阅读说明：本技术 由硅基陶瓷或cmc制成的部件以及生产这种部件的方法 (Component made of silicon-based ceramic or CMC and method for producing such a component ) 是由 艾玛尔·撒伯恩德吉 休格斯·丹尼斯·朱伯特 P·皮克特 卢克·帕特里斯·比安基 于 2020-04-30 设计创作，主要内容包括：本发明涉及由硅基陶瓷材料或硅基陶瓷基复合材料(CMC)制成的部件,该部件包括环境屏障涂层(EBC),所述涂层(12、13)包括沉积在陶瓷材料或陶瓷基复合材料(CMC)的表面上的粘合层(12),所述结合层(12)的顶部具有一个或多个层共同形成的多功能屏障结构(13),其特征在于,该结合层(12)在与多功能结构的界面处具有多晶氧化硅制成的层(12)或子层(12b)。(The invention relates to a component made of a silicon-based ceramic material or a silicon-based Ceramic Matrix Composite (CMC), comprising an Environmental Barrier Coating (EBC), said coating (12, 13) comprising a bonding layer (12) deposited on the surface of the ceramic material or Ceramic Matrix Composite (CMC), said bonding layer (12) having on top of it one or more layers forming together a multifunctional barrier structure (13), characterized in that the bonding layer (12) has, at the interface with the multifunctional structure, a layer (12) or a sub-layer (12b) made of polycrystalline silicon oxide.)

1. A component made of a silicon-based ceramic material or a silicon-based Ceramic Matrix Composite (CMC), said component comprising an Environmental Barrier Coating (EBC), said coating (12, 13) comprising a bonding layer (12) deposited on the surface of said ceramic material or said Ceramic Matrix Composite (CMC), the top of said bonding layer (12) having a multifunctional barrier structure (13) formed by one or more layers together, characterized in that said bonding layer (12) has a layer (12) or sub-layer of polycrystalline silicon oxide at the interface with said multifunctional structure.

2. The component of claim 1, wherein the polycrystalline silicon oxide layer or sub-layer comprises Hf and/or HfO₂And/or phosphorus doped grain boundaries.

3. A method for producing a component according to any one of the preceding claims, characterized in that the following steps are carried out:

depositing a silicon layer on a surface of the ceramic material or ceramic matrix composite (step 20);

thermal oxidation (step 21);

a dopant is introduced (step 22).

4. A method for producing a component according to claim 1 or 2, characterized in that the following steps are carried out:

depositing a first silicon layer on a surface of the ceramic material or ceramic matrix composite (step 30);

depositing a second silicon layer, said layer being a doped layer (step 31);

and thermally oxidized (step 32).

5. A method according to claim 3 or according to claim 4, characterized in that said thermal oxidation is a dry oxidation carried out in the presence of oxygen.

6. Method according to claim 3 or 4, characterized in that the dopant is Hf and/or HfO₂And/or a phosphorous dopant.

7. The method of claim 3, wherein the step of introducing the dopant performs ion implantation.

8. Aeronautical or aerospace device (5) comprising at least one component according to claim 1 or 2.

9. Turbine (5) comprising at least one component according to claim 1 or 2.

Technical Field

The present invention relates to components made of silicon-based ceramic materials or silicon-based Ceramic Matrix Composite (CMC) materials.

Background

CMC materials are currently under general consideration in the aerospace field, especially for turbine components that are subjected to high operating temperatures.

Economic and environmental constraints have prompted engine manufacturers in the aviation industry to develop new methods for reducing noise pollution, fuel consumption, and NOx and CO₂Investigation of emissions.

In order to meet these requirements, and in particular the last two, one solution is to increase the temperature of the gases in the turbojet combustion chamber. This improves engine performance (reduced kerosene consumption) and allows operation with a lean fuel mixture (NOx reduction). However, the materials used in the combustion chamber must be able to withstand higher temperatures.

Currently, the materials used for components that are subjected to high operating temperatures in aircraft engines are superalloys. However, the temperatures reached (about 1100 ℃) are already close to their use limits.

In the last years, the use of silicon-based ceramics has been proposed: silicon carbide SiC ceramics or SiC/SiC Ceramic Matrix Composites (CMCs) are used to significantly increase these service temperatures (up to 1400 ℃).

In fact, these materials are promising candidates due to their mechanical and thermal properties and their stability at high temperatures. In addition, silicon carbide-based CMC materials have the advantage of being less dense than the metal materials they replace, in addition to their high temperature characteristics.

Much research has focused on the introduction of these materials into extreme applications (high temperature, high pressure, corrosive atmospheres, mechanical stresses).

Under these conditions, a thin layer of silicon oxide is formed, which limits the diffusion of oxygen to the substrate. However, starting at 1200 ℃ in the presence of water, as the layer is exposed to HxSiyOz species (e.g., Si (OH))₄Or SiO (OH)₂) The form of (2) volatilizes and surface recession occurs. This phenomenon results in a decrease in the net growth rate of the oxide, its thickness tends towards the limit and the accelerated degradation of the SiC present in the CMC.

