• 专利附录
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    • 专利摘要:
    method of fabricating a thermal barrier protection and multilayer coating capable of forming a thermal barrier. The invention relates to a method of manufacturing a thermal barrier shield covering a superalloy metal substrate and comprising at least one metal sublayer (13) and an yttrium-stabilized zirconium ceramic layer (14) having a Columnar structure, defining pores. The following steps apply: Soil gel is impregnated by a portion of the pores of the ceramic layer (14) by a zirconium-based soil, to form a fixing sublayer (22). On this ceramic layer, supermounted by this fixing sublayer (22), a continuous oxide-based protective layer (20) is formed by means of a soil-gel route and heat treated. a layer of external protection against the attack of the thermal barrier walls (11). application to the protection of aircraft engine parts.
    公开号:BR112012022932B1
    申请号:R112012022932-0
    申请日:2011-03-11
    公开日:2019-11-05
    发明作者:Viazzi Céline；Ansart Florence；Bonino Jean-Pierre；Fenech Justine；Menuey Justine
    申请人:Centre Nat Rech Scient；Snecma；Univ Toulouse 3 Paul Sabatier；
    IPC主号:
    专利说明:

    “METHOD OF MANUFACTURING A THERMAL BARRIER PROTECTION AND MULTI-LAYER COATING SUITABLE TO FORM A THERMAL BARRIER” [0001] The present invention relates to a method of manufacturing a thermal barrier protection that covers a superalloy metal substrate, a coating multilayer capable of forming a thermal barrier on a superalloy metallic substrate, as well as the thermomechanical part resulting from this manufacturing method and / or comprising this coating.
    [0002] The quest to increase the efficiency of turbomachinery, particularly in the aeronautical field and to reduce fuel consumption and pollutant gas and unburnt emissions, has led to the approach of fuel combustion stoichiometry. This situation is accompanied by an increase in the temperature of the gases leaving the combustion chamber towards the turbine. [0003] Currently, the temperature limits the use of superalloys is of the order of 1100 ° C, the temperature of the gases at the outlet of the combustion chamber or at the turbine inlet, which can reach 1600 ° C.
    [0004] Consequently, it was necessary to adapt the turbine materials to this temperature rise, improving the cooling techniques of the turbine blades (hollow blades) and / or improving the high temperature resistance properties of these materials. This second route, in combination with the use of nickel and / or cobalt-based superalloys, led to several solutions, including the deposit of a thermal insulating coating called a thermal barrier composed of several layers, on the superalloy substrate.
    [0005] The use of thermal barriers in aeronautical engines became widespread twenty years ago and allows to increase the temperature of gases entering the turbines, reducing the flow of cooling air and thus improving the performance of the engines.
    [0006] In effect, this insulating coating allows a thermal gradient to be created on a cooled piece, in a permanent operating regime, the total amplitude of which can exceed 100 ° C for a coating of approximately 150 to 200 pm thick, presenting a conductivity
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    2/17 of 1.1 Wm -1 .K -1 . The operating temperature of the underlying metal, which forms the substrate for the coating, is reduced by the same gradient, which induces important gains in the volume of cooling air required, the life of the part and the specific consumption of the turbine engine .
    [0007] It is known to resort to the use of a thermal barrier, comprising a ceramic layer based on zirconia stabilized to yttrium oxide, namely an itriat zirconia, comprising a molar content of yttrium oxide between 4 and 12%, which presents a coefficient of expansion different from the superalloy, constituting the substrate and a very low thermal conductivity. The stabilized zirconia may also contain in some cases at least one oxide of an element chosen from the group consisting of rare earths, preferably in the subgroup: Y (yttrium), Dy (dysprosium), Er (erbium), Eu (europium), Gd (gadolinium), Sm (samarium), Yb (ytterbium) or a combination of a tantalum oxide (Ta) and at least one rare earth oxide, or with a combination of a niobium oxide (Nb) and at least a rare earth oxide.
    [0008] Among the coatings used, mention will be made of the rather general use of a ceramic layer based on zirconia, partially stabilized with yttrium oxide, for example, Zr0.92 Yo, o8Oi, 96.
