EP2841614B2 - Verfahren zum herstellen eines znalmg-beschichteten blechs, das das einbringen von mechanischen kräften auf das blech umfasst und entsprechendes blech - Google Patents

Verfahren zum herstellen eines znalmg-beschichteten blechs, das das einbringen von mechanischen kräften auf das blech umfasst und entsprechendes blech Download PDF

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Publication number
EP2841614B2
EP2841614B2 EP13727381.9A EP13727381A EP2841614B2 EP 2841614 B2 EP2841614 B2 EP 2841614B2 EP 13727381 A EP13727381 A EP 13727381A EP 2841614 B2 EP2841614 B2 EP 2841614B2
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Prior art keywords
metal
magnesium
adhesive
outer surfaces
coatings
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English (en)
French (fr)
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EP2841614B1 (de
EP2841614A1 (de
Inventor
Joëlle RICHARD
Eric Jacqueson
Audrey LHERMEROULT
Pascale FELTIN
Jean-Michel LEMAIRE
Jean-Michel Mataigne
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ArcelorMittal SA
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ArcelorMittal SA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—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
    • 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

Definitions

  • the present invention relates to a sheet comprising a steel substrate having two faces each coated with a metallic coating comprising zinc, magnesium and aluminum.
  • Such sheets are particularly intended for the manufacture of parts for the automotive industry, without being limited to it.
  • Metallic coatings comprising mainly zinc and aluminium in small proportions (typically of the order of 0.1% by weight) are traditionally used for their good protection against corrosion. These metallic coatings are now competing in particular with coatings comprising zinc, magnesium and aluminium.
  • Such metallic coatings will be generally referred to herein as zinc-aluminum-magnesium or ZnAlMeg coatings.
  • US 2011/0008644 discloses a method for preparing ZnAlMg coated sheets and joining them with a second sheet using an adhesive.
  • magnesium significantly increases the corrosion resistance of these coatings, which can make it possible to reduce their thickness or increase the guarantee of protection against corrosion over time.
  • sheet metal is frequently assembled using adhesives to produce certain parts of vehicles, such as, for example, door sills.
  • adhesives are chosen from structural, reinforced structural (for example, “crash” type) or semi-structural adhesives, sealing mastics or even packing mastics which are of various chemical natures, such as epoxy, polyurethane or rubber.
  • the bond between a sheet metal and an adhesive is usually assessed by means of a tensile test on a specimen formed of two tabs of the sheet metal, these tabs being bonded on part of their surface by the adhesive.
  • the adhesion of the adhesive to the sheet metal is assessed on the one hand by measuring the tensile stress at break and on the other hand the compatibility of the adhesive and the sheet metal by visually determining the nature of the break.
  • An aim of the invention is therefore to propose a method for producing a ZnAlMg coated sheet which has better compatibility with adhesives and therefore limits the risks of adhesive rupture.
  • the invention has as its first subject a method according to claim 1.
  • the method may also comprise the features of claims 2 to 11, taken alone or in combination.
  • the invention also relates to an assembly according to claim 12.
  • Sheet 1 of the figure 1 comprises a steel substrate 3 covered on each of its two faces 5 by a metal coating 7.
  • the coatings 7 present on the two faces 5 are similar and only one will be described in detail later.
  • the coating 7 generally has a thickness less than or equal to 25 ⁇ m and is conventionally intended to protect the substrate 3 against corrosion.
  • each coating 7 comprises zinc, aluminum and magnesium. According to the invention, each coating 7 comprises between 0.1 and 10% by weight of magnesium and between 0.7 and 6% 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 1 and 6% by weight of aluminum.
  • the Mg/Al mass ratio between the magnesium and the aluminum in the coating 7 is less than or equal to 1, or even strictly less than 1, or even strictly less than 0.9.
  • a substrate 3 is used, obtained for example by hot and then cold rolling.
  • 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 molten zinc bath containing magnesium and aluminum.
  • the bath may 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 can finally contain residual elements originating 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 wrung out using nozzles projecting a gas on either side of the substrate 3.
  • the coatings 7 are then left to cool in a controlled manner.
  • the strip thus treated can then be subjected to a stage called skin-pass which allows it to be work-hardened so as to erase the elasticity level, to fix the mechanical characteristics and to give it a roughness adapted to the subsequent operations which the sheet must undergo.
  • the means of adjusting the skin-pass operation is the elongation rate 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 sheet 1 thus obtained can be coiled before being cut, possibly shaped. Sheet 1 is assembled with other sheets by users.
  • an adhesive 13 may be applied locally to an outer surface 15 of a coating 7 to enable, for example, the sheet metal 1 to be assembled to another sheet metal and thus constitute a part of a motor vehicle.
