Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
  • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
  • C04B41/81—Coating or impregnation
  • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
• • 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
  • F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
  • F01D25/005—Selecting particular materials
• • 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
  • F01D5/282—Selecting composite materials, e.g. blades with reinforcing filaments
• • 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
  • F01D5/284—Selection of ceramic materials
• • 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
  • F01D5/286—Particular treatment of blades, e.g. to increase durability or resistance against corrosion or erosion
• • 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
  • 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
  • F05D2300/60—Properties or characteristics given to material by treatment or manufacturing
  • F05D2300/603—Composites; e.g. fibre-reinforced

Definitions

• a particular field of application of the invention is the protection of composite materials with at least partially ceramic matrix ("CMC materials") forming hot parts of gas turbines, such as combustion chamber walls, or rings.
• CMC materials ceramic matrix
• CMC materials are known to possess both good mechanical properties allowing their use for structural elements and the ability to maintain these properties at high temperatures. Due to their better resistance to high temperatures, CMC materials require less cooling. This cooling traditionally comes from a sample in the compressor which impacts the efficiency of the turbomachine, CMC materials therefore make it possible to improve engine efficiency which reduces fuel consumption. Furthermore, their use contributes to optimizing the performance of turbomachines, in particular by reducing the overall mass of the turbomachine, which further contributes to a reduction in fuel consumption and therefore to a significant reduction in polluting emissions.
• CMC materials can include a fibrous reinforcement made of refractory fibers, typically carbon or ceramic, which is densified by a ceramic matrix, for example silicon carbide.
• CMC materials are sensitive to the phenomenon of corrosion. Corrosion of CMC results from the oxidation of silicon carbide to silica which, in the presence of water vapor, volatilizes in the form of silicon hydroxides Si(OH) 4 . Corrosion phenomena cause a recession of the CMC and affect its lifespan. In order to limit this degradation in operation, it was envisaged to form environmental barriers (“Environmental Barrier Coating”; “EBC”) on the surface of the CMC materials.
• EBC Environmental Barrier Coating
• the environmental barriers may include a silicon bond layer as well as a rare earth silicate layer positioned over the bond layer.
• the bonding layer makes it possible, on the one hand, to improve the adhesion of the rare earth silicate layer and, on the other hand, to form a protective silica layer, whose low permeability to oxygen contributes to protection of the CMC against oxidation.
• the rare earth silicate layer makes it possible to limit the diffusion of water vapor towards the silica layer formed by oxidation of the silicon and consequently to limit the recession of the latter.
• the invention relates to a coated part intended to be mounted in a turbomachine, comprising:
• an environmental barrier on the substrate comprising: (i) an adhesion layer comprising silicon present on a surface of the substrate, and (ii) an environmental barrier layer covering the adhesion layer, said environmental barrier layer comprising an internal barrier region to uncracked oxidizing and corrosive species and located on the side of the bonding layer, and an external region, opposite the bonding layer and covering the internal region, presenting a network of thermomechanical adaptation cracks having a distance between adjacent cracks of between 10 pm and 50 pm and the cracks of which extend over a depth of between 50% and 95% of a thickness of said environmental barrier layer.
• the inventors have noted that the environmental barriers of the prior art can exhibit uncontrolled cracking during operation which can be explained by the fact that the barrier is initially, from its manufacture, in compression. This compressive stress relaxes through creep when subjected to the high temperatures encountered in operation, which then results in cracking upon cooling due to a return to a tensile field. This cracking can reach the bonding layer, which leads to uncontrolled growth of the protective silica layer which can lead to flaking of the environmental barrier by increasing localized stresses at the interface of the bonding layer with the environmental barrier layer.
• thermomechanical adaptation crack network makes it possible to avoid uncontrolled cracking of the barrier by dissipation of energy via the pre-existing crack network, while maintaining an uncracked internal region conferring the desired seal to oxidizing and corrosive species in order to to control the growth of the protective silica layer and avoid flaking.
• the distance between adjacent cracks of the thermomechanical adaptation crack network is between 15 pm and 30 pm.
• Such a characteristic contributes to further improving the accommodation of thermomechanical constraints in operation.
• the cracks of the thermomechanical adaptation crack network extend over a depth of between 75% and 90% of the thickness of said environmental barrier layer. Such a characteristic contributes to further improving the accommodation of thermomechanical constraints in operation, while conferring optimal sealing against oxidizing and corrosive species, ensured by the internal region.
• the environmental barrier layer comprises a silicate of at least one rare earth, in particular the environmental barrier layer may comprise a yttrium disilicate, an ytterbium disilicate, or a mixture of these two compounds. .
