elements and compounds present on the surface of the cementitious coating that have positive effects on the processability of the flat steel product and its ability to be coated or glued are removed with the pickling.
  • EP 2 824 213 A1 describes a method for improving the adhesiveness of a device provided with a protective coating based on Zn-Al-Mg
  • the steel sheet with a protective coating is first dressed and then treated with an aqueous fluoride-containing composition while reducing the MgO content.
  • US 2015/0352825 A1 also describes a method for producing metal sheets with a coating based on Zn-Al-Mg, which are said to have improved compatibility with adhesion promoters or adhesives by adding a Zn-Al-Mg-coated first metal sheet is treated with an acidic solution, which has a pH value of 1 to 4, and then an adhesion promoter or adhesive is applied to the coating treated with the acidic solution. A second sheet of metal is then joined to the first sheet of metal via the adhesion promoter or adhesive.
  • the object has arisen to provide a method with which the surface of a Zn-Al-Mg-based metallic protective layer applied to a flat steel product can be modified in such a way that an improved lacquer or Adhesion is achieved.
  • a flat steel product should have a metallic
  • Protective layer based on Zn-Al-Mg are specified, which has an improved paint adhesion and / or breaking properties.
  • the invention has achieved this object in that, in order to modify the surface, a steel flat product
  • Process according to the invention can also be carried out if there is a need for this.
  • a flat steel product that achieves the object specified above has at least the features listed in claim 16.
  • Wets phosphating solution which contains at least phosphate, b 1) wherein the wetting is carried out over a wetting period which is at least until a reduction in the magnesium oxide and / or aluminum oxide content occurs in the areas of the surface of the surface covered with magnesium oxide and / or aluminum oxide metallic protective layer lasts, and b.2) the wetting is completed before a zinc phosphate layer is formed on the areas of the surface of the metallic protective layer that are covered with magnesium oxide and / or aluminum oxide.
  • the flat steel product with a ZM coating to be modified on its surface is subjected to phosphating, in which, unlike conventional phosphating, the wetting time with the phosphating solution is selected so that only those that impair the paint or adhesive adhesion Metal cations, in particular magnesium cations, are dissolved from the near-surface oxide layer present on the cementitious coating, whereas the constituents of the oxide layer that are favorable for adhesion remain present or are only formed there by the phosphating.
  • the method according to the invention makes use of the time difference between the start of phosphating, i.e. the first contact of the surface with the phosphating solution, and the point in time at which conversion chemical processes start in a conventionally carried out phosphating process.
  • the process according to the invention does not completely detach the oxide layer from the cementitious coating, but only the lacquer or
  • Such zinc-rich areas are formed, for example, by mechanically induced changes in the homogeneous, magnesium and / or
  • the ZM coating is applied to the freshly coated flat steel products. For example, one after the coating process to improve the dimensional accuracy and the Optimization of the surface quality, especially the
  • this oxide layer is pressed into the cementitious coating or gives way to the side as a result of the pressure forces acting during skin pass. This can lead to the oxide layer tearing open, particularly in the edge area of the flat steel product. This freed from the native oxide layer
  • the phosphating carried out according to the invention now leads to a thinning and modification in the area of the native oxide layer by
  • Magnesium and / or aluminum components are removed from the oxide layer, so that the correspondingly modified surface is proportionally significantly richer in zinc.
  • Zinc-rich surface chemically more like a surface, as it can be found on zinc-coated surfaces with a very high zinc content.
  • the surfaces of such coatings also known as “Z” or “ZE coatings” in technical terms, with a very high zinc content can be painted and bonded significantly better with the paint or adhesive systems available today than surfaces of ZM coatings, since the existing lacquer or adhesive systems are usually optimized for Z-coatings.
  • Adhesive properties can also be improved there.
  • the phosphating carried out is carried out on the one hand so briefly that no zinc phosphate layer can form over the entire surface of the cementitious coating treated according to the invention (condition b.2)).