  • the adhesive 13 may be any type of glue or mastic conventionally used in the automotive industry.
  • X-ray Photoemission Spectroscopy (XPS) analyses of the exterior surfaces of the coatings 7 revealed the predominant presence of magnesium oxide or magnesium hydroxide, even when the coatings 7 have similar aluminum and magnesium contents.
  • XPS spectroscopy was also used to measure the thickness of the magnesium oxide or magnesium hydroxide layers present on the exterior surfaces 15. These layers appear to be a few nm thick.
  • FIGS. 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 XPS spectroscopy.
  • the corresponding atomic percentages are plotted on the ordinate and the analysis depth 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 classic 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.
  • the method for producing the sheet metal 1 comprises at least one step of alteration, by application of mechanical forces, of layers of magnesium oxide or magnesium hydroxide present on the external surfaces 15 of the coatings 7, before possible subsequent application of an adhesive 13.
  • the planer which is characterized by the application of plastic deformation by bending between rollers, is adjusted to deform the sheet metal passing through it sufficiently to create cracks in the layers of magnesium oxide or magnesium hydroxide.
  • the application of mechanical forces to the outer surfaces 15 of the metal coatings 7 may be combined with the application of an acid solution or the application of a degreasing agent, for example based on an alkaline solution, to the outer surfaces 15.
  • the acidic 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 may comprise, for example, hydrochloric acid, sulfuric acid or phosphoric acid.
  • the duration of application of the acid solution may be between 0.2 s and 15 s, more preferably between 0.5 s and 15 s, depending on the pH of the solution, the time and the manner in which it is applied.
  • This solution can be applied by immersion, spraying or any other system.
  • the temperature of the solution can for example be room temperature or any other temperature and subsequent rinsing and drying steps can be used.
  • magnesium oxide or magnesium hydroxide layers can be altered by applying an acid solution and without applying mechanical forces.
  • the possible degreasing step aims to clean the exterior surfaces 15 and therefore to remove traces of organic dirt, metal 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 surface layer of aluminum oxide/hydroxide.
  • the solution used for this degreasing step is non-oxidizing. Therefore, no magnesium oxide or magnesium hydroxide is formed on the exterior surfaces 15 during the degreasing step and more generally before the step of applying the adhesive 13.
  • a degreasing step it occurs before or after the acid solution application step.
  • the possible degreasing step and the step of applying the acid solution occur before a possible surface treatment step, that is to say a step making it possible to form on the external surfaces 15 layers (not shown) 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 applying to the exterior surfaces 15 a surface treatment solution which reacts with the exterior surfaces 15 to form said layers.
  • the surface treatment solution is a conversion solution and the layers formed are conversion layers.
  • the conversion solution does not contain chromium. It may thus be a solution based on hexafluorotitanic or hexafluorozirconic acid.
  • the mechanical forces will preferably be applied before the acid solution or while it is present on the exterior surfaces 15 to promote the action of the acid solution.
  • the step of applying the acid solution and the surface treatment step are combined.
  • the surface treatment solution used that is acidic.
  • the pH may be strictly greater than 3, especially if the surface treatment solution is applied at a temperature above 30°C.
  • each test piece 17 is prepared as follows. Tabs 29 are cut from the sheet metal 1 to be evaluated. These tabs 29 have dimensions of 25 mm by 100 mm. The tabs 29 are glued by a joint 31 of the adhesive BM1496V, which is a so-called "crash" glue based on epoxy and marketed by the company Dow Automotive.
  • This adhesive was selected because it is one of the adhesives that most commonly leads to adhesive failures.
  • test piece 27 thus formed is then brought to 180°C and maintained at this temperature for 30 minutes.
  • the tensile test is then carried out at an ambient temperature of 23°C by imposing a tensile speed of 10 mm/min on a tab 29, parallel to it, while the other tab 29 is fixed. The test is continued until the test piece 27 breaks.
  • the sheets 1 which have undergone mechanical treatment to alter layers of magnesium oxide or magnesium hydroxide promote the appearance of superficial cohesive ruptures, unlike the reference sheets for which only adhesive ruptures are observed.
  • Reference sheet 1 had not undergone any mechanical treatment to alter layers of magnesium oxide or magnesium hydroxide. Test reference sheet 1 had been subjected to a plane tensile deformation of 10%. Table 1 Reference Test 1 Tensile stress at break (in MPa) 15.5 ⁇ 0.1 24.2 ⁇ 0.3 Types of breakup 100% RA 25% RCS 75% RA
  • This effect is enhanced by the application of an acid solution, possibly as a surface treatment, or a degreasing step.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating With Molten Metal (AREA)