• the environmental barrier layer comprises mullite.
• the part further comprises an additional coating located on the external region of the environmental barrier layer, said additional coating being a thermal barrier with a thickness greater than or equal to 100 ⁇ m, or a protective layer against calcium and magnesium aluminosilicates with a thickness greater than or equal to 50 pm.
• Such a characteristic advantageously makes it possible to further functionalize the protective coating and thus improve the protection conferred.
• the internal region and the external region of the environmental barrier layer are made of the same material.
• Such a characteristic advantageously makes it possible to optimize the thermomechanical compatibility between the two regions and therefore to optimize the control of the pre-cracking of the environmental barrier.
• the internal region and the external region of the environmental barrier layer may be made of yttrium disilicate, ytterbium disilicate, or a mixture of these two compounds.
• Figure 1 represents, schematically and partially, an example of a coated part according to the invention.
• Figure 2 represents, schematically and partially, a precursor deposit of the environmental barrier layer of the part of Figure 1.
• Figure 3 represents, schematically and partially, the effect of a thermal cracking treatment on the precursor deposit of Figure 2.
• Figure 4 is a snapshot of an example of an environmental barrier layer usable in the context of the invention obtained after cracking treatment of a precursor deposit.
• Figure 1 shows an example of part 1 comprising a 3 CMC material provided with an environmental barrier 12.
• the 3 CMC material may comprise a fibrous reinforcement which may be made of carbon fibers (C) or of ceramic fibers, for example fibers of silicon carbide (SiC) or formed essentially of SiC, including fibers made of Si-C-0 or Si-CON, that is to say also containing oxygen and possibly nitrogen.
• Such fibers are produced by the company NGS under the reference “Nicalon” or “Hi-Nicalon” or “Hi-Nicalon Type-S”, or by the company Ube Industries under the reference “Tyranno-ZMI”.
• Ceramic fibers can be coated with a thin interphase layer of pyrolytic carbon (PyC), boron nitride (BN) or boron-doped carbon (BC, with 5 at.% to 20 at.% of B, the complement being C).
• the fibrous reinforcement is densified by a matrix that is at least partially ceramic, for example predominantly ceramic in volume.
• the ceramic matrix may comprise silicon carbide or a ternary Si-BC system, for example.
• the matrix can be at least partly formed by CVI in a manner known per se.
• the matrix can be at least partly formed by liquid means (impregnation with a precursor resin of the matrix and transformation by crosslinking and pyrolysis, the process being able to be repeated) or by infiltration of silicon in the molten state (process of “Melt-Infiltration”).
• a powder is introduced into the possibly partially densified fibrous reinforcement, this powder possibly being a carbon or ceramic powder, for example silicon carbide, or a mixture of such powders, and a metallic composition based on silicon. in the molten state is then infiltrated to form a SiC-Si type matrix.
• the fibrous reinforcement can be woven or not, we do not depart from the scope of the invention when the fibrous reinforcement is in the form of fibers short particles dispersed in the material 3.
• particulate reinforcement may be used in the form of grains dispersed in the material 3.
• the environmental barrier 12 can be formed on the entire external surface S of the material 3 CMC or on only part of this surface S, for example when only part of the surface S must be protected.
• the environmental barrier 12 comprises an attachment layer 5 and an environmental barrier layer 7 covering the attachment layer 5.
• the attachment layer 5 is present in contact with the surface S of the composite material 3
• layer 7 is in contact with bonding layer 5.
• the bonding layer 5 can, in a manner known per se, form in operation a protective silica layer against oxidation (so-called “TGO” layer for “Thermally Grown Oxide”).
• the bonding layer 5 can be made of silicon.
• Layer 7 provides protection against oxidation and corrosion at high temperatures by limiting in particular the diffusion of water vapor and oxygen towards the bonding layer 5 and the CMC material 3.
• Layer 7 may comprise a rare earth silicate, for example a rare earth monosilicate and/or a rare earth disilicate.
• Layer 7 may include at least one rare earth element chosen from yttrium Y, scandium Sc and lanthanides.
• the rare earth element can be chosen from yttrium Y and ytterbium Yb. It will be noted that we do not depart from the scope of the invention if layer 7 comprises several rare earth elements, for example yttrium and ytterbium.
• Figure 1 represents an environmental barrier layer 7 which comprises an internal region 73 which is not cracked and located on the side of the bonding layer 5.
• the internal region 73 provides impermeability to oxidizing and corrosive species. Region 73 may be located in contact with the bonding layer 5.