  • condition b.2 this does not exclude the possibility that individual zinc phosphate crystals or individual clusters of zinc phosphate crystals can be present in the areas of the surface covered with magnesium oxide and / or aluminum oxide.
  • the wetting time over which the surface of the ZM coating is exposed to the phosphating solution according to the invention is such that the magnesium oxide and / or aluminum oxide components on the surface of the flat steel product provided with a metallic protective layer based on Zn-Al-Mg after the end of the wetting are reduced (condition b.1)).
  • the duration of the wetting thus depends on the time required to detach the oxide layer present on a surface of a cementitious cement coating to be modified according to the invention. Suitable for this
  • wetting times are 0.5 - 600 seconds
  • a wetting time of at least 0.5 seconds, in particular at least 1 second, ensures that the effects used and aimed for according to the invention are achieved.
  • wetting time of a maximum of 60 seconds prevents large areas of closed phosphate layer from forming on the
  • the thickness is favorable
  • Oxide layer largely unchanged due to the increase in the proportion of zinc oxide associated with the reduction in the proportion of magnesium and / or aluminum oxide.
  • wetting times in the process according to the invention in the range from 1 to 15 seconds. The latter applies in particular to the application of the phosphating agent by spraying.
  • Wetting times of in particular up to 5 seconds are particularly suitable for the efficient detachment of the oxide layer.
  • the wetting time is also at least 0.5 seconds, in particular at least 1 second, in this case being at
  • the effects desired according to the invention can be set in a particularly reliable manner.
  • the maximum duration of wetting, even with dip or coating phosphating is limited to 600 seconds, in particular 300 seconds or 120 seconds, and in this case too, wetting times of a maximum of 60 seconds have proven to be particularly practical.
  • Layers of the cementitious cement coating close to the surface in the sense of the invention are in particular layers adjoining the surface and having a thickness of 75 nm, i.e. starting from the free surface of the
  • the concentration in the atomic monolayer on the surface is determined by means of Time-of-Flight Secondary Ion Mas.s Spectrometry, "ToF-SIMS" for short, in a layer adjoining the surface with a thickness of 5 nm from the surface (i.e. based on onto the free surface of the flat steel product to a depth of 5 nm)
  • XPS X-ray photoelectron spectroscopy
  • glow discharge spectroscopy Glow Discharge Optical Emission Spectroscopy, GDOS / GDOES
  • Aluminum and an increase in the relative concentration of zinc causes.
  • the occurrence of the elements zinc, magnesium and aluminum within the meaning of the invention is recorded regardless of the form in which they are present. It does not matter whether these elements are present as neutral atoms or as ions, in a compound such as an alloy or in intermetallic phases or in a compound such as in a complex or as oxides, salts, hydroxides or the like.
  • Magnesium takes place according to the invention by determining the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value of the absolute value
  • Sum of the concentration of zinc, aluminum and magnesium is set equal to 100 and the proportion of the respective element in this 100% is evaluated or weighted as a relative concentration, i.e. based on 100%.
  • the relative concentration of an element Al, Mg, Zn therefore relates to the total of the concentrations of the three elements Al, Mg, Zn, representing 100%.
  • XPS X-ray Photoelectron Spectroscopy
  • Concentration of Mg on the surface before the method is carried out a reduction in the relative concentration of Mg by at least 5%, in particular by at least 10%, by at least 12%, by at least 15%, by at least 18%, by at least 20%, by at least 22%, by at least 25%, by at least 27%, by at least 30%, by
  • X-ray photoelectron spectroscopy is carried out with an information depth of 5 nm and the relative concentration is based on the total amount of Mg, Al and Zn and compared with the relative concentration of Zn and Al on the surface before the method is carried out. Since the absolute concentration of the elements Ai, Mg and Zn of
  • Coating to coating can vary, according to the invention the information for the method to be used in general is given as relative
  • An untreated comparative sample within the meaning of the invention is a substrate with a Zn-Al-Mg coating which, including the coating, is identical to the sample that is used according to the invention. That is, the comparison sample (“control”) has the same except for the method according to the invention
  • the substrate used according to the invention with a Zn-Al-Mg coating is that the control is not subjected to the method according to the invention.
