Part comprising a substrate and an environmental barrier

Abstract

A part includes a substrate, having, adjacent to a surface of the substrate, at least a portion that is made from a material that contains silicon, and an environmental barrier formed on the surface of the substrate, the environmental barrier including at least a first layer including a rare earth disilicate of formula RE.sup.a.sub.2Si.sub.2O.sub.7 present at a molar content lying in the range 70% to 99.9%, where RE.sup.a is a rare earth element; and at least one rare earth oxide of formula RE.sup.b.sub.2O.sub.3 present at a molar content lying in the range 0.1% to 30%, where RE.sup.b is a rare earth element different from RE.sup.a.

Claims

1. A part comprising a substrate, having, adjacent to a surface of the substrate, at least a portion that is made from a material that contains 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.sup.a.sub.2Si.sub.2O.sub.7 present at a molar content lying in the range 85% to 95%, where RE.sup.a is a rare earth element, wherein RE.sup.a is selected from yttrium Y and ytterbium Yb; and at least one rare earth oxide of formula RE.sup.b.sub.2O.sub.3 present at a molar content lying in the range 5% to 15%, where RE.sup.b is a rare earth element different from RE.sup.a, wherein RE.sup.b is selected from terbium Tb, erbium Er, dysprosium Dy and lutetium Lu, wherein 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.sup.c.sub.2SiO.sub.5, where RE.sup.c is a rare earth element at a molar content lying in the range 85% to 99.9%; and at least one rare earth oxide of formula RE.sup.d.sub.2O.sub.3 present at a molar content lying in the range 0.1% to 15%, where RE.sup.d is a rare earth element different from RE.sup.c.

2. A part according to claim 1, wherein RE.sup.d is selected from terbium Tb, erbium Er, dysprosium Dy, gadolinium Gd, europium Eu, lutetium Lu, samarium Sm, yttrium Y, and ytterbium Yb.

3. A part according to claim 2, wherein RE.sup.d is selected from terbium Tb, erbium Er, and dysprosium Dy.

4. A part according to claim 1, wherein the rare earth monosilicate of formula RE.sup.c.sub.2SiO.sub.5 is present in the second layer at a molar content lying in the range 85% to 95%, and wherein said at least one rare earth oxide of formula RE.sup.d.sub.2O.sub.3 is present in the second layer at a molar content lying in the range 5% to 15%.

5. A part according to claim 1, wherein RE.sup.c is selected from yttrium Y and ytterbium Yb.

6. A part according to claim 1, wherein RE.sup.a is yttrium Y, RE.sup.c is ytterbium Yb, and RE.sup.d is selected from terbium Tb, erbium Er, and dysprosium Dy.

7. A part according to claim 1, wherein 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.sup.a.sub.2Si.sub.2O.sub.7 at a molar content equal to A.Math.Ta, where Ta is the molar content of RE.sup.a.sub.2Si.sub.2O.sub.7 in the first layer; said at least one rare earth oxide of formula RE.sup.b.sub.2O.sub.3 at a molar content equal to A.Math.Tb, where Tb is the molar content of RE.sup.b.sub.2O.sub.3 in the first layer; and the rare earth monosilicate of formula RE.sup.c.sub.2SiO.sub.5 at a molar content equal to (1−A).Math.Tc, where Tc is the molar content of RE.sup.c.sub.2SiO.sub.5 in the second layer; where A designates a weighting coefficient that is strictly greater than 0 and strictly less than 1.

8. A method of fabricating a part according to claim 1, comprising forming the first layer of the environmental barrier on the surface of the substrate.

9. A method of using a part according to claim 1, comprising using said part at a temperature higher than or equal to 800° C. in a medium that is oxidizing and wet.

10. A part according to claim 7, wherein the molar content of RE.sup.d.sub.2O.sub.3 in the second layer is less than the molar content of RE.sup.b.sub.2O.sub.3 in the first layer.

