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WO2020193548A1 - Procédé de reconditionnement de surfaces galvanisées à chaud - Google Patents

Procédé de reconditionnement de surfaces galvanisées à chaud Download PDF

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Publication number
WO2020193548A1
WO2020193548A1 PCT/EP2020/058152 EP2020058152W WO2020193548A1 WO 2020193548 A1 WO2020193548 A1 WO 2020193548A1 EP 2020058152 W EP2020058152 W EP 2020058152W WO 2020193548 A1 WO2020193548 A1 WO 2020193548A1
Authority
WO
WIPO (PCT)
Prior art keywords
protective layer
zinc
eutectic
magnesium
metallic protective
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.)
Ceased
Application number
PCT/EP2020/058152
Other languages
German (de)
English (en)
Inventor
Fabian JUNGE
Jennifer Schulz
Tobias LEWE
Burak William Cetinkaya
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.)
ThyssenKrupp Steel Europe AG
Original Assignee
ThyssenKrupp Steel Europe AG
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
Application filed by ThyssenKrupp Steel Europe AG filed Critical ThyssenKrupp Steel Europe AG
Priority to EP20714977.4A priority Critical patent/EP3947777A1/fr
Publication of WO2020193548A1 publication Critical patent/WO2020193548A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals

Definitions

  • the invention relates to a method for at least regionally removing a eutectic phase from a metallic protective layer based on zinc-magnesium and a flat steel product which has eutectic-free and / or magnesium-free areas on the surface.
  • US 2015125714A describes a method for producing a metal sheet, both sides of which have a metal coating containing zinc, 0.1-20 wt% aluminum and 0.1-10 wt% magnesium.
  • the substrate is coated in an immersion bath and after cooling down, the layers of magnesium oxide or magnesium hydroxide are deposited have formed a metal coating on the outer surface by applying an acid solution to the outer surfaces and / or by applying mechanical forces using a roll straightener, a brushing device or a sandblasting device. A layer of oil is then applied to the outer surface of the metal coating.
  • US 2015/0352825 A1 also describes a method for producing metal sheets with a coating based on Zn-Al-Mg, which should have improved compatibility with adhesion promoters or adhesives by using a Zn-Al-Mg -coated first metal sheet is treated with an acidic solution, which has a pH of 1 to 4, and then an adhesion promoter or adhesive is applied to the coating treated with the acidic solution. A second metal sheet is then joined to the first metal sheet via the adhesion promoter or adhesive.
  • metal coatings in particular hot-dip galvanized surfaces, have alloying elements in the area close to the surface which have a disruptive effect on properties such as, for example, the breaking behavior of bonded surfaces or paint adhesion.
  • ZM zinc-magnesium
  • top relates to the surface of the metallic protective layer and the term “bottom” relates to the substrate, which is accordingly arranged below the protective layer.
  • binary (zinc-magnesium) or ternary (zinc-aluminum-magnesium) eutectic phases develop locally to varying degrees between, above and below the primarily precipitated zinc grains.
  • These eutectic phases are composed of the eutectic and pure metals, i.e. H.
  • these eutectic phases also have (secondary) zinc grains and possibly Al grains.
  • These secondary zinc grains and possibly Al grains are not to be confused with the zinc grains that are primarily separated (primary zinc grains), since they have a volume that is several orders of magnitude smaller than the volume of the primary zinc grains.
  • the primary zinc grains have a diameter of in some cases over 30 ⁇ m
  • the diameter of the secondary zinc grains located in the eutectic phases is up to 2 ⁇ m.
  • these secondary grains are excreted before or after the eutectic.
  • the eutectic phases described above are referred to as hypo- or hyper-eutectic phases, depending on whether they are eliminated before or after the eutectic.
  • the layer structure of a ZM coating shows an enrichment of eutectic phases that are not surface-covering but are distributed over the entire sample and are arranged over the zinc grains (and possibly also in the zinc grains).
  • the eutectic and eutectic phases are magnesium-rich phases, for example in comparison to the primary tin grains.
  • the aging of the cementitious coatings when stored in air or in oxygen-containing atmospheres can result in a change in the chemical composition of the layers close to the surface, and thus also lead to a growth of the oxide layers in and on the metallic protective layer.
  • the growth of these oxide layers is with the penetration of Oxygen is connected in the eutectic phases of the protective layer and leads to an additional worsening of further processing.
  • Elementary metal atoms from the eutectic and the eutectic phases are oxidized to oxides and / or hydroxides or similar compounds; these are generally summarized below under the term metal oxides.
  • the metal oxides are arranged in layers close to the surface, i.e. in the upper layers of the protective layer, in particular at a depth of up to 75 nm.
  • the present invention relates to a method for at least regionally removing a eutectic phase from a metallic protective layer based on zinc-magnesium comprising at least or consisting of the following steps, a) providing a substrate with a metallic protective layer; b) at least regionally removing at least one eutectic phase close to the surface by wetting the surface with an inorganic acid; c) exposing the upper surface of at least one zinc grain of the metallic protective layer; d) Ending the wetting as soon as the surface of the at least one zinc grain exposed in c) has essentially no eutectic phase.
