EP2841615B1 - Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante - Google Patents

Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante Download PDF

Info

Publication number
EP2841615B1
EP2841615B1 EP13727384.3A EP13727384A EP2841615B1 EP 2841615 B1 EP2841615 B1 EP 2841615B1 EP 13727384 A EP13727384 A EP 13727384A EP 2841615 B1 EP2841615 B1 EP 2841615B1
Authority
EP
European Patent Office
Prior art keywords
metal coatings
outer surfaces
magnesium
coatings
acid solution
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
Application number
EP13727384.3A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2841615A1 (fr
Inventor
Tiago MACHADO AMORIM
Joëlle RICHARD
Eric JACQUESON
Audrey LHERMEROULT
Pascale FELTIN
Jean-Michel LEMAIRE
Luc Diez
Jean-Michel Mataigne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ArcelorMittal SA
Original Assignee
ArcelorMittal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=48577189&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2841615(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by ArcelorMittal SA filed Critical ArcelorMittal SA
Priority to PL13727384T priority Critical patent/PL2841615T3/pl
Publication of EP2841615A1 publication Critical patent/EP2841615A1/fr
Application granted granted Critical
Publication of EP2841615B1 publication Critical patent/EP2841615B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • Y10T428/12542—More than one such component
    • Y10T428/12549—Adjacent to each other