    [0009] In order to ensure the fixation of this ceramic layer, a metallic sublayer, with a coefficient of expansion close to the substrate, is usually interposed between the substrate of the piece and the ceramic layer. This sublayer ensures the adhesion between the substrate of the piece and the ceramic layer, knowing that the adhesion between the sublayer and the substrate of the piece is made by interdiffusion, and the adhesion between the sublayer and the ceramic layer is made by fixing mechanics and the propensity of the sublayer to develop at high temperature, in the ceramic / sublayer interface, a thin oxide layer that ensures chemical contact with the ceramic. In addition, this metallic sublayer ensures protection of the part against corrosion phenomena.
    [0010] In particular, it is known to use a sublayer formed from an alloy of the type MCrAlY, M being a metal chosen from nickel, cobalt,
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    3/17 iron or a mixture of these metals, which consists of a gamma matrix of nickel cobalt with, in solution, chromium containing β NiAl precipitates.
    [0011] It is also known to use a sub-layer consisting of a nickel aluminide comprising a metal chosen from platinum, chromium, palladium, ruthenium, iridium, osmium, rhodium, or a mixture of these metals and / or a reactive element chosen from zirconium (Zr), cerium (Ce), lanthanum (La), titanium (Ti), tantalum (Ta), hafnium (Hf), silicon (Si) and yttrium (Y), or a metallic sub-layer of type MCrAlYPt, Ma being a metal chosen from nickel, cobalt, iron or a mixture of these metals, or based on Pt.
    [0012] This sublayer can finally correspond to a platinum coating diffused alone that consists of a raw gamma-gamma matrix of cobalt nickel with PT in solution.
    [0013] Usually, the ceramic layer is deposited on the piece to be coated, either by a projection technique (in particular plasma projection) or by physical deposition in the vapor phase, that is, by evaporation (for example, by EBPVD or “Electron Beam Physical Vapor Deposition”, forming a coating deposited in a vacuum evaporation compartment under electronic bombardment).
    [0014] In the case of a projected coating, a deposit of oxide based on zirconia, is made by techniques of the plasma projection type under controlled atmosphere, which leads to the formation of a coating consisting of a pile of molten droplets, then tempered by shock, flattened and stacked, to form an imperfectly densified deposit of a thickness generally between 50 micrometers and 1 millimeter.
    [0015] A coating deposited physically, and, for example, by evaporation under electronic bombardment, generates a coating consisting of a connection of columns directed perpendicularly to the surface to be coated, over a thickness comprised between 20 and 600 micrometers . Advantageously, the space between the columns allows the coating to effectively compensate for thermomechanical stresses due to,
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    4/17 service, to the expansion differential with the superalloy substrate.
    [0016] Thus, parts with long life durations are obtained in thermal fatigue at high temperature.
    [0017] Classically, these thermal barriers create, therefore, a discontinuity of thermal conductivity between the external coating of the mechanical part, forming this thermal barrier, and the substrate of this coating that forms the part's constitutive material.
    [0018] In service, the ingestion of sand in the engine leads to phenomena of erosion of the ceramic surface and to the deposit of remains, impurities and molten salts. By "molten salts" are meant oxide compositions containing oxides of calcium, magnesium, aluminum, silicon, mixtures of these oxides, and / or any other residue from the upstream part of the engine. These systems, mainly composed of oxides of calcium, magnesium, aluminum and silicon in mixture (Ca-Mg-Al-SiO) are called “CMAS”.
    [0019] In particular, the spaces of the columnar structure of the ceramic can be the infiltration site of these deposits of molten salts for temperatures above 1100 ° C. After infiltration of these melting CMAS into the porous surface structure of the thermal barrier coating, these molten salts cool, and solidify within the porous structure, notably between the columns, the solidified CMAS generate an accumulation of efforts, which leads to premature cracking and peeling, total or partial, of the thermal barrier.
    [0020] In effect, these CMAS form high temperature eutectic and become almost liquid, they infiltrate the porosities and the interstices of the ceramic layer, sometimes going to the interface between the ceramic and the metallic sublayer.
    [0021] It is necessary to note that, in this state, the CMAS react with the zirconia partially stabilized to itrin (yttrium oxide), which generates a weakening of the ceramic which then loses its integrity.
