COATED PART COMPRISING A PROTECTIVE COATING BASED ON MAX PHASES

Abstract

A coated part includes a metallic substrate, a thermal barrier comprising a ceramic material and covering the metallic substrate, wherein the coated part further includes a protective coating covering the thermal barrier, the protective coating including, in a first region, a first MAX phase, denoted PZ2, of formula (Zr.sub.xTi.sub.1-x,).sub.2AlC or a first MAX phase, denoted PC2, of formula (Cr.sub.xTi.sub.1-x,).sub.2AlC with x non-zero and less than or equal to 1 in the MAX phases PZ2 and PC2, and the protective coating includes, in a second region covering the first region, a second MAX phase of formula Ti.sub.2AlC.

Claims

1. A coated part comprising: a metallic substrate, a thermal barrier comprising a ceramic material and covering the metallic substrate, wherein the coated part further comprises a protective coating covering the thermal barrier, the protective coating comprising, in a first region, a first MAX phase, denoted PZ2, of formula (Zr.sub.xTi.sub.1-x).sub.2AlC or a first MAX phase, denoted PC2, of formula (Cr.sub.xTi.sub.1-x).sub.2AlC with x non-zero and less than or equal to 1 in the MAX phases PZ2 and PC2, and the protective coating comprising, in a second region covering the first region, a second MAX phase of formula Ti.sub.2AlC.

2. A coated part comprising: a metallic substrate, a thermal barrier comprising a ceramic material and covering the metallic substrate, wherein the coated part further comprises a protective coating covering the thermal barrier, the protective coating comprising, in a first region, a first MAX phase, denoted PZ3, of formula (Zr.sub.xTi.sub.1-x).sub.3AlC.sub.2 or a first MAX phase, denoted PC3, of formula (Cr.sub.xTi.sub.1-x).sub.3AlC.sub.2 with x non-zero and less than or equal to 1 in the MAX phases PZ3 and PC3, and the protective coating comprising, in a second region covering the first region, a second MAX phase of formula Ti.sub.3AlC.sub.2.

3. The coated part according to claim 1, wherein a thickness of the first region is greater than or equal to 0.5 times a thickness of the second region.

4. The coated part according to claim 1, wherein the protective coating further comprises an intermediate region located between the first region and the thermal barrier, the intermediate region comprising zirconium or an alloy of zirconium, or chromium or an alloy of chromium.

5. The coated part according to claim 2, wherein the protective coating further comprises an additional protective layer covering the second region and comprising a MAX phase of formula Ti.sub.2AlC.

6. The coated part according to claim 1, wherein the metallic substrate is a turbomachine part.

7. A turbomachine comprising a coated part according to claim 6.

8. A method for manufacturing a coated part according to claim 1, and with x less than 1 in the MAX phases PZ2 and PC2, the method comprising, when the first region comprises the first MAX phase PZ2: depositing zirconium or a zirconium alloy on the thermal barrier, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, depositing the second MAX phase of formula Ti.sub.2AlC on the previously deposited zirconium or zirconium alloy, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, and a heat treatment for zirconium diffusion into the second MAX phase of formula Ti.sub.2AlC by imposing a temperature greater than or equal to 900° C. in order to obtain the coated part, or the method comprising, when the first region comprises the first MAX phase PC2: depositing chromium or a chromium alloy on the thermal barrier, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, depositing the second MAX phase of formula Ti.sub.2AlC on the previously deposited chromium or chromium alloy, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, and a heat treatment for chromium diffusion into the second MAX phase of formula Ti.sub.2AlC by imposing a temperature greater than or equal to 900° C. in order to obtain the coated part.

