EP3099848B1 - Verfahren zur lokalisierten reparatur einer beschädigten wärmedämmschicht - Google Patents

Verfahren zur lokalisierten reparatur einer beschädigten wärmedämmschicht Download PDF

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Publication number
EP3099848B1
EP3099848B1 EP14828044.9A EP14828044A EP3099848B1 EP 3099848 B1 EP3099848 B1 EP 3099848B1 EP 14828044 A EP14828044 A EP 14828044A EP 3099848 B1 EP3099848 B1 EP 3099848B1
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EP
European Patent Office
Prior art keywords
damaged
thermal barrier
particles
equal
ceramic coating
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EP14828044.9A
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English (en)
French (fr)
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EP3099848A1 (de
Inventor
André Hubert Louis MALIE
Sarah Hamadi
Florence Ansart
Jean-Pierre Bonino
Hélène CERDA
Guillaume PUJOL
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.)
Safran Aircraft Engines SAS
Centre National de la Recherche Scientifique CNRS
Institut National Polytechnique de Toulouse INPT
Universite Toulouse III Paul Sabatier
Original Assignee
Safran Aircraft Engines SAS
Centre National de la Recherche Scientifique CNRS
Institut National Polytechnique de Toulouse INPT
Universite Toulouse III Paul Sabatier
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Application filed by Safran Aircraft Engines SAS, Centre National de la Recherche Scientifique CNRS, Institut National Polytechnique de Toulouse INPT, Universite Toulouse III Paul Sabatier filed Critical Safran Aircraft Engines SAS
Priority to EP20203886.5A priority Critical patent/EP3789518B1/de
Publication of EP3099848A1 publication Critical patent/EP3099848A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/005—Repairing methods or devices
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/18—Electrophoretic coating characterised by the process using modulated, pulsed, or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288—Protective coatings for blades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2220/00—Application
    • F05D2220/30—Application in turbines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/30—Manufacture with deposition of material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/40—Heat treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/90—Coating; Surface treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/20—Oxide or non-oxide ceramics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/50—Intrinsic material properties or characteristics
    • F05D2300/502—Thermal properties
    • F05D2300/5023—Thermal capacity