    [0022] The degradation of the thermal barrier intervenes either by the dissolution of this ceramic layer, due to the preferential attack of the elements that constitute the
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    5/17 ceramics, either by decreasing the tolerance to deformation of the ceramics, whose columnar structure can no longer exercise its role of absorbing efforts, since the CMAS infiltrate, along the columns of the ceramics. These degradations are formed mainly by flaking the ceramic layer. [0023] As a result, the substrate is no longer (locally) protected by the insulating ceramic layer, it is subjected to higher temperatures and is then damaged very quickly. Thus, the parts referred to (in particular the combustion chamber walls, the blades, ferrules or rings and high pressure turbine distributors) suffer premature damage.
    [0024] Numerous attempts in the prior art to prevent or delay the onset of the harmful effects of CMAS are based on techniques of depositing an additional layer formed of an enamel layer (layer of glazed matter) on the surface of the thermal barrier, constituting a layer hermetic outer layer designed to prevent the infiltration of the melted CMAS into the porous structure. EP 1 428 908 discloses one of the techniques.
    [0025] However, these techniques have a number of drawbacks, among which the fact that they require the deposit of a layer of supplementary material with a relatively heavy process to apply.
    [0026] The purpose of the present invention, therefore, is to propose a method of manufacturing a simple to use thermal barrier protection and a thermal barrier structure resulting from this method that prevents or delays the degradation caused by the molten salts on the porous structure of the thermal barrier, or minimizes its importance.
    [0027] The present invention also aims to propose a multilayer coating able to form a thermal barrier on a metallic substrate in superalloy, and whose structure allows to protect degradations generated by these CMAS. [0028] The invention also aims to provide a thermomechanical part in superalloy resulting from this treatment method that limits the damage of the ceramic resulting from the molten salts, when the part works, in particular a turbine blade, at high temperature and this at in order to significantly increase the
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    6/17 lifetime of the thermal barrier system.
    [0029] For this, according to the present invention, it is proposed a method of manufacturing a thermal barrier protection that covers a superalloy metal substrate, that thermal barrier comprising at least one metallic sublayer and a stabilized zirconia-based ceramic layer to the yttrium, presenting a columnar structure, defining pores. According to the invention, this method is characterized by the fact that the following steps are used:
    - a layer of continuous oxide-based protection is formed on this ceramic layer, using a soil-gel method, using a soil comprising precursors of this oxide; and
    - a heat treatment is carried out, so an external protection layer against the attack of the CMAS of the thermal barrier is constituted.
    [0030] This protective layer is, in certain cases, able to constitute a sacrificial layer that slows the infiltration of CMAS in the ceramic.
    [0031] Thanks to this method, it is thus possible to treat the classic thermal barriers already formed, creating the protective layer on top, according to a very simple use that takes place at room temperature (soil-gel process) and, therefore, avoiding the use of deposits at high temperature and / or under projection-type vacuum.
    [0032] In this way, it is understood that it is possible to form a protective layer that has very variable, but controllable characteristics, notably in terms of thickness, composition, porosity rates ...
    [0033] This solution also has the additional advantage of allowing, in addition, the formation of a porous protective layer, which allows to avoid stiffening the columnar structure of the ceramic layer and to preserve a thermal barrier capable of accommodating the resulting thermal stresses temperature variations in operation.
    [0034] It is necessary to note that the pores of this protection layer obtained by soil-gel that do not have a privileged direction, this absence of
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    7/17 directivity of the porous texture of the protective layer prevents any direct infiltration without the molten salts.
    [0035] According to a complementary provision, before the formation of the protective layer, at least one part of the pores of the ceramic layer is impregnated by a zirconia-based soil, in order to form a zirconia-based underlay for the protective layer.
    [0036] This way, due to the presence of this fixation sublayer, which is in accordance with the structure and composition of the ceramic layer, it is easier to fit the protective layer, which is then deposited later.
    [0037] According to a first method of use, this protective layer comprises essentially zirconia doped with yttrium and / or with at least one element belonging to the group of lanthanides.
    [0038] Thus, with a protective layer based on zirconia, a composition close to that of the ceramic layer is found for the protective layer.