Definitions

  • a sheet comprising a steel substrate having two faces each coated with a metal coating comprising zinc, magnesium and aluminum.
  • Such sheets are more particularly intended for the manufacture of parts for the automotive industry, without being limited thereto.
  • Metallic coatings essentially comprising zinc and aluminum in small proportion are traditionally used for their good protection against corrosion. These metallic coatings are now in competition with coatings including zinc, magnesium and aluminum.
  • Such metallic coatings will be generally designated here under the term of zinc-aluminum-magnesium coatings or ZnAIMg.
  • magnesium significantly increases the corrosion resistance of these coatings, which can make it possible to reduce their thickness or to increase the guarantee of protection against corrosion over time.
  • Requirement US 2010/055344 describes a ZnAIMg coated steel sheet subjected to skin-pass steps, application of an oil, alkaline cleaning then application of a primer and a lacquer.
  • Requirement JP 2003/013192 describes a steel sheet coated with ZnAIMg subjected to a skin-pass and then to the application of an oil.
  • Requirement JP 2007/131906 describes a process for the preparation of sheets coated with a ZnAIMg coating and varnished comprising the steps consisting in supplying steel sheets coated with quenching by a ZnAIMg coating, subjecting them to polishing, oxidizing the surface by immersion in an alkaline solution, optionally immerse in a sulfuric acid solution containing Co and / or Ni ions, possibly chromating, then applying a varnish.
  • Sheet metal coils with such surface coatings can sometimes remain in storage sheds for several months and must not see this surface deteriorate by the appearance of surface corrosion, before being shaped by the end user.
  • no corrosion initiation should appear whatever the storage environment, even in the event of exposure to the sun and / or to a humid or even salty environment.
  • Standard galvanized products that is to say whose coatings mainly consist of zinc and aluminum in low proportion, are also subject to these stresses and are coated with a protective oil which is generally sufficient to provide corrosion protection during storage.
  • An object of the invention is to improve the temporary protection of sheets with ZnAIMg coatings.
  • the invention firstly relates to a method according to claim 1.
  • the method may also include the features of claims 2 to 14, taken in isolation or in combination.
  • the application describes a sheet 1 having two faces 5 each coated with a metallic coating 7 comprising zinc, aluminum and magnesium and with a layer of oil, the metallic coatings 7 comprising between 0.1 and 20% by weight of aluminum and between 0.1 and 10% by weight of magnesium, the sheet being capable of being obtained by the process described below.
  • Sheet 1 of the figure 1 comprises a steel substrate 3 covered on each of its two faces 5 by a metallic coating 7.
  • the coatings 7 present on the two faces 5 are similar and only one will be described in detail below.
  • the coating 7 generally has a thickness less than or equal to 25 ⁇ m and aims conventionally to protect the substrate 3 against corrosion.
  • the coating 7 comprises zinc, aluminum and magnesium. It is particularly preferred that the coating 7 comprises between 0.1 and 10% by weight of magnesium and between 0.1 and 20% by weight of aluminum.
  • the coating 7 comprises more than 0.3% by weight of magnesium or even between 0.3% and 4% by weight of magnesium and / or between 0.5 and 11% or even between 0.7 and 6% by weight of aluminum, or even between 1 and 6% by weight of aluminum.
  • the Mg / Al mass ratio between the magnesium and the aluminum in the coating 7 is strictly less than or equal to 1, preferably strictly less than 1, or even strictly less than 0.9.
  • the substrate 3 is in the form of a strip which is passed through a bath to deposit the coatings 7 by hot dipping.
  • the bath is a bath of molten zinc containing magnesium and aluminum.
  • the bath can also contain up to 0.3% by weight of each of the optional addition elements such as Si, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni, Zr or Bi.
  • the bath may finally contain residual elements from the feed ingots or resulting from the passage of the substrate 3 in the bath, such as iron at a content of up to 5% by weight and generally between 2 and 4% by weight .
  • the substrate 3 is for example drained by means of nozzles projecting a gas on either side of the substrate 3.
  • the coatings 7 are then allowed to cool in a controlled manner.
  • the strip thus treated can then be subjected to a so-called skin-pass step which makes it possible to work harden it so as to erase the bearing of elasticity, to fix the mechanical characteristics and to confer on it a roughness suitable for subsequent operations such as sheet metal. must undergo.
  • the means of adjusting the skin-pass operation is the rate of elongation which must be sufficient to achieve the objectives and minimum to maintain the capacity for subsequent deformation.
  • the elongation rate is usually between 0.3 to 3%, and preferably between 0.3 and 2.2%.
  • the outer surfaces 15 of the coverings 7 are then oiled to provide temporary protection.
  • the oils used can conventionally be Quaker or Fuchs oils and the grammage of the layers of oils deposited on each external surface 15 is for example less than or equal to 5 g / m 2 .
  • the layers of oil deposited were not shown on the figure 1 .
  • the sheet 1 thus obtained can be wound before being cut, possibly shaped and assembled with other sheets 1 or other elements by users.
  • XPS spectroscopy has also been used to measure the thickness of the magnesium oxide or magnesium hydroxide layers present on the exterior surfaces 15. It appears that these layers have a thickness of a few nm.