Therefore, to extend the time of use and/or higher temperatures, the CMC must be protected to avoid evaporation of the protective silicon oxide layer. This is particularly true for CMC materials used in combustors, high pressure turbines, and to a lesser extent for engine exhaust components.

Typically, CMC materials are protected by an Environmental Barrier Coating (known as EBC or "Environmental Barrier Coating" according to the common English terminology).

As shown in fig. 1, such EBC coatings typically include a silicon bond coat layer 2 (or bond coat) covering the CMC layer 1 to be protected and on top of a multifunctional ceramic structure 3.

For example, the multifunctional structure 3 is composed of:

one or more layers of mullite (intended to prevent the diffusion of oxygen into the silicon layer 2);

one or more layers intended to protect the layer 2 from the diffusion of water vapour.

For example, multilayer environmental barriers of the type Si/mullite/BSAS (barium strontium aluminosilicate) or comprising a binding layer of silicon and a rare earth silicate are known(e.g. Y)₂Si₂O₇) Those of the layers. These experimental barriers may be deposited by thermal spraying, physical phase deposition (PVD) or slurry deposition processes (e.g. "dip coating" or "spray coating") in a manner known per se.

However, such a structure may still deteriorate over time due to non-uniformity of the silicon oxide (dashed lines 4a and agglomerates 4b in fig. 1) formed between the silicon layer and the other layers of the EBC coating.

These non-uniformities in the formation of silicon oxide can create residual stresses in the EBC coating.

This initiates and propagates cracks in the clad layer (cracks 4c in fig. 1).

This can lead to ceramic layer spalling, exposing the CMC sub-layer to the corrosive environment of water vapor, causing its accelerated decay, limiting the useful life of the CMC.

This can lead to premature system degradation due to the layer separation mechanism.

Disclosure of Invention

A general object of the present invention is to alleviate the drawbacks of the known arrangements in the prior art.

In particular, it is an object of the invention to propose an EBC structure that enables an improved service life.

The invention therefore proposes a component made of a silicon-based ceramic material or a silicon-based Ceramic Matrix Composite (CMC) material, comprising an Environmental Barrier Coating (EBC) comprising a bonding layer deposited on the surface of the ceramic material or the Ceramic Matrix Composite (CMC) material, said bonding layer having on top one or more layers together forming a multifunctional barrier structure, characterized in that the bonding layer has a layer or sub-layer of polycrystalline silicon oxide at the interface with the multifunctional structure.

In particular, the polycrystalline silicon oxide layer or sub-layer has Hf and/or HfO₂And/or phosphorus doped grain boundaries.

According to one embodiment, the component is produced by carrying out the following steps:

depositing a silicon layer on the surface of the ceramic material or the ceramic matrix composite;

thermal oxidation;

a dopant is introduced.

As a variant, the above production is carried out by carrying out the following steps:

depositing a first silicon layer on a surface of the ceramic material or ceramic matrix composite;

depositing a second silicon layer, said layer being a doped layer;

and (4) carrying out thermal oxidation.

The invention also proposes an aeronautical or aerospace device, in particular a turbine, comprising at least one component of the proposed type.

Drawings

Other characteristics and advantages of the present invention will emerge from the following description, which is purely illustrative and non-limiting and should be read in conjunction with the accompanying drawings, in which:

FIG. 1, already discussed, illustrates defect formation and degradation of structures known in the prior art;

FIG. 2 shows an example of a component according to the present invention;

FIGS. 3a and 3b show an EBC coated stack (FIG. 3a) according to an embodiment of the present invention;

figure 4 shows a possible embodiment of the invention for producing a laminate of the type of figure 3 a;

fig. 5 and 6 show another possible embodiment of the method according to the invention.

Detailed Description

The components 5 shown in fig. 2 comprise, as an example, blades 5a and blade roots 5b of the turbine high-pressure turbine rotor.

The component 5 is a ceramic matrix composite CMC coated with a protective barrier EBC, which will be described in more detail below.

It is noted that the use of CMC ceramics for turbine high-pressure turbine rotor blades is particularly advantageous because it can eliminate, where applicable, the holes for cooling air circulation that are normally provided on the blades. Eliminating these holes can further improve engine performance.

It will be appreciated that the turbine high pressure turbine blade is just one example of an application of the proposed EBC structure: it can be applied more generally, in particular to components operating at high temperatures (above 1100 ℃) in the aerospace field: turbine combustors, engine exhaust components, and the like.

Production of CMC structures

The material of the CMC structure of the component 5 is a silicon-based ceramic (e.g. silicon carbide SiC) or a Ceramic Matrix Composite (CMC).

Herein and throughout, CMC materials refer to composite materials comprising a matrix, also ceramic, with a set of ceramic fibers incorporated therein.

The fibers are, for example, carbon (C) and silicon carbide (SiC) fibers.

They may also be aluminum oxides or aluminum oxides (Al)₂O₃) Fibres, or aluminium oxide and silicon oxide or silicon oxide (SiO)₂) Mixed crystals of (2), e.g. mullite (3 Al)₂O₃、2SiO₂)。

The matrix is silicon carbide SiC or any mixture comprising silicon carbide.