  • regionally is to be interpreted three-dimensionally in the context of the present invention.
  • the wetting acts in layers of the metallic protective layer close to the surface, i.e. in the depth and also in the third dimension. Due to the wetting with an inorganic acid, deeper layers of the metallic protective layer are exposed, until finally the upper surface of at least one (primary) zinc grain of the metallic layer is exposed.
  • At least one eutectic phase close to the surface is removed in areas to a depth of at least 100 nm, preferably 120 nm, 125 nm, 150 nm, 175 nm, 200 nm, 250 nm, 300 nm, particularly preferably 400 nm, in particular 500 nm up to maximum 2 pm, before particularly 1.8 pm, 1.75 pm, 1.7 pm, particularly preferably 1.6 pm, 1.25 pm, in particular 1 mhh, in relation to the surface of an undressed protective layer.
  • the eutectic phase arranged over the (primary) zinc grains is preferably removed. This can be retained between and below the (primary) zinc grains, provided that it is present before wetting. The same applies to the eutectic.
  • the depth of a layer is always determined from the top atom of the respective surface.
  • metallic protective layer based on zinc-magnesium metallic protective layer
  • protective layer protective layer
  • ZM coating are equivalent according to the invention and are used synonymously.
  • the term “essentially no eutectic phase” means that the exposed surface of the primary zinc grains only accounts for 40%, preferably 30%, 25%, particularly preferably 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 1 1%, in particular 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or 0.5%, 0, 1% of eutectic and eutectic phase or is only covered with the aforementioned portion with eutectic and eutectic phase.
  • the remaining and larger proportion of the exposed surface, i.e. well over 50%, is formed by zinc or zinc oxide or hydroxide (for the term zinc oxide, see the definition of metal oxide given above).
  • the exposed surface relates to a layer which is close to the surface in relation to the primary zinc grain and has at least one atomic layer to a depth of 99 nm, preferably 75 nm.
  • the detection of a surface of the primary zinc grain essentially free of eutectic phase is determined by at least one of the following methods: SEM images (scanning electron microscope SEM) of a cross section, EDX mapping (energy dispersive X-ray spectroscopy, English energy dispersive X-ray spectroscopy), AES (Auger electron spectroscopy), XPS measurement, GD-OES measurement or ToF-SIMS measurement.
  • a relative magnesium concentration of a maximum of 20%, preferably 15%, particularly preferably 10%, 8%, is used in this regard on the entire exposed surface of the protective layer, i.e. not just on the exposed surface of the at least one primary zinc grain. 7%, in particular 5%, 4%, 3%, 2%, one percent or less, in an alternative with a lower limit of the magnesium concentration below the detection limit, or a lower limit of a maximum of 0.001%, 0.01% or 0, 1 %.
  • the determination is made in an alternative by means of XPS measurement, GD-OES measurement or ToF-SIMS measurement.
  • the relative concentration of zinc, magnesium and possibly aluminum is determined by determining the absolute concentration of these elements and then normalizing to 100%; the sum of the concentration of zinc, magnesium and possibly aluminum 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 refers to the sum of the concentrations of the elements Mg, Zn and possibly Al, in that this sum represents 100%.
  • the information for the method to be generally used is given as a relative concentration and in percentage points in order to precisely define changes.
  • zinc, magnesium and aluminum within the meaning of the invention is recorded regardless of the form in which they are present, so it does not matter whether these elements are neutral atoms or ions, in a compound such as an alloy or inter-metallic phases or in a compound such as complexes, oxides, salts, hydroxides or the like.
  • the terms “zinc”, “aluminum” and “magnesium” in the context of the invention can encompass not only the elements in pure form, but also oxidic and / or hydroxidic or any form of compounds that contain these elements.
  • the substrate is a flat steel product.
  • Flat steel products are understood here as rolled products, the length and width of which are each significantly greater than their thickness.
  • sheet metal product rolled products such as steel strips or sheets which are cut off or blanks for the production of, for example, body parts.
  • Sheet metal parts” or “sheet metal parts” are made from such flat or sheet steel products, the terms “sheet metal part” and “sheet metal part” being used synonymously here.
  • Another embodiment relates to a method in which the metallic protective layer is a Zn-Al-Mg coating. Accordingly, the term ZM coating in an alternative also includes a Zn-Al-Mg coating.
  • the metallic protective layer is produced by hot-dip coating.
  • a coating based on zinc and magnesium is present on the substrate used according to the invention.
  • the coating according to the invention preferably contains 0.1 to 3.0% by weight of Mg, preferably 0.6 to 2.0% by weight of Mg, and unavoidable impurities 0.1 to 3.0% by weight.
