• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The invention relates to a part (1) comprising a substrate (3), of which at least a portion adjacent to a surface (S) of the substrate is made of a material containing silicon, and an environmental barrier (2) formed on the surface of the substrate. substrate, the environmental barrier comprising at least a first layer (7) comprising: a rare earth disilicate of formula REa2Si2O7 present in an atomic content of between 70% and 99.9%, where REa is a rare earth element, and at least a rare earth oxide of formula REb2O3 present in an atomic content of between 0.1% and 30%, where REb is a rare earth element other than REa.
    公开号:FR3061710A1
    申请号:FR1750126
    申请日:2017-01-06
    公开日:2018-07-13
    发明作者:Lisa PIN；Simon ARNAL；Francis Rebillat；Fabrice Mauvy
    申请人:Centre National de la Recherche Scientifique CNRS；Universite de Bordeaux；Safran Ceramics SA；
    IPC主号:
    专利说明:

    ® Agent (s): CABINET BEAU DE LOMENIE.
    FR 3 061 710 - A1 ® PART COMPRISING A SUBSTRATE AND AN ENVIRONMENTAL BARRIER. (® The invention relates to a part (1) comprising a substrate (3), at least part of which is adjacent to a surface (S) of the substrate is made of a material containing silicon, and an environmental barrier (2) formed on the surface of the substrate, the environmental barrier comprising at least a first layer (7) comprising:
    a rare earth disilicate of formula RE a 2 Si2O 7 present in an atomic content of between 70% and 99.9%, where
    RE a is a rare earth element, and at least one rare earth oxide of formula RE b 2 O 3 present in an atomic content between 0.1% and 30%, where RE b is a rare earth element different from RE a .

    Invention background
    The invention relates to the protection of a substrate of which at least a portion adjacent to a surface of the substrate is made of a material containing silicon, when used at high temperature in an oxidizing medium, by the formation of an environmental barrier on the surface. of the substrate.
    A particular field of application of the invention is the protection of parts made of ceramic matrix composite material (CMC) forming hot parts of gas turbines, such as combustion chamber walls, or turbine rings, distributors turbine or turbine blades, for aeronautical engines or industrial turbines.
    For such gas turbines, the concern to improve the efficiency and reduce the polluting emissions leads to consider ever higher temperatures in the combustion chambers.
    It has therefore been proposed to replace metallic materials with CMC materials, in particular for walls of combustion chambers or turbine rings. In fact, CMC materials are known to have both good mechanical properties allowing their use for structural elements and the ability to maintain these properties at high temperatures. CMC materials include a fibrous reinforcement of refractory fibers, typically carbon or ceramic, which is densified by a ceramic matrix, for example SiC.
    Under the operating conditions of aeronautical turbines, that is to say at high temperature under an oxidizing and humid atmosphere, CMC materials are sensitive to the phenomenon of corrosion. Corrosion of CMC results from the oxidation of SiC to silica which, in the presence of water vapor, volatilizes in the form of silicon hydroxides Si (OH) 4 . Corrosion phenomena lead to a recession of the CMC and affect the life of the latter. In order to limit this degradation in operation, it has been envisaged to form environmental barrier coatings on the surface of CMC materials. Such coatings can include a silicon bonding layer as well as a rare earth silicate layer positioned on the bonding layer. The bonding layer makes it possible, on the one hand, to improve the adhesion of the layer of rare earth silicate and, on the other hand, to form a protective silica layer, whose low oxygen permeability contributes to protection of the CMC against oxidation. The rare earth silicate layer makes it possible to limit the diffusion of water vapor towards the silica layer formed by oxidation of the silicon and consequently to limit the recession thereof. However, the rare earth silicate layer can itself be sensitive to the phenomenon of recession and volatilize in operation, thus negatively affecting the life of the coated substrate. In addition, it is desirable to improve the barrier effect to oxidizing species provided by the environmental barrier coating.
    There is therefore a need to have new environmental barriers conferring on the underlying material an improved service life in operation.
    Subject and summary of the invention
    To this end, the invention proposes, according to a first aspect, a part comprising a substrate, at least part of which is adjacent to a surface of the substrate is made of a material containing silicon, and an environmental barrier formed on the surface of the substrate, the environmental barrier comprising at least a first layer comprising:
    a rare earth disilicate of formula RE a 2 Si 2 O 7 present in an atomic content of between 70% and 99.9%, where RE a is a rare earth element, and at least one rare earth oxide of formula RE b 2 O3 present in an atomic content between 0.1% and 30%, where RE b is a rare earth element different from RE a .
