Background of the invention
The present invention relates to the general field of protective coatings used for thermally insulating parts in high temperature environments such as parts used in hot parts of aircraft turbine engines and land.
To improve the efficiency of turbomachines, in particular of high-pressure turbines (TuHP) Terrestrial stationnâmes systems or aircraft engines, temperatures of higher and higher are contemplated. Under these conditions, the materials used, such as metal alloys or materials ceramic matrix composites (CMC), require protection, primarily to maintain a sufficiently low surface temperature guaranteeing their functional integrity and limiting their oxidation / corrosion by the ambient atmosphere .
The protection type "thermal barrier" (BT) or "environmental barrier" (EBC for "Environmental Barrier Coating" in English), are complex multilayer stacks typically consist of a sub-layer for protection against oxidation / corrosion deposited on the surface of the base material (metal alloy or composite material) of the substrate, itself surmounted by a ceramic coating whose primary function is to limit the surface temperature of the coated components. In order to perform its function of protection against the oxidation / corrosion and promote the attachment of the ceramic coating, the underlayer may be pre-oxidized to form on its surface a dense alumina layer called "Thermally Growth oxide '( TGO) in the case of thermal barriers.

The lifetime of these systems (BT and EBC) depends on the resistance of the stack to thermal cycling on the one hand, and the resistance of the outer layer to environmental stress (erosion by the solid particles, chemical resistance, corrosion, ...), on the other.

In particular, these systems degrade very quickly when exposed to an environment rich in particles of sand or volcanic ash (rich in silica type inorganic compounds) is commonly characterized by the CMAS generic name (for oxides calcium, Magnesium, Aluminum and Silicon). The CMAS infiltration of the melt in a thermal barrier or environmental barrier typically occurs degradation:

• stiffening the infiltrated layer leading to mechanical failure (delamination);

· Destabilization by chemical dissolution of the thermal barrier and formation of recrystallized product having mechanical properties and / or different volumes.

To overcome this problem, compositions called "anti-CMAS" have been developed, these compositions for the formation of a chemical reaction by tight barrier layer with the CMAS as described in particular in document CG Levi, JW Hutchinson, M . -H. Vidal-Sétif, CA Johnson, "Environmental degradation of thermal barrier coatings by molten deposits", MRS Bulletin, 37, 2012, pp 932-941.

However, these systems still have functional limitations reducing their effectiveness, among which may be cited:

• Cracking of the BT service thermomechanical effect inducing privileged paths of infiltration by molten CMAS; · The persistence of infiltrated variable thickness due to competition between the capillary infiltration of CMAS into the coating and the reaction kinetics of formation of the sealed barrier phase. More infiltrated this thickness, the greater the risk of mechanical weakening of BT's strong. Indeed, a stiffening of the system is to fear inducing durations limited life despite stopping the infiltration of CMAS;

• The need to use an anti-CMAS coating having a dense morphology and free of vertical cracks to minimize the capillary infiltration liquid contaminant. In this case, the system becomes sensitive to thermomechanical stresses induced by differences in thermal expansion coefficient of the different elements of the system, thus resulting in limited lifetimes again.

There is therefore a need for a turbine engine component fitted with a protective layer against CMAS that limits the penetration depth of CMAS melted into the protective layer.

Purpose and Summary of the Invention

The present invention therefore has the main purpose to restrict the wicking of CMAS melted in an anti-CMAS protection layer promoting the reaction of formation of the protective barrier layer closer to the surface of the coating by providing a turbine engine component coated comprising a substrate and at least one layer of protection against calcium and magnesium aluminosilicates CMAS present on said layer, the layer comprising a first phase of a protective material against calcium aluminosilicates and magnesium CMAS and a second phase comprising particles of an anti-wetting material liquid CMAS dispersed in the protective layer. By "anti-wetting material to CMAS"

The addition of a non-wetting phase to the CMAS divided form in the first phase or matrix phase of the anti-CMAS protection layer will allow not only to limit the contact between the molten CMAS and the protective layer against the CMAS to the surface of the latter, but also to limit the infiltration of contaminants liquids in vertical cracks. Thus, the reactivity of the protective layer to form by chemical reaction with the CMAS tight continuous layer other contamination

(Barrier layer) is preferred over capillary infiltration mechanisms.