  • the figures 2 and 3 illustrate respectively the spectra of the elements for the energy levels C1s (curve 17), O1s (curve 19), Mg1s (curve 21), Al2p (curve 23) and Zn2p3 (curve 25) during an analysis by spectroscopy XPS.
  • the corresponding atomic percentages are plotted on the ordinate and the depth of analysis on the abscissa.
  • the sample analyzed on the figure 2 corresponds to coatings 7 comprising 3.7% by weight of aluminum and 3% by weight of magnesium and subjected to a conventional skin-pass step with an elongation rate of 0.5% while the sample of the figure 3 has not been subjected to such a step.
  • the thickness of the magnesium oxide or magnesium hydroxide layers is approximately 5 nm.
  • ZnAIMg coated sheets have a low ability to be wetted with oil. This visually translates into a deposition of protective oil in the form of droplets while it is continuous or film-forming on conventional galvanized coatings.
  • the inventors have also observed phenomena of dewetting of the deposited oil, so that certain zones are no longer covered with oils. Such an area is identified by the reference 41 on the figure 4 . Temporary protection is therefore heterogeneous.
  • tarnishing phenomena linked or not to dewetting, may appear after a few weeks under certain storage conditions.
  • This alteration step can be carried out by the means described in claim 1, such as, for example, the application of mechanical forces.
  • Such mechanical forces are applied by a leveler, a brushing device or a blasting device.
  • a leveler which is characterized by the application of plastic deformation by bending between rollers, can be adjusted to deform the sheet which passes through it enough to create cracks in the layers of magnesium oxide or hydroxide magnesium.
  • the application of mechanical forces to the external surfaces 15 of the metallic coatings 7 can be combined with the application of an acid solution or the application of a degreasing, for example based on an alkaline solution, on the surfaces exterior 15.
  • the acid solution has for example a pH of between 1 and 4, preferably between 1 and 3.5, preferably between 1 and 3, and more preferably between 1 and 2.
  • This solution can comprise, for example hydrochloric acid , sulfuric acid or phosphoric acid.
  • the duration of application of the acid solution can be between 0.2 s and 30 s, preferably between 0.2 s and 15 s, and more preferably between 0.5 s and 15 s, depending on the pH of the solution, when and how it is applied.
  • This solution can be applied by immersion, sprinkling or any other system.
  • the temperature of the solution can for example be room temperature or a whole other temperature and subsequent rinsing and drying steps can be used.
  • the layers of magnesium oxide or magnesium hydroxide can be altered by applying an acid solution and without applying mechanical forces.
  • the purpose of the possible degreasing step is to clean the external surfaces 15 and therefore to remove the traces of organic dirt, metallic particles and dust.
  • this step does not modify the chemical nature of the exterior surfaces 15, with the exception of the alteration of a possible layer of surface aluminum oxide / hydroxide.
  • the solution used for this degreasing step is non-oxidizing. No magnesium oxide or magnesium hydroxide is therefore formed on the outer surfaces during the degreasing step and more generally before the oil application step.
  • a degreasing step it occurs before or after the step of applying the acid solution.
  • the possible degreasing step and the step of applying the acid solution take place before a possible surface treatment step, that is to say a step making it possible to form layers (not shown) on the outer surfaces. ) improving the resistance to corrosion and / or the adhesion of other layers subsequently deposited on the external surfaces 15.
  • Such a surface treatment step comprises the application to the exterior surfaces 15 of a surface treatment solution which reacts chemically with the exterior surfaces 15.
  • this solution is a conversion solution and the layers formed are conversion layers.
  • the conversion solution does not contain chromium. It can thus be a solution based on hexafluorotitanic or hexafluorozirconic acid.
  • the mechanical forces will preferably be applied before the acid solution or when it is present on the external surfaces 15 to promote the action of the acid solution.
  • the mechanical forces may be less intense.
  • the step of applying the acid solution and the step of surface treatment are combined.
  • the surface treatment solution is acidic.
  • the pH can be strictly greater than 3, in particular if the surface treatment solution is applied at a temperature above 30 ° C.
  • Table 1 Sample Alkaline degreasing Type of acid pH Acid exposure time in s Oil distribution observed with the naked eye 1 / / / / Discontinued 2 Gardoclean S5117 at 25g / l at a temperature of 55 ° C, applied for 15s, HCl 2 5 keep on going 3 / HCl 2 5 keep on going 4 / HCl 1 5 keep on going 5 / HCl 2 10 keep on going 6 / H2SO4 2 5 keep on going
  • Samples 1 to 6 were also exposed to the ambient atmosphere for 12 weeks under the conditions described in standard VDA230-213 in order to assess their temporary protection.
  • Sample 1 (curve 51 on the figure 5 ), which constitutes the reference, has a ⁇ L greater than 2, which is consistent with the distribution of the discontinuous oil observed visually.
  • Samples 2 to 6 (curves 52 to 56 respectively on the figure 5 ) have a variation in luminescence of less than 2, therefore imperceptible to the naked eye.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Lubricants (AREA)
EP13727384.3A 2012-04-25 2013-04-25 Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante Active EP2841615B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13727384T PL2841615T3 (pl) 2012-04-25 2013-04-25 Sposób wykonania blachy z olejowanymi powłokami znalmg oraz odpowiednia blacha