    The presence of the rare earth oxide RE b 2O3 in the first layer in particular proportions advantageously makes it possible to confer on the environmental barrier a better barrier effect with respect to the diffusion of oxidizing species as well as resistance to recession improved. The fact that the oxide RE b 2 O 3 is present in the first layer at a rate of at least 0.1% in atomic percentages advantageously makes it possible to improve the barrier effect to oxidizing species and the resistance to recession. The barrier effect to oxidizing species can however be negatively affected if the atomic content of RE b 2O3 oxide in the first layer is too high, this is why this content of RE b 2O 3 is limited to at most 30% in atomic percentages. . It should also be noted that the presence of the rare earth oxide RE b 2O3 in the proportions indicated makes it possible to confer on the first layer an improved resistance with respect to calcium and magnesium aluminosilicates (CMAS). Indeed, the RE b 2O 3 rare earth oxide has a higher reactivity with respect to CMAS compared to the rare earth silicate and will therefore react preferentially with the latter forming thermochemically stable compounds and preventing CMAS from migrating further. towards the substrate. The invention thus provides an environmental barrier conferring, on the underlying substrate, an improved lifetime at high temperature in an oxidizing and humid environment.
    In an exemplary embodiment, RE b is chosen from terbium Tb, erbium Er, dysprosium Dy, gadolinium Gd, europium Eu, lutetium Lu, samarium Sm, yttrium Y and ytterbium Yb . In particular, RE b is chosen from terbium Tb, erbium Er and dysprosium Dy. When RE b is yttrium Y, RE a may be ytterbium Yb. When RE b is ytterbium Yb, RE a may be yttrium Y.
    In an exemplary embodiment, the rare earth disilicate of formula RE a 2Si2O7 is present, in the first layer, in an atomic content of between 80% and 95%, and said at least one rare earth oxide of formula RE b 2O 3 is present, in the first layer, in an atomic content of between 5% and 20%.
    In an exemplary embodiment, the rare earth disilicate of formula RE a 2Si2O7 is present, in the first layer, in an atomic content of between 85% and 95%, and said at least one rare earth oxide of formula RE b 2O 3 is present, in the first layer, in an atomic content of between 5% and 15%.
    In an exemplary embodiment, RE a is chosen from yttrium Y and ytterbium Yb.
    In an exemplary embodiment, the environmental barrier further comprises a second layer present on the first layer, the second layer comprising at least one rare earth monosilicate of formula RE c 2 SiO 5 , where RE C is a rare earth element.
    The presence of the second layer based on the monosilicate RE ^ SiOs advantageously makes it possible to further improve the resistance of the environmental barrier to recession since the rare earth monosilicates are less sensitive to this phenomenon than the rare earth disilicates .
    In an exemplary embodiment, the second layer comprises at least:
    the rare earth monosilicate of formula RE ^ SiOs in an atomic content between 85% and 99.9%, and at least one rare earth oxide of formula RE d 2 O3 present in an atomic content between 0.1% and 15%, where RE d is a rare earth element different from RE C.
    The addition of the rare earth oxide RE d 2O3 in the second layer makes it possible, as described above for the first layer, to confer on it a resistance to recession and a barrier effect with respect to the improved oxidizing species. . As for the first layer, the presence of the rare earth oxide RE d 2O 3 makes it possible to confer on the second layer an improved resistance with respect to calcium and magnesium aluminosilicates (CMAS).
    In an exemplary embodiment, RE d is chosen from terbium Tb, erbium Er, dysprosium Dy, gadolinium Gd, europium Eu, lutetium Lu, samarium Sm, yttrium Y and ytterbium Yb . In particular, RE d is chosen from terbium Tb, erbium Er and dysprosium Dy. When RE d is yttrium Y, RE C can be ytterbium Yb. When RE d is ytterbium Yb, RE C can be yttrium Y.
    In an exemplary embodiment, the rare earth monosilicate of formula RE c 2 SiO5 is present, in the second layer, in an atomic content of between 85% and 95%, and said at least one rare earth oxide of formula RE d 2O 3 is present, in the second layer, in an atomic content of between 5% and 15%.
    In an exemplary embodiment, RE C is chosen from yttrium Y and ytterbium Yb.
    In an exemplary embodiment, RE a is yttrium Y, RE C is ytterbium Yb and RE b and RE d are, independently of one another, chosen from terbium Tb, erbium Er and dysprosium Dy.
    In an exemplary embodiment, the environmental barrier further comprises a third layer present between the first layer and the second layer, the third layer comprising:
    the rare earth disilicate of formula RE a 2S2O7 in an atomic content equal to A.Ta, where Ta is the atomic content of RE a 2Si 2 O7 in the first layer,
    - Said at least one rare earth oxide of formula RE b 2O3 in an atomic content equal to A.Tb, where Tb is the atomic content of RE b 2C> 3 in the first layer, and
    the rare earth monosilicate of formula RE c 2 SiO 5 in an atomic content equal to (lA) .Tc, where Te is the atomic content of RE ^ SiOs in the second layer,
    A designating a weighting coefficient strictly greater than 0 and strictly less than 1.