11. A part according to claim 1, wherein RP is yttrium Y.

12. A part according to claim 1, wherein the at least one rare earth oxide of formula RE.sup.b.sub.2O.sub.3 is present at a molar content lying in the range 5% to 10%.

13. A part comprising a substrate, having, adjacent to a surface of the substrate, at least a portion that is made from a material that contains 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.sup.a.sub.2Si.sub.2O.sub.7 present at a molar content lying in the range 85% to 95%, where RP is a rare earth element, wherein RE.sup.a is selected from yttrium Y and ytterbium Yb; and at least one rare earth oxide of formula RE.sup.b.sub.2O.sub.3 present at a molar content lying in the range 5% to 15%, where RE.sup.b is a rare earth element different from RE.sup.a, wherein RE.sup.b is erbium Er.

14. A part according to claim 13, wherein RE.sup.a is yttrium Y.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Other characteristics and advantages of the invention appear from the following description given by way of non-limiting example and with reference to the accompanying drawings, in which:

(2) FIG. 1 is a diagram showing a part in a first embodiment of the invention;

(3) FIG. 2 is a diagram showing a part in a second embodiment of the invention;

(4) FIG. 3 is a diagram showing a part in a third embodiment of the invention;

(5) FIG. 4 is a flow chart showing the steps performed for fabricating the part shown in FIG. 3;

(6) FIG. 5 shows a test result comparing the barrier effect against diffusion of oxidizing species presented by first layers suitable for use in the context of the invention and by an environmental barrier layer of the prior art; and

(7) FIG. 6 shows a test result comparing the resistance to recession of a first layer suitable for use in the context of the invention and an environmental barrier layer of the prior art.

DETAILED DESCRIPTION OF EMBODIMENTS

(8) In the following detailed description, an environmental barrier is to formed on a substrate made of CMC material containing silicon. Nevertheless, the invention is applicable to substrates of monolithic refractory material containing silicon, and more generally to substrates in which at least a portion adjacent to an outside surface of the substrate is made of a refractory material (composite or monolithic) that contains silicon. Thus, the invention seeks in particular to protect refractory materials constituted by monolithic ceramic, e.g. made of silicon carbide (SiC) or of silicon nitride (Si.sub.3N.sub.4), and more particularly it seeks to protect refractory materials such as ceramic matrix composite (CMC) composite materials containing silicon, e.g. CMC materials having a matrix made at least in part out of SiC.

(9) FIG. 1 shows a part 1 made on a substrate 3 provided with an environmental barrier 2, in a first embodiment of the invention. The surface S of the substrate 3 is made of a refractory material containing silicon.

(10) The substrate 3 made of CMC material containing silicon comprises fiber reinforcement, which may be made of carbon (C) fibers or of ceramic fibers, e.g. of SiC fibers or of fibers that are made essentially out of SiC, including Si—C—O or Si—C—O—N fibers, i.e. fibers also containing oxygen and possibly nitrogen. Such fibers are produced by the supplier Nippon Carbon under the reference “Nicalon” or “Hi-Nicalon” or “Hi-Nicalon Type-S”, or by the supplier Ube Industries under the reference “Tyranno-ZMI”. The ceramic fibers may be coated in a thin interphase layer made out of pyrolytic carbon (PyC), out of boron nitride (BN), or out of boron-doped carbon (BC), having 5 at % to 20 at % of B, the balance being C).

(11) The fiber reinforcement is densified by a matrix that is formed, throughout the reinforcement or at least in an outer phase thereof, by a material containing silicon, such as a compound of silicon, e.g. SiC or a ternary Si—B—C system. The term “outer” phase of a matrix is used to mean a matrix phase that is formed last, being furthest away from the reinforcing fibers. Thus, the matrix may be made up of a plurality of phases of different kinds, and may for example comprise:

(12) a mixed C—SiC matrix (with SiC being on the outside); or

(13) a sequenced matrix having alternating phases of SiC and matrix phases of lower stiffness, e.g. made out of pyrolytic carbon (PyC), out of boron nitride (BN), or out of boron-doped carbon (BC), with a terminal matrix phase made out of SiC; or

(14) a self-healing matrix with matrix phases made out of boron carbide (B.sub.4C) or out of a ternary Si—B—C system, possibly including free carbon (B.sub.4C+C, Si—B—C+C), and with a terminal phase made out of Si—B—C or out of SiC.