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/FR2012/050906 WO2013160566A1 (fr) 2012-04-25 2012-04-25 Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante.
PCT/IB2013/053286 WO2013160871A1 (fr) 2012-04-25 2013-04-25 Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante.

Publications (2)

Publication Number Publication Date
EP2841615A1 EP2841615A1 (fr) 2015-03-04
EP2841615B1 true EP2841615B1 (fr) 2020-06-24

Family

ID=48577189

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13727384.3A Active EP2841615B1 (fr) 2012-04-25 2013-04-25 Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante

Country Status (16)

Country Link
US (2) US10294558B2 (ko)
EP (1) EP2841615B1 (ko)
JP (2) JP6143845B2 (ko)
KR (1) KR101656166B1 (ko)
CN (2) CN107012419B (ko)
BR (1) BR112014026681B1 (ko)
CA (1) CA2871672C (ko)
ES (1) ES2808663T3 (ko)
HU (1) HUE051979T2 (ko)
IN (1) IN2014DN09954A (ko)
MA (1) MA37452B1 (ko)
MX (1) MX2014013007A (ko)
PL (1) PL2841615T3 (ko)
RU (1) RU2583193C1 (ko)
UA (1) UA114627C2 (ko)
WO (2) WO2013160566A1 (ko)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112016013855A2 (pt) 2013-12-19 2017-08-08 Nisshin Steel Co Ltd Chapa de aço de alta resistência, e, método para fabricar uma chapa de aço de alta resistência
KR20170075046A (ko) * 2015-12-22 2017-07-03 주식회사 포스코 내식성이 우수한 열간 프레스 성형품 및 그 제조방법
DE102018216317A1 (de) * 2018-09-25 2020-03-26 Thyssenkrupp Ag Verfahren zur Modifikation von feuerverzinkten Oberflächen
DE102019204224A1 (de) 2019-03-27 2020-10-01 Thyssenkrupp Steel Europe Ag Verfahren zur Neukonditionierung von feuerverzinkten Oberflächen
DE102019107933A1 (de) * 2019-03-27 2020-10-01 Thyssenkrupp Steel Europe Ag Verfahren zur Modifizierung der Oberfläche einer auf einem Stahlflachprodukt aufgebrachten metallischen Schutzschicht auf Zn-Al-Mg-Basis und Stahlflachprodukt
DE102020202171A1 (de) 2020-02-20 2021-08-26 Thyssenkrupp Steel Europe Ag Verfahren zur Herstellung eines oberflächenveredelten Stahlblechs und oberflächenveredeltes Stahlblech
DE102021105210A1 (de) 2021-03-04 2022-09-08 Thyssenkrupp Steel Europe Ag Oberflächenmodifikation von metallischen Beschichtung auf Basis von Zink im Feuerbeschichtungsprozess
DE102022127491A1 (de) * 2022-10-19 2024-04-25 Thyssenkrupp Steel Europe Ag Dressiertes Stahlblech mit intakter Oxidschicht auf einem metallischen Überzug

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09241828A (ja) 1996-03-08 1997-09-16 Nisshin Steel Co Ltd 塗膜耐水密着性に優れたＺｎ−Ｍｇ系めっき鋼板及びその製造方法
DE19740953A1 (de) 1997-09-17 1999-03-18 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
US20030175547A1 (en) 1992-03-27 2003-09-18 The Louis Berkman Company, An Ohio Corporation Corrosion-resistant coated metal and method for making the same
EP1350865A2 (de) 2002-04-05 2003-10-08 ThyssenKrupp Stahl AG Verzinktes und phosphatiertes Blech sowie Verfahren zur Herstellung eines solchen Blechs
EP1524326A1 (en) 2002-07-24 2005-04-20 Nisshin Steel Co., Ltd. Zinc-base hot dip galvanized steel sheet excellent in retention of gloss
JP2007131906A (ja) * 2005-11-09 2007-05-31 Nippon Steel Corp Ｚｎ系合金めっき鋼材
EP1857567A1 (de) 2006-05-15 2007-11-21 ThyssenKrupp Steel AG Verfahren zum Herstellen eines mit einem Korrosionsschutzsystem überzogenen Stahlflachprodukts
WO2011032890A1 (de) 2009-09-18 2011-03-24 Bwg Bergwerk- Und Walzwerk-Maschinenbau Gmbh Verfahren und vorrichtung zum kontinuierlichen streckbiegerichten von metallbändern
WO2011052269A1 (ja) 2009-10-26 2011-05-05 新日本製鐵株式会社 合金化溶融亜鉛めっき鋼板とその製造方法
EP2474649A1 (de) 2011-01-05 2012-07-11 Voestalpine Stahl GmbH Verfahren zur Oberflächenbehandlung eines schutzbeschichteten Substrats
EP2537954A1 (en) 2010-02-18 2012-12-26 Nippon Steel&Sumikin Coated Sheet Corporation Hot-dipped steel material and method for producing same

