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 or stationary systems for 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 is pre-oxidized to form on its surface a dense alumina layer called "Thermally Grown 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. Anti-CMAS compositions employed will undergo dissolution in the CMAS to form a protective dense phase having a higher melting point than CMAS. In the case of the family of rare earth zirconates, anti-CMAS materials very promising, this solution allows the formation of a phase apatite type Ca 2 RE 8 (Si0 4) 602 (RE = rare earth) which will be blocking but also phases "noise" or secondary type partially stabilized zirconia (largely in the form fluorite), spinels, silicates or rare earth as particularly described in the documents S. rowing J. Yang, CG Levi, "Infiltration-inhibiting reaction of gadolinium zirconate thermal barrier coatings with CMAS melts," Journal of the American Ceramic Society, 91, 2008, pp 576-583 and H. Wang, "reaction mechanism of CaO-MgO -Al 2 0 3 -Si02 (CMAS) one lanthanide zirconia thermal

barrier coatings ", PhD Thesis, Auburn University, USA, 2016. However, these secondary phases have volume and / or thermomechanical or mechanical properties that can lessen the beneficial effect of anti-CMAS.

There is therefore a need for a turbine engine component fitted with a protective layer against CMAS that allows confining the reaction zone with the CMAS near the surface of the protective layer and to limit the formation of secondary phases.

Purpose and Summary of the Invention

The present invention therefore has the main purpose to increase the capacity or kinetic reaction of a protective layer against CMAS to form a layer or phase of blocking vis-à-vis liquid contaminants to limit their penetration depth in the coating by providing a coated turbine engine part comprising a substrate and at least one layer of protection against calcium and magnesium aluminosilicates CMAS present on said substrate, the layer comprising a first phase of a protective material against calcium aluminosilicates and magnesium CMAS capable of forming an apatite type phase or anorthite in the presence of calcium aluminosilicates and magnesium CMAS and a second phase comprising particles ofat least one rare earth silicate RE hasdispersed in the first phase.

The addition of a phase rare earth silicates in divided form in the first phase or matrix phase of the anti-CMAS protective layer can increase the reactivity of the latter in order to limit the penetration depth of the capillary CMAS liquid within the pores and / or vertical cracks present in the network layer. Indeed, rare earth silicates are protective apatite phase precursors. The second phase is therefore here a phase "activating" protective apatite phase. Therefore, the life of the anti-CMAS protection layer thus obtained is increased relative to that expected for the same protective layer without addition of this second phase. In addition, the inclusion of particles

According to a particular aspect of the invention, the earth silicate rarely used for the second phase of the protective layer is a rare earth RE mono-silicates has 2 Si0 5 or di-silicates Rare earth RE has two If 2 07, where RE is selected from: 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).

According to another particular aspect of the invention, the rare earth silicate particles RE has dispersed in the protective layer against CMAS have an average size of between 5 nm and 50 pm, more preferably between 5 nm and 1 pm.

According to another particular aspect of the invention, the protective layer against CMAS has a volume content of particles of the rare earth silicate of between 1% and 80%.

According to another particular aspect of the invention, the volume percent rare earth RE silicate ceramic particles is present in the protective layer against CMAS varies in the direction of the thickness of the protective layer, the volume percentage rare earth RE silicate ceramic particles is gradually increasing from 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 between 1 and 1,000 pm.

According to another particular aspect of the invention, the protective material against calcium aluminosilicates and magnesium CMAS the first phase capable of forming apatite phases or anorthite type matches one of the following materials or a mixture of several of the the following materials: the earth zirconates uncommon RE b 2 Zr 2 0 7 , where RE b = 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), zirconias totally

stabilized, delta phases A4B3O12, where A = Y → Mo and B = Zr, Hf, the composite Y 2 0 3 with Zr0 2 , garnets yttrium and aluminum (YAG), the YSZ-Al composite 2 0 3 or YSZ-Al 2 0 3 -Ti0 2 .