    [0039] This is particularly true in the case where the protective layer is formed from zirconia doped as yttrium or itrine oxide: there is then a composition identity between the protective layer and the ceramic layer, while the different structure between these layers it allows the protection layer to constitute a sacrificial layer on top of the thermal barrier, CMAS not being able to infiltrate directly there, but reacting with the protection layer without reaching, for a certain time, the ceramic layer.
    [0040] It is also true in the case where the protective layer is formed from zirconia doped with at least one element belonging to the group of lanthanides (lanthan, cerium, praseodymium, neodymium, prometium, samarium, europium, gadolinium, termium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, as well as niobium).
    [0041] Thus, in this first embodiment, the protective layer based on zirconia contains itrin, in order to avoid the presence in the protective layer of a compound capable of inducing the formation of eutectic with CMAS.
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    8/17 [0042] According to a second mode of use, this protective layer does not contain zirconium oxide, but it essentially contains one or more rare earth oxides.
    [0043] “Rare earth” means the elements that belong to the groups of lanthanides (lanthanum, cerium, praseodymium, neodymium, prometium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium , as well as niobium), scandium, yttrium, zirconium and hafnium.
    [0044] According to a preferred mode of use, the protection layer is formed by the soil-gel route, using a loaded soil.
    [0045] Thus, thanks to the use of a soil containing particles, thicker deposits for the protective layer can be reached, going up to 100 pm.
    [0046] In a preferred variant, when a loaded soil is used for the formation of the protective layer, the same soil is used, but not loaded for the formation of the fixation sublayer, which allows to preserve a great chemical affinity between the fixing sublayer and the protective layer with a higher viscosity for the soil, to form the fixing sublayer which thus fills the pores of the ceramic layer more easily and more deeply.
    [0047] Thus, in this case, the formation of the fixation sublayer is carried out with an unloaded soil and the loaded soil used for the formation of the protective layer by soil-gel route presents a ligand formed from a soil having the same composition that this unloaded soil and a load formed of dust particles. Advantageously, these dust particles are obtained from the same unloaded soil as that used to form the fixation sublayer.
    [0048] The present invention also refers to the multilayer coating resulting from the aforementioned manufacturing method, as well as the superalloy parts, comprising this coating.
    [0049] The coating object of the present invention is a multilayer coating capable of forming a thermal barrier on a superalloy metallic substrate, comprising at least one metallic sublayer disposed on the
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    9/17 substrate, a ceramic layer based on yttrium-stabilized zirconia that covers this sublayer and that presents a columnar structure, defining pores and an oxide-based protective layer that covers the ceramic layer, forming a continuous film.
    [0050] It is generally noted that this protective layer is, moreover, infiltrated in at least part of the pores of the ceramic layer.
    [0051] According to an additional provision, this coating also includes a fixation sublayer based on zirconia resulting from a soil, disposed between the ceramic layer and the protective layer and in at least part of the pores of the ceramic layer.
    [0052] Indeed, it has been shown that depositing the protective layer directly on the ceramic layer could generate important efforts, when the heat treatment, can lead to premature de-cohesion of the multilayer coating.
    [0053] Within the scope of the invention, the fixing sublayer has the role of increasing the chemical affinity of the protective layer vis-à-vis the ceramic layer. For this, the fixation sublayer is thin and dense, and ensures a good adhesion with the substrate: it allows to develop chemical bonds with the ceramic layer and increase the cohesion of the multilayer coating set. It acts as a chemical interface between the ceramic layer and the protective layer.
    [0054] According to the invention, this protective layer preferably has a thickness comprised between one and 100 pm, preferably between two and 50 pm, and preferably between two and 10 pm.
    [0055] According to the invention, this protective layer has a non-oriented porosity: in fact, as previously exposed, thanks notably to the application by the soil-gel process, any presence of oriented porosity in the protection layer is prevented, and this in order to prevent direct infiltration of CMAS.
    [0056] Advantageously, this protective layer is thicker than this fixation sublayer (considering the thickness of the fixation sublayer
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    10/17 such as the one above the ceramic layer). For example, this protective layer is 2 to 50 times thicker than this fixation sublayer and preferably 5 to 40, advantageously 10 to 20 times thicker than this fixation sublayer.