Claims (12)

  1. Verfahren zum Herstellen eines Blechs (1), das mindestens die Schritte umfasst:
    - Liefern eines Substrats (3) aus Stahl, das zwei Seiten (5) aufweist, die jeweils mit einer Metallbeschichtung (7), die durch Eintauchen des Substrats (3) in ein Bad und durch Abkühlen erhalten wird, beschichtet sind, wobei jede Metallbeschichtung (7) Zink, zwischen 0,7 und 6 Gew.-% Aluminium und zwischen 0,1 und 10 Gew.-% Magnesium enthält, dann
    - Verändern von Magnesiumoxid- oder Magnesiumhydroxidschichten, die auf den Außenflächen (15) gebildet sind, durch Aufbringen von mechanischen Kräften, die von einer Walzrichtvorrichtung auf die Außenflächen (15) der Metallbeschichtungen (7) aufgebracht werden, wobei die mechanischen Kräfte angepasst sind, die Magnesiumoxid- oder Magnesiumhydroxidschichten, die auf den Außenflächen (15) der Metallbeschichtungen (7) gebildet sind, mit Rissen zu versehen, dann
    - Aufbringen eines Klebemittels (13), ausgewählt aus Struktur-, verstärkten Struktur- oder Semistrukturklebstoffen, Dichtungsmassen und Versiegelungsmassen, lokal auf mindestens einer Außenfläche (15) einer Metallbeschichtung (7),
    - Zusammenfügen mittels des Klebemittels (13) mit einem zweiten Blech.
  2. Verfahren nach Anspruch 1, bei dem die Metallbeschichtung (7) zwischen 0,3 und 10 Gew.-% Magnesium, vorzugsweise zwischen 0,3 und 4 Gew.-% Magnesium enthalten.
  3. Verfahren nach Anspruch 1 oder 2, bei dem die Metallbeschichtungen (7) zwischen 1 und 6 Gew.-% Aluminium enthalten.
  4. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Massenverhältnis zwischen Magnesium und Aluminium der Metallbeschichtungen (7) streng kleiner oder gleich 1, vorzugsweise streng kleiner als 1 und vorzugsweise streng kleiner 0,9 ist.
  5. Verfahren nach einem der vorhergehenden Ansprüche, außerdem vor dem Schritt des Aufbringens des Klebemittels (13) einen Schritt des Entfettens durch Aufbringen einer alkalischen Lösung auf die Außenflächen (15) der Metallbeschichtungen (7) umfassend.
  6. Verfahren nach einem der vorhergehenden Ansprüche, außerdem vor dem Schritt des Aufbringens des Klebemittels (13) einen Schritt des Aufbringens einer Lösung zur Behandlung von Oberflächen auf die Außenflächen (15) der Metallbeschichtungen (7) umfassend, um auf den Außenflächen (15) Schichten zu bilden, die die Korrosionswiderstandsfähigkeit und/oder die Haftfähigkeit verbessern.
  7. Verfahren nach einem der vorhergehenden Ansprüche, außerdem vor dem Schritt des Aufbringens des Klebemittels (13) Aufbringen einer Säurelösung auf die Außenflächen (15) der Metallbeschichtungen (7) umfassend.
  8. Verfahren nach Anspruch 7, bei dem die Säurelösung während einer Dauer zwischen 0,2 s und 15 s, vorzugsweise zwischen 0,5 s und 15 s auf die Außenflächen (15) der Metallbeschichtungen (7) aufgebracht wird.
  9. Verfahren nach einem der Ansprüche 7 bis 8, bei dem die Säurelösung einen pH-Wert zwischen 1 und 4, insbesondere zwischen 1 und 3,5, typischerweise zwischen 1 und 3, vorzugsweise zwischen 1 und 2 aufweist.
  10. Verfahren nach einem der Ansprüche 7 bis 9, bei dem die Säurelösung eine Säurelösung zur Behandlung von Oberflächen, vorzugsweise eine Umwandlungs-Säurelösung ist.
  11. Verfahren nach einem der Ansprüche 7 bis 10, bei dem die mechanischen Kräfte auf die Außenflächen (15) der Metallbeschichtungen (7) vor dem Aufbringen der Säurelösung oder während die Säurelösung auf den Außenflächen (15) vorhanden ist, aufgebracht werden.
  12. Baugruppe eines ersten Bleches (1) mit einem zweiten Blech, die durch ein Verfahren nach einem der vorhergehenden Ansprüche erhalten wird, wobei die Baugruppe umfasst:
    - ein erstes Blech (1) das zwei Seiten (5) aufweist, die jeweils mit einer Metallbeschichtung (7) beschichtet sind, die Zink, Aluminium und Magnesium enthält, wobei die Metallbeschichtungen (7) zwischen 0,7 und 6 Gew.-% Aluminium und zwischen 0,1 und 10 Gew.-% Magnesium umfassen,
    - ein zweites Blech,
    wobei das erste Blech (1) und das zweite Blech (1) mittels eines Klebemittels (13) ausgewählt aus Struktur-, verstärkten Struktur- oder Semistrukturklebstoffen, Dichtungsmassen und Versiegelungsmassen
    mit einander verbunden sind, wobei das Klebemittels (13) lokal auf mindestens eine Außenfläche (15) einer Beschichtung (7) des ersten Bleches aufgebracht ist.
EP13727381.9A 2012-04-25 2013-04-25 Verfahren zum herstellen eines znalmg-beschichteten blechs, das das einbringen von mechanischen kräften auf das blech umfasst und entsprechendes blech Active EP2841614B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13727381.9T PL2841614T5 (pl) 2012-04-25 2013-04-25 Sposób wytwarzania blachy z powłokami ZnAlMg obejmujący przykładanie sił mechanicznych do powłok i spoiwa, odpowiednia blacha oraz układ