  • the relative concentration of Mg can be reduced by at least 5%, in particular by at least 10%, by at least 12%, by at least 15%, by at least 18%
  • X-ray photoelectron spectroscopy with an information depth of 5 nm, based on a total amount of Mg, Al and Zn and compared to the relative concentration of Mg on the surface before the method is carried out.
  • the method according to the invention takes place in a layer adjoining the surface with a thickness that is equal to the XPS-typical information depth, a reduction in the relative concentration of magnesium by at least 10 percentage points, in particular at least 20 percentage points, with a reduction of at least 30 percentage points, in particular at least 35
  • Percentage points as particularly advantageous.
  • the absolute concentration of zinc, magnesium and aluminum can be determined using XPS and is then viewed in relative terms.
  • the absolute concentration of zinc, magnesium and aluminum in the relevant layer depth can be determined using GD-OES and is then viewed in relative terms.
  • the method according to the invention results in a reduction in the relative atomic monolayer located on the surface
  • the absolute concentration is determined using ToF-SIMS, in which the absolute concentrations of zinc, magnesium and aluminum are determined by the respective signal intensities
  • an increase in the relative concentration of zinc can be determined by means of one of the methods described above from at least 4 percentage points each, in particular at least 7
  • Percentage points particularly preferably 10 percentage points or more, can be achieved.
  • the inventive "selective phosphating" can be in a
  • Hot-dip galvanizing step provided with the ZM coating
  • the flat steel products to be modified according to the invention have a metallic protective layer based on Zn-Al-Mg, which is formed in a conventional manner and applied to the steel substrate.
  • the surface of the cementitious coatings to be treated according to the invention contain (in% by weight) 0.1-3.0% by weight Al and 0.1-3.0% by weight Mg, the remainder being zinc, depending on the manufacturing process unavoidable impurities in technically ineffective levels.
  • Particularly good processing properties can be achieved with ZM coatings that contain 1.0-2.0% by weight of Al and 0.6-2.0% by weight % Mg contain.
  • the method according to the invention and the resulting modification of the oxide layer present on the surface of a ZM coating are particularly suitable when the ZM coating has been applied to the respective steel substrate by hot dip coating.
  • the coating can be applied to the steel substrate in different thicknesses.
  • the metallic protective layer on a Zn-Al-Mg basis provided according to the invention has particularly good corrosion protection in one
  • the wetting time takes place in such a way that the phosphating according to the invention is terminated before the one used in the usual phosphating
  • Phosphating solutions are used. Such watery
  • Phosphating solutions typically contain 0.1 - 35 g / l phosphoric acid.
  • the removal of magnesium and / or aluminum oxide from the surface of a flat steel product treated according to the invention is particularly successful, in particular with a phosphating solution which contains 0.1-8 g / l phosphoric acid.
  • the phosphating solution contains zinc, nickel and / or manganese, so can
  • Phosphate can also be introduced into the phosphating solution in the form of metal phosphates.
  • the phosphating solution contains
  • the proportion of phosphoric acid in the The total amount of phosphate can be determined by the pH value
  • the phosphating solution contains 1 - 8 g / i
  • Phosphoric acid in particular 1-4 g / l or 1-3 g / l phosphoric acid.
  • the phosphating solution contains at least one compound selected from the group “zinc, nickel, manganese”, with the proviso that in the case of the respective
  • the content of nickel! 0.5 - 8 g / l and the manganese content is 0.5 - 8 g / l. If nickel and / or manganese are present in the phosphating solution, in areas of the surface of the cementitious coating there are not or only those which were not or only present before the phosphating carried out according to the invention
  • magnesium oxide and / or aluminum oxide particularly fine zinc phosphate crystals, which particularly improve the paint and adhesive in the areas concerned.