Definitions

  • the invention relates to methods of localized repair of damaged thermal barriers.
  • the blades of the high pressure turbines of aero engines are exposed to a very aggressive environment. These parts are generally coated with an oxidative protective coating as well as a thermal barrier coating.
  • the thermal barrier coating provides thermal insulation of the underlying part in order to maintain it at temperatures where its mechanical performance and life are acceptable.
  • CMAS calcium and magnesium aluminosilicates
  • the invention provides, according to a first aspect, a method according to claim 1
  • the part is formed of an electrically conductive material and the damaged thermal barrier allows the conduction of electricity in the damaged area to be repaired and therefore the deposition of the ceramic coating by electrophoresis in this area during step a).
  • the ceramic coating obtained during step a) is formed by depositing the particles on the part. Most of the ceramic coating can be deposited in the damaged area. In other words, a mass of ceramic coating greater than or equal to 50% of the total mass of the ceramic coating deposited during step a) can be deposited in the damaged zone. This mass of ceramic coating deposited in the damaged zone may for example be greater than or equal to 75%, or even 90%, of the total mass of the ceramic coating deposited during step a). In an exemplary embodiment, the ceramic coating can be deposited only in the damaged area.
  • the invention advantageously makes it possible to repair the damaged thermal barrier in a rapid, inexpensive and localized manner and thus to avoid the scrapping of partially degraded parts or the complete stripping of the damaged thermal barrier.
  • the invention therefore makes it possible to extend the life of the parts and to limit the cost of putting parts into operation again, the thermal barrier of which has been damaged.
  • the electrophoresis deposition process has the advantage of being usable for parts having complex geometries.
  • the repaired thermal barrier may be intended for use in an environment where the temperature at the surface of the thermal barrier is greater than or equal to 1000 ° C.
  • the part can advantageously be made of a metallic material and, for example, include nickel.
  • the damaged thermal barrier may have a lack of material in the damaged area.
  • the agglomerated particles may have an average size less than or equal to 10 ⁇ m.
  • average size denotes the dimension given by the statistical particle size distribution at half of the population, called D50.
  • the particles, in the non-agglomerated state have an average size of between 20 nm and 1 ⁇ m.
  • Such particle sizes advantageously make it possible to obtain a stable suspension.
  • the method comprises, before step a), a step of forming the particles by implementing a sol-gel method. These particles can then be dispersed in the liquid medium to form the electrolyte.
  • the particles of the electrolyte can, for example, be particles of yttria-containing zirconia (YSZ; “Yttria-Stabilized Zirconia”) which have been obtained by the sol-gel route.
  • Zirconium oxide particles can also be used. More generally, it is possible to use for the deposition by electrophoresis any particles capable of exhibiting an electric charge within the electrolyte (thus allowing them to move during the application of the electric field). It is thus possible, for example, to use particles of the following chemical formula: ZrO 2- ReO 1.5 (where Re denotes a Rare Earth element, for example: Gd, Sm or Er), Y 2 O 3 , Al 2 O 3 , TiO 2 or CeO 2 .
  • the particles are formed of a material different from the ceramic material present in the damaged thermal barrier.
  • the material constituting the particles and the ceramic material of the damaged thermal barrier are advantageously compatible thermomechanically and chemically.
  • the difference between the thermal expansion coefficients of the ceramic material present in the damaged thermal barrier and of the material constituting the particles can in absolute value advantageously be less than or equal to 2.10 -6 K -1 .
  • the use of a different material can advantageously make it possible to provide an additional property, for example an anti-CMAS property or a heat-sensitive material, and thus to functionalize the thermal barrier while repairing it.
  • the liquid medium can, for example, be chosen from: alcohols, for example ethanol or isopropanol, ketones, for example acetylacetone, water and their mixtures.
  • the particles may be present in the liquid medium, before the start of step a), in a concentration greater than or equal to 0.1 g / L, preferably greater than or equal to 1 g / L .
  • the thickness of the ceramic coating deposited may be greater than or equal to 50 nm, for example greater than or equal to 30 ⁇ m. In an exemplary embodiment, the thickness of the ceramic coating deposited may be less than or equal to 200 ⁇ m.
  • the part can be coated with a bonding layer allowing the attachment of the thermal barrier to the part and the ceramic coating can be deposited on the bonding layer.
  • the bonding layer advantageously makes it possible to improve the bonding of the thermal barrier to the part.
  • the bonding layer can, moreover, advantageously make it possible to protect the part against oxidation and corrosion.
  • the tie layer can, for example, be metallic.
  • the thermal barrier can be present directly on the part.
  • the thermal barrier can be present directly on the part.
  • the duration of step a) may be greater than or equal to 1 minute, preferably 5 minutes.