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 nickel or cobalt base superalloy and has on its surface 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:

- plasma spraying of slurry from a 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 silicate rare earth RE or any combination of these,

- flame spraying at high speed from a suspension containing a powder or a precursor of a protective material against calcium aluminosilicates and magnesium CMAS and a powder or a precursor of a rare earth RE silicate 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 ceramic precursor silicate rare earth RE or a powder of ceramic silicate rare earth RE 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:

- Figures 1A and 1B show the infiltration of liquid contaminants in a layer of protection against calcium and magnesium aluminosilicates CMAS according to the prior art,

- Figures 2A and 2B show the infiltration of liquid contaminants in a layer of protection against calcium and magnesium aluminosilicates CMAS according to the invention,

- Figure 3 is a first example of implementation of a method for making a turbine engine part according to the invention,

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

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

- Figure 6 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 the infiltration of CMAS melted in the protective layer including training of at least one phase apatite or anorthosite.

By way of non-limiting examples, the protective material against calcium aluminosilicates and magnesium CMAS capable of forming apatite phases or anorthite type matches one of the following materials or a mixture of several of the following materials:

- les zirconates de terre rare RE 2Zr207, où REb = Y (Yttrium), La (Lanthane), Ce (Cérium), Pr (Praséodyme), Nd (Néodyme), Pm (Prométhium), Sm (Samarium), Eu (Europium), Gd (Gadolinium), Tb (Terbium), Dy (Dysprosium), Ho (Holmium), Er (Erbium), Tm (Thulium), Yb (Ytterbium), Lu (Lutécium),

- zirconia fully stabilized,

- phases delta A4B3O12, where A is 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 Zr0 2 ,

- garnet yttrium-aluminum (YAG)

- the YSZ-Al2O3 composite or YSZ-Al2O3-TiO2.

The invention applies especially to rare earth zirconates RE b 2 Zr 2 0 7 , where RE b = Y, La, Nd, Sm, Gd, Dy, Yb, the phases with delta A = Y, Dy or Yb and composite Y 2 0 3 -Zr0 2 .

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 rare earth RE silicate dispersed in the protective layer, the matrix is ​​formed by the first phase.

The inventors have found that mono-or di-silicates, silicates of rare earth are capable of reacting in the presence of CMAS to form a phase apatite, blocking stage which limits the depth of infiltration of the liquid CMAS in the protective layer, and without being dissolved in the liquid glass. The inventors have therefore determined that the addition form of a mono-silicate filler and / or di-earth silicates rarely dispersed in a protective material against CMAS is a "activator" phase for the formation of apatite phases. By exacerbating the reactivity of the protective material against CMAS with loads distributed in the protective material against the CMAS it is possible to form the blocking phase to the CMAS liquid by the involvement of different reaction mechanisms, the formation of blocking layers being generated independently between the protective material against CMAS the first phase and silicate particles Rare earth Phase. This limits the infiltration of CMAS liquid in the volume of the material. Therefore, by limiting the depth of infiltration of CMAS into the protective layer, the changes of thermomechanical properties or volumes, from the formation of blocking layers, as well as secondary phases from the dissolution of the protective material against the CMAS is limited. Mechanical stresses in the heart of the protective layer are then also Blocking the formation of phases being generated independently between the protective material against CMAS the first phase and the rare earth silicate particles of the second phase. This limits the infiltration of CMAS liquid in the volume of the material. Therefore, by limiting the depth of infiltration of CMAS into the protective layer, the changes of thermomechanical properties or volumes, from the formation of blocking layers, as well as secondary phases from the dissolution of the protective material against the CMAS is limited. Mechanical stresses in the heart of the protective layer are then also Blocking the formation of phases being generated independently between the protective material against CMAS the first phase and the rare earth silicate particles of the second phase. This limits the infiltration of CMAS liquid in the volume of the material. Therefore, by limiting the depth of infiltration of CMAS into the protective layer, the changes of thermomechanical properties or volumes, from the formation of blocking layers, as well as secondary phases from the dissolution of the protective material against the CMAS is limited. Mechanical stresses in the heart of the protective layer are then also Therefore, by limiting the depth of infiltration of CMAS into the protective layer, the changes of thermomechanical properties or volumes, from the formation of blocking layers, as well as secondary phases from the dissolution of the protective material against the CMAS is limited. Mechanical stresses in the heart of the protective layer are then also Therefore, by limiting the depth of infiltration of CMAS into the protective layer, the changes of thermomechanical properties or volumes, from the formation of blocking layers, as well as secondary phases from the dissolution of the protective material against the CMAS is limited. Mechanical stresses in the heart of the protective layer are then also

reduced, which increases the lifetime of protection in terms of use.