  • the aqueous phosphating solution used according to the invention can each optionally contain 1-20 mg / l Fe or 0.01-3 g / l F in order to accelerate the detachment process of the magnesium oxide and / or aluminum oxide or to help stabilize the modified oxide layer. pH values of 1 - 5 of the aqueous phosphating solution contribute to the
  • the aqueous phosphating solution according to the invention has a pH value of 1 - 4, pH values of 1 - 3, in particular 1.0 - 2.1 or 1.0 - 1, 7 have proven particularly beneficial.
  • the aqueous solution has a concentration of phosphoric acid of 1 mM to 100 mM, Bes a phosphating solution used according to the invention, which for
  • pH values of at least 2 are particularly suitable. At the same time it has been shown that a
  • the phosphating solution contains 30-35 g / l
  • compositions and this pH value are in a
  • Phosphating solution found to be particularly suitable contains 20-35 g / l phosphate, 0.5-8 g / l nickel, 0.5-8 g / l manganese, 0.5-8 g / l zinc and
  • Phosphating solution here has a pH of 3 to 5.
  • the aqueous phosphating solution can be heated to 30-80 ° C. for the wetting according to the invention.
  • the inventive wetting of the surface of the flat steel product provided with the metallic protective layer on a Zn-Al-Mg basis with the aqueous phosphating solution can take place in a conventional manner.
  • Known spraying, spraying / dipping, dipping or coating systems can be used for this purpose.
  • spray systems for strip phosphating in a manner known per se, a particularly high Productivity can be achieved.
  • diving systems on the other hand, it is possible to produce particularly cost-effectively in an equally known manner.
  • the method according to the invention is particularly suitable for an application of the phosphating solution in a continuous flow, as it is especially in
  • An activation of the surface to be modified of the cementitious coating is basically not necessary. However, if larger areas free of Al or Mg oxides with increased Zn oxide proportions are present on the surface in question, it can be advantageous to carry out activation in these areas with regard to the formation of the finest possible zinc phosphate crystals. This is especially true if
  • Wetting times of longer than 10 seconds can be selected. By 'activation is prevented in this case, that containing fields that form thick zinc phosphate crystals in the high Zn oxide that would adversely affect the adhesive bond.
  • Such an activating solution typically contains 0.8-15 g / l activating agent, the activating agent consisting of one or more compounds from the group of titanium compounds "titanium dioxide, potassium titanium fluoride,
  • Tin tetrachloride or tin sulfate, arsenic, in particular arsenic oxide, zirconium, in particular zirconium chloride or zirconium sulfate, iron and lithium is selected.
  • the surface in question can be rinsed with a rinsing liquid after wetting has ended. This rinse also ensures that there are any loose items on the surface
  • Rinsing can be carried out in a two-stage process, in which rinsing is first carried out with water and then with an alcohol or an aqueous solution of an alcohol. Alternatively, a mixture of alcohol and water can be applied in a one-step rinsing step. The surface can be rinsed particularly carefully by using water and an alcohol.
  • a flat steel product according to the invention which is provided with a metallic protective layer based on Zn-Al-Mg and has at least individual phosphate crystals applied to the protective layer, the proportion of Al and Mg on the surface is the metallic
  • the “total amount” is the sum of the amounts according to the invention Amounts of Mg, Al and Zn present on the modified surface
  • the surface shows excellent corrosion resistance as well as optimized paint and adhesive adhesion. Here one gets involved
  • a flat steel product according to the invention is distinguished in particular by the fact that zinc phosphate crystals are present in areas of the phosphate layer in which the proportion of Zn in the total amount of Al, Mg and Zn amounts present in the respective area is more than 85 atom% .
  • Dual-phase or multi-phase steels which in particular have TRIP properties.
  • These and other possible steels are in the brochures "Product overview: Steels for the automotive industry - product information", as of August 2018, version 0, and "Steel DP-W and DP-K - product information for dual-phase steels", as of February 2018, version 0, both published by thyssenkrupp Steel Europe AG, Duisburg, Germany.
