EP3250730B1 - Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve corrosion resistance - Google Patents
Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve corrosion resistance Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- amino acid
- aqueous solution
- neutral
- metal coating
- proline
- 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.)
- Active
Links
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- 229910052751 metal Inorganic materials 0.000 title claims description 145
- 239000002184 metal Substances 0.000 title claims description 144
- 239000007864 aqueous solution Substances 0.000 title claims description 107
- 238000000034 method Methods 0.000 title claims description 42
- 238000005260 corrosion Methods 0.000 title claims description 37
- 230000007797 corrosion Effects 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000576 coating method Methods 0.000 claims description 161
- 235000001014 amino acid Nutrition 0.000 claims description 159
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- 230000007935 neutral effect Effects 0.000 claims description 63
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- 239000000203 mixture Substances 0.000 claims description 57
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- 239000000853 adhesive Substances 0.000 claims description 32
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- 229930182817 methionine Natural products 0.000 claims description 17
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 16
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 16
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 15
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- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 14
- 235000004554 glutamine Nutrition 0.000 claims description 14
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- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 13
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 13
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- 235000018977 lysine Nutrition 0.000 claims description 10
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 9
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
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- 238000001035 drying Methods 0.000 claims description 6
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- 238000007493 shaping process Methods 0.000 claims description 5
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- 238000001912 gas jet deposition Methods 0.000 claims description 4
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- 239000004519 grease Substances 0.000 claims description 3
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- 238000012360 testing method Methods 0.000 description 20
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- 229910001335 Galvanized steel Inorganic materials 0.000 description 9
- 239000008397 galvanized steel Substances 0.000 description 9
- 229960001153 serine Drugs 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
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- 239000011133 lead Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
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- 239000010936 titanium Substances 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 241000282485 Vulpes vulpes Species 0.000 description 5
- 238000005246 galvanizing Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
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- 239000011135 tin Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 229930182821 L-proline Natural products 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229960004452 methionine Drugs 0.000 description 4
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- 230000035882 stress Effects 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 210000002105 tongue Anatomy 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 3
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- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 238000009304 pastoral farming Methods 0.000 description 3
- 238000004846 x-ray emission Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
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- -1 zinc-aluminum-magnesium Chemical compound 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 2
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- 230000000295 complement effect Effects 0.000 description 2
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Images
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
- 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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Description
La présente invention est relative à une tôle comprenant un substrat en acier présentant deux faces dont au moins l'une est revêtue par un revêtement métallique comprenant au moins 40% en poids de zinc, à son procédé de préparation et à l'utilisation d'un aminoacide pour améliorer la résistance à la corrosion de tôles revêtues de revêtements à base de zinc.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.
L'invention concerne une tôle en acier revêtue. Avant d'être utilisées, les tôles en acier revêtues sont généralement soumises à divers traitements de surface.The invention relates to a coated steel sheet. Before being used, the coated steel sheets are generally subjected to various surface treatments.
La demande
La demande
La demande
La demande
Ces tôles en acier revêtues sont par exemple destinées au domaine de l'automobile. Les revêtements métalliques comprenant essentiellement du zinc sont traditionnellement utilisés pour leur bonne protection contre la corrosion.These 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.
Un but de l'invention est de de proposer un procédé de préparation d'une tôle en acier revêtue par un revêtement métallique comprenant du zinc qui présente une résistance à la corrosion encore accrue.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.
A cet effet, l'invention concerne un procédé selon la revendication 1.For this purpose, the invention relates to a method according to
Le procédé peut également comprendre les caractéristiques des revendications 2 à 14, prises isolément ou en combinaison.The method may also include the features of claims 2 to 14, taken alone or in combination.
L'invention concerne également une tôle selon la revendication 15 à 17, et les utilisations selon les revendications 18 et 19.The invention also relates to a sheet according to
L'invention va à présent être illustrée par des exemples donnés à titre indicatif, et non limitatif, et en référence à la figure annexée, qui est une vue schématique en coupe illustrant la structure d'une tôle 1 obtenue par un procédé selon l'invention.The invention will now be illustrated by examples given by way of indication, and not by way of limitation, and with reference to the appended figure, which is a diagrammatic sectional view illustrating the structure of a
La tôle 1 de la figure comprend un substrat 3 en acier recouvert sur chacune de ses deux faces 5 par un revêtement métallique 7. On observera que les épaisseurs relatives du substrat 3 et des revêtements 7 le recouvrant n'ont pas été respectées sur la figure afin de faciliter la représentation.
Les revêtements 7 présents sur les deux faces 5 sont analogues et un seul sera décrit en détail par la suite. En variante (non-représentée), seule une des faces 5 présente un revêtement métallique 7.The
Le revêtement métallique 7 comprend plus de 40% en poids de zinc, notamment plus de 50% en poids de zinc, de préférence plus de 70% en poids de zinc, plus préférentiellement plus de 90%, de préférence plus de 95%, de préférence plus de 99%. Le complément peut être constitué des éléments métalliques Al, Mg, Si, Fe, Sb, Pb, Ti, Ca, Sr, Mn, Sn, La, Ce, Cr, Ni ou Bi, pris seul ou en combinaison. La mesure de la composition d'un revêtement est généralement réalisée par dissolution chimique du revêtement. Le résultat donné correspond à une teneur moyenne dans l'ensemble de la couche.The
Le revêtement métallique 7 peut comprendre plusieurs couches successives de compositions différentes, chacune de ces couches comprenant plus de 40% en poids de zinc (ou plus, comme défini ci-dessus). Le revêtement métallique 7, ou l'une de ses couches constitutives, peut également présenter un gradient de concentration en un élément métallique donné. Lorsque le revêtement métallique 7, ou l'une de ses couches constitutives, présente un gradient de concentration en zinc, la proportion moyenne en zinc dans le revêtement métallique 7, ou dans cette couche constitutive, est de plus de 40% en poids de zinc (ou plus, comme défini ci-dessus).The
Pour réaliser la tôle 1, on peut par exemple procéder comme suit.To produce the
Le procédé peut comprendre une étape préalable de préparation du substrat 3 en acier présentant deux faces 5, dont au moins l'une est revêtue par un revêtement métallique 7 comprenant au moins 40% en poids de zinc. On utilise un substrat 3 en acier obtenu par exemple par laminage à chaud puis à froid. Le revêtement métallique 7 comprenant plus de 40% en poids de zinc peut être déposé sur le substrat 3 par toute méthode de dépôt connue, notamment par électrozingage, dépôt en phase vapeur (« physical vapor deposition » PVD en anglais), dépôt par jet de vapeur sonique (« Jet Vapor Déposition » JVD en anglais) ou galvanisation à chaud au trempé.The method may comprise a prior step of preparing the substrate 2 made of steel having two
Selon une première alternative, le substrat 3 en acier présentant deux faces 5, dont au moins l'une est revêtue par un revêtement métallique 7 comprenant au moins 40% en poids de zinc est obtenu par électrozingage du substrat 3 en acier. L'application du revêtement peut avoir lieu sur une face (la tôle 1 ne comprend alors qu'un revêtement métallique 7), ou sur deux faces (la tôle 1 comprend alors deux revêtements métalliques 7).According to a first alternative, the
