EP3250730B1 - Verfahren zur herstellung eines beschichteten blechs mit anwendung einer wässrigen lösung mit aminosäure, und zugehörige verwendung zur verbesserung der korrosionsbeständigkeit - Google Patents

Verfahren zur herstellung eines beschichteten blechs mit anwendung einer wässrigen lösung mit aminosäure, und zugehörige verwendung zur verbesserung der korrosionsbeständigkeit Download PDF

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Publication number
EP3250730B1
EP3250730B1 EP16704480.9A EP16704480A EP3250730B1 EP 3250730 B1 EP3250730 B1 EP 3250730B1 EP 16704480 A EP16704480 A EP 16704480A EP 3250730 B1 EP3250730 B1 EP 3250730B1
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Prior art keywords
amino acid
aqueous solution
neutral
metal coating
proline
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EP16704480.9A
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English (en)
French (fr)
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EP3250730A1 (de
EP3250730B8 (de
Inventor
Lydia Rachiele
Herve Derule
Delphine THAÏ
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ArcelorMittal SA
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ArcelorMittal SA
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Priority to PL16704480T priority Critical patent/PL3250730T3/pl
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Publication of EP3250730B1 publication Critical patent/EP3250730B1/de
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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
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • 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
    • C23C22/82—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
    • 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
    • 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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing 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
    • 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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/144—Aminocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component

Definitions

  • the present invention relates to a sheet comprising a steel substrate having two faces of which at least one is coated with a metal coating comprising at least 40% by weight of zinc, its preparation process and the use of an amino acid for improving the corrosion resistance of zinc-coated coatings.
  • the invention relates to a coated steel sheet. Before being used, the coated steel sheets are generally subjected to various surface treatments.
  • the demand US 2010/0261024 discloses the application of an aqueous solution of glycine or neutral form glutamic acid or salt to a steel sheet coated with a zinc-based coating to improve the corrosion resistance of the sheet.
  • the demand WO 2008/076684 discloses the application to zinc-coated steel sheet, electrogalvanised steel plate or galvanized steel sheet of a pretreatment composition consisting of an aqueous solution comprising a compound comprising a Group IIIB (Sc, Y) metal , La, Ac) or group IVB (Ti, Zr, Hf, Rf) and a copper-based compound, for example aspartate or copper glutamate, followed by the application of a composition comprising a resin film-forming material and a yttrium-based compound.
  • a pretreatment composition consisting of an aqueous solution comprising a compound comprising a Group IIIB (Sc, Y) metal , La, Ac) or group IVB (Ti, Zr, Hf, Rf) and a copper-based compound, for example aspartate or copper glutamate, followed by the application of a composition comprising a resin film-forming material and a yttrium-based compound.
  • a pretreatment composition consist
  • the demand EP 2 458 031 describes the application on a galvanized steel sheet GI, or galvanized alloy GA, a conversion treatment solution comprising a compound (A) selected from water-soluble titanium or zirconium compounds and an organic compound (B) which can in particular, be glycine, alanine, asparagine, glutamic acid or aspartic acid in neutral form or salt.
  • the compound (A) forms on the sheet a conversion film which improves the compatibility of the sheet with subsequently applied coatings, such as cataphoretic paints, and its resistance to corrosion.
  • Compound (B) is described as stabilizing compound (A).
  • the demand US2014 / 0360630 discloses a zinc-based pretreatment process performed prior to the application of an anti-corrosion coating, which can be implemented for the manufacture of automotive parts.
  • This pretreatment process is a "ferrization” process by forming a homogeneous layer of iron oxide and / or iron on the surface to improve the resistance to corrosion.
  • coated steel sheets are for example intended for the automotive field.
  • Metal coatings essentially comprising zinc are traditionally used for their good protection against corrosion.
  • An object of the invention is to provide a method for preparing a steel sheet coated with a metal coating comprising zinc which has an even greater corrosion resistance.
  • the invention relates to a method according to claim 1.
  • the method may also include the features of claims 2 to 14, taken alone or in combination.
  • the invention also relates to a sheet according to claim 15 to 17, and uses according to claims 18 and 19.
  • Sheet 1 of the figure comprises a substrate 3 made of steel coated on each of its two faces 5 by a metal coating 7. It will be observed that the relative thicknesses of substrate 3 and coatings 7 covering it have not been respected in FIG. to facilitate representation.
  • the coatings 7 present on the two faces 5 are similar and only one will be described in detail later. Alternatively (not shown), only one of the faces 5 has a metal coating 7.
  • the metal coating 7 comprises more than 40% by weight of zinc, in particular more than 50% by weight of zinc, preferably more than 70% by weight of zinc, more preferably more than 90%, preferably more than 95%, of preferably more than 99%.
  • the complement may consist of metal elements Al, Mg, Si, Fe, Sb, Pb, Ti, Ca, Sr, Mn, Sn, La, Ce, Cr, Ni or Bi, taken alone or in combination.
  • the measurement of the composition of a coating is generally carried out by chemical dissolution of the coating. The result given corresponds to an average content throughout the layer.
  • the metal coating 7 may comprise several successive layers of different compositions, each of these layers comprising more than 40% by weight of zinc (or more, as defined above).
  • the metal coating 7, or one of its constituent layers may also have a concentration gradient in a given metal element.
  • the average proportion of zinc in the metal coating 7, or in this constituent layer is more than 40% by weight of zinc (or more, as defined above).
  • the method may comprise a prior step of preparing the substrate 2 made of steel having two faces 5, at least one of which is coated with a metal coating 7 comprising at least 40% by weight of zinc.
  • a steel substrate 3 is used, for example obtained by hot rolling and then cold rolling.