  • Fig. 1 is a diagram in which the invention in coating
  • Fig. 2 is a diagram in which the conventional coating
  • Fig. 3 is a diagram in which for different each im
  • Fig. 4 is a diagram in which for different each im
  • Fig. 5 is a diagram in which the relative concentrations of Mg, Al and
  • Fig. 6 is a diagram in which for different each im
  • Fig. 7 is a diagram in which the flow chart of a
  • Fig. 8 is a diagram in which the relative concentrations of Mg, Al and
  • Fig. 9 is a diagram in which for different each im
  • Fig. 10 is a diagram in which the method steps in a
  • Fig. 11 is a diagram in which the relative concentrations of Mg, Al and
  • Fig. 12 is a diagram in which the relative concentrations of Mg, Al and
  • Zn are shown in the atomic monolayer, after application of the method according to the invention in comparison with a reference, control on a trained ZM coating;
  • Fig. 13 is a diagram in which the relative concentrations of Mg, Al and
  • Zn are shown on the surface, after application of the method according to the invention in comparison to a reference, control on an undressed ZM coating;
  • Fig. 15 is a diagram in which for different each im
  • the flat steel product to be coated first undergoes a conventional hot-dip coating in which it is coated with a conventionally composed and created ZM coating
  • the ZM-coated flat steel product is then optionally pass-rolled in order to achieve its dimensional accuracy in a known manner
  • the one with the ZM coating optionally skin-pass rolled
  • selective phosphating according to the invention, in which it is wetted with an aqueous phosphating solution P1 or P2. This selective phosphating reduces the proportion of magnesium oxide and / or aluminum oxide on the surface of the metallic protective layer.
  • the flat steel product is then rinsed, dried and oiled in a conventional manner, in order to then be sent to the respective customer, i.e. to be transported to the point where the flat steel product is processed.
  • the flat steel product is then formed into a sheet metal component at the customer's facility.
  • the sheet metal component obtained in this way can be combined with other sheet metal components can be assembled into a larger structure.
  • the assembly with a different component is typically carried out
  • the selective phosphating according to the invention offers optimal conditions for joining the sheet metal components.
  • the respective component or the structure assembled from several prefabricated components are then degreased in the customary manner at the customer and freed from superficial deposits. This can be done before or after degreasing or cleaning during manufacture and
  • the surfaces of the degreased and cleaned component can be activated in a conventional manner in order to create the best prerequisites for the adhesion of the second phosphating, which is finally carried out by the customer and carried out conventionally.
  • the second phosphating takes place in an equally conventional manner, after which the sheet metal component obtained is optimally protected against corrosion and offers the best prerequisites for painting or the like.
  • the respective flat steel product is hot-dip coated by hot-dip coating with a ZM coating, then optionally pass-rolled, then pretreated or post-treated for oil the transport to the customer, transported to the customer, formed by the customer, cleaned,
  • compositions of the ZM coating on the surface before and after the modification according to the invention were determined by means of XPS.
  • the absolute, near-surface concentrations of the elements zinc, magnesium and aluminum were initially determined in an information depth of about 5 nm, which is typical for XPS and measured from the free surface of the coating. The absolute values recorded in this way are then normalized to 100% and viewed relative to one another.
  • the XPS measurement was carried out with a Phi Quantera II SXM Scanning XPS Microprobe device from Physical Electronics GmbH, which had the following parameters:
  • Working pressure in main chamber 1 x 10 6 Pa; Lock pressure: ⁇ 2.7 x 10 4 Pa; X-ray source: A1 1486.6 eV monochromatic; maximum sample size 70 mm x 70 mm x 15 mm (height); Neutralizing agents: Ar and electrons; Neutralization voltage: 1.5 V; Neutralization current 20.0 mA;
  • Beam diameter 100 pm; Pass Energy: 280 eV; Spectral resolution: 1 eV.
  • the composition of the metallic protective layer was determined by means of GD-OES measurement.