Selon une deuxième alternative, le substrat 3 en acier présentant deux faces 5, dont au moins l'une est revêtue par un revêtement métallique 7 comprenant au moins 40% en poids de zinc est obtenu par galvanisation à chaud du substrat 3 en acier.According to a second alternative, the
Généralement, le substrat 3 est alors sous forme d'une bande que l'on fait défiler dans un bain pour déposer le revêtement métallique 7 par trempé à chaud. La composition du bain varie selon que la tôle 1 désirée est une tôle en acier galvanisée GI (« galvanized steel sheet » en anglais), GA (galvanisée alliée ou « galvannealed steel sheet » en anglais) ou une tôle revêtue par un alliage de zinc et de magnésium, un alliage de zinc et d'aluminium ou un alliage de zinc, de magnésium et d'aluminium. Le bain peut également contenir jusqu'à 0,3% en poids d'éléments optionnels additionnels tels que Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni ou Bi. Ces différents éléments additionnels peuvent notamment permettre d'améliorer la ductilité ou l'adhésion du revêtement métallique 7 sur le substrat 3. L'homme du métier, qui connaît leurs effets sur les caractéristiques du revêtement métallique 7, saura les employer en fonction du but complémentaire recherché. Le bain peut enfin contenir des éléments résiduels provenant des lingots d'alimentation, ou résultant du passage du substrat 3 dans le bain, source d'impuretés inévitables dans le revêtement métallique 7.Generally, the
Dans un mode de réalisation, le substrat 3 en acier présentant deux faces 5, dont au moins l'une est revêtue par un revêtement métallique 7 comprenant au moins 40% en poids de zinc, est une tôle en acier galvanisée GI. Le revêtement métallique 7 est alors un revêtement de zinc GI. Un tel revêtement comprend plus de 99% en poids de zinc.In one embodiment, the
Dans un autre mode de réalisation, le substrat 3 en acier présentant deux faces 5, dont au moins l'une est revêtue par un revêtement métallique 7 comprenant au moins 40% en poids de zinc est une tôle en acier galvanisée GA. Le revêtement métallique 7 est alors un revêtement de zinc GA. Une tôle en acier galvanisée GA est obtenue par recuit (« annealing » en anglais) d'une tôle en acier galvanisée GI. Dans ce cas, le procédé comprend donc une étape de galvanisation à chaud du substrat 3 en acier, puis une étape de recuit. Le recuit provoque la diffusion du fer du substrat 3 en acier dans le revêtement métallique 7. Le revêtement métallique 7 d'une tôle GA comprend typiquement de 10% à 15% en poids de fer.In another embodiment, the
Dans un autre mode de réalisation, le revêtement métallique 7 est un alliage de zinc et d'aluminium. Le revêtement métallique 7 peut par exemple comprendre 55% en poids d'aluminium, 43,5% en poids de zinc et 1,5% en poids de silicium, comme l'Aluzinc® vendu par ArcelorMittal.In another embodiment, the
Dans un autre mode de réalisation, le revêtement métallique 7 est un alliage de zinc et de magnésium, comprenant de préférence plus de 70% en poids de zinc. Les revêtements métalliques comprenant du zinc et du magnésium seront globalement désignés ici sous le terme de revêtements zinc-magnésium ou ZnMg. L'ajout de magnésium au revêtement métallique 7 augmente nettement la résistance à la corrosion de ces revêtements, ce qui peut permettre de réduire leur épaisseur ou d'augmenter la garantie de protection contre la corrosion dans le temps.In another embodiment, the
Le revêtement métallique 7 peut notamment être un alliage de zinc, de magnésium et d'aluminium, comprenant de préférence plus de 70% en poids de zinc. Les revêtements métalliques comprenant du zinc, du magnésium et de l'aluminium seront globalement désignés ici sous le terme de revêtements zinc- aluminium- magnésium ou ZnAIMg. L'ajout d'aluminium (typiquement de l'ordre de 0,1% en poids) à un revêtement à base de zinc et de magnésium permet également d'améliorer la résistance à la corrosion, et rend la tôle revêtue plus facile à être mise en forme. Ainsi, les revêtements métalliques comprenant essentiellement du zinc sont à présent concurrencés par les revêtements comprenant du zinc, du magnésium et éventuellement de l'aluminium.The
Typiquement, le revêtement métallique 7 de type ZnMg ou ZnAIMg comprend entre 0,1 et 10% en poids, typiquement entre 0,3 et 10% en poids, notamment entre 0,3 et 4% en poids de magnésium. En dessous de 0,1% en poids de Mg, la tôle revêtue résiste moins bien à la corrosion et au-delà de 10% en poids de Mg, le revêtement ZnMg ou ZnAIMg s'oxyde trop et ne peut être utilisé.Typically, the
Au sens de la présente demande, lorsqu'une plage de chiffre est décrite comme étant entre une borne basse et une borne haute, il est sous-entendu que ces bornes sont incluses. Par exemple un revêtement comprenant 0,1% ou 10% en poids de magnésium est inclut lorsque l'expression « Le revêtement métallique 7 comprend entre 0,1 et 10% en poids de magnésium » est utilisée.For the purposes of the present application, when a range of numbers is described as being between a low terminal and a high terminal, it is understood that these terminals are included. For example a coating comprising 0.1% or 10% by weight of magnesium is included when the expression "The
Le revêtement métallique 7 de type ZnAIMg comprend de l'aluminium, typiquement entre 0,5 et 11% en poids, notamment entre 0,7 et 6% en poids, de préférence entre 1 et 6% en poids d'aluminium. Typiquement, le rapport massique entre le magnésium et l'aluminium dans le revêtement métallique 7 de type ZnAIMg est strictement inférieur ou égal à 1, de préférence strictement inférieur à 1, et de préférence encore strictement inférieur à 0,9.The
L'impureté inévitable la plus courante présente dans le revêtement métallique 7 et résultant du passage du substrat dans le bain est le fer qui peut être présent à une teneur allant jusqu'à 3% en poids, généralement inférieure ou égale à 0,4% en poids, typiquement comprise entre 0,1 et 0,4% en poids par rapport au revêtement métallique 7.The most common unavoidable impurity present in the
Les impuretés inévitables provenant des lingots d'alimentation, pour les bains ZnAIMg, sont généralement le plomb (Pb), présent à une teneur inférieure à 0,01% en poids par rapport au revêtement métallique 7, le Cadmium (Cd), présent à une teneur inférieure à 0,005% en poids par rapport au revêtement métallique 7et l'étain (Sn), présent à une teneur inférieure à 0,001% en poids par rapport au revêtement métallique 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
Des éléments additionnels choisis parmi Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni ou Bi peuvent être présents dans le revêtement métallique 7. La teneur en poids de chaque élément additionnel est généralement inférieure à 0,3%.Additional elements selected from Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni or Bi may be present in the
Le revêtement métallique 7 a généralement une épaisseur inférieure ou égale à 25 µm et vise de manière classique à protéger le substrat 3 en acier contre la corrosion.The
Après dépôt du revêtement métallique 7, le substrat 3 est par exemple essoré au moyen de buses projetant un gaz de part et d'autre du substrat 3.After depositing the
On laisse ensuite refroidir le revêtement métallique 7 de façon contrôlée pour qu'il se solidifie. Le refroidissement contrôlé du revêtement métallique 7 est assuré à une vitesse de préférence supérieure ou égale à 15°C/s ou encore supérieure à 20°C/s entre le début de la solidification (c'est-à-dire lorsque le revêtement métallique 7 tombe juste sous la température du liquidus) et la fin de solidification (c'est-à-dire lorsque le revêtement métallique 7 atteint la température du solidus).The
En variante, l'essorage peut être adapté pour enlever le revêtement métallique 7 déposé sur une face 5 de sorte qu'une seule des faces 5 de la tôle 1 ne soit en définitive revêtue par un revêtement métallique 7.In a variant, the spin may be adapted to remove the
La bande ainsi traitée peut ensuite être soumise à une étape dite de skin-pass qui permet de l'écrouir et lui conférer une rugosité facilitant sa mise en forme ultérieure.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.
La surface extérieure 15 du revêtement métallique 7 est soumise à une étape de traitement de surface qui consiste à leur appliquer une solution aqueuse comprenant un aminoacide choisi parmi l'alanine, l'arginine, l'acide aspartique, la cystéine, la glutamine, la lysine, la méthionine, la proline, la sérine, la thréonine, et un mélange de ceux-ci. Chaque aminoacide peut être sous forme neutre ou de sel. Au sens de la demande, un aminoacide est un des 22 aminoacides protéinogènes (isomère L) ou un de leurs isomères, notamment leurs isomères D. L'aminoacide est de préférence un aminoacide L pour des raisons de coût.The
L'invention repose sur la découverte inattendue que l'application sur la surface extérieure 15 du revêtement métallique 7 d'une solution aqueuse comprenant un aminoacide de la liste mentionnée ci-dessus permet d'améliorer la résistance à la corrosion de la tôle obtenue. Cette amélioration n'est pas observée quel que soit l'aminoacide utilisé. Par exemple, la résistance à la corrosion n'a pas été améliorée en appliquant de la valine sur une tôle revêtue par un revêtement métallique 7 comprenant au moins 40% en poids de zinc. Aucune théorie n'a pour l'instant été mise en avant pour expliquer pourquoi certains aminoacides permettent d'améliorer la résistance à la corrosion et pas d'autres.The invention is based on the unexpected discovery that the application on the outer surface of the
La solution aqueuse appliquée peut comprendre un aminoacide choisi parmi l'alanine, l'arginine, l'acide aspartique, la cystéine, la glutamine, la lysine, la méthionine, la proline, la sérine, la thréonine, et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel.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.