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52117333A (en) * 1976-03-27 1977-10-01 Shinto Paint Co Ltd Primer composite
JPH072994B2 (ja) * 1989-01-14 1995-01-18 住友軽金属工業株式会社 金属材料の表面浄化法
JPH04165084A (ja) * 1990-10-27 1992-06-10 Nkk Corp 表面処理鋼板
US5397652A (en) * 1992-03-27 1995-03-14 The Louis Berkman Company Corrosion resistant, colored stainless steel and method of making same
US5795661A (en) * 1996-07-10 1998-08-18 Bethlehem Steel Corporation Zinc coated steel sheet and strip having improved formability and surface quality and method thereof
JP4375827B2 (ja) * 1998-05-11 2009-12-02 古河スカイ株式会社 合金表面の処理方法及び表面経時劣化耐性に優れた合金
FR2789084B1 (fr) 1999-01-28 2001-03-09 Lorraine Laminage Emulsion d'huile dans l'eau comprenant au moins un additif de lubrification
JP3367466B2 (ja) * 1999-05-13 2003-01-14 住友金属工業株式会社 合金化溶融亜鉛めっき鋼板
US6465114B1 (en) * 1999-05-24 2002-10-15 Nippon Steel Corporation -Zn coated steel material, ZN coated steel sheet and painted steel sheet excellent in corrosion resistance, and method of producing the same
JP2001279414A (ja) * 2000-03-31 2001-10-10 Nisshin Steel Co Ltd 黒色化溶融Ｚｎ−Ａｌ基合金めっき鋼板
JP3702193B2 (ja) 2001-04-06 2005-10-05 新日本製鐵株式会社 加工後の加工部の耐食性に優れた非脱膜型潤滑めっき鋼板
JP3600804B2 (ja) * 2001-06-27 2004-12-15 新日本製鐵株式会社 成形性に優れた溶融亜鉛めっき鋼板
JP3547414B2 (ja) * 2001-08-17 2004-07-28 新日本製鐵株式会社 加工部の耐食性に優れ環境負荷の小さい非脱膜型潤滑めっき鋼板
JP2003138385A (ja) 2001-10-29 2003-05-14 Nippon Steel Corp 塗膜密着性と加工部の耐食性に優れ環境負荷の小さい非脱膜型潤滑めっき鋼板
JP3779941B2 (ja) 2002-01-09 2006-05-31 新日本製鐵株式会社 塗装後耐食性と塗装鮮映性に優れた亜鉛めっき鋼板
JP3675419B2 (ja) * 2002-03-25 2005-07-27 住友金属工業株式会社 溶融Ｚｎ−Ａｌ−Ｍｇ合金めっき鋼板と成形加工品
FR2864552B1 (fr) 2003-12-24 2006-07-21 Usinor Traitement de surface par hydroxysulfate
JP4579714B2 (ja) 2004-03-08 2010-11-10 日新製鋼株式会社 成形加工後の皮膜密着性に優れた化成処理鋼板
JP4546848B2 (ja) * 2004-09-28 2010-09-22 新日本製鐵株式会社 ヘアライン外観を有する高耐食性Ｚｎ系合金めっき鋼材
JP2007002288A (ja) * 2005-06-22 2007-01-11 Nippon Steel Corp 塗装下地用めっき鋼板とその製造方法及び塗装鋼板
RU2417273C2 (ru) * 2006-03-20 2011-04-27 Ниппон Стил Корпорейшн Стальной материал с высокой коррозионной стойкостью, получаемый с помощью горячего цинкования методом погружения
DE102007022174B3 (de) 2007-05-11 2008-09-18 Voestalpine Stahl Gmbh Verfahren zum Erzeugen und Entfernen einer temporären Schutzschicht für eine kathodische Beschichtung
CN101466254B (zh) * 2008-04-30 2010-11-03 海尔集团公司 一种涂层金属板
JP4778083B2 (ja) * 2008-08-21 2011-09-21 川田工業株式会社 溶射被覆性に優れた溶融亜鉛めっき部材
KR20110111283A (ko) * 2008-12-04 2011-10-10 바스프 에스이 단면 또는 양면 아연도금 강판으로 성형 부품을 제조하는 방법