  • the metal coating 7 comprising more than 40% by weight of zinc may be deposited on the substrate 3 by any known deposition method, in particular by electrogalvanization, vapor deposition ("physical vapor deposition" PVD in English), deposition by jet of Sonic steam (“Jet Vapor Deposition” JVD in English) or hot dip galvanizing.
  • the steel substrate 3 having two faces 5, at least one of which is coated with a metal coating 7 comprising at least 40% by weight of zinc is obtained by electrogalvanizing the substrate 3 made of steel.
  • the application of the coating may take place on one side (the sheet 1 then comprises only a metal coating 7), or on both sides (the sheet 1 then comprises two metal coatings 7).
  • the steel substrate 3 having two faces 5, at least one of which is coated with a metal coating 7 comprising at least 40% by weight of zinc is obtained by hot-dip galvanizing the steel substrate 3.
  • the substrate 3 is then in the form of a strip which is scrolled in a bath to deposit the metal coating 7 by hot dipping.
  • the composition of the bath varies according to whether the desired sheet 1 is a galvanized steel sheet GI, a galvanized steel sheet or a galvanized steel sheet coated with a zinc alloy. and magnesium, an alloy of zinc and aluminum or an alloy of zinc, magnesium and aluminum.
  • the bath may also contain up to 0.3% by weight of additional optional elements such as Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni or Bi. These various additional elements can in particular make it possible to improve the ductility or adhesion of the metal coating 7 to the substrate 3.
  • the bath may finally contain residual elements from the ingots, or resulting from the passage of the substrate 3 in the bath, a source of unavoidable impurities in the metal coating 7.
  • the steel substrate 3 having two faces 5, at least one of which is coated with a metal coating 7 comprising at least 40% by weight of zinc is a galvanized steel sheet GI.
  • the metal coating 7 is then a GI zinc coating.
  • Such a coating comprises more than 99% by weight of zinc.
  • the steel substrate 3 having two faces 5, at least one of which is coated with a metal coating 7 comprising at least 40% by weight of zinc is a galvanized steel sheet GA.
  • the metal coating 7 is then a coating of zinc GA.
  • a galvanized steel sheet GA is obtained by annealing ("annealing" in English) of a sheet galvanized steel GI.
  • the method therefore comprises a step of hot-dip galvanizing the steel substrate 3, and then an annealing step.
  • the annealing causes the iron of the steel substrate 3 to diffuse into the metal coating 7.
  • the metal coating 7 of a GA sheet typically comprises from 10% to 15% by weight of iron.
  • the metal coating 7 is an alloy of zinc and aluminum.
  • the metal coating 7 may for example comprise 55% by weight of aluminum, 43.5% by weight of zinc and 1.5% by weight of silicon, such as Aluzinc® sold by ArcelorMittal.
  • the metal coating 7 is an alloy of zinc and magnesium, preferably comprising more than 70% by weight of zinc.
  • Metal coatings comprising zinc and magnesium will be generally referred to herein as zinc-magnesium or ZnMg coatings.
  • the addition of magnesium to the metal coating 7 significantly increases the corrosion resistance of these coatings, which can reduce their thickness or increase the guarantee of protection against corrosion over time.
  • the metal coating 7 may especially be an alloy of zinc, magnesium and aluminum, preferably comprising more than 70% by weight of zinc.
  • Metal coatings comprising zinc, magnesium, and aluminum will generally be referred to herein as zinc-aluminum-magnesium or ZnAIMg coatings.
  • the addition of aluminum (typically of the order of 0.1% by weight) to a coating based on zinc and magnesium also improves the corrosion resistance, and makes the coated sheet easier to be formatting.
  • metal coatings essentially comprising zinc are now competing with coatings comprising zinc, magnesium and possibly aluminum.
  • the metal coating 7 of ZnMg or ZnAIMg type comprises between 0.1 and 10% by weight, typically between 0.3 and 10% by weight, especially between 0.3 and 4% by weight of magnesium. Below 0.1% by weight of Mg, the coated sheet is less resistant to corrosion and above 10% by weight of Mg, the ZnMg or ZnAIMg coating oxidizes too much and can not be used.
  • the metal coating 7 of ZnAIMg type comprises aluminum, typically between 0.5 and 11% by weight, especially between 0.7 and 6% by weight, preferably between 1 and 6% by weight of aluminum.
  • the mass ratio between the magnesium and the aluminum in the metal coating 7 of the ZnAIMg type is strictly less than or equal to 1, preferably strictly less than 1, and more preferably strictly less than 0.9.
  • the most common unavoidable impurity present in the metal coating 7 and resulting from the passage of the substrate in the bath is iron which may be present at a content of up to 3% by weight, generally less than or equal to 0.4% by weight, typically between 0.1 and 0.4% by weight relative to the metal coating 7.
  • the unavoidable impurities from the ingots, for the ZnAIMg baths, are generally lead (Pb), present at a content of less than 0.01% by weight with respect to the metal coating 7, Cadmium (Cd), present at a content of less than 0.005% by weight with respect to the metal coating 7 and tin (Sn) present at a content of less than 0.001% by weight relative to the metal coating 7.
  • Additional elements selected from Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni or Bi may be present in the metal coating 7.
  • the content by weight of each additional element is generally less than 0 , 3%.
  • the metal coating 7 generally has a thickness less than or equal to 25 microns and conventionally aims to protect the steel substrate 3 against corrosion.
  • the substrate 3 is for example spun by means of nozzles throwing a gas on either side of the substrate 3.
  • the metal coating 7 is then allowed to cool in a controlled manner to solidify.
  • Controlled cooling of the metal coating 7 is provided at a rate of preferably greater than or equal to 15 ° C / s or more than 20 ° C / s between the onset of solidification (i.e. when the metal coating 7 falls just below the temperature of the liquidus) and the end of solidification (that is to say when the metal coating 7 reaches the temperature of the solidus).