This increases the lifetime of a turbine engine part including the protective layer against CMAS accordance with the invention by promoting the formation of the protective barrier layer closer to the surface of the protective layer. The sacrificial aspect of the protective layer is mitigated, as his stiffening. The lifetime of the protective layer and, therefore, the coated turbine engine part is further increased by allowing the vertical split protective layers against the enhanced reactivity to CMAS that allows to accommodate thermomechanical deformation without that vertical cracks are infiltrated by CMAS.

In a particular aspect of the invention, the anti-wetting material used for the second stage of the protection layer corresponds to a material or mixture of materials selected from the following materials: CaF 2 , LnPO 4 in which Ln = La (Lanthanum ), Gd (gadolinium), Sm (Samarium), Nd (neodymium)), MAX phases (M n + Iax n (n = 1,2,3) where M = Sc (Scandium), Y (yttrium), La ( lanthanum), Mn (manganese), Re (rhenium), W (Tungsten), Hf (hafnium), Zr (zirconium), Ti (Titanium), A = groups IIIA, IVA, VA, VIA and X = C, N, AlN, BN, SiC and SiOC.

According to another particular aspect of the invention, the anti-wetting material particles dispersed in the protective layer against CMAS have an average size between 10 nm and 10 pm.

According to another particular aspect of the invention, the protective layer against CMAS has a volume content of particles of anti-wetting material between 1% and 80%.

According to another particular aspect of the invention, the volume percentage of anti-wetting material particles present in the protective layer against CMAS varies in the direction of the thickness of the protective layer, the volume percentage of particulate material anti-wetting gradually increasing between a first region of said layer adjacent the substrate and a second region of said layer remote from the first zone.

According to another particular aspect of the invention, the protective layer against CMAS has a thickness of between 1 .mu.m and 1000 .mu.m.

According to another particular aspect of the invention, the protective material against calcium aluminosilicates and magnesium CMAS of the first phase corresponds to the following materials or a mixture of the following materials: earth zirconates uncommon RE2Zr2Û7 where RE = Y (yttrium), La (Lanthanum), Ce (cerium), Pr (Praseodymium), Nd (Neodymium), Pm (Promethium), Sm (Samarium), Eu (Europium), Gd (Gadolinium), Tb (Terbium) , Dy (Dysprosium), Ho (Holmium), Er (Erbium), Tm (Thulium), Yb (Ytterbium), Lu (Lutetium), zirconia partially or fully stabilized, the phases delta A4B3O12, where A = Y → Lu and B = Zr, Hf, the composite with Y2O3 ZrO2, Al 2 0 3 or Ti0 2The hexaa read minâtes, spinels, mono-silicates and di-silicates, rare earth RE where RE = Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, tm, Yb, Lu).

According to another particular aspect of the invention, a thermal barrier layer is interposed between the substrate and the protective layer against calcium aluminosilicates and magnesium CMAS.

According to another particular aspect of the invention, the substrate is a superalloy based on nickel or cobalt and has on its surface an alumino-shaper bonding layer or a layer composite ceramic matrix composite (CMC), or a layer of ceramic matrix composite (CMC) coated with a bonding layer alumino-forming machine.

The invention also relates to a method for manufacturing a turbine engine part according to the invention, comprising at least a step of forming a protective layer against calcium aluminosilicates and magnesium CMAS directly on the substrate or on a layer of thermal barrier present on the substrate, the forming step being carried out with one of the following methods:

- suspension plasma spraying from at least one slurry containing a powder or a precursor of a protective material against calcium aluminosilicates and magnesium CMAS and a powder or a precursor of a non-wetting material or any combination of these,

- flame spraying at high speed from at least one slurry containing a powder or a precursor of a protective material against calcium aluminosilicates and magnesium CMAS and a powder or a precursor of a non-wetting material or any combination thereof,

- atmospheric pressure plasma spraying a powder of a barrier material against aluminosilicates of calcium and magnesium in combination with CMAS suspension plasma spraying or by flame spraying at high speed from a solution containing a powder or a precursor of non-wetting material in suspension ..