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030175547A1 (en) 1992-03-27 2003-09-18 The Louis Berkman Company, An Ohio Corporation Corrosion-resistant coated metal and method for making the same
JPH09241828A (ja) 1996-03-08 1997-09-16 Nisshin Steel Co Ltd 塗膜耐水密着性に優れたＺｎ−Ｍｇ系めっき鋼板及びその製造方法
DE19740953A1 (de) 1997-09-17 1999-03-18 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
EP1350865A2 (de) 2002-04-05 2003-10-08 ThyssenKrupp Stahl AG Verzinktes und phosphatiertes Blech sowie Verfahren zur Herstellung eines solchen Blechs
EP1524326A1 (en) 2002-07-24 2005-04-20 Nisshin Steel Co., Ltd. Zinc-base hot dip galvanized steel sheet excellent in retention of gloss
JP2007131906A (ja) * 2005-11-09 2007-05-31 Nippon Steel Corp Ｚｎ系合金めっき鋼材
EP1857567A1 (de) 2006-05-15 2007-11-21 ThyssenKrupp Steel AG Verfahren zum Herstellen eines mit einem Korrosionsschutzsystem überzogenen Stahlflachprodukts
WO2007132008A1 (de) 2006-05-15 2007-11-22 Thyssenkrupp Steel Ag Verfahren zum herstellen eines mit einem korrosionsschutzsystem überzogenen stahlflachprodukts
US20100055344A1 (en) * 2006-05-15 2010-03-04 Thyssenkrupp Steel Ag Process for Producing a Sheet Steel Product Coated with an Anticorrosion System
WO2011032890A1 (de) 2009-09-18 2011-03-24 Bwg Bergwerk- Und Walzwerk-Maschinenbau Gmbh Verfahren und vorrichtung zum kontinuierlichen streckbiegerichten von metallbändern
WO2011052269A1 (ja) 2009-10-26 2011-05-05 新日本製鐵株式会社 合金化溶融亜鉛めっき鋼板とその製造方法
EP2537954A1 (en) 2010-02-18 2012-12-26 Nippon Steel&Sumikin Coated Sheet Corporation Hot-dipped steel material and method for producing same
EP2474649A1 (de) 2011-01-05 2012-07-11 Voestalpine Stahl GmbH Verfahren zur Oberflächenbehandlung eines schutzbeschichteten Substrats