  • the spin may be adapted to remove the metal coating 7 deposited on one face 5 so that only one of the faces 5 of the sheet 1 is finally coated with a metal coating 7.
  • the band thus treated can then be subjected to a so-called skin-pass step which allows the harden and give it a roughness facilitating its subsequent shaping.
  • the outer surface 15 of the metal coating 7 is subjected to a surface treatment step which comprises applying to them an aqueous solution comprising an amino acid selected from alanine, arginine, aspartic acid, cysteine, glutamine, lysine, methionine, proline, serine, threonine, and a mixture thereof.
  • Each amino acid can be in neutral form or salt.
  • an amino acid is one of the 22 proteinaceous amino acids (L isomer) or an isomer thereof, especially their D isomers.
  • the amino acid is preferably an L-amino acid for cost reasons.
  • the invention is based on the unexpected discovery that the application on the outer surface of the metal coating 7 of an aqueous solution comprising an amino acid from the above mentioned list makes it possible to improve the corrosion resistance of the sheet obtained. This improvement is not observed regardless of the amino acid used. For example, the corrosion resistance has not been improved by applying valine to a metal-coated sheet comprising at least 40% by weight of zinc. No theory has yet been put forward to explain why some amino acids can improve corrosion resistance and not others.
  • the aqueous solution applied may comprise an amino acid selected from alanine, arginine, aspartic acid, cysteine, glutamine, lysine, methionine, proline, serine, threonine, and a mixture of these. ci, each amino acid being in neutral form or salt.
  • the aqueous solution applied may comprise an amino acid selected from alanine, arginine, aspartic acid, glutamine, lysine, methionine, proline, serine, threonine, and a mixture thereof, each amino acid being in neutral form or salt.
  • the aqueous solution applied can in particular comprise an amino acid chosen from alanine, aspartic acid, cysteine, glutamine, methionine, proline, serine, threonine, and a mixture thereof, each amino acid being under neutral form or salt.
  • the aqueous solution applied may, for example, comprise an amino acid chosen from alanine, aspartic acid, glutamine, methionine, proline and serine. threonine, and a mixture thereof, each amino acid being in neutral form or salt.
  • the amino acid of the aqueous solution applied is selected from aspartic acid, cysteine, methionine, proline and threonine, and a mixture of of these, each amino acid being in neutral or salt form, in particular among aspartic acid, methionine, proline and threonine, and a mixture thereof, each amino acid being in neutral or salt form.
  • the amino acid of the aqueous solution applied is chosen from alanine, arginine, glutamine and lysine. , methionine, proline, serine, threonine and a mixture thereof, each amino acid being in neutral form or salt.
  • the amino acid of the applied aqueous solution is selected from alanine, glutamine, methionine, proline, serine, threonine and a mixture thereof, each amino acid being in neutral form or salt.
  • the amino acid of the aqueous solution applied is chosen from methionine, proline and threonine and a mixture thereof, each amino acid being in neutral form or salt.
  • the amino acid is especially selected from proline in neutral form or salt, cysteine in neutral form or salt, and a mixture thereof.
  • Proline is particularly effective in improving corrosion resistance.
  • the cysteine advantageously makes it possible to assay the amount of amino acid deposited on the surface by virtue of its thiol function, for example by X-ray fluorescence spectrometry (SFX).
  • the amino acid is selected from proline in neutral form or salt, threonine in neutral form or salt, and a mixture thereof.
  • Proline and threonine not only make it possible to improve the corrosion resistance of the sheet, but also to improve the compatibility of the surface with an adhesive and to improve the tribological properties of the surface of the sheet (this which makes it well adapted to its subsequent shaping, especially by stamping).
  • the improvement of the compatibility of the surface of the sheet with an adhesive can for example be demonstrated by carrying out tensile tests on samples of sheets assembled by means of an adhesive and possibly aged, up to rupture of the assembly and by measuring the maximum tensile stress and the nature of the fracture.
  • the improvement of the tribological properties can for example be demonstrated by measuring the coefficient of friction ( ⁇ ) as a function of the contact pressure (MPa), for example from 0 to 80 MPa.
  • the aqueous solution applied generally comprises from 1 to 200 g / l, in particular from 5 g / l to 150 g / l, typically from 5 g / l to 100 g / l, for example from 10 to 50 g / l of amino acid. in neutral form or salt or mixture of amino acid in neutral form or salts.
  • the most significant improvement in the corrosion resistance of the metal coating 7 of the sheet 1 was observed using an aqueous solution comprising from 5 g / l to 100 g / l, in particular from 10 to 50 g / l d amino acid or amino acid mixture.
  • the aqueous solution applied generally comprises from 10 to 1750 mmol / l, especially from 40 mmol / l to 1300 mmol / l, typically from 40 mmol / l to 870 mmol / l, for example from 90 to 430 mmol / l of amino acid. in neutral form or salt or mixture of amino acid in neutral form or salts.
  • the most significant improvement in the corrosion resistance of the metal coating 7 of the sheet 1 was observed using an aqueous solution comprising from 40 mmol / L to 870 mmol / L, in particular from 90 to 430 mmol / L amino acid or amino acid mixture.
  • the mass and molar proportions of the amino acid (or of each of the amino acids when an amino acid mixture is used) in the aqueous solution can not be greater than the proportions corresponding to the limit of solubility of the amino acid at the temperature. to which the aqueous solution is applied.
  • the mass percentage of dry extract of the amino acid in neutral form or of salt or of the mixture of neutral amino acids or of salts in the aqueous solution is greater than or equal to 75%, in particular greater than or equal to 90%, preferably greater than or equal to 95%.
  • the molar percentage of dry extract of the amino acid in neutral form or of salt in the aqueous solution is greater than or equal to 75%, especially greater than or equal to 90%, preferably greater than or equal to 95%.