  • Al preferably 0.5 to 2.5% by weight of Al, particularly preferably 1.0 to 2.0% by weight of Al.
  • the coating in particular made of zinc or a zinc alloy, is preferably at a coating weight of at least 1 to a maximum of 600 g / m2, ie at least 0.5 to a maximum of 300 g / m2 per side, particularly preferably at least 20 to a maximum of 300 g / m2, i.e. at least 10 to a maximum of 150 g / m2 per side.
  • metal oxide layers of the metallic protective layer that are close to the surface are also removed in step b).
  • step c) of the method according to the invention an upper area of at least one zinc grain is also removed so that an exposed surface of the zinc grain is formed that is essentially free of eutectic and eutectic phase and possibly magnesium.
  • the at least one eutectic phase is removed from the upper surface of at least one (primary) zinc grain or from at least one (primary) zinc grain.
  • the method is characterized in that an inorganic acid selected from the group containing or consisting of: H2S04, HCl, HN03, H3P04, H2S03, HN02, H3P03, HF, or a mixture of 2 or more of these acids as aqueous Solution is used.
  • an inorganic acid selected from the group containing or consisting of: H2S04, HCl, HN03, H3P04, H2S03, HN02, H3P03, HF, or a mixture of 2 or more of these acids as aqueous Solution is used.
  • an aqueous solution of an inorganic acid with a pH between 0.01 and 2, preferably at least 0.01; particularly preferably at least 0.1 and at most 1.8, preferably at most 1.7, in particular a pH value less than 1.0 is used.
  • the invention also relates to an embodiment in which the metallic protective layer is wetted with the aqueous solution of an inorganic acid for a time of 0.5-600 seconds and / or at a temperature of 10 ° C. to 90 ° C.
  • the protective layer is applied for a time of at least 0.5 seconds, preferably at least 1 second, particularly preferably at least 2, 3, 4 seconds, in particular at least 5 seconds, and a maximum of 600 seconds, preferably a maximum of 300 seconds, particularly preferably a maximum of 180 seconds, 120 seconds, 60 seconds, in particular a maximum of 50 seconds, 40 seconds, 30 seconds, 20 seconds, 10 seconds, 5 seconds with wetted by the inorganic acid.
  • the coated substrate is wetted with the inorganic acid at a temperature of 10 ° C to 90 ° C, 20 ° C to 70 ° C, preferably 20 ° C to 50 ° C, particularly preferably 20 ° C to 40 ° C, especially 10 ° C to 30 ° C, 20 ° C to 30 ° C.
  • the coated substrate is wetted with the inorganic acid continuously in an alternative.
  • the inorganic acid is applied to the coated substrate by a method selected from the group or consisting of spraying, spraying, dipping and coil coating methods.
  • the coated substrate is wetted with the inorganic acid in batches, for example by a method selected from the group or consisting of spraying, spraying and dipping.
  • wetting is ended in step d) by rinsing with water or an aqueous solution.
  • wetting with the inorganic acid is interrupted by rinsing with water and / or an alcohol, preferably selected from the group containing or consisting of methanol, ethanol, propanol, isopropanol, ethanol, preferably isopropanol or an aqueous solution.
  • rinsing takes place in 2 sub-steps, in a first sub-step with water; in a second sub-step with an alcohol or an aqueous solution of an alcohol as indicated above.
  • step d) is also carried out continuously, a process selected from the group or consisting of spraying, spraying, dipping and coil coating processes being used.
  • step d) takes place batch-wise, a method selected from the group or consisting of spraying, spraying and being used.
  • the protective layer is used for a time of 0.5-600 seconds, preferably 1-300 seconds, 1-180 seconds, particularly preferably 1-120 seconds, 1-60 seconds, in particular 5-60 seconds, 10-50 seconds , 20 - 40 seconds, 5 - 30 seconds with Water or an aqueous solution is brought into contact.
  • the protective layer is dried by increasing the temperature (up to a maximum of 100 ° C) or by using a blower.
  • the protective layer is air-dried without any further aids. Another alternative is to dry the protective layer by reducing the pressure.
  • a further embodiment relates to the method according to the invention, characterized in that after wetting and / or termination of wetting, the protective layer is brought into contact with air or an oxygen-containing atmosphere in a further substep.
  • the coated substrate is dried in this step, preferably by blowing in air, preferably with air at a temperature below room temperature.
  • the coated substrates are degreased with alkaline cleaning agents before they are wetted with the inorganic acid.
  • the substrate provided with the metallic protective layer is subjected to a dressing step prior to wetting with the aqueous solution of an inorganic acid.
  • the exposed surface with at least one (primary) zinc grain has essentially no magnesium or magnesium oxide (for the definition of metal oxides, including magnesium oxide, see above).
  • the method according to the invention with its features and effects achieved, i.e. in particular the exposed surface of the (primary) zinc grains relates to at least 40%, preferably 50%, 60%, particularly preferably 70%, 75%, 80%, in particular 85%, 90% and more of the zinc grains arranged in a previously defined area.
  • the present invention also relates to a method for activating or reactivating the surface of a cementitious protective layer, in which the above-mentioned steps are carried out.