  • the glow discharge spectrometer "Spectruma GDA750” offered by Spectruma Analytik GmbH was used for this.
  • This vacuum simultaneous spectrometer has a focal length of 750 mm and a discharge source constructed according to the Grimm type as well a measurement option in DC and RF mode. In the experiments reported here, the measurement was carried out in RF mode.
  • the glow discharge spectrometer was operated with a 4 mm anode and argon 5.0 (99.999%) gas at an anode voltage of 800 V, an anode current of 20 mA, a power of 16 W and a lamp pressure of 3-10 hPa.
  • a measuring device offered by 10N-T0F GmbH, Weg, Germany, under the designation "TOF.SIMS 5" has been used, whereby a primary ion beam with 25 keV Bi3 + ⁇ 0.3 pA and a pulse duration ⁇ 1 ns was used and the measuring chamber vacuum was about 2E 9 mbar and the measuring field in variant (a) 500 x 500 pm 2 with 512 x 512 pixels, 30 scans, random shaving, and in variant (b) 3.08 x 3.08 mm 2 (308 X 308 pixels) with 50 shots per pixel, random shave (within each stitching measuring field of approx. 300 x 300 pm 2 ) From the absolute concentrations determined in this way, the relative concentrations have been determined.
  • Example 1 For the tests in Example 1, five steel sheet samples Ph-12 to Ph-16 made of a steel S, the composition of which is given in Table 1, were provided.
  • Hot-dip coating (hot-dip galvanizing) provided with a ZM coating.
  • the compositions of the ZM coatings of the samples Ph-12 - Phi 6 are given in Table 2 and were determined by means of GD-OES measurement.
  • Ph-12 - Ph-16 were then wetted with a phosphating solution P1, the phosphating solution P1 having the following composition:
  • the phosphating solution P1 heated to 55 ° C., was sprayed in a conventional spray or
  • Phosphating solution P1 have been exposed.
  • the duration t and the application method used in each case are given in Table 3.
  • each of the samples was rinsed in the conventional manner with tap water to ensure that no residues of the phosphating solution were left on the surface of the steel sheet sample, so that zinc phosphate layers could not form on the areas covered with magnesium oxide and / or aluminum oxide .
  • composition of the ZM coating on the surface of the samples treated in the manner explained above was determined and with the untreated reference condition Ref., ie a flat steel product » which has gone through the same process steps, but without the
  • Zn content adjusts.
  • a wetting of the samples by conventional spray application proves to be particularly effective.
  • FIG. 3 The mean values of the tensile shear strengths determined in five tensile shear tests each on the unaged adhesive samples K-12 - K-16 are shown in FIG. 3, whereas FIG. 4 shows the mean values of the five in each case
  • Adhesive samples K-12 - K-16a formed from Ph-12 - Ph-16 also proved to be satisfactory. Both in the unaged and in the aged condition, the bonded sheet steel samples almost exclusively (> 95%)
  • SCF special cohesive fracture
  • Phosphating solution P2 5.1 g / l phosphorus in the form of P2O5 (corresponds to
  • the phosphating solution P2 heated to 55 ° C. was applied to the surface of the steel sheet samples Ph-06-Ph-08 in a conventional spraying process.
  • the duration t over which the samples were exposed to the phosphating solution P2 was varied.
  • the duration t and the application method used in each case are given in Table 4.
  • the process steps listed in Example 1 were then carried out accordingly for the modified steel sheet samples Ph-06 - Ph-08.
  • Sections of the samples Ph-06 - Ph-08 each made an adhesive bond.
  • a commercially available adhesive sold under the name "DOW Betamate 1485 S" with an adhesive layer thickness of 0.2 mm was applied to each of the first of the sections separated from the samples Ph-06 - Ph-08 and the relevant, with The section provided with the adhesive is joined to a second section of the same sample Ph-06 - Ph-08.
  • the curing of the adhesive connections between the sections bonded to one another to form an adhesive sample K-06 - K-08 each took place at 175 ° C. (object temperature) over a period of 20 minutes.