  • the aqueous solution may comprise zinc sulfate and / or iron sulfate.
  • the proportion of zinc sulphate in the aqueous solution is generally less than 80 g / l, preferably less than 40 g / l.
  • the aqueous solution is free of zinc sulfate and iron sulfate.
  • the aqueous solution comprising an amino acid comprises less than 10 g / l, typically less than 1 g / l, generally less than 0.1 g / l, especially less than 0.05 g / l, for example less than 0.01 g. / L of zinc ions.
  • the aqueous solution is free of zinc ion (in addition to unavoidable traces, which could for example arise from the pollution, by the substrate, of the bath of aqueous solution).
  • the aqueous solution comprising an amino acid generally comprises less than 0.005 g / L of iron ions.
  • the aqueous solution comprising an amino acid generally comprises few metal ions other than potassium, sodium, calcium and zinc, typically less than 0.1 g / l, especially less than 0.05 g / l, for example less 0.01 g / L, preferably less than 0.005 g / L of metal ions other than potassium, sodium, calcium and zinc.
  • the aqueous solution is free of metal ions other than zinc, calcium, sodium and potassium.
  • the aqueous solution comprising an amino acid generally comprises few metal ions other than zinc, typically less than 0.1 g / l, especially less than 0.05 g / l, for example less than 0.01 g / l, preferably less than 0.005 g / L of metal ions other than zinc.
  • the aqueous solution is free of metal ions other than zinc.
  • the aqueous solution comprising an amino acid generally comprises few cobalt and / or nickel ions, typically less than 0.1 g / l, especially less than 0.05 g / l, for example less than 0.01 g / l of cobalt and / or nickel ions.
  • the aqueous solution is free of cobalt ions and / or free of nickel ions and / or free of copper ions and / or free of chromium ions.
  • the aqueous solution is free of a compound comprising a Group IIIB metal (Sc, Y, La, Ac) or Group IVB (Ti, Zr, Hf, Rf).
  • it is free of metal ions (in addition to unavoidable metallic impurities, which could for example come from the pollution, by the substrate, of the aqueous solution bath).
  • the absence of metal ions in the aqueous solution makes it possible to avoid disturbing the action of the active ingredient that is the amino acid or the mixture of amino acids.
  • the aqueous solution comprising an amino acid generally comprises less than 0.1 g / l, in particular less than 0.05 g / l, for example less than 0.01 g / l of compounds comprising chromium VI, or more generally chromium. Generally, it is free of compounds comprising chromium VI, or more generally chromium.
  • the aqueous solution is generally free of oxidizing agent.
  • the aqueous solution is generally free of resin, in particular of organic resin.
  • a resin is a polymeric product (natural, artificial or synthetic) which is a raw material for manufacturing, for example, plastics, textiles, paints (liquid or powder), adhesives, varnishes, polymer foams. It can be thermoplastic or thermosetting. More generally, the aqueous solution is generally free of polymer.
  • the pH of the aqueous solution applied is generally comprised of a pH equal to the [isoelectric point of the 3-amino acid] at a pH equal to the [isoelectric point of the amino acid + 3], in particular of a pH equal to isoelectric point of the amino acid - 2] at a pH equal to the [isoelectric point of the amino acid + 2], preferably of a pH equal to the [isoelectric point of the amino acid - 1] at a pH equal to isoelectric of the amino acid + 1].
  • the pH of the aqueous solution is generally from 3.3 to 9.3, especially from 4.3 to 8.3, preferably from 5.3 to 7.3.
  • the pH of the aqueous solution applied is generally comprised of a pH equal to the [isoelectric point of the amino acid -3] at a pH equal to the [isoelectric point of the amino acid + 1], preferably of a pH equal to [isoelectric point of the amino acid - 3] at a pH equal to the [isoelectric point of the amino acid - 1], in particular of a pH equal to the [isoelectric point of the amino acid - 2.5] at a pH equal to [isoelectric point of the amino acid - 1.5], typically a pH equal to the [isoelectric point of the amino acid - 2].
  • the pH of the aqueous solution is preferably from 3.3 to 5.3, especially from 3.8 to 4.8, typically from the order of 4.0, such as 4.3.
  • a process carried out with a solution having such a pH makes it possible to obtain a sheet which retains its properties. improved corrosion resistance, even when subjected to a washing / re-oiling treatment.
  • the sheet according to the invention can be blanked before forming, typically by stamping.
  • a washing / re-oiling treatment can be implemented. This consists in applying a low-viscosity oil to the surfaces of the sheet, then in brushing and then applying an oil of greater viscosity. Without wishing to be bound by any particular theory, it is assumed that a solution having such a pH makes it possible to obtain the amino acid in protonated form (NH 3 + ), which would promote the bond between the amino acid and the metal coating 7 and therefore the maintenance of the amino acid on the surface despite the washing / re-oiling treatment.
  • the amine of the amino acid is little or not protonated: the bonds between the amino acid and the metal coating 7 would be weaker and the amino acid would be more likely to dissolve in the oil used during the washing / re-oiling treatment, leading to its at least partial removal, and therefore to less good corrosion resistance properties.
  • a base or an acid is indifferently in neutral form and / or salt.
  • the proportion of acid is less than 10 g / l, in particular 1 g / l in the solution.
  • the phosphoric acid is added together in neutral form and in salt form (for example sodium, calcium or potassium), for example in a H 3 PO 4 / NaH 2 PO 4 mixture.
  • Phosphoric acid advantageously makes it possible to measure the amount of aqueous solution (and therefore of amino acid) deposited on the surface by means of phosphorus and / or sodium, for example by X-ray fluorescence spectrometry (SFX).
  • the aqueous solution consists of a mixture of water, amino acid in neutral form or salt or a mixture of amino acids independently in neutral forms or salts and optionally a base or a mixture of bases, or an acid or a mixture of acids.