La solution aqueuse appliquée peut comprendre un aminoacide choisi parmi l'alanine, l'arginine, l'acide aspartique, la glutamine, la lysine, la méthionine, la proline, la sérine, la thréonine, et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel. La solution aqueuse appliquée peut notamment comprendre un aminoacide choisi parmi l'alanine, l'acide aspartique, la cystéine, la glutamine, la méthionine, la proline, la sérine, la thréonine, et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel.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.
La solution aqueuse appliquée peut par exemple comprendre un aminoacide choisi parmi l'alanine, l'acide aspartique, la glutamine, la méthionine, la proline, la sérine, la thréonine, et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel.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.
De préférence, dans la première alternative dans laquelle la tôle 1 est une tôle en acier électrozinguée, l'aminoacide de la solution aqueuse appliquée est choisi parmi l'acide aspartique, la cystéine, la méthionine, la proline et la thréonine, et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel, en particulier parmi l'acide aspartique, la méthionine, la proline et la thréonine, et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel.Preferably, in the first alternative in which the
De préférence, dans la seconde alternative dans laquelle la tôle 1 est une tôle obtenue par galvanisation à chaud du substrat 3 en acier, l'aminoacide de la solution aqueuse appliquée est choisi parmi l'alanine, l'arginine, la glutamine, la lysine, la méthionine, la proline, la sérine, la thréonine et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel. Par exemple, l'aminoacide de la solution aqueuse appliquée est choisi parmi l'alanine, la glutamine, la méthionine, la proline, la sérine, la thréonine et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel.Preferably, in the second alternative in which the
De préférence, dans la troisième alternative dans laquelle la tôle 1 est indifféremment une tôle en acier électrozinguée ou une tôle obtenue par galvanisation à chaud du substrat 3 en acier, l'aminoacide de la solution aqueuse appliquée est choisi parmi la méthionine, la proline et la thréonine et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel.Preferably, in the third alternative in which the
L'aminoacide est notamment choisi parmi la proline sous forme neutre ou de sel, la cystéine sous forme neutre ou de sel, et un mélange de celles-ci. La proline est particulièrement efficace pour améliorer la résistance à la corrosion. La cystéine permet avantageusement de doser la quantité d'aminoacide déposé en surface grâce à sa fonction thiol, par exemple par spectrométrie de fluorescence X (SFX).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).
De préférence, l'aminoacide est choisi parmi la proline sous forme neutre ou de sel, la thréonine sous forme neutre ou de sel, et un mélange de celles-ci. La proline et la thréonine permettent en effet non seulement d'améliorer la résistance à la corrosion de la tôle, mais aussi d'améliorer la compatibilité de la surface avec un adhésif et d'améliorer les propriétés tribologiques de la surface de la tôle (ce qui la rend bien adaptée à sa mise en forme ultérieure, notamment par emboutissage).Preferably, 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).
L'amélioration de la compatibilité de la surface de la tôle avec un adhésif peut par exemple être mise en évidence en effectuant des tests de traction sur des échantillons de tôles assemblés par l'intermédiaire d'un adhésif et éventuellement vieillies, jusqu'à rupture de l'assemblage et en mesurant la contrainte maximale de traction et la nature de la rupture. L'amélioration des propriétés tribologiques peut par exemple être mise en évidence en mesurant le coefficient de frottement (µ) en fonction de la pression de contact (MPa), par exemple de de 0 à 80 MPa.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 (μ) as a function of the contact pressure (MPa), for example from 0 to 80 MPa.
Il est particulièrement surprenant que la thréonine et/ou la proline permettent d'améliorer ces trois propriétés à la fois. Dans les conditions testées, les autres aminoacides n'ont pas permis une amélioration de ces trois propriétés sur tout type de revêtement métallique comprenant au moins 40% en poids de zinc (au mieux, les autres aminoacides ont permis d'observer une amélioration de deux de ces propriétés, mais pas des trois).It is particularly surprising that threonine and / or proline make it possible to improve these three properties at the same time. In the conditions tested, the other amino acids did not allow an improvement of these three properties on any type of metal coating comprising at least 40% by weight of zinc (at best, the other amino acids have allowed to observe an improvement of two of these properties, but not of the three).
La solution aqueuse appliquée comprend généralement de 1 à 200 g/L, notamment de 5 g/L à 150 g/L, typiquement de 5 g/L à 100 g/L, par exemple de 10 à 50 g/L d'aminoacide sous forme neutre ou de sel ou de mélange d'aminoacide sous forme neutres ou de sels. L'amélioration la plus importante de la résistance à la corrosion du revêtement métallique 7 de la tôle 1 a été observée en utilisant une solution aqueuse comprenant de 5 g/L à 100 g/L, en particulier de 10 à 50 g/L d'aminoacide ou de mélange d'aminoacide.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
La solution aqueuse appliquée comprend généralement de 10 à 1750 mmol/L, notamment de 40 mmol/L à 1300 mmol/L, typiquement de 40 mmol/L à 870 mmol/L, par exemple de 90 à 430 mmol /L d'aminoacide sous forme neutre ou de sel ou de mélange d'aminoacide sous forme neutres ou de sels. L'amélioration la plus importante de la résistance à la corrosion du revêtement métallique 7 de la tôle 1 a été observée en utilisant une solution aqueuse comprenant de 40 mmol/L à 870 mmol/L, en particulier de 90 à 430 mmol/L d'aminoacide ou de mélange d'aminoacide.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
Bien entendu, les proportions massiques et molaires de l'aminoacide (ou de chacun des aminoacides quand un mélange d'aminoacides est utilisé) dans la solution aqueuse ne peuvent être supérieures aux proportions correspondant à la limite de solubilité de l'aminoacide à la température à laquelle la solution aqueuse est appliquée. Le pourcentage massique en extrait sec de l'aminoacide sous forme neutre ou de sel ou du mélange d'aminoacides sous forme neutres ou de sels dans la solution aqueuse est supérieur ou égal à 75%, notamment supérieur ou égal à 90%, de préférence supérieur ou égal à 95%. De même, généralement, le pourcentage molaire en extrait sec de l'aminoacide sous forme neutre ou de sel dans la solution aqueuse est supérieur ou égal à 75%, notamment supérieur ou égal à 90%, de préférence supérieur ou égal à 95%.Of course, 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%. Likewise, generally, 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%.
La solution aqueuse peut comprendre du sulfate de zinc et/ou du sulfate de fer. La proportion en sulfate de zinc dans la solution aqueuse est généralement inférieure à 80 g/L, de préférence inférieure à 40 g/L. De préférence, la solution aqueuse est exempte de sulfate de zinc et de sulfate de fer.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. Preferably, the aqueous solution is free of zinc sulfate and iron sulfate.
Généralement, la solution aqueuse comprenant un aminoacide comprend moins de 10g/L, typiquement moins de 1g/L, généralement moins de 0,1 g/L, notamment moins de 0,05 g/L, par exemple moins de 0,01 g/L d'ions zinc. De préférence, la solution aqueuse est exempte d'ion zinc (outre les traces inévitables, qui pourraient par exemple provenir de la pollution, par le substrat, du bain de solution aqueuse).Generally, 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. Preferably, 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).