  • a voltage greater than or equal to 1 V can be imposed during all or part of step a) between the part and a counter-electrode.
  • the voltage imposed during all or part of step a) may preferably be greater than or equal to 50 V.
  • the damaged area may, before step a), have been subjected to a stripping step.
  • Carrying out a stripping advantageously makes it possible to eliminate the thermal barrier residues and the oxide layers that may be present and thus improve the electrically conductive nature of the damaged area to be repaired in order to promote the formation of the deposit of ceramic coating by electrophoresis.
  • the stripping can be carried out mechanically, for example by sandblasting, sanding, grinding, high pressure water jet or by laser stripping.
  • the pickling can be a chemical pickling, for example an electrolytic pickling or a pickling in an acidic or basic medium.
  • the damaged thermal barrier may, at the start of step a), exhibit a lack of material in the damaged area.
  • the method may comprise, after step a), a step b) of consolidation by heat treatment of the deposited ceramic coating.
  • Step b) can, for example, include subjecting the part obtained after implementation of step a) to a temperature greater than or equal to 1000 ° C, for example greater than or equal to 1100 ° C.
  • the part may constitute a turbine engine blade.
  • a part 1 for example made of a nickel-based superalloy coated with a bonding layer 2 on which is present a damaged thermal barrier 3.
  • An oxide layer 2a is present between the bonding layer 2 and the thermal barrier 3 damaged.
  • Layer 2a can consist of ⁇ -Al 2 O 3 alumina.
  • the damaged thermal barrier 3 is made of a ceramic material and has a damaged area 4 to be repaired.
  • the damaged zone 4 can have at least one adjacent undamaged zone. In the example illustrated, the damaged zone 4 is present between two adjacent undamaged zones 5a and 5b.
  • the part 1 bearing the damaged thermal barrier 3 is present in an electrolyte 10 comprising a suspension of particles 11 in a liquid medium.
  • the particles 11 can, for example, be particles of yttriated zirconia (zirconia stabilized with yttrium oxide).
  • the oxide powder (yttriated zirconia) thus obtained is then suspended in a liquid medium consisting for example of isopropanol in order to form the electrolyte 10.
  • the part 1 coated with the damaged thermal barrier 3 constitutes an electrode of the electrophoresis system opposite which a counter-electrode 20.
  • the counter-electrode 20 is, for example, made of platinum. Due to the conductive nature of the part 1 and of the damaged zone 4, a deposition by electrophoresis is carried out in the damaged zone 4.
  • the damaged zone 4 consists, in the example illustrated, by a region devoid of material.
  • the damaged area comprises a first region devoid of material as well as a second region in which a ceramic layer is present, the thickness of the ceramic layer present in the second region being sufficiently small for this second region is a conductor of electricity.
  • the damaged zone is constituted by a region in which a ceramic layer is present, the thickness of the ceramic layer being sufficiently small for this region to be electrically conductive.
  • the deposit is preferably carried out in the most conductive areas (sufficiently low thickness of the ceramic layer or total absence of ceramic layer) because the electric field will be relatively high in these areas.
  • the damaged thermal barrier 3 has a single damaged zone 4 to be repaired, but it is not beyond the scope of the present invention if the damaged thermal barrier has a plurality of zones. damaged to repair. In this case, each of the damaged areas to be repaired conducts electricity.
  • a generator G imposes a potential difference between the part 1 and the counter-electrode 20.
  • the generator G has direct or pulsed current.
  • Part 1 is polarized at an opposite charge to that of the particles 11. Due to the application of an electric field between the part 1 and the counter-electrode 20, the particles 11 move and are deposited on the part 1 for forming a ceramic coating 6.
  • the deposition of the ceramic coating 6 in the damaged zone 4 makes it possible to obtain a repaired thermal barrier 7.
  • the deposition of the ceramic coating 6 in the damaged zone 4 induces a progressive decrease in the electrical conductivity of this zone at over time. In fact, as the ceramic coating 6 is deposited, this zone becomes more and more insulating, which slows down or even stops the formation of the ceramic coating 6 on the part 1.
  • the ceramic coating 6 is deposited in the damaged area 4 and covers the entire surface of the damaged area 4.
  • the damaged thermal barrier 3 is not covered with a mask having an opening superimposed with the damaged zone 4 to be repaired.
  • the ceramic coating 6 may have a thickness e greater than or equal to 50 nm, for example greater than or equal to 30 ⁇ m.
  • the thickness e of the ceramic coating 6 corresponds to its largest dimension measured perpendicular to the surface S of the coated part 1.
  • step a drying and then a heat treatment for consolidation of the ceramic coating 6 can be carried out.
  • the thermal barrier was first damaged by water jet.
  • the figure 4A shows the result obtained after damage.
  • a deposition by electrophoresis was carried out from a suspension of YSZ powder in isopropanol (10 g / L) at a voltage of 100 V for 6 minutes.
  • a photograph of the part after treatment by the method according to the invention is given at figure 4B .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Coating By Spraying Or Casting (AREA)