  • the unaged and aged adhesive samples (K-06 - K-08; K-06a - K-08a) were then each subjected to a tensile shear test in accordance with DIN EN 1465 at room temperature and a test speed of 10 mm / min.
  • the breaking behavior of the bonds formed with samples Ph-06-Ph-08 treated according to the invention is shown in FIG. In the unaged state, all three adhesive samples show only special ones close to the substrate
  • the steel roll was produced as shown in
  • the belt speed for the process was set at 90 m / min.
  • the metallic protective layer applied to the steel had a. Composition according to GD-OES measurement of 97.1% by weight Zn, 1.8% by weight Al and 1.1% by weight Mg.
  • Phosphating solution P3 3.7 g / l phosphorus in the form of phosphate (corresponds to
  • Oxide layer surface of the modified steel sheet sample was with a corresponding reference, in which in the procedure on the
  • the relative zinc content on the surface could already be increased considerably, with aluminum oxide in particular being detached from the surface.
  • the modified flat steel product obtained in this way was glued in accordance with Examples 1 and 2 and partly subjected to aging in accordance with Examples 1 and 2. Then the unaged and the aged sample became one
  • the tensile shear test according to Examples 1 and 2 was subjected to test the breaking behavior of the glued flat steel product.
  • the results in Fig. 9 show; that the fracture behavior still shows> 90% SCF even after aging.
  • the flat steel product also exhibits partially adhesive breakage between. the adhesive and the oxide layer.
  • a ZM-coated steel roller was subjected to the method according to the invention in a coil coating system at varying belt speeds and varying temperatures of the phosphating solution.
  • the protective layer had a composition according to GD-OES measurement of 97.1% by weight of Zn, 1.8% by weight of Al and 1.1% by weight of Mg.
  • the procedural steps are shown in FIG.
  • the unrolled ZM-coated steel sheet was first degreased, then alkaline passivated, then subjected to a phosphating step and
  • Test conditions V1 - V5 are listed in Table 5.
  • the temperature of the phosphating solution was set to 60 ° C (V1 - V3) or 75 ° C (V4 - V5).
  • the belt speeds were 31 m / min (V2, V4), 40
  • V1 50 m / min (V3) or 80 m / min (V5), with wetting times of 1.5 s (80 m / min) to 4 s (31 m / min).
  • Phosphating solution P4 3.7 g / l phosphorus in the form of phosphate (corresponds to
  • Alumina components can be achieved.
  • boards in A4 size which had a Zn-Al-Mg protective layer on both sides, were immersed in an aqueous solution of phosphoric acid for 30 seconds or with such an aqueous solution of
  • circuit boards prepared in this way were exposed to the natural air atmosphere until the concentration of zinc, aluminum and magnesium was determined.
  • substrates with dressed Zn-Al-Mg coating were degreased with alkaline cleaning agents and then immersed in the appropriate solution of diluted phosphoric acid for 30 seconds. It was then rinsed with water and isopropanol.
  • Phosphoric acid solution containing 0.1 ml / l phosphoric acid at a concentration of 85% and a substrate was treated with an aqueous
  • Phosphoric acid solution containing 5 ml / l phosphoric acid with a concentration of 85% was treated, a significant reduction in the Mg and Al content on the surface.
  • the surface was determined using GD-OES so that the composition could be determined down to a depth of 75 nm. It can be seen here that the lower layers are not severely affected by the phosphoric acid treatment.
  • the surface composition of the treated samples and a reference were measured using ToF-SIMS (FIG. 12), using GD-OES (FIG. 13) and using XPS (FIG. 14), with the GD-OES measurement up to 75 nm deep was measured in the surface and only the top 5 nm were measured with the XPS measurement.
  • the fracture surface was examined after the adhesive bond had been separated from substrates, the cementitious coating of which was wetted, rinsed and dried as described above and then bonded using an epoxy-based adhesive. Some of the bonded samples were aged according to the aging described in Examples 1-3. The breaking behavior was then tested as in Examples 1-3.