Brief Description of Drawings

Other features and advantages of the present invention will be apparent from the description given below, with reference to the accompanying drawings which illustrate embodiments having no limiting character. In the figures:

- Figure 1 shows the infiltration of liquid contaminants in a turbomachine component provided with a layer of protection against calcium and magnesium aluminosilicates CMAS according to the prior art,

- Figures 2 and 3 show the infiltration of liquid contaminants in a turbomachine component provided with a layer of protection against calcium and magnesium aluminosilicates CMAS according to the invention,

- Figure 4 is a first example of implementation of a method for making a turbine engine part according to the invention,

- Figure 5 is a second example of implementation of a method for making a turbine engine part according to the invention,

- Figure 6 is a third example of implementation of a method for making a turbine engine part according to the invention,

- Figure 7 is a fourth example of implementation of a method for making a turbine engine part according to the invention.

Detailed Description of the Invention

The invention applies generally to any turbomachine part coated with a protective layer comprising a phase of a protective material against calcium aluminosilicates and magnesium CMAS. By "protective material against CMAS" means all materials that prevent or reduce

infiltration of CMAS melted in the protective layer in particular by forming at least a waterproof barrier layer. There may be mentioned by way of example among the most frequently encountered waterproof barrier layers, the formation of apatite phases of generic formula (Ca 4 Re 6 (SiO 4 ) 6 O) or Ca 2 Re 8 (SiO 6O2 or of anortithe phases of generic formula CaAl 2 If 2 O8.

By way of non-limiting examples, the protective material against the aluminosilicates of calcium and magnesium CMAS capable of forming by chemical reaction with CMAS a waterproof layer or continuous phase at any other contamination such as apatite type phase matching of the following materials or a mixture of several of the following materials: the earth zirconates uncommon RE 2 Zr 2 O 7 , where RE = Y (yttrium), La (Lanthanum), Ce (cerium), Pr (Praseodymium), Nd (neodymium), Pm (Promethium), Sm (samarium), Eu (europium), Gd (Gadolinium), Tb (Terbium), Dy (Dysprosium), Ho (Holmium), Er (Erbium), Tm (Thulium), Yb (Ytterbium), Lu (Lutetium), zirconia partially or fully stabilized, delta phases A'4B 3 O12 , wherein A 'represents any element selected from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu and B = Zr, Hf, composites comprising Y2O3 with ZrO 2 , AI 2 O 3 , or TiO 2 , the hexaaluminates, spinels, monosilicates and di-silicates of rare earth RE where RE = Y, La, Ce, Pr, Nd, Pm, Sm, . Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu preferably, the protective material against calcium aluminosilicates and magnesium CMAS is selected from zirconates rare earth zirconias doped silicates rare earth and mixtures thereof.

According to the invention, is added to this first phase, constitutes the matrix of the protective layer against CMAS, a second phase in the form of particles of at least one anti-wetting material to CMAS dispersed in the protective layer whose matrix is ​​formed by the first phase.

Indeed, the presence of a non-wetting phase in the volume of the protective layer against CMAS can limit the capillary infiltration of molten CMAS in the layer and thus to localize the reaction of forming the barrier layer anti-CMAS closest to the surface of the protective layer. Thus, changes of thermomechanical properties or volumes, from the formation of new phases, do not induce high mechanical stresses in the heart of the protective layer. This increases the lifetime of protection and, consequently, of the turbine engine component coated conditions. The presence of a non-wetting phase to CMAS in the volume of layer of protection against CMAS also keeps all the interest of the vertical split initial or induced thermomechanical effect in use, the protective layer, by limiting infiltration of these cracks by the liquid contaminant. Again, increasing the lifetime of protection and, consequently, of the turbine engine room in terms of use. In addition, the presence of the non-wetting phase in the volume of the protective layer against the CMAS in finely dispersed form increases its anti-wetting efficiency.