(15) In known manner, the matrix may be formed at least in part by chemical vapor infiltration (CVI). In a variant, the matrix may be formed at least in part using a liquid technique (impregnation with a matrix-precursor resin and transformation by cross-linking and pyrolysis, which process may be repeated), or by infiltrating molten silicon (known as “melt-infiltration”). With melt-infiltration, a powder is introduced into the fiber reinforcement that might possibly already be partially densified, which powder may be a carbon powder and optionally a ceramic powder, and a metal composition based on silicon in the molten state is then infiltrated so as to form a matrix of the SiC—Si type.

(16) The environmental barrier 2 is formed on the entire outside surface S of the substrate 3 or on only a portion of that surface S, e.g. when only a portion of the surface S needs to be protected. In the example shown in FIG. 1, the environmental barrier 2 comprises a first layer 7 and an adhesion layer 5 present between the substrate 3 and the first layer 7. In the example shown, the adhesion layer 5 is present in contact with the surface S of the substrate 3. In addition, in this example, the first layer 7 is in contact with the adhesion layer 5.

(17) The first layer 7 may be in the form of a system constituted by 70% molar to at most 99.9% molar of a rare earth disilicate RE.sup.a.sub.2Si.sub.2O.sub.7 and 0.1% molar to at most 30% molar of at least one rare earth oxide RE.sup.b.sub.2O.sub.3, where RE.sup.b designates a rare earth element different from the rare earth element RE.sup.a. Said at least one oxide RE.sup.b.sub.2O.sub.3 and the disilicate RE.sup.a.sub.2Si.sub.2O.sub.7 are present in the first layer 7. Said at least one oxide RE.sup.b.sub.2O.sub.3 may be present as a dopant in the first layer 7.

(18) As mentioned above, the particular composition of the first layer 7 gives it in particular reduced ionic conductivity, making it more difficult for oxidizing and corrosive reactive species to diffuse, and also imparting increased resistance to the recession phenomenon.

(19) The first layer 7 may comprise a disilicate of formula RE.sup.a.sub.2Si.sub.2O.sub.7 that is present in the first layer 7 at a molar content lying in the range 70% to 99.9% and a single oxide RE.sup.b.sub.2O.sub.3 present in the first layer 7 at a molar content lying in the range 0.1% to 30%. In a variant, the first layer 7 may comprise i) a rare earth disilicate of formula RE.sup.a.sub.2Si.sub.2O.sub.7 present in the first layer 7 at a molar content lying in the range 70% to 99.9%, and ii) a plurality of rare earth oxides, each comprising a different rare earth element and each having the formula RE.sup.b.sub.2O.sub.3, the total molar content of oxides of formula RE.sup.b.sub.2O.sub.3 in the first layer lying in the range 0.1% to 30%, and each RE.sup.b being different from RE.sup.a.

(20) The molar content of rare earth oxide(s) RE.sup.b.sub.2O.sub.3 in the first layer 7 may lie in the range 5% to 20%. In certain embodiments, the first layer 7 may be in the form of a system constituted by 80% molar to at most 95% molar of the rare earth disilicate RE.sup.a.sub.2Si.sub.2O.sub.7 together with 5% molar to at most 20% molar of said at least one rare earth oxide RE.sup.b.sub.2O.sub.3. In particular, in certain embodiments, the first layer 7 may be in the form of a system constituted by 87% molar to at most 93% molar of the rare earth disilicate RE.sup.a.sub.2Si.sub.2O.sub.7 together with 7% molar to at most 13% molar of said at least one rare earth oxide RE.sup.b.sub.2O.sub.3.