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
"8th International Conference on Zinc and Zinc Alloy Coated Steel Sheet GALVATECH 2011", AIMNET.IT, 2011, XP055797508, ISBN: 978-88-85298-82-8
"Charakteristische Merkmale 095 - Schmelztauchveredeltes Band und Blech", STAHL-INFORMATIONS-ZENTRUM, 2010, Düsseldorf, XP055650430
ANONYMOUS: "Schmelztauchveredeltes Band und Blech", CHARAKTERISTISCHE MERKMALE 095, 2010, Düsseldorf, pages 1 - 30, XP055643288, ISSN: 0175-2006
C.K. RIENER ET AL.: "Nano-characterisation of the surface of HDG Zn-Al-Mg-coated steel sheets", PROCEEDINGS / 8TH INTERNATIONAL CONFERENCE ON ZINC AND ZINC ALLOY COATED STEEL SHEET, GALVATECH 2011, 21 June 2011 (2011-06-21), Genova (Italy), pages 1 - 10, XP055650409
G. RIHA ET AL.: "Galvatech", vol. 6, 2004, INTERNATIONAL CONFERENCE ON ZINC AND ZINC ALLOY COATED STEEL SHEET, ISBN: 1-886362-71-8, article "The New Galvanizing Line No. 3 at voestalpine Stahl GmbH", pages: 173 - 184, XP055800618
NAGATA ET AL.: "Nisshin-Steel's Toyo works starts up a state-of-the-art galvanizing line", INTERNATIONAL CONFERENCE ON ZINC AND ZINC ALLOY COATED STEEL SHEET, vol. 6, 2004, pages 185 - 196, XP055800616, ISBN: 1-886362-71-8
P. GREIS: "Die neue Feuerverzinkungsanlage der Thyssen Stahl AG in Duisburg", STAHL UND EISEN, vol. 113, no. 8, 16 August 1993 (1993-08-16), pages 77 - 80, XP055800675
SCHWENZFEIER W., A. HERZOG, J. HOHENWATER: "6 Richten", 1979, SPRINGER VERLAG, ISBN: 3-211-81545-7, article "Walzwerktechnik. Ein Leitf. für Studium u. Praxis", pages: 214 - 230, XP055800613
UWE B.: "Surface defects on hot-dip metal coated steel sheet", 1998, pages 97, XP055800678, ISBN: 3-514-00620-2
W. WARNECKE ET AL.: "Leistungsspektrum moderner Zink-Magnesium- Schmelztauchüberzüge", STAHL UND EISEN, vol. 129, no. 6, 2009, pages 53 - 59, XP001547855
W. ZIMNIK ET AL.: "Modernisierung der Horizontal-Feuerverzinkungsanlage bei der Preussag Stahl AG", STAHL UND EISEN, vol. 118, no. 6, 16 June 1998 (1998-06-16), pages 55 - 61, XP000769954

Also Published As

Publication number Publication date
CN107012419B (zh) 2019-12-24
JP2017128810A (ja) 2017-07-27
KR101656166B1 (ko) 2016-09-08
MA20150099A1 (fr) 2015-03-31
ES2808663T3 (es) 2021-03-01
WO2013160566A1 (fr) 2013-10-31
US20150125714A1 (en) 2015-05-07
CA2871672A1 (fr) 2013-10-31
BR112014026681B1 (pt) 2020-10-20
US10865483B2 (en) 2020-12-15
RU2583193C1 (ru) 2016-05-10
MA37452B1 (fr) 2016-04-29
WO2013160871A1 (fr) 2013-10-31
KR20150012256A (ko) 2015-02-03
IN2014DN09954A (ko) 2015-08-14
MX2014013007A (es) 2015-08-07
JP6143845B2 (ja) 2017-06-07
CN104334764B (zh) 2017-07-14
JP6487474B2 (ja) 2019-03-20
CN107012419A (zh) 2017-08-04
HUE051979T2 (hu) 2021-04-28
EP2841615A1 (fr) 2015-03-04
CN104334764A (zh) 2015-02-04
US20190169754A1 (en) 2019-06-06
UA114627C2 (uk) 2017-07-10
JP2015521233A (ja) 2015-07-27
US10294558B2 (en) 2019-05-21
PL2841615T3 (pl) 2020-11-16
CA2871672C (fr) 2017-01-17
BR112014026681A2 (pt) 2017-06-27