The particles dispersed in the matrix phase or the first layer of protection against CMAS can in particular consist of an anti-wetting material to CMAS corresponding to a material or mixture of materials selected from the following materials: CaF 2 , LnP0 4 where Ln = La (lanthanum), Gd (gadolinium), Sm (Samarium), Nd (neodymium)), MAX phases (M n + Iax n (n = l, 2 or 3) where M = Sc (Scandium), Y (yttrium), La (lanthanum), Mn (manganese), Re (rhenium), W (Tungsten), Hf (hafnium), Zr (zirconium), Ti (Titanium), a is any element of groups IIIA, IVA, . VA or VIA and X = C, N, AlN, BN, SiC and SiOC More preferably, the anti-wetting to CMAS material is selected from the following materials: CaF2 , LnP0 4 , BN et leurs mélanges.

The second non-wetting phase in the form of particles dispersed in the protective layer against CMAS can be obtained from powders and suspensions.

The particles of anti-wetting material to CMAS dispersed in the first phase preferably have an average size between 10 nm and 10 microns and preferably between 10 nm and 1 pm. In this presentation, the words "between ... and ..." should be understood as including the terminals.

The protection layer has a volume content of particles of anti-wetting material to CMAS which may be between 1% and 80%, preferentially between 1% and 30%.

The protective layer may have a following composition gradient wherein the volume percentage of the first phase consists of the material against the CMAS and the second phase consisting of anti-wetting material particles to CMAS moving in the direction of the thickness of the protective layer. Specifically, the percentage volume of anti-wetting material particles present in the protective layer against may vary in the direction of the thickness of the protective layer, the volume percentage of particles of anti-wetting material increasing progressively between a first region of said layer adjacent the substrate and a second region of said layer remote from the first region in order to concentrate the content of the protective layer of anti-wetting agent in the vicinity of its surface.

The protection layer has preferably a porous structure, which allows it to have good thermal insulation properties. The protective layer may also have vertical cracks, initially present in the layer or formed in use, that can give the layer a greater deformation capacity and reach thus high lifetimes . The porous and fractured microstructure (initially or during use) of the protective layer is mainly achieved by controlling the shaping method (deposition) of the layer as well known per se.

Thanks to the presence of a second anti-wetting phase to CMAS in the protective layer for retaining the liquid CMAS the vicinity of the surface of the layer, these porosities and cracks no longer constitute privileged paths for the infiltration of CMAS melt as in the prior art. The efficiency of the protective material against the CMAS constituent of the first phase is thus preserved.

Figures 1, 2 and 3 illustrate the effects produced by a layer of protection against calcium and magnesium aluminosilicates CMAS according to the invention, namely a composite protective layer comprising the first and second stages described above, and protective layer against calcium aluminosilicates and magnesium CMAS according to the prior art. More specifically, Figure 1 shows a part 10 consists of a substrate 11 in nickel base superalloy coated in the order of a bonding layer alumino-shaper 12, a thermal barrier layer 13 of Zr0 2 - Y2O3 (8% by mass) commonly denoted YSZ and a protective layer against CMAS

14 according to the prior art made of Gd 2 Zr 2 0 7 , the part being in the presence of CMAS 15 liquid (molten).

2 shows a piece 20 consists of a substrate 21 based superalloy of nickel coated, in order, a layer of binding alumino-shaper 22, a thermal barrier layer 23 of YSZ and a protective layer against CMAS 24, the layer 24 here comprising a first phase 240 made of Gd 2 Zr 2 0 7 as a covering material against the CMAS and a second phase 241 dispersed in the 24 and layer comprised of fluoride calcium CaF 2 as anti-wetting material to CMAS, the part being in the presence of CMAS 25 liquid (molten).

In the case of a protective layer according to the prior art as shown in Figure 1, CMAS type of liquid contaminants

15 deeply seep into cracks of the protective layer 14 as well as the thermal barrier layer 13.