    [0057] As an example, the fixation sublayer has a thickness of the order of 1 to 5 pm, and the protective layer that superimposes it has a thickness of the order of 40 to 60 pm, which is 10 to 15 times more.
    [0058] Advantageously, the grain size of the protective layer is larger than the grain size of the fixing sublayer: the average grain size of the protective layer is, for example, from 5 to 20, advantageously from 8 to 10 times larger than the average grain size of the fixation sublayer.
    [0059] As an example, the fixation sublayer has a grain size in the range of 80 to 100 nm (nanometers) and the protective layer that the superposes has a grain size in the range of 800 nm (nanometers) to 2 pm (micrometers).
    [0060] Advantageously, the distribution of the grain size of the fixing sublayer is more homogeneous than the distribution of the grain size of the protective layer.
    Thus, according to the invention, a coating structure is advantageously found in which the fixing sublayer has a microstructure with fine and homogeneous grains and the protective layer, forming a thicker active layer, presents a micro -structure with larger grains and less monodispersed.
    [0062] Other advantages and features of the invention will stand out by reading the following description made by way of example, and with reference to the attached drawings, in which:
    figure 1 represents a micrographic section showing the different layers of the thermal barrier on the surface of a mechanical part coated with a thermal barrier, according to the prior art;
    - figure 2 represents a schematic showing the structure
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    11/17 of the thermal barrier shortly after exposure to the infiltration of molten salts or CMAS;
    figures 3 and 4 represent micrographic sections showing the degradation of the surface of the thermal barrier, respectively shortly after and later after exposure to the infiltration of molten salts or CMAS; and
    figure 5 represents the multilayer coating, according to the present invention.
    [0063] The surface of the thermomechanical part shown partially in figure 1 comprises a thermal barrier coating 11 deposited on a superalloy substrate 12, such as nickel and / or cobalt-based superalloys. The thermal barrier coating 11 comprises a metal sublayer 13 deposited on the substrate 12, and a ceramic layer 14, deposited on the sublayer 13.
    [0064] The connection sublayer 13 is a metallic sublayer consisting of a nickel aluminide.
    [0065] The ceramic layer 14 is made up of itriated zirconia, comprising a molar content of yttrium oxide between 4 and 12% (partially stabilized zirconia). The stabilized zirconia 14 may also contain in some cases at least one oxide of an element chosen from the group consisting of rare earths, preferably in the subgroup: Y (yttrium), Dy (dysprosium), Er (erbium), Eu (europium), Gd (gadolinium), SM (samarium), Yb (ytterbium) or a combination of tantalum oxide (Ta) and at least one rare earth oxide, or with a combination of niobium oxide (Nb) and hair least a rare earth oxide.
    [0066] During manufacture, the bonding sublayer 13 was oxidized prior to the deposition of the ceramic layer 14, hence the presence of an intermediate layer of alumina 15 between the sublayer 13 and the ceramic layer
    14.
    [0067] In the view of figure 2 there is a diagram that represents the different layers mentioned above, with a columnar structure typical of the ceramic layer 14 present on the surface.
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    12/17 [0068] During service, the part (for example, a turbine blade) undergoes hundreds of high temperature cycles (in the order of 1100 ° C), during which 16 molten salts (CMAS) are capable of surface and infiltrate the pores and interstices of the columnar structure in a correct thickness of the ceramic layer 14 (see figure 2).
    [0069] These molten salts 16 solidify and lead to the formation of stresses that generate, by thermal shock, when the piece cools, cracks 18 in the ceramic layer 14, which leads to a delamination, namely when a part starts surface of the ceramic layer 14.
    [0070] The efforts of thermal expansion also cause the detachments of certain columns of the ceramic layer in the vicinity of the connection sublayer 13 (see locations 19 in figure 2).
    [0071] If referring to figures 3 and 4, respectively, it appears that the deposit of CMAS, in the form of molten salts 16 that cover the ceramic layer 14, penetrating between its columns (figure 3), causes degradation of the thermal barrier, notably due to the reaction between these molten salts 16 and the itrin contained in the ceramic layer 14, which then tends to dissolve (see the breakdown of the ceramic layer 14 in figure 4).