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Abstract

La présente invention concerne un procédé de modification de la surface d'une couche de protection métallique à base de Zn-Al-Mg déposée sur un produit plat en acier, qui comprend des régions recouvertes d'oxyde de magnésium et/ou d'oxyde d'aluminium. Pour modifier la surface d'une couche de protection métallique à base de Zn-Al-Mg déposée sur un produit plat en acier avec un tel procédé de sorte qu'une adhérence améliorée de l'adhésif ou de la laque soit obtenue, la présente invention propose de mouiller la surface de la couche de protection métallique avec une solution de phosphatation aqueuse qui comprend au moins du phosphate. Le mouillage est réalisé sur une durée de mouillage qui dure au moins jusqu'à l'instauration d'une réduction de la proportion d'oxyde de magnésium et/ou d'oxyde d'aluminium sur les régions recouvertes d'oxyde de magnésium et/ou d'oxyde d'aluminium de la surface de la couche de protection métallique. En même temps, le mouillage est achevé avant qu'une couche de phosphate de zinc se forme sur les zones de la surface de la couche de protection métallique recouvertes d'oxyde de magnésium et/ou d'oxyde d'aluminium.
PCT/EP2020/058375 2019-03-27 2020-03-25 Procédé de modification de la surface d'une couche de protection métallique à base de zn-al-mg déposée sur un produit plat en acier et produit plat en acier Ceased WO2020193637A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2824213A1 (fr) 2013-07-12 2015-01-14 Voestalpine Stahl GmbH Procédé d'amélioration de l'adhérence sur une tôle d'acier dotée d'un revêtement de protection
US20150125714A1 (en) * 2012-04-25 2015-05-07 ArcelorMittal Investigación y Desarrollo, S.L. Method for producing a metal sheet having oiled zn-al-mg coatings, and corresponding metal sheet
US20150352825A1 (en) 2012-04-25 2015-12-10 ArcelorMittal Investigación y Desarrollo, S.L. Method for producing a metal sheet having zn-al-mg coatings comprising the application of an acid solution and an adhesive, and corresponsing metal sheet and assembly
WO2020064546A1 (fr) * 2018-09-25 2020-04-02 Thyssenkrupp Steel Europe Ag Procédé pour modifier des surfaces galvanisées

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008004728A1 (de) * 2008-01-16 2009-07-23 Henkel Ag & Co. Kgaa Phosphatiertes Stahlblech sowie Verfahren zur Herstellung eines solchen Blechs
JP5469556B2 (ja) * 2010-07-16 2014-04-16 日新製鋼株式会社 化成処理めっき鋼板およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150125714A1 (en) * 2012-04-25 2015-05-07 ArcelorMittal Investigación y Desarrollo, S.L. Method for producing a metal sheet having oiled zn-al-mg coatings, and corresponding metal sheet
US20150352825A1 (en) 2012-04-25 2015-12-10 ArcelorMittal Investigación y Desarrollo, S.L. Method for producing a metal sheet having zn-al-mg coatings comprising the application of an acid solution and an adhesive, and corresponsing metal sheet and assembly
EP2824213A1 (fr) 2013-07-12 2015-01-14 Voestalpine Stahl GmbH Procédé d'amélioration de l'adhérence sur une tôle d'acier dotée d'un revêtement de protection
WO2020064546A1 (fr) * 2018-09-25 2020-04-02 Thyssenkrupp Steel Europe Ag Procédé pour modifier des surfaces galvanisées

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Steel DP-W und DP-K- Produktinformation für Dualphasenstähle", February 2018, STEEL EUROPE AG
"ZINC-MAGNESIUM-ALUMINIUM COATINGS FOR AUTOMOTIVE INDUSTRY", 2013, STEEL INSTITUTE VDEH
PRODUKTÜBERSICHT: STÄHLE FÜR DIE AUTOMOBILINDUSTRIE - PRODUKTINFORMATION, August 2018 (2018-08-01)

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