    One such embodiment relates to the case where a third layer of mixed composition is interposed between the first layer and the second layer. This example is advantageous in order to further improve the compatibility between the first layer and the second layer in terms of coefficient of thermal expansion.
    A can for example be between 0.25 and 0.75. The third layer may further comprise said at least one rare earth oxide of formula RE d 2C> 3 in an atomic content equal to (lA). Td where Td is the atomic content of RE d 2O 3 in the second layer.
    In an exemplary embodiment, the environmental barrier comprises, in addition to the third layer, a fourth layer present between the third layer and the second layer, the fourth layer comprising:
    - the rare earth disilicate of formula RE a 2 Si 2 O7 in an atomic content equal to B.Ta,
    - said at least one rare earth oxide of formula RE b 2O3 in an atomic content equal to B.Tb,
    the rare earth monosilicate of formula RE c 2 SiO 5 in an atomic content equal to (1B) .Tc, and
    - optionally said at least one rare earth oxide of formula RE d 2 O 3 in an atomic content equal to (1B) .Td,
    B designating a weighting coefficient strictly greater than 0 and strictly less than 1 and the coefficient B being strictly less than the coefficient A.
    Such an example advantageously makes it possible to further improve the compatibility between the first layer and the second layer in terms of coefficient of thermal expansion.
    In an exemplary embodiment, the environmental barrier further comprises a bonding layer comprising silicon present between the first layer and the surface of the substrate.
    The present invention also relates to a method of manufacturing a part as described above, the method comprising at least one step of forming the first layer of the environmental barrier on the surface of the substrate.
    The method can also include a step of forming the second layer of the environmental barrier on the first layer.
    The method can also include a step of forming the third layer of the environmental barrier on the first layer before the second layer is formed. The method can also include a step of forming the fourth layer of the environmental barrier on the third layer before forming the second layer.
    The method can also comprise, before the formation of the first layer, a step of forming the bonding layer on the surface of the substrate.
    The present invention also relates to a method of using a part as described above, the method comprising at least one step of using said part at a temperature greater than or equal to 800 ° C. in an oxidizing and humid medium.
    Brief description of the drawings
    Other characteristics and advantages of the invention will emerge from the following description, given without limitation, with reference to the appended drawings, in which:
    FIG. 1 illustrates, schematically, a part according to a first embodiment of the invention,
    FIG. 2 diagrammatically illustrates a part according to a second embodiment of the invention,
    FIG. 3 illustrates, schematically, a part according to a third embodiment of the invention,
    FIG. 4 is a flowchart showing the steps implemented to manufacture the part illustrated in FIG. 3,
    - Figure 5 is a test result comparing the barrier effect vis-à-vis the diffusion of oxidizing species presented by first layers used in the context of the invention and by an environmental barrier layer of art anterior, and
    - Figure 6 is a test result comparing the resistance to recession of a first layer usable in the context of the invention and an environmental barrier layer of the prior art.
    Detailed description of embodiments
    In the detailed description which follows, it is envisaged the formation of an environmental barrier on a substrate made of CMC material containing silicon. The invention is however applicable to substrates made of monolithic refractory material containing silicon and, more generally, to substrates of which at least a part adjacent to an external surface of the substrate is made of a refractory material (composite or monolithic) containing silicon. Thus, the invention relates in particular to the protection of refractory materials constituted by monolithic ceramics, for example made of silicon carbide SiC or silicon nitride Si 3 N 4 , but more particularly the protection of refractory composite materials such as matrix composite materials ceramic (CMC) containing silicon, for example CMCs with an matrix at least partially made of SiC.
    Figure 1 shows a part 1 formed of a substrate 3 provided with an environmental barrier 2 according to a first embodiment of the invention. The surface S of the substrate 3 is formed of a refractory material containing silicon.
    The substrate 3 of CMC material containing silicon comprises a fibrous reinforcement which may be made of carbon fibers (C) or ceramic fibers, for example fibers of SiC or formed essentially of SiC, including fibers of Si-C-0 or Si-CON, that is to say also containing oxygen and possibly nitrogen. Such fibers are produced by the company Nippon Carbon under the reference "Nicalon" or "HiNicalon" or "Hi-Nicalon Type-S", or by the company Ube Industries under the reference "Tyranno-ZMI". The ceramic fibers can be coated with a thin interphase layer of pyrolytic carbon (PyC), boron nitride (BN) or boron doped carbon (BC, with 5% at. To 20% at. Of B, the complement being C).