    [0072] Within the scope of the present invention, the applicant sought to protect the microstructure of the ceramic layer 14, in its upper part, in order to delay limiting, even stopping the infiltration of molten salts at high temperature in the ceramic layer 14 and thus increase the life of the coated part of the thermal barrier.
    [0073] The solution was found by using a protective layer 20 (see figure 5) that covers the entire surface of the ceramic layer 14, in order to protect it from attack not the CMAS.
    [0074] As previously mentioned, and as shown in figure 5, it is planned to interpose between the protective layer 20 and the ceramic layer 14, a fixation layer 22.
    [0075] The protective layer 20 and the fixation layer 22 are deposited
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    13/17 on ceramic layer by soil-gel.
    [0076] This deposit, made by liquid, allows the soil to penetrate into the pores, and especially between the columns, the ceramic layer 14 (it is the fixation layer 22 and, in certain cases, the fixation layer 22 and the protective layer 20).
    [0077] Remember that the soil-gel route is a process of synthesis of "soft chemistry" used for the preparation, at low temperature (notably at room temperature), of powders and oxide-type ceramic layers. This process uses a mixture of ionic precursors (metallic salt) and / or molecular (metallic alkoxides). In this liquid phase, called soil, the chemical reactions of hydrolysis and condensation contribute to the formation of a three-dimensional inorganic network (gel) with infinite viscosity in which the solvent remains.
    [0078] To evacuate this solvent, there are two possible drying modes. On the one hand, the conventional drying that allows for a stew at low temperature and atmospheric pressure, to dry the zirconia precursor gel to form a xerogel in which the three-dimensional network of the gel disappears. On the other hand, it is possible to perform drying in supercritical conditions, which allows, after evaporation of the solvent, to preserve the three-dimensional network of the gel. In this case, an airgel is formed which, at the end of a subsequent calcination step, leads, as in the case of a xerogel, to the formation of dust particles. These particles can serve as loads in the formation of a loaded soil. It is noted that in the case of an airgel, the particles are much more finite (size less than 500 nm), monodisperse and with a higher specific surface.
    [0079] In addition to decreasing the synthesis temperatures, in relation to the classic projection processes (notably EPBVD), the soil gel route also allows obtaining, for the protection layer 20, zirconium oxides of great purity, but also zirconium oxides doped with elements like yttrium, or other rare earths.
    [0080] The soil gel route is, therefore, a process of synthesis of oxide-type ceramic materials, but also a forming process, since several techniques
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    14/17 can be associated to make soil deposits, aiming at it with ceramic layers.
    [0081] The most used depositing process for a layer of oxide of ceramic type via soil gel is tempering (or Dip Coating). It consists of immersing the substrate to be coated, in the species, the coated part of the thermal barrier 11, in a soil, then removing it at a pure controlled speed so that a film of the desired thickness can homogeneously cover the surface with good adhesion. There are other deposition techniques, such as centrifugation (or Spin-Coating) or spraying (or Spray Coating).
    [0082] In general, deposits obtained from a soil have thicknesses that reach a maximum of 2 to 3 pm. To make a thicker deposit (usually up to 100 pm) the deposit medium used is a soil containing particles, called a loaded soil. In the latter case, this deposit medium is composed of soil molecular precursors, to which particles of chemical and structural compositions identical to those of the sought oxide are added and whose size, whose morphology and physico-chemical characteristics lead to a suspension stable. These particles may come from the soil gel pathway, but also from any other process leading to the development of nanometric and monodisperse particles.
    [0083] The protective layers 20 (and possibly the fixation layers 22) obtained by immersion from a loaded soil are, therefore, composite and consist, after drying, of a xerogel phase (from the soil) in which they are particles initially present in the deposit suspension are dispersed.
    [0084] To finish the formation of the protective layer 20 in ceramic and the fixation layer 22, they then undergo a thermal treatment in the air during which the evaporation of the solvents (100 ° C) will successively intervene, after calcination organic compounds (300 to 450 ° C), thus leading to the formation of an amorphous oxide.
    [0085] Other types of heat treatments are possible, modifying the atmosphere, the speed of rise in temperature, as well as the values of
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    15/17 ramp and landing temperature, and this to obtain the oxide phase sought with pre-defined structural parameters.