Differently, in the case of a protective layer according to the invention as shown in Figure 2, the depth of infiltration of CMAS type liquid contaminants 25 in the protective layer 24 is limited by the presence of the second phase 241 consists of particles of anti-wetting material to CMAS dispersed in the protective layer 24. More specifically, as illustrated in Figure 3, the CMAS 25 type liquid contaminants are retained on the surface of the protective layer 24 from their contact with the second phase 241,thereby greatly limiting the depth of penetration of CMAS liquid 25 into the pores and cracks of the protective layer 24 and forming by chemical reaction with the first phase layers or continuous phases and tight contaminants closer to the surface of the protective layer.

By "anti-wetting to CMAS material" herein is meant a material which provides the protection layer against calcium aluminosilicates and magnesium CMAS 24 the property of having a contact angle Θ between the exposed surface 24a of the layer protection 24 and 250 drops of liquid CMAS 24 greater than or equal to 45 °, preferably greater than or equal to 90 °.

The addition of a non-wetting phase to CMAS within the layer of protection against CMAS not only limits the contact between the molten CMAS and layer of protection against CMAS to the surface of the latter, but also limit the infiltration of contaminants liquids in vertical cracks. Thus, the reactivity of the barrier layer, for forming by chemical reaction with the CMAS a sealed continuous layer to any other contamination, is preferred over capillary infiltration mechanisms.

The protective layer against calcium aluminosilicates and magnesium CMAS according to the invention has a thickness between 1 and 1000 μιτι μηι and preferably between 5 pm and 200 pm.

The substrate of the part of object turbomachine of the invention may in particular be a superalloy based on nickel or cobalt. In this case, the substrate may further comprise on its surface a bonding layer alumino-forming machine. For example, the alumino-shaper bonding layer may include MCrAlY type alloys (where M = Ni, Co, Ni, and Co), nickel aluminides such β-NiAl (modified or not by Pt, Hf , Zr, Y, Si or combinations thereof), aluminides alloys γ-γ'-Νϊ Νί- 3 ΑΙ (modified or not by Pt, Cr, Hf, Zr, Y, Si or combinations these elements), MAX phases (M n + Iax n(N = 1,2,3) where M = Sc, Y, La, Mn, Re, W, Hf, Zr, Ti; A = groups IIIA, IVA, VA, VIA; X = C, N), or any other sublayer connecting suitable, as well as all mixtures thereof. The substrate may also consist of AMI superalloys, MC-NG, CMSX4 and derivatives, or René and derivatives.

The bonding layer protects the substrate from corrosion and oxidation while ensuring a good mechanical grip and / or chemical interaction between the substrate and the overlying layer in particular corresponding to the layer of protection against CMAS of the invention or a thermal barrier layer.

bonding the layers may be formed and deposited in particular by PVD (deposition by physical evaporation, in English "Physical Vapor Deposition"), APS, HVOF, LPPS (low pressure plasma spraying, in English "Low Pressure Plasma Spraying") or derivatives , IPS (in an inert atmosphere plasma spraying, in English "inert plasma spraying"), CVD (deposition by chemical vapor, in English "chemical Vapor deposition"), APHA (Aluminizing Vapor Snecma), spark plasma sintering (in English "Spark plasma sintering "), electroplating, and any other deposition method, and put into suitable form.

The substrate used in the invention has a shape corresponding to that of the turbine engine body to be produced. The turbomachine of parts comprising the protective layer according to the invention can be, but not limited to, blades, distributors, high pressure turbine rings and combustion chamber walls.

The protective layer against calcium aluminosilicates and magnesium composite, that is to say including the first and second phases as defined above, can be directly deposited on the substrate of the turbine engine part. The protective layer of the invention is in this case a thermal barrier to the substrate.