    The fibrous reinforcement is densified by a matrix which is formed, in its entirety or at least in an external phase thereof, by a material containing silicon, such as a silicon compound, for example SiC or a ternary system Si -BC. By external matrix phase is meant a matrix phase formed last, the furthest from the fibers of the reinforcement. Thus, the matrix can be formed of several phases of different natures, and can for example be:
    a mixed C-SiC matrix (SiC being on the external side), or a sequenced matrix with alternating SiC phases and less rigid matrix phases, for example made of pyrolytic carbon (PyC), boron nitride (BN) or carbon doped with boron (BC), with a terminal matrix phase in SiC, or a self-healing matrix with matrix phases in boron carbide (B 4 C) or in a ternary Si-BC system, possibly with free carbon (B 4 C + C, Si-BC + C), and with a terminal phase SiB-C or SiC.
    The matrix can be at least partially formed by CVI in a manner known per se. As a variant, the matrix can be at least partially formed by the liquid route (impregnation with a precursor resin of the matrix and transformation by crosslinking and pyrolysis, the process being able to be repeated) or by infiltration of silicon in the molten state (process of "Melt-Infiltration"). In the latter case, a powder is introduced into the fibrous reinforcement possibly partially densified, this powder possibly being a carbon and possibly ceramic powder, and a metallic composition based on silicon in the molten state is then infiltrated to form a matrix. of SiC-Si type.
    The environmental barrier 2 is formed over the entire external surface S of the substrate 3 or over only a part of this surface S, for example when only a part of the surface S must be protected. In the example illustrated in FIG. 1, the environmental barrier 2 comprises a first layer 7 and a bonding layer 5 present between the substrate 3 and the first layer 7. In the example illustrated, the bonding layer 5 is present in contact with the surface S of the substrate 3. Furthermore, in this example, the first layer 7 is in contact with the bonding layer 5.
    The first layer 7 may be in the form of a system consisting of 70 mol% to at most 99.9 mol% of a rare earth disilicate RE a 2Si2O7 and 0.1 mol% to at most 30 mol% d '' at least one rare earth oxide RE b 2O 3 where RE b denotes a rare earth element different from the rare earth element RE a . Said at least one oxide RE b 2O3 and the disilicate RE a 2Si 2 O7 are present in the first layer 7. Said at least one oxide RE b 2 O 3 may be present as a dopant in the first layer 7.
    As mentioned above, the particular composition of the first layer 7 in particular gives it a reduced ionic conductivity, making it more difficult for diffusion of reactive oxidizing and corrosive species as well as increased resistance to the phenomenon of recession.
    The first layer 7 may comprise a disilicate of formula RE a 2Si2O7 present, in the first layer 7, in an atomic content of between 70% and 99.9% and a single oxide RE b 2O 3 present, in the first layer 7, in an atomic content of between 0.1% and 30%. As a variant, the first layer 7 may comprise (i) a rare earth disilicate of formula RE a 2Si2O7 present, in the first layer 7, in an atomic content of between 70% and 99.9%, and (ii) several oxides of rare earth each comprising a different rare earth element and each of formula RE b 2O 3 , the total atomic content of oxides of formula RE b 2 O 3 in the first layer being between 0.1% and 30% and each RE b being different from the RE a .
    The atomic content of RE b 2 O 3 rare earth oxide (s) in the first layer 7 can be between 5% and 20%. The first layer 7 can, in certain embodiments, be in the form of a system consisting of 80 mol% to at most 95 mol% of the rare earth disilicate RE a 2S2O7 and 5 mol% to at most 20 mol% said at least one RE b 2O3 rare earth oxide. In particular, the first layer 7 can, in certain embodiments, be in the form of a system consisting of 87 mol% to at most 93 mol% of the rare earth disilicate RE a 2S2O7 and 7 mol% to at most 13 mol% of said at least one rare earth oxide RE b 2 O3.
    In particular and apart from the inevitable impurities, the first layer 7 comprises only the rare earth disilicate RE a 2Si2O7 and said at least one rare earth oxide RE b 2O 3 . The first layer 7 can in particular be devoid of aluminum, in particular of alumina. The first layer 7 can in particular be devoid of alkali metal or alkaline earth metal.
    RE a is a rare earth element chosen from yttrium Y, scandium Sc and lanthanides. In particular, RE a is chosen from yttrium Y and ytterbium Yb. RE b is a rare earth element chosen from yttrium Y, scandium Sc and lanthanides and RE b is different from RE a . In particular, RE b is chosen from terbium Tb, erbium Er and dysprosium Dy.
    The thickness ei of the first layer 7 can for example be between 50 μm and 1.5 mm.