The particles dispersed in the matrix phase or the first layer of protection against CMAS can in particular be made of a rare earth silicate single-RE has 2 Si0 5 or di-silicates Rare earth RE has two If 2 0 7 / where RE is selected from: 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). More preferably, the rare earth RE is mono-silicate rare earth RE has 2SiO or di-silicate rare earth RE has 2 ši 2 0 7 , is selected from: La, Gd, Dy, Yb, Y, Sm, Nd.

The second phase "activator" for the formation of apatite phases present as particles dispersed in the protection layer against CMAS can be obtained from powders, suspensions, precursors in solution or a combination of these different forms.

Rare earth silicate particles RE has dispersed in the first phase preferably have an average size of between 5 nm and 50 m and preferentially between 5 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 rare earth silicate particles can 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 consists of ground silicate particles rarely moves in the direction of the thickness of the layer protection. Specifically, the volume percentage of rare earth silicate ceramic particles RE is present in the protective layer against CMAS can vary in the direction of the thickness of the protective layer, the volume percentage of silicate ceramic particles rare earth RE is increasing progressively between a first region of said layer adjacent the substrate and a second zone of said layer

remote from the first zone. By introducing such a gradient grade rare earth RE silicate particles hasin the protective layer, the preferred reactivity and anti-CMAS effect near the top of the protective layer with a high concentration of rare earth silicate at this point of said protective layer while preserving the resistance thermo system with a lower concentration of rare earth silicate in the protective layer in the vicinity of the substrate. Indeed, silicate rare earth has a low coefficient of thermal expansion that can lessen the strength of the protective layer in the vicinity of the substrate, differences in expansion coefficient between the silicate rare earth and the substrate material being important.

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 phase "activator" in the protective layer for blocking phase of training for CMAS liquid in the vicinity of the surface of the layer, these porosities and cracks no longer constitute privileged paths for infiltration CMAS melted as in the prior art. The efficiency of the protective material against the CMAS constituent of the first phase is thus preserved.

1A, 1B, 2A and 2B 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 phases as described above, and a protective layer against calcium aluminosilicates and magnesium CMAS according to the prior art. More specifically, Figure 1A shows a part 10 consists of a substrate 11 based superalloy

AMI type nickel and coated with a protective layer against CMAS 12 according to the prior art made of Gd 2 Zr 2 0 7 / the workpiece being in the presence of CMAS 13 while Figure 1B shows the workpiece 10 when is exposed to high temperatures that result in the fusion of CMAS infiltration and 13 as contaminants CMAS type liquid 14 in the protective layer 12.

2A shows a part 20 made of a superalloy substrate 21 in AMI type nickel base and coated with a protective layer against CMAS 22 according to the invention, the layer 22 comprising here a first phase 220 made of Gd 2 Zr 2 0 7 and a second phase 221 dispersed in the layer 22 and consists of Gd 2 If 2 0 7 , the part being in the presence of CMAS 23 while Figure 2B shows the piece 20 when exposed to high temperatures that result in the fusion of CMAS infiltration and 23 as liquid contaminants type CMAS 24 in the protective layer 22.

In the case of a protective layer according to the prior art as shown in Figure 1B, the type of liquid contaminants CMAS 14 deeply seep into the protective layer 12 prior to forming an apatite blocking stage 15 while forming further in this zone the secondary phase 16 in large quantities such as fluorite Zr (Gd, Ca) O x which cause the occurrence of cracks 17 in the underlying portion 12 of the protective layer.

Differently, in the case of a protective layer according to the invention as shown in Figure 2B, the depth of infiltration of CMAS type liquid contaminants 24 in the protective layer 22 is limited by the rapid formation of apatite phases 25 and 26 blocking type Ca 2 Gd 8 (Si0 4 ) 6 0 2 , which allows to contain the type of liquid contaminants CMAS 24 in the vicinity of the surface of the protective layer 24. further, if the phases side 27 (such as fluorite Zr (Gd, Ca) O x) Appear at the apatite phases 25 and 26, these secondary phases are present in much smaller quantity than the protective layer of the prior art and does not result here of occurrence of cracks in the underlying portion of the protective layer 22.

The protective layer against calcium aluminosilicates and magnesium CMAS according to the invention has a thickness

between 1 and 1000 μηι μηη and preferably between 5 and 200 μιτι μητι.