La solution aqueuse comprenant un aminoacide comprend généralement moins de 0,005 g/L d'ions fer. La solution aqueuse comprenant un aminoacide comprend généralement peu d'ions métalliques autres que le potassium, le sodium, le calcium et le zinc, typiquement moins de 0,1 g/L, notamment moins de 0,05 g/L, par exemple moins de 0,01 g/L, de préférence moins de 0,005 g/L d'ions métalliques autres que le potassium, le sodium, le calcium et le zinc. Typiquement, la solution aqueuse est exempte d'ions métalliques autres que le zinc, le calcium, le sodium et le potassium. La solution aqueuse comprenant un aminoacide comprend généralement peu d'ions métalliques autres que le zinc, typiquement moins de 0,1 g/L, notamment moins de 0,05 g/L, par exemple moins de 0,01 g/L, de préférence moins de 0,005 g/L d'ions métalliques autres que le zinc. Typiquement, la solution aqueuse est exempte d'ions métalliques autres que le zinc. En particulier, la solution aqueuse comprenant un aminoacide comprend généralement peu d'ions cobalt et/ou nickel, typiquement moins de 0,1 g/L, notamment moins de 0,05 g/L, par exemple moins de 0,01g/L d'ions cobalt et/ou nickel. De préférence, la solution aqueuse est exempte d'ions cobalt et/ou exempte d'ions nickel et/ou exempte d'ions cuivre et/ou exempte d'ions chrome. La solution aqueuse est exempte de composé comprenant un métal du groupe IIIB (Sc, Y, La, Ac) ou du groupe IVB (Ti, Zr, Hf, Rf). De préférence, elle est exempte d'ions métalliques (outre les impuretés métalliques inévitables, qui pourraient par exemple provenir de la pollution, par le substrat, du bain de solution aqueuse).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. Typically, 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. Typically, the aqueous solution is free of metal ions other than zinc. In particular, 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. Preferably, 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). Preferably, 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).
De façon générale, l'absence d'ions métalliques dans la solution aqueuse permet d'éviter de perturber l'action du principe actif qu'est l'aminoacide ou le mélange d'aminoacides.In general, 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.
De plus, la solution aqueuse comprenant un aminoacide comprend généralement moins de 0,1 g/L, notamment moins de 0,05 g/L, par exemple moins de 0,01 g/L de composés comprenant du chrome VI, ou plus généralement du chrome. Généralement, elle est exempte de composés comprenant du chrome VI, ou plus généralement du chrome.In addition, 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.
Par ailleurs, la solution aqueuse est généralement exempte d'agent oxydant.Moreover, the aqueous solution is generally free of oxidizing agent.
Par ailleurs, la solution aqueuse est généralement exempte de résine, en particulier de résine organique. Une résine désigne un produit polymère (naturel, artificiel ou synthétique) qui est une matière première pour fabriquer par exemple des matières plastiques, textiles, peintures (liquides ou en poudre), adhésifs, vernis, mousses de polymère. Elle peut être thermoplastique ou thermodurcissable. De manière plus générale, la solution aqueuse est généralement exempte de polymère.On the other hand, 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.
L'absence de résine permet d'obtenir une couche de traitement de faible épaisseur et d'ainsi faciliter son élimination lors du dégraissage précédant la phosphatation et la mise en peinture. Une résine a, dans ces conditions, tendance à laisser des résidus qui perturbent la phosphatation.The absence of resin makes it possible to obtain a thin treatment layer and thus to facilitate its removal during degreasing before phosphating and painting. Under these conditions, a resin tends to leave residues which disturb phosphatation.
Le pH de la solution aqueuse appliquée est généralement compris d'un pH égal au [point isoélectrique de l'aminoacide - 3] à un pH égal au [point isoélectrique de l'aminoacide + 3], notamment d'un pH égal au [point isoélectrique de l'aminoacide - 2] à un pH égal au [point isoélectrique de l'aminoacide + 2], de préférence d'un pH égal au [point isoélectrique de l'aminoacide - 1] à un pH égal au [point isoélectrique de l'aminoacide + 1]. Par exemple, lorsque l'aminoacide est la proline dont le point isoélectrique est de 6,3, le pH de la solution aqueuse est généralement de 3,3 à 9,3, notamment de 4,3 à 8,3, de préférence de 5,3 à 7,3.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]. For example, when the amino acid is proline whose isoelectric point is 6.3, 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.
Le pH de la solution aqueuse appliquée est généralement compris d'un pH égal au [point isoélectrique de l'aminoacide - 3] à un pH égal au [point isoélectrique de l'aminoacide + 1], de préférence d'un pH égal au [point isoélectrique de l'aminoacide - 3] à un pH égal au [point isoélectrique de l'aminoacide - 1], notamment d'un pH égal au [point isoélectrique de l'aminoacide - 2,5] à un pH égal au [point isoélectrique de l'aminoacide - 1,5], typiquement un pH égal au [point isoélectrique de l'aminoacide - 2]. Par exemple, lorsque l'aminoacide est la proline dont le point isoélectrique est de 6,3, le pH de la solution aqueuse est de préférence de 3,3 à 5,3, notamment de 3,8 à 4,8, typiquement de l'ordre de 4,0, comme 4,3. Un tel pH permet en effet de favoriser la liaison entre l'aminoacide et le revêtement métallique 7. En particulier, un procédé mis en oeuvre avec une solution ayant un tel pH permet d'obtenir une tôle qui conserve ses propriétés améliorées de résistance à la corrosion, même lorsqu'elle a subi un traitement de lavage/rehuilage. Généralement, une fois que la tôle selon l'invention a été préparée, elle peut être découpée en flan avant sa mise en forme, typiquement par emboutissage. Afin d'éliminer les impuretés déposées sur la tôle issues de cette découpe, un traitement de lavage/rehuilage peut être mis en oeuvre. Celui-ci consiste à appliquer sur les surfaces de la tôle une huile de faible viscosité, puis à brosser, puis à appliquer une huile de viscosité plus importante. Sans vouloir être lié par une théorie particulière, on suppose qu'une solution ayant un tel pH permet d'obtenir l'aminoacide sous forme protonée (NH3 +), ce qui favoriserait la liaison entre l'aminoacide et le revêtement métallique 7 et donc le maintien de l'aminoacide à la surface malgré le traitement de lavage/rehuilage. A des pH différents et notamment supérieurs au [point isoélectrique de l'aminoacide - 1], l'amine de l'aminoacide est peu ou pas protonée : les liaisons entre l'aminoacide et le revêtement métallique 7 seraient moins fortes et l'aminoacide aurait plus tendance à se dissoudre dans l'huile utilisée lors du traitement de lavage/rehuilage, conduisant à son élimination au moins partielle, et donc à de moins bonnes propriétés de résistance à la corrosion.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]. For example, when the amino acid is proline whose isoelectric point is 6.3, 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. Such a pH makes it possible to promote the bond between the amino acid and the
L'homme du métier sait comment adapter le pH de la solution aqueuse, par ajout d'une base s'il souhaite augmenter le pH, ou d'un acide, tel que l'acide phosphorique, s'il souhaite le diminuer. Au sens de la demande, une base ou un acide est indifféremment sous forme neutre et/ou de sel. Généralement, la proportion en acide est inférieure à 10 g/L, notamment 1 g/L dans la solution. De préférence, l'acide phosphorique est ajouté conjointement sous forme neutre et sous forme de sel (par exemple de sodium, de calcium ou encore de potassium) par exemple en mélange H3PO4/NaH2PO4. L'acide phosphorique permet avantageusement de doser la quantité de solution aqueuse (et donc d'acide aminé) déposée en surface grâce aux phosphore et/ou sodium, par exemple par spectrométrie de fluorescence X (SFX).Those skilled in the art know how to adapt the pH of the aqueous solution, by adding a base if it wishes to increase the pH, or an acid, such as phosphoric acid, if it wishes to reduce it. In the sense of the application, a base or an acid is indifferently in neutral form and / or salt. Generally, the proportion of acid is less than 10 g / l, in particular 1 g / l in the solution. Preferably, 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).
Dans un mode de réalisation, la solution aqueuse consiste en un mélange d'eau, d'aminoacide sous forme neutre ou de sel ou d'un mélange d'aminoacides indépendamment sous formes neutres ou de sels et éventuellement d'une base ou d'un mélange de bases, ou d'un acide ou d'un mélange d'acides. La base ou l'acide sert à adapter le pH de la solution aqueuse. L'aminoacide confère les propriétés d'amélioration de la résistance à la corrosion. La base ou l'acide permettent de renforcer cet effet. L'ajout d'autres composés n'est pas nécessaire.In one embodiment, 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.
Dans le procédé selon l'invention, la solution aqueuse comprenant un aminoacide peut être appliquée à une température comprise entre 20 et 70°C. La durée d'application de la solution aqueuse peut être entre 0,5s et 40s, de préférence entre 2s et 20s.In the process according to the invention, 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.
La solution aqueuse comprenant un aminoacide peut être appliquée par immersion, aspersion ou tout autre système.The aqueous solution comprising an amino acid can be applied by immersion, spraying or any other system.