    The bonding layer 5 comprises silicon and may for example be made of silicon or mullite (3AI 2 O3.2SiO 2 ). The bonding layer 5 can in a manner known per se form a passivating protective layer of silica in operation (“Thermally Grown Oxide”).
    Is shown, in connection with Figure 2, a part 11 according to a second embodiment according to the invention. According to this example, the part 11 comprises a substrate 13 at the surface S of which an environmental barrier is present 12. The substrate 13 can have the same characteristics as the substrate 3 described above. The environmental barrier 12 comprises a bonding layer 15 which can have the same characteristics as the bonding layer 5 described above and a first layer 17, present on the bonding layer 15, which can have the same characteristics as the first layer 7 described above.
    In the example according to FIG. 2, the environmental barrier 12 also comprises a second layer 19 which comprises at least one rare earth monosilicate RE c 2 SiO 5 where RE C denotes a rare earth element.
    As mentioned above, the presence of the second layer advantageously makes it possible to further improve the resistance of the environmental barrier to recession.
    In particular, the second layer 19 may be in the form of a system consisting of 85 mol% to at most 99.9 mol% of the rare earth monosilicate RE c 2SiOs and 0.1 mol% to at most 15 mol% at least one rare earth oxide RE d 2O 3 where RE d denotes a rare earth element different from the rare earth element RE C. Said at least one RE d 2O3 oxide and the monosilicate RE c 2 SiOs are present in the second layer 19. Said at least one RE d 2 O 3 oxide may be present as a dopant in the second layer 19.
    As mentioned above, such a second layer has better resistance to recession as well as an improved barrier effect against reactive species and CMAS.
    The second layer 19 may comprise a monosilicate RE c 2SiO5 present, in the second layer 19, in an atomic content of between 85% and 99.9% and a single oxide RE d 2O 3 present, in the second layer 19, in a atomic content between 0.1% and 15%. As a variant, the second layer 19 may comprise (i) a rare earth monosilicate of formula RE c 2SiO5 present, in the second layer 19, in an atomic content of between 85% and 99.9%, and (ii) several oxides of rare earth each comprising a different rare earth element and each of formula RE d 2O 3 , the total atomic content of oxides of formula RE d 2 O 3 in the second layer being between 0.1% and 15% and each RE d being different from RE C.
    Said at least one RE b 2O3 rare earth oxide may be present in the first layer 17 in a first atomic content and said at least one RE d 2O 3 rare earth oxide may be present in the second layer 19 in a second atomic content which may be less than the first atomic content. Such a characteristic makes it possible to further improve the compatibility between the first and the second layers in terms of coefficient of thermal expansion. The atomic content of RE d 2 O 3 rare earth oxide (s) in the second layer 19 can be between 5% and 15%. The second layer 19 can, in certain embodiments, be in the form of a system consisting of 85% molar to at most 95% molar of the rare earth monosilicate RE c 2SiOs and 5% molar to at most 15% molar of said at least one rare earth oxide RE d 2O 3 . In particular, the second layer 19 can, in certain embodiments, be in the form of a system consisting of 87 mol% to at most 93 mol% of the rare earth monosilicate RE c 2SiO5 and 7 mol% to at most 13 mol% of said at least one rare earth oxide RE d 2O 3 .
    In particular and apart from the inevitable impurities, the second layer 19 comprises only the rare earth monosilicate RE c 2SiO5 and said at least one rare earth oxide RE d 2O 3 . The second layer 19 can in particular be devoid of aluminum, in particular alumina. The second layer 19 can in particular be devoid of alkali metal or no-earth alkali metal.
    RE C is a rare earth element chosen from yttrium Y, scandium Sc and lanthanides. In particular, RE C is chosen from yttrium Y and ytterbium Yb. RE d is a rare earth element chosen from yttrium Y, scandium Sc and lanthanides and RE d is different from RE C. In particular, RE d is chosen from terbium Tb, erbium Er and dysprosium Dy. RE C can be the same or different from RE a . In particular, RE C is ytterbium Yb and RE a yttrium Y. RE d may be the same or different from RE b .
    The thickness e 2 of the second layer 19 can for example be between 50pm and 500pm.
    FIG. 2 shows an embodiment where a second layer 19 comprising a rare earth monosilicate is present on the first layer 17 comprising the rare earth disilicate. Alternatively, instead of the second layer 19, an additional layer could be positioned on the first layer 17, this additional layer comprising a rare earth disilicate RE e 2Si2O7 and at least one rare earth oxide RE f 2O 3 in the same ranges of atomic contents as for the first layer and where RE f is a rare earth element different from the rare earth element RE e . In this case, RE e can be the same or different from RE a . One can for example have RE e = Yb and RE a = Y. In addition in this case, RE f can be identical or different from RE b .