• Layer 7 further comprises an external region 71, opposite the bonding layer 5, and presenting a network of cracks 75 for thermomechanical adaptation. Region 73 and region 71 can be made of the same material, for example yttrium disilicate, ytterbium disilicate, or a mixture of these two compounds. Details relating to the formation of environmental barrier 12 will be described below.
• the external region 71 covers the internal region 73.
• the cracks 75 extend over the entire thickness of region 71 up to region 73 which is not cracked.
• the network of cracks 75 can extend over the entire surface of the region 71.
• the network of cracks 75 has a controlled distance d between adjacent cracks of between 10 pm and 50 pm, preferably between 15 pm and 30 pm.
• the average distance between adjacent cracks 75 is between 10 pm and 50 pm, preferably between 15 pm and 30 pm.
• the distance d between adjacent cracks can be regular on layer 7 and correspond to a cracking step.
• this distance d can be variable between different pairs of adjacent cracks while always being between 10 pm and 50 pm, preferably between 15 pm and 30 pm, for all of the cracks 75 present.
• all of the distances d between adjacent cracks can be between m/2 and 2m, where m designates the average distance between adjacent cracks 75.
• the cracks 75 can each extend over a depth p75 of between 50% and 95%, preferably between 75% and 90%, of the thickness e7 of the environmental barrier layer 7.
• the cracks 75 do not reach the bonding layer 5 and make it possible to preserve the internal sealing region 73 in order to control the growth of the protective silica layer in operation, and avoid flaking.
• the thickness e 7 of layer 7 may be greater than or equal to 50 pm, for example greater than or equal to 200 pm, for example greater than or equal to 250 pm.
• This thickness e 7 can be between 50 pm and 1000 pm, for example between 200 pm and 1000 pm or between 250 pm and 1000 pm, for example between 200 pm and 700 pm or between 250 pm and 700 pm.
• the thickness e73 of the internal sealing region 73 can be between 1 pm and 10 pm, for example between 2 pm and 5 pm.
• an additional coating for thermal barrier or protection against CMAS can be deposited on region 71, in a manner known per se, or region 71 can define an external surface of the coated part 1.
• the bonding layer 5 can be formed by chemical vapor deposition from a precursor comprising silicon comprising for example a silane, a monochlorosilane, a dichlorosilane, and/or a trichlorosilane. Two examples of formation of the bonding layer 5 by chemical vapor deposition are described below.
• the temperature imposed during the deposition of the bonding layer 5 can be between 900°C and 1150°C, for example between 1100°C and 1150°C, and the pressure imposed during this deposition can be between 15.3 kPa and 20 kPa, for example between 16.7 kPa and 18 kPa.
• the precursor comprising silicon can be introduced into the reaction chamber in which the material 3 CMC is present with a flow rate of between 0.05 gram/minute and 0.3 gram/minute, for example between 0.1 gram /minute and 0.2 grams/minute.
• the bonding layer 5 obtained has a crystalline microstructure.
• the bonding layer 5 can be made of silicon, this bonding layer 5 comprising for example columnar grains of crystalline silicon.
• the bonding layer 5 can be made of silicon alloy, for example of a eutectic silicon alloy or of silicide.
• the bonding layer 5 comprises an amorphous silicon phase having grains of crystalline silicon distributed inside, these grains being able to have an average size of between 0.03 pm and 3 pm.
• the amorphous silicon phase may be formed from pure silicon or silicon with boron, oxygen and/or nitrogen dispersed therein.
• the bonding layer 5 can be formed at a deposition temperature which prevents the crystallization of the deposited silicon, followed by a heat treatment of the bonding layer at a treatment temperature higher than the temperature imposed during of the deposition in order to form the crystalline silicon grains distributed in the amorphous silicon phase.
• the temperature imposed during deposition can be between 300°C and 700°C or between 700°C and 1000°C, and the pressure imposed during deposition can be between 1.2 kPa and 1013 hPa.
• the operating conditions are chosen depending on the precursor used.
• the treatment temperature can be between 1000°C and 1400°C, for example between 1200°C and 1350°C.
• the precursor comprising silicon can be introduced into the reaction chamber in which the material 3 CMC is present with a flow rate of between 0.1 gram/minute and 2 gram/minute.
• the bonding layer 5 can be formed by other techniques.
• the environmental barrier layer 7 can be formed by implementing the following steps:
• step (b) cracking treatment of the precursor layer deposited in step (a) by subjecting it to a temperature of between 1250°C and 1350°C for a period of between 5 hours and 50 hours, for example between 10 hours and 50 hours .