L'application de la solution aqueuse sur la surface extérieure 15 du revêtement métallique 7 peut être effectuée par tout moyen, par exemple par immersion, par pulvérisation (« spray » en anglais) ou par enduction au rouleau (« roll coat » en anglais). Cette dernière technique est préférée car elle permet de contrôler plus facilement la quantité de solution aqueuse appliquée tout en assurant une répartition homogène de la solution aqueuse sur la surface. Généralement, l'épaisseur de film humide constitué de la solution aqueuse appliquée sur la surface extérieure 15 du revêtement métallique 7 est de 0,2 à 5 µm, typiquement entre 1 et 3 µm.The application of the aqueous solution on the
Par « application sur la surface extérieure 15 du revêtement métallique 7 d'une solution aqueuse comprenant un aminoacide», on entend que la solution aqueuse comprenant un aminoacide est mise en contact avec la surface extérieure 15 du revêtement métallique 7. Il est donc sous-entendu que la surface extérieure 15 du revêtement métallique 7 n'est pas recouverte d'une couche intermédiaire (un film, un revêtement ou une solution) qui empêcherait la mise en contact de la solution aqueuse comprenant un aminoacide avec la surface extérieure 15 du revêtement métallique 7.By "application on the
Typiquement, le procédé comprend, après l'étape d'application sur la surface extérieure 15 du revêtement métallique 7 d'une solution aqueuse comprenant un aminoacide, une étape de séchage, qui permet d'obtenir sur la surface extérieure 15 du revêtement métallique 7 une couche comprenant (ou constituée de) un aminoacide (sous forme neutre ou de sel) ou un mélange d'aminoacides (indépendamment sous formes neutres ou de sels). Celle-ci peut être effectuée en soumettant la tôle 1 à une température comprise entre 70 et 120°C, par exemple entre 80 et 100°C, généralement pendant 1 à 30 secondes, notamment 1 à 10 secondes, par exemple 2 s. En particulier, un procédé mis en oeuvre avec une telle étape de séchage permet d'obtenir une tôle qui conserve ses propriétés améliorées de résistance à la corrosion, même lorsqu'elle a subi un traitement de lavage/rehuilage.Typically, the method comprises, after the step of applying to the outer surface of the
Le revêtement métallique 7 de la tôle 1 obtenue est alors typiquement revêtu par une couche comprenant de 0,1 à 200 mg/m2, notamment de 25 à 150 mg/m2, en particulier de 50 à 100 mg/m2, par exemple de 60 à 70 mg/m2 d'aminoacide (sous forme neutre ou de sel) ou d'un mélange d'aminoacides (indépendamment sous formes neutres ou de sels). La quantité d'aminoacide déposé sur la surface extérieure 15 du revêtement métallique 7 peut être déterminée en dosant la quantité d'aminoacide déposé (par exemple par infrarouge), ou bien en dosant la quantité d'aminoacide restant dans la solution aqueuse (par exemple par dosage acidobasique et/ou par conductimétrie), étant donné que la concentration initiale en aminoacide de la solution aqueuse est connue. De plus, lorsque que l'aminoacide ou un des aminoacides est la cystéine, la quantité de cystéine déposée en surface peut être déterminée par spectrométrie de fluorescence X (SFX).The
Généralement, la couche comprenant un aminoacide (sous forme neutre ou de sel) ou un mélange d'aminoacides (indépendamment sous formes neutres ou de sels) qui revêt le revêtement métallique 7 de la tôle 1 obtenue comprend de 75 à 100% en poids, typiquement de 90 à 100% en poids d'aminoacide (sous forme neutre ou de sel) ou de mélange d'aminoacides (indépendamment sous formes neutres ou de sels).Generally, 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
Le procédé peut comprendre (ou être exempt) d'autre(s) étape(s) de traitement de surface que celui consistant à appliquer une solution aqueuse comprenant un aminoacide (par exemple un traitement de surface par oxydation alcaline et/ou un traitement de conversion chimique). Lorsque cette(s) étape(s) de traitement de surface conduit(sent) à la formation d'une couche sur le revêtement métallique 7, cette(ces) autre(s) étape(s) de traitement de surface est(sont) effectuée(s) simultanément ou après l'étape d'application d'une solution aqueuse comprenant un aminoacide sur la surface extérieure 15 du revêtement métallique 7, afin qu'il n'y ait pas de couche intermédiaire entre la surface extérieure 15 du revêtement métallique 7 et la solution aqueuse comprenant un aminoacide. Ces éventuelles étapes de traitement de surface susmentionnées peuvent comprendre d'autres sous-étapes de rinçage, de séchage....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). When this (s) surface treatment step (s) leads (s) to the formation of a layer on the
Après avoir appliqué la solution aqueuse comprenant un aminoacide, un film de graisse ou d'huile est généralement appliqué sur la surface extérieure 15 du revêtement métallique 7 revêtue d'une couche comprenant un aminoacide ou un mélange d'aminoacides afin de le protéger contre la corrosion.After applying the aqueous solution comprising an amino acid, a film of fat or oil is generally applied to the outer surface of the
La bande peut éventuellement être bobinée avant d'être stockée. Typiquement, avant de mettre la pièce en forme, la bande est découpée. Un film de graisse ou d'huile peut alors être de nouveau appliqué sur la surface extérieure 15 du revêtement métallique 7 revêtue d'une couche comprenant un aminoacide ou d'un mélange d'aminoacides avant la mise en forme.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
De préférence, le procédé est exempt d'étape de dégraissage (typiquement réalisée en appliquant une solution aqueuse basique de pH généralement supérieur à 9 sur la surface extérieure 15 du revêtement métallique 7) avant mise en forme. En effet, le traitement par une solution aqueuse basique sur la surface extérieure 15 du revêtement métallique 7 revêtue d'une couche comprenant un aminoacide ou d'un mélange d'aminoacides pourrait conduire à l'élimination partielle ou totale de l'(des) aminoacide(s) qui a(ont) été déposé(s) sur la surface extérieure 15 du revêtement métallique 7, ce que l'on cherche à éviter.Preferably, the process is free of a degreasing step (typically performed by applying a basic aqueous solution of pH generally greater than 9 to the
La tôle peut ensuite être mise en forme par tout procédé adapté à la structure et à la forme des pièces à fabriquer, de préférence par emboutissage, tel que par exemple l'emboutissage à froid. La tôle 1 mise en forme correspond alors à une pièce, par exemple une pièce automobile.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
Une fois que la tôle 1 a été mise en forme, le procédé peut alors comprendre (ou être exempt d') :
- une étape de dégraissage, typiquement réalisée en appliquant une solution aqueuse basique sur la surface extérieure 15 du revêtement métallique 7, et/ou
- d'autre(s) étape(s) de traitement de surface, par exemple une étape de phosphatation, et/ou
- une étape de cataphorèse.
- a degreasing step, typically performed by applying a basic aqueous solution to the
outer surface 15 of themetal coating 7, and / or - other step (s) of surface treatment, for example a phosphating step, and / or
- a stage of cataphoresis.
La divulgation concerne également la tôle 1 susceptible d'être obtenue par le procédé. Un telle tôle comprend au moins une partie d'au moins une surface extérieure 15 du revêtement métallique 7 revêtue par une couche comprenant de 0,1 à 200 mg/m2, notamment de 25 à 150 mg/m2, en particulier de 50 à 100 mg/m2, par exemple de 60 à 70 mg/m2 d'aminoacide sous forme neutre ou de sel.The disclosure also relates to the
La divulgation concerne également l'utilisation d'une solution aqueuse comprenant un aminoacide choisi parmi l'alanine, l'arginine, l'acide aspartique, la cystéine, la glutamine, la lysine, la méthionine, la proline, la sérine, la thréonine, et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel, la solution aqueuse étant exempte de composé comprenant un métal du groupe IIIB ou du groupe IVB, pour améliorer la résistance à la corrosion d'une surface extérieure 15 d'un revêtement métallique 7 revêtant au moins une face 5 d'un substrat 3 en acier, où le revêtement métallique 7 comprend au moins 40% en poids de zinc.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
Les modes de réalisation préférentiels décrits ci-dessus pour la solution aqueuse, les conditions d'application de la solution aqueuse et le revêtement métallique 7 sont bien sûr applicables.The preferred embodiments described above for the aqueous solution, the conditions of application of the aqueous solution and the
La divulgation concerne également un procédé pour améliorer la résistance à la corrosion d'une surface extérieure 15 d'un revêtement métallique 7 revêtant au moins une face 5 d'un substrat 3 en acier, comprenant au moins les étapes de :
- fourniture d'un substrat 3 en acier présentant deux faces 5, dont au moins l'une est revêtue par
un revêtement métallique 7 comprenant au moins 40% en poids de zinc, - application sur la surface extérieure 15 du revêtement métallique 7 d'une solution aqueuse comprenant un aminoacide choisi parmi l'alanine, l'arginine, l'acide aspartique, la cystéine, la glutamine, la lysine, la méthionine, la proline, la sérine, la thréonine, et un mélange de ceux-ci, chaque aminoacide étant sous forme neutre ou de sel, la solution aqueuse étant exempte de composé comprenant un métal du groupe IIIB ou du groupe IVB.