    Furthermore, in the example of FIG. 2, the second layer 19 is in contact with the first layer 17. It could alternatively have a third layer, and possibly a fourth layer, as described above between the first layer 17 and the second layer 19.
    In the embodiment of FIG. 3, the part 21 comprises a substrate 23, a bonding layer 25, a first layer 27 and a second layer 29. The substrate 23, the bonding layer 25, the first layer 27 and the second layer 29 can be as described above. The environmental barrier 22 further comprises an upper layer 24 present on the second layer 29. This upper layer 24 is, in the example illustrated, a ceramic thermal barrier layer having a porous structure. The upper layer 24 may be made of rare earth silicate. Alternatively, an upper layer could be formed which would constitute an abradable coating, for example in the case of CMC parts forming turbine rings. The upper layer could still constitute a protective coating against CMAS. The deposition of the upper layer 24 makes it possible to further functionalize the environmental barrier. One could alternatively have a part, devoid of the upper layer 24, in which the first or the second layer would further present a thermal barrier function, protection against CMAS or constitute an abradable coating.
    FIG. 4 illustrates the different steps implemented to manufacture the part 21 illustrated in FIG. 3.
    Firstly, the bonding layer 25 can be formed, in a manner known per se, on the substrate 23 by thermal spraying from a powder or a mixture of powders having the desired composition (step 100).
    The first layer 27 can be formed on the bonding layer 25 by thermal spraying from a mixture of solid powders of RE a 2S2O7 and rare earth oxide (s) RE b 2O3 in the desired proportions (step 200 ). Similarly, the second layer 29 can be formed on the first layer 27 by thermal spraying from a mixture of solid powders of RE c 2SiOs and rare earth oxide (s) RE d 2O 3 in the desired proportions. (step 300). The first and second layers Tl and 29 could alternatively be formed by other processes such as processes originating from the liquid route, for example by dip coating (“dip-coating”), spray coating (“spray-coating”) , electrophoresis or sol-gel.
    The upper thermal barrier layer 24 can be formed, in a manner known per se, by thermal spraying (step 400).
    Once manufactured, the part can be used at a temperature greater than or equal to 800 ° C in an oxidizing and humid atmosphere. It can, in particular, be used at a temperature between 800 ° C and 1500 ° C, or even between 800 ° C and 1300 ° C. The part can, in particular, be used in humid air.
    The part thus produced can be a part for aeronautical or aerospace application. The part can be a hot part part of a gas turbine of an aeronautical or aerospace engine or of an industrial turbine. The part can be a turbomachine part. The part can constitute at least part of a distributor, at least part of a nozzle or of a thermal protection coating, a wall of a combustion chamber, a turbine ring sector or a vane of turbomachine.
    Example
    Three examples of first layers according to the invention were produced. The first three layers produced had the following compositions:
    - yttrium disilicate at 95 atomic% and erbium oxide Er 2 O 3 at 5 atomic%, this layer is denoted “DSY + 5% at Er 2 O 3 ”,
    - yttrium disilicate at 90 atomic% and erbium oxide Er 2 O 3 at 10 atomic%, this layer is denoted “DSY + 10% at Er 2 O 3 ”, and
    - yttrium disilicate at 85 atomic% and erbium oxide Er 2 O 3 at 15 atomic%, this layer is denoted “DSY + 15% at Er 2 O 3 ”.
    An environmental barrier layer of the prior art made entirely of yttrium disilicate was manufactured. This layer is denoted “DSY layer”.
    FIG. 5 is a test result comparing the barrier effect vis-à-vis the oxidizing species conferred by each of these first three layers with the barrier effect vis-à-vis these same species conferred by the DSY layer. FIG. 5 shows that the conductivity of the oxidizing species in each of the first layers is significantly lower than the conductivity of these same species in the DSY layer. This test was performed at different temperatures in the range 950 ° C-1050 ° C. The ionic conductivity measurements were carried out by complex impedance spectroscopy under ambient air between 950 ° C and 1050 ° C.
    FIG. 6 is a result of a corrosion test and shows that the first layer according to the invention has a resistance to recession greater than that presented by a layer formed solely of yttrium disilicate. The recession measures were determined from corrosion tests carried out in a corrosion furnace at 1400 ° C under 50kPa of H2O and 50kPa of air with gas velocities of 5cm / s in the cold zone of the furnace.
    The expression "included between ... and ..." must be understood as including the limits.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Part (1; 11; 21) comprising a substrate (3; 13; 23), at least part of which is adjacent to a surface (S) of the substrate is made of a material containing silicon, and an environmental barrier (2; 12; 22) formed on the surface of the substrate, the environmental barrier comprising at least a first layer (7; 17; 27) comprising:
    a rare earth disilicate of formula RE a 2 Si 2 O7 present in an atomic content of between 70% and 99.9%, where RE a is a rare earth element, and at least one rare earth oxide of formula RE b 2 O 3 present in an atomic content between 0.1% and 30%, where RE b is a rare earth element different from RE a .