(21) In particular, and ignoring inevitable impurities, the first layer 7 may comprise solely the rare earth disilicate RE.sup.a.sub.2Si.sub.2O.sub.7 together with said at least one rare earth oxide RE.sup.b.sub.2O.sub.3. In particular, the first layer 7 may have no aluminum, and in particular no alumina. The first layer 7 may in particular have no alkali metal or no alkaline earth metal.

(22) RE.sup.a is a rare earth element selected from yttrium Y, scandium Sc, and the lanthanides. In particular, RE.sup.a is selected from yttrium Y and ytterbium Yb. RE.sup.b is a rare earth element selected from yttrium Y, scandium Sc, and the lanthanides, and RE.sup.b is different from RE.sup.a. In particular, RE.sup.b is selected from terbium Tb, erbium Er, and dysprosium Dy.

(23) By way of example, the thickness e.sub.1 of the first layer 7 may lie in the range 50 micrometers (μm) to 1.5 millimeters (mm).

(24) The adhesion layer 5 comprises silicon, and by way of example, it may be made out of silicon or out of mullite (3Al.sub.2O.sub.3.2SiO.sub.2). In known manner, the adhesion layer 5 may form a protective layer that serves in operation to passivate silica (known as a “thermally grown oxide”).

(25) With reference to FIG. 2, there is shown a part 11 in a second embodiment of the invention. In this example, the part 11 may comprise a substrate 13 having present on its surface S an environmental barrier 12. The substrate 13 may present the same characteristics as the substrate 3 described above. The environmental barrier 12 comprises an adhesion layer 15 that may present the same characteristics as the adhesion layer 5 described above, and a first layer 17 present on the adhesion layer 15, which first layer may present the same characteristics as the first layer 7 as described above.

(26) In the example of FIG. 2, the environmental barrier 12 further comprises a second layer 19 that comprises at least one rare earth monosilicate RE.sup.c.sub.2SiO.sub.5, where RE.sup.c designates a rare earth element.

(27) As mentioned above, the presence of the second layer serves advantageously to still further improve the ability of the environmental barrier layer to withstand recession.

(28) In particular, the second layer 19 may be in the form of a system constituted by 85% molar to at most 99.9% molar of the rare earth monosilicate RE.sup.c.sub.2SiO.sub.5 together with 0.1% molar to at most 15% molar of at least one rare earth oxide RE.sup.d.sub.2O.sub.3, where RE.sup.d designates a rare earth element different from the rare earth element RE.sup.c. Said at least one oxide RE.sup.d.sub.2O.sub.3 and the monosilicate RE.sup.c.sub.2SiO.sub.5 are present in the second layer 19. Said at least one oxide RE.sup.d.sub.2O.sub.3 may be present as a dopant in the second layer 19.

(29) As mentioned above, such a second layer presents better ability to withstand recession and also presents a barrier effect that is improved against reactive species and CMASes.

(30) The second layer 19 may comprise a monosilicate RE.sup.c.sub.2SiO.sub.5 that is present in the second layer 19 at a molar content lying in the range 85% to 99.9% together with a single oxide RE.sup.d.sub.2O.sub.3 that is present in the second layer 19 at a molar content lying in the range 0.1% to 15%. In a variant, the second layer 19 may comprise i) a rare earth monosilicate of formula RE.sup.c.sub.2SiO.sub.5 that is present in the second layer 19 at a molar content lying in the range 85% to 99.9%, and ii) a plurality of rare earth oxides, each comprising a different rare earth element and each being of formula RE.sup.d.sub.2O.sub.3, the total molar content of oxides of formula RE.sup.d.sub.2O.sub.3 in the second layer lying in the range 0.1% to 15%, and each RE.sup.d being different from RE.sup.c.