- supplying a steel substrate 2 having two
faces 5, at least one of which is coated with ametal coating 7 comprising at least 40% by weight of zinc, - application on the
outer surface 15 of themetal coating 7 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 metal or Group IVB.
Les modes de réalisation préférentiels décrits ci-dessus pour la solution aqueuse, les conditions d'application de la solution aqueuse, le revêtement métallique 7 et les éventuelles étapes supplémentaires dans le procédé sont bien sûr applicables.The preferred embodiments described above for the aqueous solution, the conditions of application of the aqueous solution, the
La divulgation concerne également l'utilisation d'une solution aqueuse comprenant un aminoacide choisi parmi la proline, la thréonine et un mélange de celles-ci, la proline et la thréonine étant indépendamment sous forme neutre ou de sel, la solution aqueuse étant exempte de composé comprenant un métal du groupe IIIB ou du groupe IVB, pour :
- améliorer la compatibilité, avec un adhésif 13, d'au moins une partie d'une surface extérieure 15 d'un revêtement métallique 7 revêtant au moins une
face 5 d'un substrat 3 en acier, - améliorer la résistance à la corrosion de la surface extérieure 15 du revêtement métallique 7 revêtant au moins une
face 5 du substrat 3 en acier, et - améliorer les propriétés tribologiques de la surface extérieure 15 du revêtement métallique 7 revêtant au moins une
face 5 du substrat 3 en acier,
- improving the compatibility, with an adhesive 13, of at least part of an
outer surface 15 of ametal coating 7 coating at least oneface 5 of asubstrate 3 made of steel, - improving the corrosion resistance of the
outer surface 15 of themetal coating 7 coating at least oneface 5 of thesteel substrate 3, and - to improve the tribological properties of the
outer surface 15 of themetal coating 7 coating at least oneface 5 of thesteel substrate 3,
Les modes de réalisation préférentiels décrits ci-dessus pour la solution aqueuse, les conditions d'application de la solution aqueuse et le revêtement métallique 7 sont bien sûr applicables. La divulgation concerne également un procédé pour :
- améliorer la compatibilité, avec un adhésif 13, d'au moins une partie d'une surface extérieure 15 d'un revêtement métallique 7 revêtant au moins une
face 5 d'un substrat 3 en acier, - améliorer la résistance à la corrosion de la surface extérieure 15 du revêtement métallique 7 revêtant au moins une
face 5 du substrat 3 en acier, et - améliorer les propriétés tribologiques de la surface extérieure 15 du revêtement métallique 7 revêtant au moins une
face 5 du substrat 3 en acier,
- fourniture d'un substrat 3 en acier présentant deux faces 5, dont au moins l'une est revêtue par
un revêtement métallique 7 comprenant au moins 40% en poids de zinc, - application sur la surface extérieure 15 du revêtement métallique 7 d'une solution aqueuse comprenant un aminoacide choisi parmi la proline, la thréonine et un mélange de celles-ci, la proline et la thréonine étant indépendamment sous forme neutre ou de sel, la solution aqueuse étant exempte de composé comprenant un métal du groupe IIIB ou du groupe IVB.
- improving the compatibility, with an adhesive 13, of at least part of an
outer surface 15 of ametal coating 7 coating at least oneface 5 of asubstrate 3 made of steel, - improving the corrosion resistance of the
outer surface 15 of themetal coating 7 coating at least oneface 5 of thesteel substrate 3, and - to improve the tribological properties of the
outer surface 15 of themetal coating 7 coating at least oneface 5 of thesteel substrate 3,
- supplying a steel substrate 2 having two
faces 5, at least one of which is coated with ametal coating 7 comprising at least 40% by weight of zinc, - applying to the
outer surface 15 of themetal coating 7 an aqueous solution comprising an amino acid selected from proline, threonine and a mixture thereof, the proline and the threonine being independently in neutral form or salt, the aqueous solution being free of a compound comprising a Group IIIB metal or Group IVB.
Les modes de réalisation préférentiels décrits ci-dessus pour la solution aqueuse, les conditions d'application de la solution aqueuse, le revêtement métallique 7 et les éventuelles étapes supplémentaires dans le procédé sont bien sûr applicables.The preferred embodiments described above for the aqueous solution, the conditions of application of the aqueous solution, the
Afin d'illustrer l'invention, des tests de résistance à la corrosion ont été réalisés selon les normes ISO 6270-2 de 2005 et/ou VDA 230-213 de 2008 sur des tôles 1 en acier recouvertes d'un revêtement métallique 7 comprenant environ 99% de zinc (tôle en acier GI), ou bien des échantillons de tôles 1 en acier électrozinguées comprenant 100% de zinc (tôle en acier EG), sur lesquelles a été appliqué :
- une solution aqueuse d'aminoacide tel que défini ci-dessus dont le pH avait été éventuellement ajusté par ajout de H3PO4, puis
- de l'huile Fuchs® 3802-39S en une quantité de 3 g/m2,
- et ayant alors été embouties.
- an aqueous solution of amino acid as defined above whose pH was possibly adjusted by adding H 3 PO 4 , then
- Fuchs® 3802-39S oil in an amount of 3 g / m2,
- and having then been stamped.
Il apparaît que les tôles 1 obtenues par un procédé selon l'invention présentent une meilleure résistance à la corrosion. Les autres propriétés des tôles 1 obtenues par le procédé selon l'invention (propriétés mécaniques, compatibilité avec une(des) étape(s) ultérieure(s) de cataphorèse et/ou phosphatation et/ou mise en peinture) n'ont pas été dégradées.It appears that the
Des tests de traction ont été réalisés et sont décrits à titre d'exemples non limitatifs.Tensile tests have been carried out and are described by way of non-limiting examples.
Des échantillons de tôles 1 en acier recouvertes d'un revêtement métallique 7 comprenant environ 99% de zinc (tôle en acier GI), ou bien des échantillons de tôles 1 en acier électrozinguées comprenant 100% de zinc (tôle en acier EG) ont été utilisées.Samples of
Chaque éprouvette 27 a été préparée de la façon suivante. On a découpé des languettes 29 dans la tôle 1 à évaluer. Ces languettes 29 avaient des dimensions de 25 mm ×12,5 mm × 0,2 mm.Each specimen 27 was prepared as follows. Tabs 29 were cut from
Les languettes 29 ont été immergées pour une durée d'immersion de 20 s à une température de 50°C dans une solution aqueuse de proline ou de thréonine dont le pH avait été ajusté par ajout de H3PO4, à l'exception des tôles de référence (Ref) n'ayant été soumises à aucun traitement par un aminoacide.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.
De l'huile Fuchs® 3802-39S a été appliquée sur les languettes 29 en une quantité de 3 g/m2.Fuchs® 3802-39S oil was applied to the tabs 29 in an amount of 3 g / m 2 .
On a collé deux languettes 29 par un joint 31 d'adhésif BM1496V, BM1440G ou BM1044, qui sont des colles dites « crash » à base d'époxy et commercialisées par la société Dow® Automotive. Ces adhésifs ont été sélectionnés car il s'agit d'adhésifs conduisant classiquement à des ruptures adhésives avant vieillissement et/ou après vieillissement de l'adhésif.Two tabs 29 were glued by a seal 31 of 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.
L'éprouvette 27 ainsi constituée a ensuite été portée à 180°C et maintenue à cette température pendant 30 minutes, ce qui permet de cuire la colle.The 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.