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'-Νί 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.

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 may have a microstructure,

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 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 3, a method for manufacturing a turbine engine part 30 according to the invention has been implemented on a superalloy substrate 31 in AMI type nickel base on which was 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 of Gd 2 Zr 2 O 7 as a covering material against calcium aluminosilicates and magnesium CMAS and a second phase of Y 2 If two O7 form of particles dispersed in the protective layer 32 as activator phase protective apatite phases.

In this example, a solution 40 containing a powder of the anti-CMAS material in suspension 42, here Gd 2 Zr 2 O7, and liquid precursor of the activating stage 41, here Y2S12O7, in volume proportions adapted for the construction of the diaper shield 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 treating the solution 40. In this example, the precursors of phase Y2S12O7 may be yttrium nitrate Y (NO 3 ) 3 and tetraethyl orthosilicate Si (OC 2 H 5) 4 dissolved in ethanol. A first phase of Gd 32 comprising a protective layer is thus obtained 2 Zr 2 O7 as anti-CMAS material and forming the matrix of the layer 32 and a second phase of Y 2 If 2 O 7 as an activator of phases apatites protective form of finely dispersed particles in the matrix of the layer 32.

The example does not exclude the possibility of using other anti-CMAS materials or other silicate materials. The example does not exclude either the use of a precursor solution for the realization of the anti-CMAS phase and / or powders in suspensions for making the silicate phase. It is also possible to produce the composite coating using either a plasma torch but a HVOF device.

example 2

As illustrated in Figure 4, 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 O 7 as a covering material against calcium aluminosilicates and magnesium CMAS and a second phase Y2S12O7 form of particles dispersed in the protective layer 52 as activator phase protective apatite phases.

In this example, a first solution 61 containing a powder of the anti-CMAS material in suspension 610, here Gd 2 Zr 2 Û 7 , and a second solution 62 containing liquid precursor phase activator 620, here Y2S12O7, in proportions by volume adapted for carrying out the protective layer 52 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. In this example, the precursor of the Y stage 2 If 2 O 7 can be of yttrium nitrate Y (NO 3) 3 and tetraethylorthosilicate Si (OC2H 5 ) 4 dissolved in ethanol. The example does not exclude the possibility of using other anti-CMAS materials or other silicate materials. A first phase of Gd 32 comprising a protective layer is thus obtained 2 Zr 2 O 7 as anti-CMAS material and forming the matrix of the layer 32 and a second phase of Y 2 If 2 O 7 as an activator protective apatite phases in the form of finely dispersed particles in the matrix of the layer 32.

The example does not exclude either the use of a precursor solution for the realization of the anti-CMAS phase and / or powders in suspensions for making the silicate phase. It is also possible to produce the composite coating using either a plasma torch but a HVOF device.

example 3

As illustrated in Figure 5, a method for manufacturing a turbine engine 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 of Gd 2 Zr 2 U7 as covering material against calcium aluminosilicates and magnesium CMAS and a second phase Y2S12O7 form of particles dispersed in the protective layer 72 as activator phase protective apatite phases.

In this example, a first solution 81 containing a powder of the anti-CMAS material in suspension 810, here Gd 2 Σr 2 O7, and a second solution 82 containing liquid precursor phase activator 820, here Y2S12O7, in proportions by volume adapted for carrying out the protective layer 72 are used. Solutions 81 and 82 are respectively injected 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 this example, the precursors of the stage can be Y2SÎ2O7 Y yttrium nitrate (N0 3 ) 3 and tetraethyl orthosilicate Si (OC2 H 5 ) dissolved in ethanol. A first phase of Gd 32 comprising a protective layer is thus obtained 2 Zr 2 O 7 as anti-CMAS material and forming the matrix of the layer 32 and a second phase Y2S12O7 as activator protective apatite phases under form of finely dispersed particles in the matrix of the layer 32.

The example does not exclude the possibility of using other anti-CMAS materials or other silicate materials. The example does not exclude either the use of a precursor solution for the realization of the anti-CMAS phase and / or powders in suspensions for making the silicate phase. It is also possible to produce the composite coating using either a plasma torch but a HVOF device.

example 4

As illustrated in Figure 6, a method of manufacturing a turbomachine part 90 according to the invention has been implemented on a substrate 91 based superalloy type nickel AMI

onto which has been deposited a layer of composite protection against calcium and magnesium aluminosilicates CMAS 92 by hybrid SPS and APS projection, the protective layer 92 comprising, according to the invention, a first phase of Gd 2 Zr 2 O 7 as shielding material against calcium aluminosilicates and magnesium CMAS and a second phase Y2S12O7 form of particles dispersed in the protective layer 92 as activator phase protective apatite phases.