    [0086] At the end of these different stages, the protective layers 20 and the fixation layers 22 obtained, with a thickness between 1 and 100 pm, have in all cases an unoriented porosity that depends essentially on the characteristics of the starting soil ( composition, size and morphology of the particles that enter the soil composition, when it is loaded, soil viscosity, presence of plasticizer and / or porogenic agents, etc.).
    [0087] Thus, it is understood that the soil gel process has an interest in protecting the thermal barriers with columnar texture, such as those arising from the EPBVD projection process.
    [0088] In effect, the soil gel route associated with a thermal post-treatment allows the elaboration of ceramic materials of the oxide type that present compositions and structural characteristics identical to those obtained by conventional techniques.
    [0089] Therefore, it is possible to deposit protective layers 20 formed of yttrium-stabilized zirconia (identical composition, but structure different from those of ceramic layer 14).
    [0090] This technique is also adapted to the synthesis of a solid replacement solution with rare earths (protective layer (20) composed essentially of one or more rare earth oxides).
    [0091] In this way, a protective layer 20 and a fixation layer 22 are obtained that have a non-directional porous texture in which the porosity rate is controlled.
    [0092] On the other hand, this liquid deposition process is, on the one hand, adapted to the impregnation of porous material (in this case, the ceramic layer 14) by the game of the physical-chemical characteristics of the deposit medium (unloaded soil) or loaded soil) and, on the other hand, it allows to cover surfaces that present a strong roughness (of the order of Ra = 15 microns) with a very important leveling effect.
    [0093] The solo gel process appears, therefore, as a very adapted solution
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    16/17 to combat the degradation of thermal barriers 11 by the molten salts of CMAS.
    [0094] This process allows, on the other hand, to adapt the characteristics of the protective layers 20 and the fixation layers 22, namely their composition, their crystallographic structure, their porosity rate ...
    [0095] They can be distinguished from the families of materials for the protective layers 20 and the fixation layer 22, which are distinguished, one from the other, by their modes of action.
    [0096] Firstly, layers 20 and 22 may constitute a sacrificial layer in the case that they are made up of a composition identical to that of the ceramic layer 14, in the case of zirconia doped with yttrium oxide. In this case, the characteristics of the loaded soil (notably the rate, size and morphology of the particles) make it possible to control the pore density of the resulting layer. The presence of non-directional porosity is a brake on the diffusion of the eutectic formed with CMAS. In this way, there will be a preferential degradation of this surface protection layer 20 coming from the soil gel pathway, which allows at least temporary protection of the underlying functional thermal barrier 11.
    [0097] Secondly, and notably to increase the effectiveness of the protective layer 20, it can be made from soils and loaded soils, containing no compounds capable of inducing the formation of eutectic with CMAS, as is the case with itrine. In this case, the soils and loaded soils used consist of precursors of zirconia doped with oxides belonging to the family of lanthanides or other precursors of oxides, notably rare earth oxide (s). The content of the soil components, in the same way that the heat treatment conditions can be adapted depending on the crystalline phase sought for the resulting protection layer 20 (and the fixation layer 22).
    [0098] It can be noted that the use of fine powder particles from the calcination of zirconia aerogels as the load of a loaded soil is an effective means to obtain, from a loaded soil, zirconia coatings that form a layer protective layer that perfectly covers the surface of the layer
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    17/17 of ceramic 14 previously coated with the fixing sublayer, being able to infiltrate any residual porosity there.
    权利要求:
    Claims (15)
    [1]
    1. Method of manufacturing a thermal barrier protection (11) covering a superalloy metal substrate, said thermal barrier (11) comprising at least one metallic sublayer (13) and a ceramic layer (14) based on stabilized zirconia to the yttrium presenting a columnar structure defining pores, characterized by the fact that the following steps are implemented:
    - the soil-gel is impregnated with at least part of the pores of the ceramic layer (14) by a zirconia-based soil, and this in order to form a fixation sublayer (22) for a layer of protection;
    - on the said ceramic layer (14) covered by said fixing sublayer (22), a continuous protective layer (20) based on oxide, using a soil-gel route, using a soil comprising precursors of said oxide; and
    - a heat treatment is carried out, so an external protection layer against CMAS attack on the thermal barrier is created.