According to an alternative embodiment, a thermal barrier layer may be interposed between the substrate and the composite protective layer of the invention, or between a bonding layer alumino-forming machine and the composite protective layer of the invention, the latter being used in this case as functionalization layer on the surface of the thermal barrier layer having or not a protection against contaminants liquid high temperature type aluminosilicates of calcium and magnesium CMAS. By way of non-limiting example, the thermal barrier layer may be made of yttria-stabilized zirconia with a mass content of Y2O3 between 7% and 8%. The thermal barrier layer, on which is formed the composite protective layer of the invention,

The thermal barrier layer may be formed and deposited in particular by EB-PVD (vapor deposition assisted by an electron beam, in English "electron beam physical vapor deposition"), APS, HVOF, sol-gel process, SPS, SPPS (plasma spraying precursor solution, in English "solution precursor plasma spraying") HVSFS or any other suitable method.

The layer of composite protection of the invention may be implemented as a layer of functionalizing the surface of a complex stack describing an environmental barrier system (EBC), or an environmental thermal barrier system (BCET), protecting items in ceramic matrix composites (CMC). The environmental thermal barrier system for protecting in particular the CMC materials may include, but not exclusively, materials: MoSi 2 , BSAS (BaOi -x -SrO x -Al 2 03-2Si02), mullite (3 Al 2 O 3 -2 Si0 2), Silicates mono- and di-silicates of rare earth RE where RE = Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconia fully or partially stabilized or doped, and any other suitable composition as well as mixtures of any thereof.

The layer of composite protection of the invention may be formed and deposited by one of the following methods:

- (APS plasma spraying at atmospheric pressure - in English "Atmospheric Plasma Spraying"),

- HVOF (flame sprayed at high speed - in English "High Velocity Oxygen Fuel")

- SPS (plasma projection suspensions - in English "Suspension Plasma Spraying")

- SPPS (plasma spraying precursor solutions - in English "Solution Precursor Plasma Spraying")

- HVSFS (suspension projection in a high-speed flame - in English "High Velocity Suspension Flame Spray"), also known as the S-HVOF (Suspension-HVOF).

example 1

As illustrated in Figure 4, a method of manufacturing a turbomachine part 30 according to the invention has been implemented on a substrate 31 based superalloy AMI type nickel onto which has been deposited a layer of composite protection against calcium aluminosilicates and magnesium CMAS projection 32 by SPS, the protective layer 32 comprising, according to the invention, a first

phase Gd2Zr 2 07 as protective material against calcium aluminosilicates and magnesium CMAS and a second phase of CaF 2 in the form of particles dispersed in the protective layer 32 as an anti-wetting material to CMAS.

In this example, a solution 40 containing a powder of the anti-CMAS material in suspension 41, here Gd 2 Zr 2 0 7 / and a powder of anti-wetting material to CMAS 42, here CaF 2 , in volume proportions adapted for the embodiment of the protective layer 32 is used. The solution 40 is injected through a single injector 42 of suspension in the heart of a plasma jet 44 generated by a plasma torch 43, allowing the thermokinetic treatment of the solution 40, namely the melting and accelerating powder .

The example does not exclude the possibility of using other anti-CMAS materials or other non-wetting materials to CMAS. In addition, it is also possible that the liquid phase of the solution contains not more powders but the precursors of either or both phases is desired to form in the composite protective layer. In this particular case, the treatment thermokinetics will train in-situ in flight phase of the melt and accelerate to generate the coating. It is also possible to produce the composite coating using either plasma but a high-speed flame resulting from this case to an embodiment HVSFS.

example 2

As illustrated in Figure 5, a method of manufacturing a turbomachine part 50 according to the invention has been implemented on a substrate 51 based superalloy AMI type nickel onto which has been deposited a layer of composite protection against calcium aluminosilicates and magnesium CMAS projection 52 by SPS, the protective layer 52 comprising, according to the invention, a first phase of Gd 2 Zr 2 0 7 as covering material against calcium aluminosilicates and magnesium CMAS and a second phase of CaF 2 in the form of particles dispersed in the protective layer 52 as an anti-wetting material to CMAS.

In this example, a first solution 61 containing a powder of the anti-CMAS material in suspension 610, here Gd 2 Zr 2 0 7 , and

second solution 62 containing a powder of an anti-wetting material with CMAS in suspension 620, here CaF 2 in suitable proportions by volume for making the protective layer 62 are used.