Similar Documents

Publication Publication Date Title
EP2841615B1 (fr) Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante
EP2430207B1 (fr) Procédé de fabrication d'une bande métallique revêtue présentant un aspect amélioré
EP2297372B1 (fr) Procede de fabrication d'une bande metallique revetue presentant un aspect ameliore
EP2859129B1 (fr) PROCÉDÉ DE RÉALISATION D'UNE TÔLE À REVÊTEMENTS ZnAlMg COMPRENANT L'APPLICATION D'UNE SOLUTION ACIDE ET D'UN ADHÉSIF, TÔLE ET ASSEMBLAGE CORRESPONDANTS
EP2652166B1 (fr) Tôle d'acier comprenant un revêtement multicouche
EP2954086B1 (fr) Ôle à revêtement znalmg à microstructure particulière et procédé de réalisation correspondant
EP3149217B1 (fr) Tôle d'acier munie d'un revêtement à protection cathodique sacrificielle comprenant du lanthane
CA2926564C (fr) Tole a revetement znalmg a flexibilite amelioree et procede de realisation correspondant
WO2016120669A1 (fr) Procédé de préparation d'une tôle revêtue comprenant l'application d'une solution aqueuse comprenant un aminoacide et utilisation associée pour améliorer la résistance à la corrosion
EP2841614B1 (fr) Procédé de réalisation d'une tôle à revêtements znalmg comprenant l'application d'efforts mécaniques sur les revêtements et d'un adhésif, tôle et assemblage correspondants
WO2016120670A1 (fr) Procédé de préparation d'une tôle revêtue comprenant l'application d'une solution aqueuse comprenant un aminoacide et utilisation associée pour améliorer la compatibilité avec un adhésif
WO2014125173A1 (fr) Procédé de préparation d'une tôle à revêtement znmg ou znaimg comprenant l'application d'une solution basique d'un agent complexant les ions magnésium et tôle obtenue
EP2841613B1 (fr) PROCÉDÉS DE RÉALISATION D'UNE TÔLE PRÉLAQUÉE À REVÊTEMENTS ZnAlMg ET TÔLE CORRESPONDANTE
WO2013160870A1 (fr) PROCÉDÉ DE RÉALISATION D'UNE TÔLE À REVÊTEMENTS ZnAlMg COMPRENANT L'APPLICATION D'UNE SOLUTION ACIDE DE TRAITEMENT DE SURFACE ET D'UN ADHÉSIF, TÔLE ET ASSEMBLAGE CORRESPONDANTS

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20141124

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ARCELORMITTAL

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180130

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200403

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MACHADO AMORIM, TIAGO

Inventor name: MATAIGNE, JEAN-MICHEL

Inventor name: RICHARD, JOELLE

Inventor name: LHERMEROULT, AUDREY

Inventor name: JACQUESON,ERIC

Inventor name: FELTIN, PASCALE

Inventor name: LEMAIRE, JEAN-MICHEL

Inventor name: DIEZ, LUC

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1283979

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013070131

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: FI

Ref legal event code: FGE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200924

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200925

REG Reference to a national code

Ref country code: SK

Ref legal event code: T3

Ref document number: E 35021

Country of ref document: SK

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200924

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201026

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201024

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2808663

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20210301

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602013070131

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

REG Reference to a national code

Ref country code: FI

Ref legal event code: MDE

Opponent name: THYSSENKRUPP STEEL EUROPE AG

Ref country code: FI

Ref legal event code: MDE

Opponent name: SALZGITTER FLACHSTAHL GMBH

Ref country code: FI

Ref legal event code: MDE

Opponent name: VOESTALPINE STAHL GMBH

26 Opposition filed

Opponent name: THYSSENKRUPP STEEL EUROPE AG

Effective date: 20210323

Opponent name: SALZGITTER FLACHSTAHL GMBH

Effective date: 20210324

Opponent name: VOESTALPINE STAHL GMBH

Effective date: 20210324

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E051979

Country of ref document: HU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1283979

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200624

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210425

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210425

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201024

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: RO

Payment date: 20230328

Year of fee payment: 11

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20230502

Year of fee payment: 11

Ref country code: DE

Payment date: 20230321

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: HU

Payment date: 20230329

Year of fee payment: 11

Ref country code: AT

Payment date: 20230322

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240320

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20240320

Year of fee payment: 12

Ref country code: CZ

Payment date: 20240326

Year of fee payment: 12

Ref country code: GB

Payment date: 20240320

Year of fee payment: 12

Ref country code: SK

Payment date: 20240326

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20240327

Year of fee payment: 12

Ref country code: SE

Payment date: 20240320

Year of fee payment: 12

Ref country code: PL

Payment date: 20240320

Year of fee payment: 12

Ref country code: IT

Payment date: 20240320

Year of fee payment: 12

Ref country code: FR

Payment date: 20240320

Year of fee payment: 12

Ref country code: BE

Payment date: 20240320

Year of fee payment: 12