SiC-SiC composites having silicon carbide fibers in a silicon carbide matrix are particularly suitable for aerospace applications due to their high thermal, mechanical and chemical stability and high strength to weight ratio.

These compounds can use high temperature carbon (or PyC) or Boron Nitride (BN) as interface materials.

It is contemplated that different techniques may be used to produce the ceramic matrix composite component.

In particular, according to a first technique, the CMC material part may be produced from a fiber preform of woven fiber texture. This fiber preform is consolidated and densified by Chemical Vapor Infiltration (CVI or "Chemical Vapor Infiltration" according to the terminology of Anglo-Saxon).

In a further variant, the preform may be a layer of fibres based on silicon carbide, the fibres of said preform being coated by CVI with a layer of boron nitride, on top of which is a layer of carbon or carbide, in particular silicon carbide.

For an example of a technique for manufacturing SiC/SiC CMC structures, reference may advantageously be made, for example, to patents US9440888 or US 8846218.

EBC structure-first embodiment

In the example of fig. 3a, the CMC layer is denoted by 11 and the multifunctional structure of the EBC coating is denoted by 13.

The adhesion layer (layer 12) is polycrystalline silicon oxide with doped grain boundaries.

The dopants implanted into the grain boundaries are, for example, hafnium (Hf) and/or hafnium oxide (HfO)₂) And/or a dopant of phosphorus.

This layer 12 (fig. 4) was produced as follows:

step 20: a layer of Si is deposited and,

step 21: carrying out thermal oxidation on the mixture,

step 22: a dopant is introduced.

The resulting structure of layer 12 is then of the type shown in figure 3 b: it comprises large SiO₂Grains (grains 12a) and doped grain boundaries (boundaries 12 b). Here, large grains mean sizes between about 10 nanometers and up to 50 microns.

This structure is dense (porosity less than 10%) and polycrystalline. It has excellent homogeneity (porosity difference less than 10%), large grains and high oxygen and water vapor tightness.

In particular, implanting dopants can enhance SiO₂Grain boundary of sublayer and SiO mitigation₂Permeability of oxygen and water vapor in the layer.

The silicon oxide layer is stabilized by blocking grain boundaries with hafnium and/or hafnium oxide and/or phosphorus.

The silicon oxide growth kinetics are thus prevented or at least slowed down.

It is also noted that the results for hafnium oxide are superior to SiO in terms of water permeability₂The result of (1).

The Si layer (step 20) may be deposited by different techniques: plasma spraying, electron beam vapor deposition, or the like, or any combination of these techniques.

Such a layer has a thickness of between 5 μm and 30 μm, for example.

The thermal oxidation (step 21) is carried out in an oven in the presence of oxygen (dry oxidation).

The oxidation is carried out under the following conditions, for example: the heat treatment temperature is as follows: 1100 ℃ to 1300 ℃; duration: 1 hour to 50 hours; oxygen flow rate: 1l/min to 20 l/min.

The dopant is then introduced by ion bombardment (step 22).

The atomic percentage of the dopant in layer 12 is, for example, 1% to 2% for Hf and less than 20% for phosphorus.

After the production of the layer 12, the multifunctional structure 13 is produced. It comprises several layers of ceramics (Yb)₂SiO₅BSAS, etc.) are intended to be selected and sized to ensure various desired seals.

EBC structure-second embodiment

In the embodiment shown in fig. 5, the bonding layer 12 includes a silicon sublayer 121 and a doped boundary silicon oxide sublayer 122.

In this second embodiment, the layer 12 is obtained as follows (fig. 6):

step 30: a first layer of silicon is deposited and,

step 31: depositing a second silicon layer, said layer being a doped layer,

step 32: and (4) carrying out thermal oxidation.

After the thermal oxidation, the deposition of the other layers of the EBC structure is then carried out (deposition of the layers of the multifunctional structure).

The silicon layer is deposited by Chemical Vapor Deposition (CVD) under the following conditions by gas flow and the following reaction (step 30): 100 to 200 mbar; t-1020 ℃ to 1050 DEG C

3AlCl(g)+(2y)Ni+H₂(g)＝＝>1AlNiy+AlCl₃+HCl

The thickness of the deposited layer is typically between 10 μm and 20 μm.

A doped silicon layer is also deposited by CVD techniques (step 31).

The thickness of the doped layer is typically between 1 μm and 5 μm.

The silicon doping is performed in advance by ion implantation.

The doping of the second silicon layer is Hf and/or phosphorous doping, wherein for Hf the atomic mass concentration is between 1% and 2% and for phosphorous the atomic mass concentration is less than 20%.

After oxidation, the bonding layer 12 is provided with a silicon sublayer 121 and a doped boundary silicon oxide sublayer 122.

The sublayer 122 has a polycrystalline structure with large SiO₂Crystal grain and Hf and HfO₂Grain boundaries.

It has high oxygen and water tightness.

It ensures a relatively uniform thickness at the silicon oxide interface between the silicon layer and the multifunctional layer 13.

The growth of silicon oxide is slower compared to the prior art.

This results in an improved service life of the EBC structure.