The two solutions 61 and 62 are injected through a single injector 63 of suspension in the heart of a plasma jet 64 generated by a plasma torch 65, allowing the thermokinetic treatment solutions 61 and

62, namely the melting and acceleration of the powders.

The example does not exclude the possibility of using other anti-CMAS materials or other non-wetting materials to CMAS. In addition, it is also possible that the liquid phase of the solution contains not more powders but the precursors of either or both phases is desired to form in the composite protective layer.

In this particular case, the thermokinetics treatment will form the ίη situ phase theft, melt and accelerate to generate the coating. It is also possible to produce the composite coating using either plasma but a high-speed flame resulting from this case to an embodiment HVSFS.

example 3

As illustrated in Figure 6, a method of manufacturing a turbomachine part 70 according to the invention has been implemented on a substrate 71 based superalloy AMI type nickel onto which has been deposited a layer of composite protection against calcium aluminosilicates and magnesium CMAS projection 72 by SPS, the protective layer 72 comprising, according to the invention, a first phase Gd 2 r 2 07 as a covering material against calcium aluminosilicates and magnesium CMAS and a second phase of CaF 2 in the form of particles dispersed in the protective layer 72 as an anti-wetting material to CMAS.

In this example, a first solution 81 containing a powder of the anti-CMAS material in suspension 810, here Gd 2 Zr 2 07 and a second solution 82 containing a powder of an anti-wetting material with CMAS in suspension 820, here CaF 2 , in suitable proportions by volume for making the protective layer 72 are used. Solutions 81 and 82 are injected respectively through a first and a second specific suspension injectors 83 and 84 in the heart of a plasma jet 85 generated by a plasma torch 86, allowing the thermokinetic treatment solutions 81 and 82 in namely the melting and acceleration of the powders.

The example does not exclude the possibility of using other anti-CMAS materials or other non-wetting materials to CMAS. In addition, it is also possible that the liquid phase of the solution contains not more powders but the precursors of either or both phases is desired to form in the composite protective layer. In this particular case, the treatment thermokinetics will train in-situ in flight phase of the melt and accelerate to generate the coating. It is also possible to produce the composite coating using either plasma but a high-speed flame resulting from this case to an embodiment HVSFS.

example 4

As illustrated in Figure 7, a method for manufacturing a turbine engine part 90 according to the invention has been implemented on a substrate 91 based superalloy AMI type nickel onto which has been deposited a layer of composite protection against calcium aluminosilicates and magnesium CMAS 92 by hybrid projection SPS and APS, the protective layer 92 comprising, according to the invention, a first phase of Gd 2 Zr 2 Û 7 as covering material against calcium aluminosilicates and CMAS magnesium and a second phase of CaF 2 in the form of particles dispersed in the protective layer 92 as an anti-wetting material to CMAS.

In this example, a 110 powder consisting of particles 111 of the anti-CMAS material, here Gd2Zr 2 07 and a solution 120 containing a powder of an anti-wetting material with CMAS in suspension 121, here CaF 2 , in proportions by volume adapted for carrying out the protective layer 92 are used. For the powder 110, APS is used in which method the powder 110 is injected through a first specific injector 101 to the heart 103 of a plasma jet generated by a plasma torch 104, allowing the thermokinetic treating the powder 110 . to the solution 120, the SPS is used in which method the solution 120 is injected through a second specific suspension injector 102 to the heart 103 of the plasma jet generated by a

plasma torch 104, allowing the thermokinetic treating the powder 120.

The example does not exclude the possibility of using other anti-CMAS materials or other non-wetting materials. In addition, it is also possible that the liquid phase contains either powders but the precursors of either or both phases is desired to form in the composite layer. In this particular case, the treatment thermokinetics will train in-situ in flight phase of the melt and accelerate to generate the coating. It is also possible to produce the composite coating using either a plasma mixture, but a high-speed flame resulting from this case to one embodiment hybrid HVOF and HVSFS.