  • aged ZM protective layers are restored or activated or reactivated for further treatment.
  • less oxygen diffuses in the same time interval into the layers near the surface of the substrates treated according to the invention because it is rich in magnesium ok
  • Another object of the present invention is a method for increasing the cohesive fracture surface portion and optionally the tensile shear strength of a disposition or connection of a substrate having a cementitious coating with a polymer layer by removing at least one near-surface eutectic phase by wetting the surface with a inorganic acid (as described above), optionally subsequent rinsing and / or drying (as described above), application, optionally curing of the polymer layer, the fracture surface fractions being determined in a tensile shear test.
  • the present invention also relates to a method for preventing or reducing the corrosion of a metallic protective layer in relation to a reference, by using an inorganic acid as described above, in particular after storage of the coated substrates, i.e. after aging of the protective layer.
  • the subject matter is also the use of an inorganic acid as described above to increase the cohesive fracture surface fraction and, if necessary, the tensile shear strength of a material or connection of a substrate having a protective coating with an organic polymer layer by removing at least one eutectic phase close to the surface by wetting the surface with an inorganic acid ( as described above), optionally subsequent rinsing and / or drying (as described above), application, optionally curing, of an organic polymer layer, the fractional area fractions being determined in a tensile shear test.
  • the invention also relates to a substrate with a metallic protective layer based on zinc-magnesium, which has at least one zinc grain on the surface with an upper, essentially eutectic-free and / or eutectic phase-free surface.
  • Another subject matter is a substrate with a metallic protective layer based on zinc-magnesium which has at least one zinc grain on the surface with an upper, essentially magnesium-free surface.
  • the present invention also provides a substrate as described above produced using the method according to the invention.
  • combinations of the embodiments and alternatives described above can also be used.
  • A4 size printed circuit boards which had a Zn-Al-Mg protective layer on both sides, were immersed in an aqueous solution of an inorganic acid for 5 seconds or sprayed with the corresponding solution of the acid.
  • the boards treated in this way were then immersed in a water bath or sprayed with water and blown off with cool air until they were dry.
  • the boards prepared in this way were exposed to the natural air atmosphere until further evaluation.
  • the measurement is carried out with a device: Phi Quantera II SXM Scanning XPS Microprobe from Physical Electronics GmbH.
  • the element concentrations measured by means of the XPS are taken from overview spectra that are recorded at a transmission energy of 280 eV in the course of at least 7 cycles and relate to a measuring area of 100 ⁇ 100 pm 2 .
  • the measurement is carried out with a glow discharge spectrometer "Spectruma GDA750" vacuum simultaneous spectrometer with a focal length of 750mm and a discharge source constructed according to the Grimm type.
  • the measurement is carried out in RF mode.
  • the basic operation of the glow discharge spectrometer is carried out according to the operating instructions of the manufacturer (Spectruma).
  • the device is operated with a 4mm anode and argon 5.0 (99.999%) gas.
  • Typical parameters of the respective device for operation with a 4mm anode are a voltage of 800V, a current of 20mA, a power of 16W and a lamp pressure of 3-10 hPa.
  • a pre-plasma lasting 25s is connected upstream as part of the measurements.
  • GD-OES glow discharge spectroscopy
  • the measurement was carried out with a device: TOF.SIMS 5, from ION-TOF GmbH, Wein.
  • FIG. 1 shows an SEM image of a sample prepared according to FIG.
  • the smooth areas (A) are the exposed zinc grains and the rough areas (B) are the continuous eutectic.
  • the eutectic and the eutectic phases above the zinc grains were essentially completely removed.
  • Substrates with a dressed Zn-Al-Mg coating were degreased with an alkaline cleaning agent and then subjected to the process according to the invention.
  • the pre-treated substrates were immersed in the appropriate solutions of the inorganic acids for 5 seconds. This was followed by rinsing with water and isopropanol. All experiments were carried out under normal air atmosphere.
  • the fracture surface was examined after the adhesive bond had been separated from the acid-treated cementitious protective layer, bonded with an epoxy-based adhesive. AF gives the adhesive and CF the cohesive part of the fracture surface (special cohesive fracture SCF close to the substrate).
  • the results are summarized in FIG. 2 and show a significant increase in the cohesive fraction of breakage due to the method according to the invention or the use according to the invention by means of various concentrations of inorganic acid before and after aging.
  • the specified milliliter amount of concentrated sulfuric acid (approx. 96%) was used.
  • the aging took place through 10 VDA, i.e. 10 cycles in the climate change test.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating With Molten Metal (AREA)