Des tests de vieillissement ont été effectués avec les éprouvettes 27 dont les languettes 29 ont été collées avec de la colle BM1044. Le vieillissement naturel de l'adhésif est simulé par un vieillissement en cataplasme humide à 70°C pendant 7 ou 14 jours.Aging tests were carried out with the test pieces 27 whose tabs 29 were glued with BM1044 glue. The natural aging of the adhesive is simulated by aging in a wet poultice at 70 ° C for 7 or 14 days.
L'essai de traction a ensuite été réalisé à une température ambiante de 23°C en imposant une vitesse de traction de 10 mm/min à une languette 29, parallèlement à celle-ci, tandis que l'autre languette 29 de l'éprouvette 27 a été fixée. L'essai a été poursuivi jusqu'à la rupture de l'éprouvette 27.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.
A l'issue de l'essai, on a noté la contrainte maximale de traction et on a évalué visuellement la nature de la rupture (rupture cohésive, lorsque la rupture a lieu dans l'épaisseur de l'adhésif - rupture adhésive, lorsque la rupture a lieu à une des interfaces entre la tôle et l'adhésif - rupture cohésive superficielle, lorsque la rupture a lieu dans l'adhésif au voisinage d'une interface entre les languettes et la tôle) (sachant que dans l'industrie automobile, on cherche à éviter les ruptures adhésives qui traduisent une mauvaise compatibilité de l'adhésif avec la tôle).At the end of the test, the maximum tensile stress was noted and the nature of the failure (cohesive failure, when the rupture occurred in the thickness of the adhesive - adhesive failure) was visually assessed rupture takes place at one of the interfaces between the sheet and the adhesive - superficial cohesive rupture, when the rupture takes place in the adhesive in the vicinity of an interface between the tongues and the sheet) (knowing that in the automotive industry, we try to avoid adhesive breaks that translate poor compatibility of the adhesive with the sheet).
Dans le tableau 1 sont regroupés les résultats sur tôle GI.In Table 1 are grouped the results on GI sheet.
Dans le tableau 2 sont regroupés les résultats sur tôle électrozinguées (EG). RCS signifie rupture cohésive superficielle.In Table 2 are grouped the results on galvanized sheet metal (EG). SCR means superficial cohesive rupture.
Comme illustré par les tableaux 1 et 2 ci-dessous, les tôles 1 qui ont subi un traitement avec une solution aqueuse comprenant de la proline ou de la thréonine favorisent l'apparition de ruptures cohésives superficielles, contrairement aux tôles de référence pour lesquelles plus de ruptures adhésives ont été constatées.As illustrated by Tables 1 and 2 below, the
En particulier, sur les tôles GI (tableau 1):
- avec l'adhésif BM1496V, les faciès de rupture observés sur les essais avec la proline ou la thréonine sont uniquement constitués de rupture cohésive superficielle, contrairement à la référence n'ayant pas subi de traitement (Ref 1) où il est constaté 30% de rupture adhésive.
- Avec l'adhésif BM1440G, les faciès de rupture observés sur les essais avec la proline ou la thréonine sont également uniquement constitués de rupture cohésive superficielle, contrairement à la référence n'ayant pas subi de traitement (Ref 2) où il est constaté 20% de rupture adhésive,
- Avec l'adhésif BM1044, il est observé que l'adhérence de l'adhésif sur les tôles avec la proline ou la thréonine (essais 7A à 7C) vieillit mieux que sur la référence, après 7 et 14 jours de cataplasme humide.
- with the BM1496V adhesive, the fracture facies observed on the proline or threonine tests only consist of superficial cohesive rupture, unlike the non-treated reference (Ref 1) where 30% of adhesive break.
- With the BM1440G adhesive, the fracture facies observed on the proline or threonine tests also consist only of superficial cohesive rupture, unlike the non-treated reference (Ref 2) where it is found to be 20% adhesive break,
- With the BM1044 adhesive, it is observed that the adhesion of the adhesive on the plates with proline or threonine (tests 7A to 7C) is better than the reference, after 7 and 14 days of wet poultice.
En particulier, sur les tôles électrozinguées (tableau 2), avec l'adhésif BM1496V, les faciès de rupture observés sur les essais 8A à 9B avec la proline ou la thréonine sont majoritairement constitués de rupture cohésive superficielle, contrairement à la référence n'ayant pas subi de traitement (Ref 6) où il est constaté 40% de rupture adhésive.
Des tests de mesure du coefficient de frottement (µ) en fonction de la pression de contact (MPa) ont été réalisés et sont décrits à titre d'exemples non limitatifs.Tests for measuring the coefficient of friction (μ) as a function of the contact pressure (MPa) have been carried out and are described by way of non-limiting examples.
Des échantillons de tôles 1 en acier recouvertes d'un revêtement métallique 7 comprenant environ 99% de zinc (tôle en acier GI qualité DX56D, épaisseur 0,7 mm), des échantillons de tôles 1 en acier électrozinguées dont le revêtement comprenait 100% de zinc (tôle en acier EG qualité DC06, épaisseur 0,8 mm), des échantillons de tôles 1 en acier Fortiform® électrozinguées dont le revêtement comprenait 100% de zinc (7,5 µm sur les deux faces) ou bien des échantillons de tôles 1 en acier revêtues par dépôt par jet de vapeur sonique (Zn JVD) dont le revêtement comprenait 100% de zinc (7,5 µm sur les deux faces) ont été utilisés.Samples of
On a découpé dans ces tôles en acier des échantillons ayant des dimensions de 450 mm x35 mm × épaisseur (0,7 mm pour GI et 0,8 mm pour EG). Les échantillons ont été immergés pour une durée d'immersion de 20 s à une température de 50°C dans une solution aqueuse de proline ou de thréonine dont le pH avait été éventuellement ajusté par ajout de H3PO4. De l'huile Fuchs® 3802-39S (en une quantité de 3 g/m2), Fuchs® 4107S (à refus) ou QUAKER 6130 (à refus) a été appliquée sur une face des échantillons.Samples having dimensions of 450 mm × 35 mm × thickness (0.7 mm for GI and 0.8 mm for EG) 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) or QUAKER 6130 (reject) were applied to one side of the samples.
On a alors mesuré le coefficient de frottement (µ) en fonction de la pression de contact (MPa) en faisant varier la pression de contact de 0 à 80 MPa :
- sur l'échantillon de la tôle traité par la solution aqueuse de proline ou de thréonine ainsi préparé, et
- sur un échantillon de tôle revêtue non traitée par un aminoacide (témoin).
- on the sample of the sheet treated with the aqueous solution of proline or threonine thus prepared, and
- on a sample of coated sheet untreated with an amino acid (control).
Plusieurs phases de tests ont été effectuées (phases A, B, et C dans le tableau 3 ci-dessous).Several test phases were performed (phases A, B, and C in Table 3 below).
Comme illustré par le tableau 3 ci-dessous, on a observé que l'application d'une solution aqueuse de proline ou de thréonine permet :
- de réduire le coefficient de frottement par rapport à une tôle revêtue non traitée par une telle solution (témoin), et/ou
- d'éviter un frottement pas à-coups ou broutage (« stick slip » en anglais), alors qu'à certaines pressions, un broutage est observé pour une tôle revêtue non traitée par une telle solution (témoin),
- de conserver les propriétés tribologiques améliorées, même lorsque la tôle revêtue traitée a subi un traitement de lavage/rehuilage.
* : pH ajusté par ajout de H3PO4
** : test après avoir subi un traitement de lavage/rehuilage
- to reduce the coefficient of friction with respect to a coated sheet untreated by such a solution (control), and / or
- to avoid a friction not jerking or grazing ("stick slip" in English), while at certain pressures, grazing is observed for a coated sheet untreated by such a solution (control),
- to preserve the improved tribological properties, even when the treated coated sheet has undergone a washing / re-oiling treatment.