In this example, a 110 powder consisting of particles 111 of the anti-CMAS material, here Gd 2 ZR20 7 , and a solution 120 containing liquid precursors of the activating stage 121, here Y 2 ši 2 0 7In suitable proportions by volume for making 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 following SPS method is used wherein 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 phase processing 121. in this example, the precursors of phase Y 2 ši 2 O may be the Y yttrium nitrate (N0 3) 3 and tetraethyl orthosilicate Si (OC 2 H 5 ) 4 dissolved in ethanol. A first phase of Gd 32 comprising a protective layer is thus obtained 2 Zr 2 O 7 as anti-CMAS material and forming the matrix of the layer 32 and a second phase of Y 2 If 2 O 7 as an activator protective apatite phases in the form of finely dispersed particles in the matrix of the layer 32.

The example does not exclude the possibility of using other anti-CMAS materials or other silicate materials. The example does not exclude either the use of a precursor solution for the realization of the anti-CMAS phase and / or powders in suspensions for making the silicate phase. It is also possible to make the coating

Composite either using a plasma torch but a HVOF device.

CLAIMS

1. turbomachine piece (20) comprising a coated substrate

(21) and at least one layer of protection against calcium and magnesium aluminosilicate (CMAS) (22) present on said substrate, the protective layer (22) comprising a first phase (220) of a protective material against calcium and magnesium aluminosilicate (CMAS) capable of forming a phase type apatite or anorthite in the presence of calcium and magnesium aluminosilicate (CMAS) and a second phase (221) comprising particles of at least one silicate rare earth RE hasdispersed in the first phase, the protective material against calcium aluminosilicates and magnesium (CMAS) of the first phase capable of forming apatite type phases or anorthite corresponding to one of the following materials or a mixture of several of the following materials : earth zirconates uncommon
WHERE RE b = 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 fully stabilized, the phases delta A4B3O12, where A = Y → Mo and B = Zr, Hf, the composite Y 2 O 3 with ZrO2, yttrium garnet and aluminum (YAG), the YSZ-Al2O3 composite or YSZ-

2. Part according to claim 1, wherein said at least silicate rare earth RE is a rare earth mono-silicates has 2 SiO or a rare earth RE di-silicates has 2SÎ2O 7 , wherein RE is selected from: 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).

3. Part according to claim 1 or 2, wherein the silicate particles of rare earth RE is dispersed in the protective layer against calcium and magnesium aluminosilicate (CMAS)

(22) have a mean size of between 5 nm and 50 pm.

4. Part according to any one of claims 1 to 3, wherein the protective layer against calcium and magnesium aluminosilicate (CMAS) (22) has a volume content of particles of said at least rare earth silicate between 1 % and 80%.

5. Part according to claim 4, wherein the volume percentage of rare earth silicate ceramic particles RE is present in the protective layer against calcium and magnesium aluminosilicate (CMAS) (22) varies in the direction of thickness of the protective layer, the volume percentage of rare earth silicate ceramic particles RE has progressively increasing between a first region of said layer adjacent the substrate (21) and a second area of said layer remote from the first zone.

6. Part according to any one of claims 1 to 5, wherein the protective layer against calcium and magnesium aluminosilicate (CMAS) (22) has a thickness of between 1 .mu.m and 1000 .mu.m.

7. Part according to any one of claims 1 to 6, further comprising a thermal barrier layer interposed between the substrate (21) and the protective layer against calcium and magnesium aluminosilicate (CMAS) (22).

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

9. A method of manufacturing a turbine engine component (20) according to any one of claims 1 to 8, comprising at least a step of forming a protective layer against calcium and magnesium aluminosilicate (CMAS) ( 22) directly on the substrate (21) or on a layer of thermal barrier 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 a rare earth silicate RE ,

- flame spraying 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 an earth silicate RE uncommon,

- 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 earth silicate ceramic rare-RE or a ceramic powder of a rare earth RE silicate suspension.