CLAIMS

Turbomachine 1. A coated article comprising a substrate (21) and at least one layer of protection against calcium and magnesium aluminosilicate (CMAS) (24) present on said substrate, the layer (24) comprising a first phase (240) a protective material against calcium and magnesium aluminosilicate (CMAS) and a second phase (241) comprising particles of an anti-wetting material dispersed in the first phase,

the anti-wetting material corresponding to a material or mixture of materials selected from the following materials:

- CaF2,

- LnPÛ4 where Ln = La (Lanthanum), Gd (Gadolinium), Sm (Samarium), Nd (Neodymium)

- MAX phases M n + Iax n with n = 2.3 wherein M = Sc (Scandium),

Y (yttrium), La (lanthanum), Mn (manganese), Re (rhenium), W (Tungsten), Hf (hafnium), Zr (Zirconium), i (Titanium), where A = groups IIIA, IVA, VA, VIA and X = C, N,

- AIN and

- BN.

2. Part according to claim 1, wherein the particles of the anti-wetting material dispersed in the first phase (240) have an average size between 10 nm and 10 μιτι.

3. Part according to claim 1 or 2, wherein the volume percentage of particles of anti-wetting material dispersed in the first phase (240) is between 1% and 80%.

4. Part according to claim 3, wherein the volume percentage of particles of anti-wetting material dispersed within the first phase material (240) varies in the direction of the thickness of the protective layer (24), the volume percent of said particles gradually increasing from a first zone of said layer

adjacent to the substrate (21) and a second region of said layer remote from the first zone.

5. Part according to any one of claims 1 to 4, wherein the protective layer against calcium and magnesium aluminosilicate (CMAS) (24) has a thickness of between 1 .mu.m and 1000 .mu.m.

6. Part according to any one of claims 1 to 5, wherein the protective material against calcium and magnesium aluminosilicate (CMAS) of the first phase (240) is capable of forming apatite type phases and corresponds to of the following materials or a mixture of the following materials:

- earth zirconates uncommon RE 2 Zr 2 0 7 , where RE = Y (yttrium), La (Lanthanum), Ce (cerium), Pr (Praseodymium), Nd (neodymium), Pm

(Prométhium), Sm (Samarium), Eu (Europium), Gd (Gadolinium), Tb (Terbium), Dy (Dysprosium), Ho (Holmium), Er (Erbium), Tm (Thulium), Yb (Ytterbium), Lu (Lutécium),

- zirconia partially or fully stabilized, - phases delta 4B3O12 A, where A '= Y → Mo and B = Zr, Hf,

- composites comprising Y2O3 with ZrCh, Al2O3, or ΤΊΟ2,

- the hexaaluminates,

- spinels,

- the mono-silicates and di-silicates of rare earth RE where RE = Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.

7. Part according to any one of claims 1 to 6, further comprising a thermal barrier coating (23) interposed between the substrate (21) and the protective layer against calcium and magnesium aluminosilicate (CMAS) (24 ).

8. Component according to any one of claims 1 to 7, wherein the substrate (21) is a nickel base superalloy or cobalt and has on its surface a bonding layer alumino-forming machine (22) or a layer of material ceramic matrix composite (CMC), or

layer composite ceramic matrix composite (CMC) coated with a bonding layer alumino-forming machine.

9. A method of manufacturing a part according to any one of claims 1 to 8, comprising at least a step of forming the protective layer against calcium and magnesium aluminosilicate (CMAS) (24) directly on the substrate (21) or a thermal barrier layer (23) present on the substrate, the forming step being carried out with one of the following methods:

- plasma spraying suspension from at least one slurry containing a powder or a precursor of a protective material against calcium and magnesium aluminosilicate (CMAS) and a powder or a precursor of an anti-wetting material,

- flame suspension projection at high speed from at least one slurry containing a powder or a precursor of a protective material against calcium and magnesium aluminosilicate (CMAS) and a powder or a precursor of a material anti-wetting,

- atmospheric pressure plasma spraying a powder of a barrier material against calcium and magnesium aluminosilicate (CMAS) in combination with suspension plasma spraying or by flame spraying at high speed from a solution containing a precursor an anti-wetting ceramic material or a powder of the ceramic material anti-wetting in suspension.