• the deposit of the precursor layer produced during step (a) may comprise a silicate of at least one rare earth and is formed at least from an alkoxysilane silicon oxide precursor and a rare earth oxide precursor rare earth beta-diketonate in the presence of a gaseous source providing oxygen.
• the silicon oxide precursor may be di-t-butoxydiacetoxysilane and the rare earth oxide precursor RE(thd) 3 , where RE designates a rare earth element and the group (thd) designates 2, 2,6,6-tetramethyl-3,5-heptanedionate, the rare earth oxide precursor being for example Y(thd) 3 (CAS no. 15632-39-0).
• the gaseous source providing oxygen may comprise at least one of the following gases: O 2 , N 2 O, H 2 O, CO 2 , O 3 .
• the temperature imposed during step (a) can be between 1000°C and 1250°C.
• the cracking treatment of step (b) can be carried out under an oxidizing atmosphere, for example under air.
• Figures 2 and 3 represent, schematically, the deposit obtained after steps (a) and (b) respectively.
• the deposit 700 has a growth cone microstructure with a first portion 701 located on the side of the bonding layer 5 formed by first contiguous growth cones having a first average size, and a second portion 702 formed by second growth cones having a second average size, greater than the first average size, and having a lower compactness than the first cones of growth.
• step (b) we obtain the structure illustrated in Figure 3 with preferential cracking at the junctions of the growth cones 702 while guaranteeing the sealing of the coating at the interface with the bonding layer 5 by the presence of the uncracked internal region 73 obtained from the cones 701.
• the heat treatment of step (b) can cause sintering of the coating, which leads to the coalescence of the growth cones 701 of smaller size but more large number in the area close to the interface with the bonding layer 5, thus leading to the formation of a sealed region 73.
• step (b) can also cause volume contraction, for example of the made of a transition between the alpha phase and the beta phase of yttrium disilicate in the case where it is used, which results in preferential cracking at the junctions of the growth cones 702.
• the part 1 thus manufactured can be a part for aeronautical or aerospace application.
• Part 1 may be a hot part part of a gas turbine of an aeronautical or aerospace engine or of an industrial turbine.
• Part 1 can be a turbomachine part.
• Part 1 may constitute at least part of a distributor, at least part of a nozzle or a thermal protection coating, a wall of a combustion chamber, a turbine ring sector or a blade of turbomachine.
• part 1 is mounted and assembled with the other elements of the turbomachine with a view to being used at high temperature, greater than or equal to 800°C, in an oxidizing and corrosive atmosphere. It can, in particular, be used at a temperature between 800°C and 1500°C, or even between 800°C and 1300°C. Part 1 can, in particular, be used in humid air.
• a precursor deposition was carried out in a chemical vapor deposition reactor of organometallic compound(s) by direct liquid injection (“DLI-MOCVD”) with hot walls, from a solution of di-t- butoxydiacetoxy silane (DADBS) and tris(2,2,6,6-tetramethyl-3,5-heptanedionato) yttrium (Y(thd) 3 ), diluted in toluene.
• the precursors are injected and vaporized using a thermostatically controlled direct liquid injection system marketed under the reference Vapbox 300 by the company KEMSTREAM, using car engine type injectors to form an aerosol.
• the precursor deposit was heat treated for 5 hours at 1350°C in air. During this heat treatment, the deposit moved from the alpha phase in the precursor deposit to the beta phase, causing regular microcracking of the upper part of the coating. Details of the development conditions are provided below:
• the coating obtained successfully passed 1500 hours of corrosion testing, without degradation.
• the interface with the bonding layer did not change during the corrosion test. This result confirms that the small thickness of the waterproof part of the environmental barrier is sufficient to ensure resistance to chipping. Furthermore, the pre-cracking network is quite well repeatable.
• - evaporation temperature of the precursors 170°C to 250°C, - potentially also applicable in a reactor in cold wall configuration.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Ceramic Engineering (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Structural Engineering (AREA)
• Organic Chemistry (AREA)
• Composite Materials (AREA)
• Turbine Rotor Nozzle Sealing (AREA)
• Other Surface Treatments For Metallic Materials (AREA)

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• 2022
  • 2022-03-25 FR FR2202685A patent/FR3133853B1/fr active Active
• 2023
  • 2023-03-23 CN CN202380034901.XA patent/CN119095811A/zh active Pending
  • 2023-03-23 EP EP23718658.0A patent/EP4499590A1/de active Pending
  • 2023-03-23 WO PCT/FR2023/050418 patent/WO2023180672A1/fr not_active Ceased

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