    [2" id="c-fr-0002]
    2. Part (1; 11; 21) according to claim 1, in which RE b is chosen from terbium Tb, erbium Er, dysprosium Dy, gadolinium Gd, europium Eu, lutetium Lu, samarium Sm, yttrium Y and ytterbium Yb.
    [3" id="c-fr-0003]
    3. Part (1; 11; 21) according to claim 2, wherein RE b is chosen from terbium Tb, erbium Er and dysprosium Dy.
    [4" id="c-fr-0004]
    4. Piece (1; 11; 21) according to any one of claims 1 to
    3, in which the rare earth disilicate of formula RE a 2Si2O7 is present, in the first layer (7; 17; 27), in an atomic content of between 80% and 95%, and in which said at least one oxide of rare earth of formula RE b 2O 3 is present, in the first layer (7; 17; 27), in an atomic content of between 5% and 20%.
    [5" id="c-fr-0005]
    5. Piece (1; 11; 21) according to any one of claims 1 to
    4, in which RE a is chosen from yttrium Y and ytterbium Yb.
    [6" id="c-fr-0006]
    6. Part (11; 21) according to any one of claims 1 to 5, wherein the environmental barrier (12; 22) further comprises a second layer (19; 29) present on the first layer (17; 27) , the second layer (19; 29) comprising at least one rare earth monosilicate of formula RE c 2 SiO 5 , where RE C is a rare earth element.
    [7" id="c-fr-0007]
    7. Part (11; 21) according to claim 6, in which the second layer (19; 29) comprises at least:
    the rare earth monosilicate of formula RE c 2 SiO 5 in an atomic content between 85% and 99.9%, and at least one rare earth oxide of formula RE d 2 Ch present in an atomic content between 0.1 % and 15%, where RE d is a rare earth element different from RE C.
    [8" id="c-fr-0008]
    8. Part (11; 21) according to claim 7, in which RE d is chosen from terbium Tb, erbium Er, dysprosium Dy, gadolinium Gd, europium Eu, lutetium Lu, samarium Sm, yttrium Y and ytterbium Yb.
    [9" id="c-fr-0009]
    9. Part (11; 21) according to claim 8, in which RE d is chosen from terbium Tb, erbium Er and dysprosium Dy.
    [10" id="c-fr-0010]
    10. Piece (11; 21) according to any one of claims 7 to 9, in which the rare earth monosilicate of formula RE c 2SiO5 is present, in the second layer (19; 29), in an atomic content of between 85 % and 95%, and in which said at least one rare earth oxide of formula RE d 2Ü3 is present, in the second layer (19; 29), in an atomic content of between 5% and 15%.
    [11" id="c-fr-0011]
    11. Part (11; 21) according to any one of claims 6 to
    10, in which RE C is chosen from yttrium Y and ytterbium Yb.
    [12" id="c-fr-0012]
    12. Part (11; 21) according to any one of claims 7 to
    11, in which RE a is yttrium Y, RE C is ytterbium Yb and RE b and RE d are, independently of one another, chosen from terbium Tb, erbium Er and dysprosium Dy .
    [13" id="c-fr-0013]
    13. Part according to any one of claims 6 to 12, in which the environmental barrier further comprises a third layer present between the first layer and the second layer, the third layer comprising:
    the rare earth disilicate of formula RE a 2Si2O7 in an atomic content equal to A.Ta, where Ta is the atomic content of RE a 2Si 2 O 7 in the first layer,
    - Said at least one rare earth oxide of formula RE b 2C> 3 in an atomic content equal to A.Tb, where Tb is the atomic content of RE b 2Û3 in the first layer, and
    the rare earth monosilicate of formula RE c 2SiO5 in an atomic content equal to (lA) .Tc, where Te is the atomic content of RE c 2SiO 5 in the second layer,
    A designating a weighting coefficient strictly greater than 0 and strictly less than 1.
    [14" id="c-fr-0014]
    14. A method of manufacturing a part (1; 11; 21) according to any one of claims 1 to 13, the method comprising at least one step of forming the first layer (7; 17; 27) of the barrier environmental (2; 12; 22) on the surface (S) of the substrate (3; 13; 23).
    [15" id="c-fr-0015]
    15. A method of using a part (1; 11; 21) according to any one of claims 1 to 13, the method comprising at least one step of using said part (1; 11; 21) at a temperature greater than or equal to 800 ° C in an oxidizing and humid environment.