(31) Said at least one rare earth oxide RE.sup.b.sub.2O.sub.3 may be present in the first layer 17 at a first molar content and said at least one rare earth oxide RE.sup.d.sub.2O.sub.3 may be present in the second layer 19 at a second molar content that may be less than the first molar content. Such a characteristic serves to still further improve compatibility between the first and second layers in terms of coefficients of thermal expansion. The molar content of rare earth oxide(s) RE.sup.d.sub.2O.sub.3 in the second layer 19 may lie in the range 5% to 15%. In certain embodiments, the second layer 19 may be in the form of a system constituted by 85% molar to at most 95% molar of the rare earth monosilicate RE.sup.c.sub.2SiO.sub.5, together with 5% molar to at most 15% molar of said at least one rare earth oxide RE.sup.d.sub.2O.sub.3. In particular, in certain embodiments, the second layer 19 may be in the form of a system constituted by 87% molar to at most 93% molar of the rare earth monosilicate RE.sup.c.sub.2SiO.sub.5 together with 7% molar to at most 13% molar of said at least one rare earth oxide RE.sup.d.sub.2O.sub.3.

(32) In particular, and ignoring inevitable impurities, the second layer 19 comprises solely the rare earth monosilicate RE.sup.c.sub.2SiO.sub.5 and said at least one rare earth oxide RE.sup.d.sub.2O.sub.3. In particular, the second layer 19 may have no aluminum, and in particular no alumina. The second layer 19 may in particular have no alkali metal or no alkaline earth metal.

(33) RE.sup.c is a rare earth element selected from yttrium Y, scandium Sc, and the lanthanides. In particular, RE.sup.c is selected from yttrium Y and ytterbium Yb. RE.sup.d is a rare earth element selected from yttrium Y, scandium Sc, and the lanthanides, and RE.sup.d is different from RE.sup.c. In particular, RE.sup.d is selected from terbium Tb, erbium Er, and dysprosium Dy. RE.sup.c may be identical to or different from RE.sup.a. In particular, RE.sup.c is ytterbium Yb, and RE.sup.a is yttrium Y. RE.sup.d may be identical to or different from RE.sup.b.

(34) By way of example, the thickness e.sub.2 of the second layer 19 may lie in the range 50 μm to 500 μm.

(35) FIG. 2 shows an embodiment in which the second layer 19 comprising a rare earth monosilicate is present on the first layer 17 comprising the rare earth disilicate. In a variant, instead of the second layer 19, it is possible to place an additional layer on the first layer 17, this additional layer comprising a rare earth disilicate RE.sup.e.sub.2Si.sub.2O.sub.7 together with at least one rare earth oxide RE.sup.f.sub.2O.sub.3 in the same ranges of molar contents as for the first layer, and in which RE.sup.f is a rare earth element different from the rare earth element RE.sup.e. Under such circumstances, RE.sup.e may be identical to or different from RE.sup.a. For example, it is possible to have RE.sup.e=Yb and RE.sup.a=Y. In addition, under such circumstances, RE.sup.f may be identical to or different from RE.sup.b.

(36) Furthermore, in the example of FIG. 2, the second layer 19 is in contact with the first layer 17. In a variant, a third layer and optionally a fourth layer, as described above, could be provided between the first layer 17 and the second layer 19.

(37) In the embodiment of FIG. 3, the part 21 comprises a substrate 23, an adhesion layer 25, a first layer 27, and a second layer 29. The substrate 23, the adhesion layer 25, the first layer 27, and the second layer 29 may be as described above. The environmental barrier 22 further comprises a top layer 24 present on the second layer 29. In the example shown, this top layer 24 is a thermal barrier layer made of ceramic presenting a porous structure. The top layer 24 may be a rare earth silicate. In a variant, a top layer may be formed that is constituted by an abradable coating, e.g. when the CMC parts form turbine rings. The top layer could also constitute a protective coating against CMASes. Depositing the top layer 24 serves to provide the environmental barrier with additional functions. In a variant, it is possible to have a part without the top layer 24 and in which the first or second layer presents, in addition to a thermal barrier function, protection against CMASes, or constitutes an abradable coating.