  • the base or acid serves to adjust the pH of the aqueous solution.
  • the amino acid imparts the properties of improving the corrosion resistance.
  • the base or the acid makes it possible to reinforce this effect. Addition of other compounds is not necessary.
  • the aqueous solution comprising an amino acid can be applied at a temperature of between 20 and 70 ° C.
  • the duration of application of the aqueous solution can be between 0.5s and 40s, preferably between 2s and 20s.
  • the aqueous solution comprising an amino acid can be applied by immersion, spraying or any other system.
  • the application of the aqueous solution on the outer surface 15 of the metal coating 7 can be carried out by any means, for example by immersion, by spraying ("spray” in English) or by roll coating ("roll coat” in English). .
  • the latter technique is preferred because it makes it easier to control the amount of aqueous solution applied while ensuring a homogeneous distribution of the aqueous solution on the surface.
  • the wet film thickness consisting of the aqueous solution applied to the outer surface of the metal coating 7 is 0.2 to 5 ⁇ m, typically between 1 and 3 ⁇ m.
  • aqueous solution comprising an amino acid is brought into contact with the outer surface 15 of the metal coating 7. It is therefore sub- It is to be understood that the outer surface 15 of the metal coating 7 is not covered with an intermediate layer (a film, a coating or a solution) which would prevent the contact of the aqueous solution comprising an amino acid with the outer surface of the coating. metallic 7.
  • the method comprises, after the step of applying to the outer surface of the metal coating 7 an aqueous solution comprising an amino acid, a drying step, which provides on the outer surface 15 of the metal coating 7 a layer comprising (or consisting of) an amino acid (in neutral or salt form) or a mixture of amino acids (independently in neutral forms or salts).
  • a drying step which provides on the outer surface 15 of the metal coating 7 a layer comprising (or consisting of) an amino acid (in neutral or salt form) or a mixture of amino acids (independently in neutral forms or salts).
  • a drying step which provides on the outer surface 15 of the metal coating 7 a layer comprising (or consisting of) an amino acid (in neutral or salt form) or a mixture of amino acids (independently in neutral forms or salts).
  • This can be done by subjecting the sheet 1 to a temperature between 70 and 120 ° C, for example between 80 and 100 ° C, generally for 1 to 30 seconds, especially 1 to 10 seconds, for example 2 s.
  • the metal coating 7 of the sheet 1 obtained is then typically coated with a layer comprising from 0.1 to 200 mg / m 2 , in particular from 25 to 150 mg / m 2 , in particular from 50 to 100 mg / m 2 , example of 60 to 70 mg / m 2 of amino acid (in neutral or salt form) or a mixture of amino acids (independently in neutral forms or salts).
  • the amount of amino acid deposited on the outer surface of the metal coating 7 can be determined by assaying the amount of amino acid deposited (eg by infrared), or by assaying the amount of amino acid remaining in the aqueous solution (for example by acidobasic and / or conductimetric assay) since the initial amino acid concentration of the aqueous solution is known.
  • the amino acid or one of the amino acids is cysteine
  • the amount of cysteine deposited on the surface can be determined by X-ray fluorescence spectrometry (SFX).
  • the layer comprising an amino acid (in neutral or salt form) or a mixture of amino acids (independently in neutral forms or salts) which coat the metal coating 7 of the sheet 1 obtained comprises from 75 to 100% by weight, typically 90 to 100% by weight of amino acid (in neutral or salt form) or mixture of amino acids (independently in neutral forms or salts).
  • the method may comprise (or be free from) other surface treatment step (s) than that of applying an aqueous solution comprising an amino acid (for example alkaline oxidation surface treatment and / or chemical conversion).
  • this (s) surface treatment step (s) leads (s) to the formation of a layer on the metal coating 7
  • this (these) other (s) surface treatment step (s) is (are) carried out simultaneously or after the step of applying an aqueous solution comprising an amino acid on the outer surface 15 of the metal coating 7, so that there is no intermediate layer between the outer surface 15 of the coating metal 7 and the aqueous solution comprising an amino acid.
  • These possible surface treatment steps mentioned above may include other sub-stages of rinsing, drying ....
  • a film of fat or oil is generally applied to the outer surface of the metal coating 7 coated with a layer comprising an amino acid or a mixture of amino acids to protect it against corrosion.
  • the band may possibly be wound before being stored. Typically, before putting the piece into shape, the strip is cut. A grease or oil film may then be reapplied to the outer surface of the metal coating 7 coated with a layer comprising an amino acid or a mixture of amino acids prior to shaping.
  • the process is free of a degreasing step (typically performed by applying a basic aqueous solution of pH generally greater than 9 to the outer surface 15 of the metal coating 7) prior to shaping.
  • a degreasing step typically performed by applying a basic aqueous solution of pH generally greater than 9 to the outer surface 15 of the metal coating 7) prior to shaping.
  • the treatment with a basic aqueous solution on the outer surface 15 of the coating metal coated with a layer comprising an amino acid or a mixture of amino acids could lead to the partial or total elimination of the amino acid (s) which has (have) been deposited on the surface outer 15 of the metal coating 7, which is sought to avoid.
  • the sheet may then be shaped by any method adapted to the structure and shape of the parts to be manufactured, preferably by stamping, such as for example cold stamping.
  • the shaped sheet 1 then corresponds to a part, for example a car part.
  • the disclosure also relates to the sheet 1 that can be obtained by the method.
  • a sheet comprises at least a portion of at least one outer surface 15 of the metal coating 7 coated with a layer comprising from 0.1 to 200 mg / m 2 , in particular from 25 to 150 mg / m 2 , in particular from 50 to at 100 mg / m 2 , for example 60 to 70 mg / m 2 of amino acid in neutral form or salt.