Claims (10)

  1. Verfahren zur lokalisierten Reparatur einer beschädigten Wärmedämmschicht (3), aufweisend den folgenden Schritt:
    a) Behandeln eines mit einer beschädigten Wärmedämmschicht (3) beschichteten Teils (1) durch Elektrophorese, wobei das Teil aus einem Elektrizität leitenden Material gebildet ist, wobei die beschädigte Wärmedämmschicht (3) ein Keramikmaterial aufweist und mindestens eine zu reparierende beschädigte Zone (4) aufweist, wobei das Teil (1) in einem Elektrolyt (10) vorhanden ist, aufweisend eine Suspension von Partikeln (11) in einem flüssigen Medium, wobei die Partikel (11) in nicht agglomeriertem Zustand eine mittlere Größe haben, die zwischen 20 nm und 1 µm liegt, wobei eine keramische Beschichtung (6) durch Elektrophorese in der beschädigten Zone (4) aufgebracht wird, um eine reparierte Wärmedämmschicht (7) zu erhalten, die bestimmt ist, bei Temperaturen von über oder gleich 1000°C verwendet zu werden,
    wobei die Partikel (11) aus einem Material gebildet sind, das sich von dem Keramikmaterial unterscheidet, das in der beschädigten Wärmedämmschicht (3) vorhanden ist,
    wobei das Verfahren vor dem Schritt a) einen Schritt des Bildens der Partikeln (11) durch Durchführen eines Sol-Gel-Verfahrens aufweist, wobei der Trocknungsschritt des Sol-Gel-Verfahrens durch superkritisches Trocknen durchgeführt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Partikel (11) in dem flüssigen Medium vor dem Beginn von Schritt a) in einer Konzentration von über oder gleich 0,1 g/L vorhanden sind.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Dauer von Schritt a) über oder gleich 1 Minute beträgt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass während dem gesamten oder einem Teil von Schritt a) eine Spannung von über oder gleich 1 V zwischen dem Teil (1) und einer Gegenelektrode (20) angelegt wird.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Dicke e der aufgebrachten keramischen Beschichtung größer oder gleich 30 µm ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Teil (1) mit einer Verankerungsschicht (2) beschichtet ist, die die Verankerung der Wärmedämmschicht (3; 7) an dem Teil (1) erlaubt und dass die keramische Beschichtung (6) auf der Verankerungsschicht (2) aufgebracht wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die beschädigte Zone (4) vor dem Schritt a) einem Abbeizschritt unterzogen wurde.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es nach dem Schritt a) einen Konsolidierungsschritt b) der aufgebrachten keramischen Beschichtung (6) durch thermische Behandlung aufweist.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das Teil eine Schaufel einer Turbomaschine darstellt.
  10. Verfahren nach einem der Ansprüche 1 bis 9, wobei die beschädigte Wärmedämmschicht eine Säulenstruktur hat.
EP14828044.9A 2014-01-29 2014-12-11 Verfahren zur lokalisierten reparatur einer beschädigten wärmedämmschicht Active EP3099848B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20203886.5A EP3789518B1 (de) 2014-01-29 2014-12-11 Verfahren zur lokalisierten reparatur einer beschädigten wärmesperre

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1400224 2014-01-29
PCT/FR2014/053268 WO2015114227A1 (fr) 2014-01-29 2014-12-11 Procede de reparation localisee d'une barriere thermique endommagee

Related Child Applications (2)

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EP20203886.5A Division-Into EP3789518B1 (de) 2014-01-29 2014-12-11 Verfahren zur lokalisierten reparatur einer beschädigten wärmesperre
EP20203886.5A Division EP3789518B1 (de) 2014-01-29 2014-12-11 Verfahren zur lokalisierten reparatur einer beschädigten wärmesperre

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EP3099848A1 EP3099848A1 (de) 2016-12-07
EP3099848B1 true EP3099848B1 (de) 2021-08-25

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EP20203886.5A Active EP3789518B1 (de) 2014-01-29 2014-12-11 Verfahren zur lokalisierten reparatur einer beschädigten wärmesperre

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US (1) US9840914B2 (de)
EP (2) EP3099848B1 (de)
CN (1) CN106414813B (de)
BR (1) BR112016017562B1 (de)
CA (1) CA2938031C (de)
RU (1) RU2678347C2 (de)
WO (1) WO2015114227A1 (de)

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Publication number Priority date Publication date Assignee Title
FR3073866B1 (fr) * 2017-11-21 2019-11-29 Safran Helicopter Engines Procede de fabrication d'une barriere thermique sur une piece d'une turbomachine
CN110129859B (zh) * 2018-02-08 2021-09-21 通用电气公司 掩蔽元件中的孔并对元件进行处理的方法
FR3099935B1 (fr) * 2019-08-12 2021-09-10 Safran Aircraft Engines Procédé de revêtement d’une pièce de turbomachine
US20230220580A1 (en) * 2022-01-12 2023-07-13 General Electric Company Formation of a barrier coating using electrophoretic deposition of a slurry

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DE10335406A1 (de) * 2003-08-01 2005-02-17 Mtu Aero Engines Gmbh Verfahren zum Reparieren von Wärmedämmschichten mit lokalen Beschädigungen

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CA2938031A1 (fr) 2015-08-06
WO2015114227A1 (fr) 2015-08-06
BR112016017562A2 (de) 2017-08-08
EP3789518B1 (de) 2023-11-29
RU2016135017A3 (de) 2018-08-22
EP3789518A1 (de) 2021-03-10
CA2938031C (fr) 2022-05-10
RU2016135017A (ru) 2018-03-05
BR112016017562B1 (pt) 2022-04-12
US20160348509A1 (en) 2016-12-01
RU2678347C2 (ru) 2019-01-28
EP3099848A1 (de) 2016-12-07
US9840914B2 (en) 2017-12-12
CN106414813A (zh) 2017-02-15
CN106414813B (zh) 2019-04-30

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