    [2]
    2. Method, according to claim 1, characterized by the fact that said protective layer (20) essentially comprises zirconia doped with yttrium and / or with at least one element belonging to the group of lanthanides.
    [3]
    3. Method according to claim 1, characterized by the fact that said protective layer (20) comprises essentially one or more rare earth oxides.
    [4]
    Method according to any one of claims 1 to 3, characterized by the fact that the protection layer (20) is formed by the soil-gel route, using a loaded soil.
    [5]
    5. Method, according to claim 4, characterized by the fact that the formation of the fixation sublayer (22) is carried out with an unloaded soil and in which the loaded soil used for the formation of the protective layer (20) by Soil-gel comprises a binder formed from a soil that has the same composition as said unloaded soil and a load formed of
    Petition 870190013485, of 2/8/2019, p. 24/27
    2/3 particles.
    [6]
    6. Method, according to claim 5, characterized by the fact that said dust particles are obtained from the same unloaded soil as that used for the formation of the fixation sublayer (22).
    [7]
    7. Multilayer coating capable of forming a thermal barrier on a superalloy metal substrate, characterized by the fact that it comprises at least one metallic sub-layer (13) arranged on the substrate, a ceramic layer (14) based on yttrium-stabilized zirconia covering said metallic sub-layer (13) and presenting a columnar structure defining pores, a protective layer (20) based on oxide covering the ceramic layer forming a continuous film and a fixing sub-layer (22) based on zirconia resulting from a soil, disposed between the ceramic layer (14) and the protective layer (20) and in at least part of the pores of the ceramic layer (14).
    [8]
    8. Coating according to claim 7, characterized by the fact that said protective layer (20) is, in addition, infiltrated in at least part of the pores of the ceramic layer (14).
    [9]
    Coating according to either of claims 7 or 8, characterized in that said protective layer (20) has a thickness between 1 and 100 pm.
    [10]
    Coating according to any one of claims 7 to 9, characterized in that said protective layer (20) has an unoriented porosity.
    [11]
    11. Coating according to any one of claims 7 to 10, characterized by the fact that said protective layer (20) comprises essentially zirconia doped with yttrium and / or with at least one element belonging to the group of lanthanides.
    [12]
    Coating according to any one of claims 7 to 10, characterized in that said protective layer (20) comprises essentially one or more rare earth oxides.
    [13]
    13. Coating according to any one of claims 7 to
    Petition 870190013485, of 2/8/2019, p. 25/27
    3/3
    12, characterized by the fact that said protective layer (20) is thicker than said fixation sublayer (22).
    [14]
    Coating according to any one of claims 7 to
    13, characterized by the fact that the grain size of the protective layer (20) is larger than the grain size of the fixation sublayer (22).
    [15]
    15. Coating according to claim 14, characterized by the fact that the grain size distribution of the fixing sublayer (22) is more homogeneous than the grain size distribution of the protective layer (20).
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    同族专利:
    公开号 | 公开日
    FR2957358B1|2012-04-13|
    US9121295B2|2015-09-01|
    CN102947485B|2014-11-19|
    CA2792518A1|2011-09-15|
    EP2545198B1|2014-01-01|
    RU2012143608A|2014-04-20|
    RU2561550C2|2015-08-27|
    FR2957358A1|2011-09-16|
    CN102947485A|2013-02-27|
    BR112012022932A2|2018-05-22|
    EP2545198A1|2013-01-16|
    US20130130052A1|2013-05-23|
    BR112012022932A8|2019-09-03|
    WO2011110794A1|2011-09-15|
    JP2013522462A|2013-06-13|
    CA2792518C|2017-10-24|
    JP5759488B2|2015-08-05|
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    法律状态:
    2018-06-05| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-05| B06T| Formal requirements before examination|
    2019-09-17| B09A| Decision: intention to grant|
    2019-11-05| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1000992A|FR2957358B1|2010-03-12|2010-03-12|METHOD FOR MANUFACTURING THERMAL BARRIER PROTECTION AND MULTILAYER COATING FOR FORMING A THERMAL BARRIER|
    PCT/FR2011/050500|WO2011110794A1|2010-03-12|2011-03-11|Method for manufacturing a thermal-barrier protection and multi-layer coating suitable for forming a thermal barrier|
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