  • the disclosure also relates to the use of an aqueous solution comprising an amino acid selected from alanine, arginine, aspartic acid, cysteine, glutamine, lysine, methionine, proline, serine, threonine and a mixture thereof, each amino acid being in neutral form or salt, the aqueous solution being free of a compound comprising a Group IIIB or Group IVB metal, to improve the corrosion resistance of an outer surface.
  • a metal coating 7 coating at least one face 5 of a substrate 3 of steel, wherein the metal coating 7 comprises at least 40% by weight of zinc.
  • the sheets 1 obtained by a process according to the invention have a better resistance to corrosion.
  • the other properties of the sheets 1 obtained by the process according to the invention have not been degraded.
  • Example 2 Tests for Measuring the Friction Coefficient ( ⁇ ) as a Function of the Contact Pressure (MPa) and Tensile Tests for the Proline and Threonine Amino Acids
  • Each specimen 27 was prepared as follows. Tabs 29 were cut from sheet 1 to be evaluated. These tongues 29 had dimensions of 25 mm ⁇ 12.5 mm ⁇ 0.2 mm.
  • Tabs 29 were immersed for an immersion time of 20 seconds at a temperature of 50 ° C. in an aqueous solution of proline or threonine whose pH had been adjusted by addition of H 3 PO 4 , with the exception of reference plates (Ref) having not been subjected to any treatment with an amino acid.
  • Fuchs® 3802-39S oil was applied to the tabs 29 in an amount of 3 g / m 2 .
  • BM1496V, BM1440G or BM1044 adhesive which are epoxy-based "crash” adhesives marketed by Dow® Automotive. These adhesives have been selected because they are adhesives conventionally leading to adhesive fractures before aging and / or after aging of the adhesive.
  • test piece 27 thus formed was then raised to 180 ° C. and held at this temperature for 30 minutes, which makes it possible to bake the adhesive.
  • the tensile test was then carried out at an ambient temperature of 23 ° C. by imposing a tensile speed of 10 mm / min on one tongue 29, parallel to the latter, while the other tongue 29 of the test specimen It was fixed. The test was continued until the test piece 27 was broken.
  • the sheets 1 which have undergone treatment with an aqueous solution comprising proline or threonine promote the appearance of superficial cohesive fractures, in contrast to the reference sheets for which more than Adhesive fractures have been observed.
  • Samples of steel sheet 1 covered with a metal coating 7 comprising approximately 99% zinc (DX56D grade steel sheet, thickness 0.7 mm), samples of electrogalvanised steel sheet 1 whose coating included 100% of Zinc (EG steel sheet grade DC06, thickness 0.8 mm), electro-galvanized Fortiform® steel sheet 1 samples with 100% zinc coating (7.5 ⁇ m on both sides) or sheet metal samples 1 steel sonic vapor deposition (Zn JVD) coated with 100% zinc (7.5 ⁇ m on both sides) were used.
  • a metal coating 7 comprising approximately 99% zinc (DX56D grade steel sheet, thickness 0.7 mm)
  • samples of electrogalvanised steel sheet 1 whose coating included 100% of Zinc EG steel sheet grade DC06, thickness 0.8 mm
  • electro-galvanized Fortiform® steel sheet 1 samples with 100% zinc coating (7.5 ⁇ m on both sides) or sheet metal samples 1 steel sonic vapor deposition (Zn JVD) coated with 100% zinc (7.5 ⁇ m on both sides) were used.
  • Samples having dimensions of 450 mm ⁇ 35 mm ⁇ thickness were cut from these steel sheets.
  • the samples were immersed for an immersion time of 20 seconds at a temperature of 50 ° C. in an aqueous solution of proline or threonine whose pH had possibly been adjusted by addition of H 3 PO 4 .
  • Fuchs® 3802-39S in an amount of 3 g / m 2
  • Fuchs® 4107S (reject)
  • QUAKER 6130 QUAKER 6130
  • phase A phase A, B, and C in Table 3 below.

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Claims (19)

  1. Verfahren zur Herstellung eines Blechs (1), welches zumindest die Schritte aufweist:
    - Bereitstellen eines Substrats (3) aus Stahl, von welchem zumindest eine Fläche (5) mit einer metallischen Beschichtung beschichtet ist, welche zumindest 40 Gew.-% Zink aufweist,
    - Aufbringen, auf die Außenfläche (15) der metallischen Beschichtung (7), einer wässrigen Lösung, welche eine Aminosäure aufweist, die aus Alanin, Arginin, Asparaginsäure, Cystein, Glutamin, Lysin, Methionin, Prolin, Serin, Threonin und einer Mischung daraus ausgewählt ist, wobei jede Aminosäure neutral oder als Salz ausgebildet ist,
    wobei die wässrige Lösung von einer Zusammensetzung frei ist, die ein Metall der Gruppe IIIB oder der Gruppe IVB aufweist, und
    die Gewichtsprozent eines Trockenextrakts der Aminosäure, welche neutral oder als Salz ausgebildet ist, oder der Mischung der Aminosäuren, welche neutral oder als Salze ausgebildet sind, in der wässrigen Lösung größer oder gleich 75% sind, vorzugsweise größer oder gleich 90%.
  2. Verfahren gemäß Anspruch 1, aufweisend einen vorhergehenden Schritt des Herstellens des Substrats (3) aus Stahl, von welchem zumindest eine Fläche (5) mit einer metallischen Beschichtung beschichtet ist, welcher aus Feuerverzinken, einem Dampfstrahlablagern mit Schallgeschwindigkeit und einem elektrolytischen Verzinken des Substrats (3) aus Stahl ausgewählt ist.