(38) FIG. 4 shows the various steps performed in order to fabricate the part 21 shown in FIG. 3.

(39) Initially, the adhesion layer 25 may be formed in known manner on the substrate 23 by thermal spraying using a powder or a mixture of powders having the desired composition (step 100).

(40) The first layer 27 may be formed on the adhesion layer 25 by thermal spraying from a mixture of solid powders of RE.sup.a.sub.2Si.sub.2O.sub.7 and rare earth oxide(s) RE.sup.b.sub.2O.sub.3 in the desired proportions (step 200). In similar manner, the second layer 29 may be formed on the first layer 27 by thermal spraying from a mixture of solid powders of RE.sup.c.sub.2SiO.sub.5 and rare earth oxide(s) RE.sup.d.sub.2O.sub.3 in the desired proportions (step 300). In a variant, the first and second layers 27 and 29 could be formed by other methods such as methods using a liquid technique, e.g. by dip-coating, spray-coating, electrophoresis, or by a sol-gel technique.

(41) The top layer 24 of the thermal barrier may be formed, in conventional manner, by thermal spraying (step 400).

(42) Once it has been made, the part can be used at a temperature that is higher than or equal to 800° C. in an atmosphere that is oxidizing and wet. In particular, it can be used at a temperature lying in the range 800° C. to 1500° C., or indeed in the range 800° C. to 1300° C. In particular, the part may be used in wet air.

(43) The part made in this way may be a part for an aviation or aerospace application. The part may be a part for the hot portion of a gas turbine in an aeroengine or an aerospace engine or in an industrial turbine. The part may be a turbine engine part. The part may constitute at least a portion of a turbine nozzle, a portion of a propelling nozzle, or of a thermal protection coating, a wall of a combustion chamber, a turbine ring sector, or a turbine engine blade or vane.

EXAMPLE

(44) Three examples of first layers of the invention have been fabricated. The three first layers that were fabricated had the following compositions:

(45) yttrium disilicate at 95% molar and erbium oxide Er.sub.2O.sub.3 at 5% molar, this layer being written “DSY+5 at % Er.sub.2O.sub.3”;

(46) yttrium disilicate at 90% molar and erbium oxide Er.sub.2O.sub.3 at 10% molar, this layer being written “DSY+10 at % Er.sub.2O.sub.3”; and

(47) yttrium disilicate at 85% molar and erbium oxide Er.sub.2O.sub.3 at 15% molar, this layer being written “DSY+15 at % Er.sub.2O.sub.3”.

(48) A prior art environmental barrier layer constituted by yttrium disilicate was fabricated. This layer is written “DSY”.

(49) FIG. 5 shows a test result comparing the barrier effect against oxidizing species as conferred by each of the three first layers with the barrier effect against the same species as conferred by the DSY layer. FIG. 5 shows that the conductivity to oxidizing species in each of the first layers is significantly less than the conductivity to those same species in the DSY layer. That test was performed at various temperatures lying in the range 950° C. to 1050° C. The ionic conductivity measurements were performed by complex impedance spectroscopy in ambient air in the range 950° C. to 1050° C.

(50) FIG. 6 shows a corrosion test result and shows that the first layer of the invention presents an ability to withstand recession that is better than the ability presented by a layer formed solely by yttrium disilicate. The recession measurements were obtained on the basis of corrosion tests performed in a corrosion oven at 1400° C. under 50 kilopascals (kPa) of H.sub.2O and 50 kPa of air with gas speeds of 5 centimeters per second (cm/s) in the cold zone of the oven.

(51) The term “lying in the range . . . to . . . ” should be understood as including the bounds.