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    同族专利:
    公开号 | 公开日
    RU2752182C2|2021-07-23|
    FR3061710B1|2019-05-31|
    EP3565794A1|2019-11-13|
    BR112019013928A2|2020-02-11|
    CA3049082A1|2018-07-12|
    US20190330121A1|2019-10-31|
    EP3565794B1|2020-09-30|
    WO2018127664A1|2018-07-12|
    RU2019123997A3|2021-03-25|
    CN110461799A|2019-11-15|
    CN110461799B|2021-01-05|
    RU2019123997A|2021-02-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2014150380A1|2013-03-15|2014-09-25|General Electric Company|Recession resistant ceramic matrix composites and environmental barrier coatings|
    US7226672B2|2002-08-21|2007-06-05|United Technologies Corporation|Turbine components with thermal barrier coatings|
    US7595114B2|2005-12-09|2009-09-29|General Electric Company|Environmental barrier coating for a component and method for fabricating the same|
    FR2940278B1|2008-12-24|2011-05-06|Snecma Propulsion Solide|ENVIRONMENTAL BARRIER FOR REFRACTORY SUBSTRATE CONTAINING SILICON|
    WO2011065417A1|2009-11-25|2011-06-03|阿南化成株式会社|Complex oxide, method for producing same and exhaust gas purifying catalyst|
    CN101768380B|2009-12-30|2014-12-17|中国科学院上海硅酸盐研究所|Thermal protection coating with component gradient change and preparation method|
    US9945036B2|2011-03-22|2018-04-17|General Electric Company|Hot corrosion-resistant coatings and components protected therewith|
    JP5953947B2|2012-06-04|2016-07-20|株式会社Ihi|Environment-coated ceramic matrix composite parts and method for producing the same|
    US10094236B2|2013-03-15|2018-10-09|General Electric Company|Recession resistant ceramic matrix composites and environmental barrier coatings|
    US20160160664A1|2013-03-15|2016-06-09|General Electric Company|Recession resistant ceramic matrix composites and environmental barrier coatings|
    US9938839B2|2014-03-14|2018-04-10|General Electric Company|Articles having reduced expansion and hermetic environmental barrier coatings and methods for their manufacture|
    CA2952599A1|2014-06-30|2016-01-07|General Electric Company|Thermal and environmental barrier coating compositions|FR3084377B1|2018-07-24|2021-10-15|Safran Ceram|ELECTROPHORESIS COATING PROCESS OF A PART IN COMPOSITE MATERIAL BY AN ENVIRONMENTAL BARRIER|
    WO2020047278A1|2018-08-30|2020-03-05|University Of Virginia Patent Foundation|Functional barrier coating and related methods thereof|
    FR3095818B1|2019-05-09|2021-04-23|Safran Aircraft Engines|Method for producing a device for measuring deformations on a composite part with a ceramic matrix and corresponding part.|
    EP3838870A1|2019-12-19|2021-06-23|Rolls-Royce Corporation|Cmas-resistant abradable coatings|
    CN110983233A|2019-12-25|2020-04-10|西安鑫垚陶瓷复合材料有限公司|Multilayer-structure rare earth silicate environment barrier coating and preparation method thereof|
    法律状态:
    2017-12-18| PLFP| Fee payment|Year of fee payment: 2 |
    2018-07-13| PLSC| Publication of the preliminary search report|Effective date: 20180713 |
    2019-12-19| PLFP| Fee payment|Year of fee payment: 4 |
    2020-12-17| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1750126A|FR3061710B1|2017-01-06|2017-01-06|PART COMPRISING A SUBSTRATE AND AN ENVIRONMENTAL BARRIER|
    FR1750126|2017-01-06|FR1750126A| FR3061710B1|2017-01-06|2017-01-06|PART COMPRISING A SUBSTRATE AND AN ENVIRONMENTAL BARRIER|
    BR112019013928-1A| BR112019013928A2|2017-01-06|2018-01-04|PIECE AND METHODS OF MANUFACTURING AND USING A PART.|
    RU2019123997A| RU2752182C2|2017-01-06|2018-01-04|Part comprising a substrate and a protective barrier|
    CN201880006106.9A| CN110461799B|2017-01-06|2018-01-04|Component comprising a substrate and an environmental barrier|
    EP18702315.5A| EP3565794B1|2017-01-06|2018-01-04|Part comprising a substrate and an environmental barrier|
    US16/475,903| US20190330121A1|2017-01-06|2018-01-04|Part comprising a substrate and an environmental barrier|
    CA3049082A| CA3049082A1|2017-01-06|2018-01-04|Part comprising a substrate and an environmental barrier|
    PCT/FR2018/050019| WO2018127664A1|2017-01-06|2018-01-04|Part comprising a substrate and an environmental barrier|
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