*: pH adjusted by addition of H 3 PO 4
**: test after having undergone a washing / re-oiling treatment
Claims (19)
- A method for preparing a metal sheet (1) comprising at least the steps of:- providing a steel substrate (3), at least one face (5) of which is coated with a metal coating (7) comprising at least 40% by weight of zinc,- applying on the outer surface (15) of the metal coating (7) an aqueous solution comprising an amino acid selected from among alanine, arginine, aspartic acid, cysteine, glutamine, lysine, methionine, proline, serine, threonine, and a mixture thereof, each amino acid being in a neutral or salt form,the aqueous solution being free of any compound comprising a metal from the group IIIB or from the group IVB, and
the mass percentage as a dry extract of the amino acid in neutral or salt form or of the mixture of amino acids in the neutral or salt forms in the aqueous solution being greater than or equal to 75%, preferably greater than or equal to 90%.. - The method according to claim 1, comprising a preliminary step for preparing the steel substrate (3), at least one face (5) of which is coated with a metal coating (7), selected from among hot galvanization, a sonic vapor jet deposition and an electro-zinc-plating of the steel substrate (3).
- The method according to any of claims 1 to 2, wherein the metal coating (7) is selected from among a zinc coating GI, a zinc coating GA, a zinc and aluminum alloy, a zinc and magnesium alloy and a zinc, magnesium and aluminum alloy, preferably the metal coating (7) is a zinc and magnesium alloy comprising between 0.1 and 10% by weight of Mg and optionally between 0.1 and 20% by weight of Al, the remainder of the metal coating being Zn, inevitable impurities and optionally one or several added elements selected from among Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni or Bi.
- The method according to one of the preceding claims, wherein the amino acid is selected from among alanine, aspartic acid, cysteine, glutamine, methionine, proline, serine, threonine, and a mixture thereof, each amino acid being in a neutral or salt form, preferably the amino acid is selected from among proline in the neutral or salt form, cysteine in the neutral or salt form, and a mixture thereof, preferably proline in a neutral or salt form.
- The method according to any of claims 1, 2 or 4, wherein the steel substrate (3), at least one face (5) of which is coated with a metal coating (7) was prepared by electro-zinc-plating and the amino acid is selected from among aspartic acid, cysteine, methionine, proline and threonine, and a mixture thereof, each amino acid being in the neutral or salt form.
- The method according to any of claims 1 to 4, wherein the steel substrate (3) at least one face (5) of which is coated with a metal coating (7) was prepared by hot galvanization and the amino acid is selected from among alanine, arginine, glutamine, lysine, methionine, proline, serine, threonine and a mixture thereof, each amino acid being in a neutral or salt form.
- The method according to any of claims 1 to 6, wherein the amino acid is threonine in the neutral or salt form or a mixture of proline and of threonine, the proline and the threonine being in the neutral or salt form.
- The method according to one of the preceding claims, wherein the aqueous solution comprises from 1 to 200 g/L of amino acid in the neutral or salt form or of a mixture of amino acids in the neutral or salt forms, or from 10 to 1,750 mmol/L of amino acid in the neutral or salt form or of a mixture of amino acids in the neutral or salt forms.
- The method according to one of the preceding claims, wherein the aqueous solution has a pH comprised between a pH equal to [isoelectric point of the amino acid -3] and a pH equal to the [isoelectric point of the amino acid +1], preferably comprised between a pH equal to the [isoelectric point of the amino acid -3] and a pH equal to the [isoelectric point of the amino acid -1].
- The method according to one of the preceding claims, wherein the aqueous solution is applied at a temperature comprised between 20 and 70°C and/or wherein the solution is applied for a period comprised between 0.5s and 40s on the outer surface (15) of the metal coating (7).
- The method according to one of the preceding claims, wherein the solution is applied by coating with a roller.
- The method according to one of the preceding claims, comprising, after the step for applying on the outer surface (15) of the metal coating (7) an aqueous solution comprising an amino acid, a drying step, preferably carried out by subjecting the metal sheet (1) to a temperature comprised between 70 and 120°C for 1 to 30 seconds.
- The method according to one of the preceding claims, comprising, after the step for applying on the outer surface (15) of the metal coating (7) an aqueous solution comprising an amino acid and the optional drying step, a step for applying a grease or oil film on the outer surface (15) of the coating (7) coated with a layer comprising an amino acid or a mixture of amino acids.
- The method according to one of the preceding claims, comprising, after the step for applying on the outer surface (15) of the metal coating (7) an aqueous solution comprising an amino acid, the optional drying step and the optional step for applying a grease or oil film, a step for shaping the metal sheet (1), preferably achieved by drawing.
- A metal sheet (1) obtainable by a method according to any of claims 1 to 14.
- The metal sheet (1) according to the preceding claim, for which at least one portion of at least one outer surface (15) of the metal coating (7) is coated with a layer comprising from 0.1 to 200 mg/m2 of amino acid in the neutral or salt form or of a mixture of amino acids in the neutral or salt forms.
- The metal sheet (1) according to claim 15 or 16, for which at least one portion of at least one outer surface (15) of the metal coating (7) is coated with a layer comprising from 75 to 100% by weight of amino acid in the neutral or salt form, or of a mixture of amino acids in the neutral or salt forms.
- Use of an aqueous solution comprising an amino acid selected from among alanine, arginine, aspartic acid, cysteine, glutamine, lysine, methionine, proline, serine, threonine, and a mixture thereof, each amino acid being in the neutral or salt form,
the aqueous solution being free of any compound comprising a metal from the group IIIB or from the group IVB, and
the mass percentage in dry extract of the amino acid in the neutral or salt form or of the mixture of amino acids in the neutral or salt forms in the aqueous solution being greater than or equal to 75%,
for improving the resistance to corrosion of an outer surface (15) of a metal coating (7) coating at least one face (5) of a steel substrate (3), wherein the metal coating (7) comprises at least 40% by weight of zinc. - Use of an aqueous solution comprising an amino acid selected from among proline, threonine and a mixture thereof, the proline and the threonine being independently in a neutral or salt form, the aqueous solution being free of any compound comprising a metal from the group IIIB or from the group IVB, for:- improving the compatibility, with an adhesive 13, of at least one portion of an outer surface (15) of a metal coating (7) coating at least one face (5) of a steel substrate (3),- improving the resistance to corrosion of the outer surface (15) of the metal coating (7) coating at least one face (5) of the steel substrate (3), and- improving the tribological properties of the outer surface (15) of the metal coating (7) coating at least one face (5) of the steel substrate (3),wherein the metal coating (7) comprises at least 40% by weight of zinc.
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PL16704480T PL3250730T3 (en) | 2015-01-30 | 2016-02-01 | Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve corrosion resistance |
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PCT/IB2015/050722 WO2016120669A1 (en) | 2015-01-30 | 2015-01-30 | Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve corrosion resistance |
PCT/IB2016/050506 WO2016120855A1 (en) | 2015-01-30 | 2016-02-01 | Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve corrosion resistance |
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EP3250730A1 EP3250730A1 (en) | 2017-12-06 |
EP3250730B1 true EP3250730B1 (en) | 2019-01-23 |
EP3250730B8 EP3250730B8 (en) | 2019-06-26 |
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US (2) | US11060174B2 (en) |
EP (1) | EP3250730B8 (en) |
JP (1) | JP6784680B2 (en) |
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CN (1) | CN107208273B (en) |
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CA (1) | CA2975370C (en) |
ES (1) | ES2713752T3 (en) |
HU (1) | HUE042791T2 (en) |
PL (1) | PL3250730T3 (en) |
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WO (2) | WO2016120669A1 (en) |
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JP6784680B2 (en) | 2020-11-11 |
BR112017015696B1 (en) | 2022-04-05 |
PL3250730T3 (en) | 2019-06-28 |
EP3250730A1 (en) | 2017-12-06 |
KR102604333B1 (en) | 2023-11-20 |
CA2975370C (en) | 2023-04-18 |
BR112017015696A2 (en) | 2018-03-20 |
JP2018503748A (en) | 2018-02-08 |
CN107208273A (en) | 2017-09-26 |
US20200040438A1 (en) | 2020-02-06 |
TR201905111T4 (en) | 2019-05-21 |
KR20170107466A (en) | 2017-09-25 |
WO2016120669A1 (en) | 2016-08-04 |
US11060174B2 (en) | 2021-07-13 |
US20180023177A1 (en) | 2018-01-25 |
CA2975370A1 (en) | 2016-08-04 |
EP3250730B8 (en) | 2019-06-26 |
WO2016120855A1 (en) | 2016-08-04 |
US11236413B2 (en) | 2022-02-01 |
ES2713752T3 (en) | 2019-05-23 |
CN107208273B (en) | 2020-03-06 |
HUE042791T2 (en) | 2019-07-29 |
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