  3. Verfahren gemäß irgendeinem der Ansprüche 1 bis 2, bei welchem die metallische Beschichtung (7) aus einer Zink-GI-Beschichtung, einer Zink-GA-Beschichtung, einer Legierung aus Zink und Aluminium, einer Legierung aus Zink und Magnesium und einer Legierung aus Zink, Magnesium und Aluminium ausgewählt ist, wobei die metallische Beschichtung (7) vorzugsweise eine Legierung aus Zink und Magnesium ist, welche zwischen 0,1 und 10 Gew.-% Mg und gegebenenfalls zwischen 0,1 und 20 Gew.-% Al enthält, wobei der Rest der metallischen Beschichtung aus Zn, aus unvermeidbaren Unreinheiten und gegebenenfalls aus einem oder mehreren zusätzlichen Elementen ist, welche aus Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni oder Bi ausgewählt sind.
  4. Verfahren gemäß irgendeinem der vorhergehenden Ansprüche, bei welchem die Aminosäure aus Alanin, Asparaginsäure, Cystein, Glutamin, Methionin, Prolin, Serin, Threonin und einer Mischung daraus ausgewählt ist, wobei jede Aminosäure neutral oder als Salz ausgebildet ist, wobei die Aminosäure vorzugsweise aus Prolin, welches neutral oder als Salz ausgebildet ist, aus Cystein, welches neutral oder als Salz ausgebildet ist, und einer Mischung daraus ausgewählt ist, vorzugsweise Prolin ist, welches neutral oder als Salz ausgebildet ist.
  5. Verfahren gemäß irgendeinem der Ansprüche 1, 2 oder 4, bei welchem das Substrat (3) aus Stahl, von welchem zumindest eine Fläche (5) mit einer metallischen Beschichtung beschichtet ist, durch elektrolytisches Verzinken hergestellt wird und die Aminosäure aus Asparaginsäure, Cystein, Methionin, Prolin und Threonin und einer Mischung daraus ausgewählt ist, wobei jede Aminosäure neutral oder als Salz ausgebildet ist.
  6. Verfahren gemäß irgendeinem der Ansprüche 1 bis 4, bei welchem das Substrat (3) aus Stahl, von welchem zumindest eine Fläche (5) mit einer metallischen Beschichtung (7) beschichtet ist, durch Feuerverzinken hergestellt wird und die Aminosäure aus Alanin, Arginin, Glutamin, Lysin, Methionin, Prolin, Serin, Threonin und einer Mischung daraus ausgewählt ist, wobei jede Aminosäure neutral oder als Salz ausgebildet ist.
  7. Verfahren gemäß irgendeinem der Ansprüche 1 bis 6, bei welchem die Aminosäure Threonin ist, welches neutral oder als Salz ausgebildet ist, oder eine Mischung aus Prolin und Threonin ist, wobei das Prolin und das Threonin neutral oder als Salz ausgebildet sind.
  8. Verfahren gemäß irgendeinem der vorhergehenden Ansprüche, bei welchem die wässrige Lösung 1 bis 200 g/L einer Aminosäure, welche neutral oder als Salz ausgebildet ist, oder einer Mischung aus Aminosäuren, welche neutral oder als Salze ausgebildet sind, oder 10 bis 1750 mmol/L einer Aminosäure, welche neutral oder als Salz ausgebildet ist, oder einer Mischung aus Aminosäuren aufweist, welche neutral oder als Salze ausgebildet sind.
  9. Verfahren gemäß irgendeinem der vorhergehenden Ansprüche, bei welchem die wässrige Lösung einen pH-Wert aufweist, welcher zwischen einem pH-Wert gleich dem [isoelektrischen Punkt der Aminosäure -3] und einem pH-Wert gleich dem [isoelektrischen Punkt der Aminosäure +1] liegt, vorzugsweise, welcher zwischen einem pH-Wert gleich dem [isoelektrischen Punkt der Aminosäure - 3] und einem pH-Wert gleich dem [isoelektrischen Punkt der Aminosäure -1] liegt.
  10. Verfahren gemäß irgendeinem der vorhergehenden Ansprüche, bei welchem die wässrige Lösung bei einer Temperatur, welche zwischen 20 und 70°C liegt, aufgetragen wird und/oder bei welchem die Lösung für eine Dauer, welche zwischen 0,5s und 40s liegt, auf die Außenfläche (15) der metallischen Beschichtung (7) aufgetragen wird.
  11. Verfahren gemäß irgendeinem der vorhergehenden Ansprüche, bei welchem die Lösung durch Walzbeschichten aufgetragen wird.
  12. Verfahren gemäß irgendeinem der vorhergehenden Ansprüche, aufweisend, nach dem Schritt des Aufbringens einer wässrigen Lösung, welche eine Aminosäure aufweist, auf die Außenfläche (15) der metallischen Beschichtung (7), einen Trocknungsschritt, vorzugsweise durch Unterziehen des Blechs (1) einer Temperatur, welche zwischen 70 und 120°C liegt, für 1 bis 30 Sekunden.
  13. Verfahren gemäß irgendeinem der vorhergehenden Ansprüche, aufweisend, nach dem Schritt des Aufbringens einer wässrigen Lösung, welche eine Aminosäure aufweist, auf die Außenfläche (15) der metallischen Beschichtung (7), und dem möglichen Trocknungsschritt, einen Schritt des Aufbringens eines Films aus Fett oder Öl auf die Außenfläche (15) der metallischen Beschichtung (7), der auf eine Schicht beschichtet wird, die eine Aminosäure oder eine Mischung aus Aminosäuren aufweist.
  14. Verfahren gemäß irgendeinem der vorhergehenden Ansprüche, aufweisend, nach dem Schritt des Aufbringens einer wässrigen Lösung, welche eine Aminosäure aufweist, auf die Außenfläche (15) der metallischen Beschichtung (7), dem möglichen Trocknungsschritt und dem möglichen Schritt des Aufbringens eines Films aus Fett oder Öl, einen Formgebungsschritt des Blechs (1), vorzugsweise durch Tiefziehen ausgeführt.