Abstract

L'invention concerne un procédé d'enlèvement au moins par endroits d'une phase eutectique d'une couche de protection sur base de zinc-magnésium, ainsi qu'un produit plat en acier dont la surface présente des endroits sans eutectique et/ou sans magnésium.
PCT/EP2020/058152 2019-03-27 2020-03-24 Procédé de reconditionnement de surfaces galvanisées à chaud Ceased WO2020193548A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20714977.4A EP3947777A1 (fr) 2019-03-27 2020-03-24 Procédé de reconditionnement de surfaces galvanisées à chaud

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019204224.4 2019-03-27
DE102019204224.4A DE102019204224A1 (de) 2019-03-27 2019-03-27 Verfahren zur Neukonditionierung von feuerverzinkten Oberflächen

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WO2020193548A1 true WO2020193548A1 (fr) 2020-10-01

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DE (1) DE102019204224A1 (fr)
WO (1) WO2020193548A1 (fr)

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DE102021107873A1 (de) 2021-03-29 2022-09-29 Thyssenkrupp Steel Europe Ag Schmelztauchbeschichtetes Stahlblech
DE102022106615A1 (de) 2022-03-22 2023-09-28 Thyssenkrupp Steel Europe Ag Verfahren zum Modifizieren einer Oberfläche eines schmelztauchbeschichteten Stahlblechs
EP4296399A1 (fr) 2022-06-23 2023-12-27 ThyssenKrupp Steel Europe AG Procédé de fabrication d'une tôle d'acier revêtue par immersion à chaud et tôle d'acier revêtue par immersion à chaud
DE102023103033A1 (de) 2023-02-08 2024-08-08 Thyssenkrupp Steel Europe Ag Kalt geformtes Bauteil
DE102023126966A1 (de) 2023-10-04 2025-04-10 Thyssenkrupp Steel Europe Ag Verfahren zum Dressieren eines schmelztauchbeschichteten Stahlbands und ein mit Schlupf dressiertes Stahlflachprodukt

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EP2474649A1 (fr) * 2011-01-05 2012-07-11 Voestalpine Stahl GmbH Procédé de traitement de surface d'un substrat ayant un revêtement de protection
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

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JP2011157579A (ja) * 2010-01-29 2011-08-18 Nisshin Steel Co Ltd 粗面化溶融Ｚｎ−Ａｌ−Ｍｇ合金めっき鋼板およびその製造方法、ならびに溶融Ｚｎ−Ａｌ−Ｍｇ合金めっき鋼板と熱可塑性樹脂成形体とが接合された複合体およびその製造方法
EP2474649A1 (fr) * 2011-01-05 2012-07-11 Voestalpine Stahl GmbH Procédé de traitement de surface d'un substrat ayant 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
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

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