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/FR2012/050914 WO2013160569A1 (fr) 2012-04-25 2012-04-25 Procédé de réalisation d'une tôle à revêtements ZnAlMg comprenant l'application d'efforts mécaniques sur les revêtements et tôle correspondante.
PCT/IB2013/053283 WO2013160868A1 (fr) 2012-04-25 2013-04-25 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

Publications (3)

Publication Number Publication Date
EP2841614A1 EP2841614A1 (de) 2015-03-04
EP2841614B1 EP2841614B1 (de) 2019-02-06
EP2841614B2 true EP2841614B2 (de) 2025-02-26

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EP (1) EP2841614B2 (de)
ES (1) ES2724539T5 (de)
FI (1) FI2841614T4 (de)
HU (1) HUE044446T2 (de)
PL (1) PL2841614T5 (de)
TR (1) TR201906423T4 (de)
WO (2) WO2013160569A1 (de)

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DE102022122771A1 (de) 2022-09-08 2024-03-14 Thyssenkrupp Steel Europe Ag Stahlblech für fleckenfreie Phosphatierung
DE102022122775A1 (de) 2022-09-08 2024-03-14 Thyssenkrupp Steel Europe Ag Stahlblech für fleckenfreie Phosphatierung
DE102022122772A1 (de) 2022-09-08 2024-03-14 Thyssenkrupp Steel Europe Ag Stahlblech für fleckenfreie Phosphatierung
DE102022122773A1 (de) 2022-09-08 2024-03-14 Thyssenkrupp Steel Europe Ag Stahlblech für fleckenfreie Phosphatierung
DE102022127491A1 (de) 2022-10-19 2024-04-25 Thyssenkrupp Steel Europe Ag Dressiertes Stahlblech mit intakter Oxidschicht auf einem metallischen Überzug
DE102023106688A1 (de) 2023-03-17 2024-09-19 Thyssenkrupp Steel Europe Ag Geklebte Bauteilgruppe

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TR201906423T4 (tr) 2019-05-21
PL2841614T5 (pl) 2025-05-05
ES2724539T3 (es) 2019-09-11
FI2841614T4 (fi) 2025-04-09
ES2724539T5 (en) 2025-05-14
PL2841614T3 (pl) 2019-07-31
WO2013160868A1 (fr) 2013-10-31
EP2841614B1 (de) 2019-02-06
EP2841614A1 (de) 2015-03-04
HUE044446T2 (hu) 2019-10-28

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