  15. Blech (1), geeignet, um durch ein Verfahren gemäß irgendeinem der Ansprüche 1 bis 14 erhaltbar zu sein.
  16. Blech (1) gemäß dem vorhergehenden Anspruch, bei welchem zumindest ein Bereich von zumindest einer Außenfläche (15) der metallischen Beschichtung (7) mit einer Schicht beschichtet ist, die 0,1 bis 200 mg/m2 einer Aminosäure, welche neutral oder als Salz ausgebildet ist, oder einer Mischung aus Aminosäuren aufweist, welche neutral oder als Salze ausgebildet sind.
  17. Blech (1) gemäß dem Anspruch 15 oder 16, bei welchem zumindest ein Bereich von zumindest einer Außenfläche (15) der metallischen Beschichtung (7) mit einer Schicht beschichtet ist, die 75 bis 100 Gew.-% einer Aminosäure, welche neutral oder als Salz ausgebildet ist, oder einer Mischung aus Aminosäuren aufweist, welche neutral oder als Salze ausgebildet sind.
  18. Verwendung einer wässrigen Lösung, welche eine Aminosäure aufweist, die aus Alanin, Arginin, Asparaginsäure, Cystein, Glutamin, Lysin, Methionin, Prolin, Serin, Threonin und einer Mischung daraus ausgewählt ist, wobei jede Aminosäure neutral oder als Salz ausgebildet ist,
    wobei die wässrige Lösung von einer Zusammensetzung frei ist, welche ein Metall der Gruppe IIIB oder der Gruppe IVB aufweist und
    wobei die Gewichtsprozent eines Trockenextrakts der Aminosäure, welche neutral oder als Salz ausgebildet ist, oder der Mischung der Aminosäuren, welche neutral oder als Salze ausgebildet sind, in der wässrigen Lösung größer oder gleich 75% sind,
    zum Verbessern des Korrosionswiderstands einer Außenfläche (15) einer metallischen Beschichtung (7), welche auf zumindest eine Fläche (5) eines Substrats (3) aus Stahl beschichtet ist, wo die metallische Beschichtung zumindest 40 Gew.-% Zink aufweist.
  19. Verwendung einer wässrigen Lösung, welche eine Aminosäure aufweist, die aus Prolin, Threonin und einer Mischung daraus ausgewählt ist, wobei das Prolin und das Threonin unabhängig neutral oder als Salz ausgebildet sind, wobei die wässrige Lösung von einer Zusammensetzung frei ist, welche ein Metall der Gruppe IIIB oder der Gruppe IVB aufweist, um:
    - die Kompatibilität mit einem Kleber von zumindest einem Bereich einer Außenfläche (15) einer metallischen Beschichtung (7) zu verbessern, die auf zumindest einer Fläche eines Substrats (3) aus Stahl beschichtet ist,
    - den Korrosionswiderstand der Außenfläche (15) der metallischen Beschichtung (7) zu verbessern, die auf zumindest eine Fläche (5) des Substrats (3) aus Stahl beschichtet ist, und
    - tribologische Eigenschaften der Außenfläche (15) der metallischen Beschichtung (7) zu verbessern, die auf zumindest einer Fläche (5) des Substrats (3) aus Stahl beschichtet ist,
    wo die metallische Beschichtung (7) zumindest 40 Gew.-% Zink aufweist.
EP16704480.9A 2015-01-30 2016-02-01 Verfahren zur herstellung eines beschichteten blechs mit anwendung einer wässrigen lösung mit aminosäure, und zugehörige verwendung zur verbesserung der korrosionsbeständigkeit Active EP3250730B8 (de)

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PL16704480T PL3250730T3 (pl) 2015-01-30 2016-02-01 Sposób wytwarzania powlekanej blachy, obejmujący nałożenie wodnego roztworu zawierającego aminokwas i związane zastosowanie dla polepszenia odporności na korozję

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PCT/IB2015/050722 WO2016120669A1 (fr) 2015-01-30 2015-01-30 Procédé de préparation d'une tôle revêtue comprenant l'application d'une solution aqueuse comprenant un aminoacide et utilisation associée pour améliorer la résistance à la corrosion
PCT/IB2016/050506 WO2016120855A1 (fr) 2015-01-30 2016-02-01 Procédé de préparation d'une tôle revêtue comprenant l'application d'une solution aqueuse comprenant un aminoacide et utilisation associée pour améliorer la résistance à la corrosion

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EP3250730A1 EP3250730A1 (de) 2017-12-06
EP3250730B1 true EP3250730B1 (de) 2019-01-23
EP3250730B8 EP3250730B8 (de) 2019-06-26

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KR20170107466A (ko) 2017-09-25
TR201905111T4 (tr) 2019-05-21
WO2016120855A1 (fr) 2016-08-04
ES2713752T3 (es) 2019-05-23
WO2016120669A1 (fr) 2016-08-04
US11236413B2 (en) 2022-02-01
EP3250730A1 (de) 2017-12-06
CN107208273A (zh) 2017-09-26
US20200040438A1 (en) 2020-02-06
JP2018503748A (ja) 2018-02-08
CN107208273B (zh) 2020-03-06
HUE042791T2 (hu) 2019-07-29
US20180023177A1 (en) 2018-01-25
JP6784680B2 (ja) 2020-11-11
EP3250730B8 (de) 2019-06-26
BR112017015696B1 (pt) 2022-04-05
US11060174B2 (en) 2021-07-13
CA2975370C (fr) 2023-04-18
CA2975370A1 (fr) 2016-08-04
BR112017015696A2 (pt) 2018-03-20
KR102604333B1 (ko) 2023-11-20
PL3250730T3 (pl) 2019-06-28

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