9. A method for manufacturing a part according to claim 1, and with x less than or equal to 1 in the MAX phases PZ2 and PC2, the method comprising, when the first region comprises the first MAX phase PZ2: depositing a first layer of the first MAX phase PZ2 forming the first region, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, and depositing a second layer of the second MAX phase of formula Ti.sub.2AlC on the first layer, the second layer forming the second region, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, or the method comprising, when the first region comprises the first MAX phase PC2: depositing a first layer of the first MAX phase PC2 forming the first region, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, and depositing a second layer of the second MAX phase of formula Ti.sub.2AlC on the first layer, the second layer forming the second region, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis.

10. A method for manufacturing a coated part according to claim 2, and with x less than 1 in the MAX phases PZ3 and PC3, the method comprising, when the first region comprises the first MAX phase PZ3: depositing zirconium or a zirconium alloy on the thermal barrier, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, depositing the second MAX phase of formula Ti.sub.3AlC.sub.2 on the previously deposited zirconium or zirconium alloy, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, and a heat treatment for zirconium diffusion into the second MAX phase of formula Ti.sub.3AlC.sub.2 by imposing a temperature greater than or equal to 900° C. in order to obtain the coated part, or the method comprising, when the first region comprises the first MAX phase PC3: depositing chromium or a chromium alloy on the thermal barrier, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, depositing the second MAX phase of formula Ti.sub.3A1C.sub.2 on the previously deposited chromium or chromium alloy, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, and a heat treatment for chromium diffusion into the second MAX phase of formula Ti.sub.3AlC.sub.2 by imposing a temperature greater than or equal to 900° C. in order to obtain the coated part.

11. A method for manufacturing a coated part according to claim 2, and with x less than or equal to 1 in the MAX phases PZ3 and PC3, the method comprising, when the first region comprises the first MAX phase PZ3: depositing a first layer of the first MAX phase PZ3 forming the first region, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, and depositing a second layer of the second MAX phase of formula Ti.sub.3AlC.sub.2 on the first layer, the second layer forming the second region, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, or the method comprising, when the first region comprises the first MAX phase PC3: depositing a first layer of the first MAX phase PC3 forming the first region, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis, and depositing a second layer of the second MAX phase of formula Ti.sub.3AlC.sub.2 on the first layer, the second layer forming the second region, the deposit being made by a spray technique, by a vapour phase deposition technique, by sol-gel route or electrophoresis.

12. A method for using a part according to claim 1, the method comprising a step of using said part at a temperature greater than or equal to 800° C. in an oxidizing environment.

13. The coated part according to claim 2, wherein the thickness of the first region is greater than or equal to 0.5 times the thickness of the second region.

14. The coated part according to claim 2, wherein the protective coating further comprises an intermediate region located between the first region and the thermal barrier, the intermediate region comprising zirconium or an alloy of zirconium, or chromium or an alloy of chromium.

15. The coated part according to claim 2, wherein the metallic substrate is a turbomachine part.

16. A turbomachine comprising a coated part according to claim 15.

17. A method for using a part according to claim 2, the method comprising a step of using said part at a temperature greater than or equal to 800° C. in an oxidizing environment.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0055] FIG. 1 schematically illustrates a first example of a coated part according to the invention.

[0056] FIG. 2 schematically illustrates a second example of a coated part according to the invention.

[0057] FIG. 3 schematically illustrates a third example of a coated part according to the invention.

[0058] FIG. 4 schematically illustrates a fourth example of a coated part according to the invention.

[0059] FIG. 5 is a perspective view of a metallic substrate able to be used in the context of the invention, which constitutes a turbomachine blade.

[0060] FIG. 6 is a perspective view of a turbomachine wheel incorporating a plurality of coated parts according to the invention.

[0061] FIG. 7 illustrates a first step of a method for manufacturing the part according to the first example illustrated in FIG. 1.

[0062] FIG. 8 illustrates a second step of a method for manufacturing the part according to the first example illustrated in FIG. 1.

[0063] FIG. 9 illustrates the obtaining of the part according to the first example illustrated in FIG. 1, after diffusion between the deposited elements.

[0064] FIG. 10 illustrates a first step of a method for manufacturing the part according to the third example illustrated in FIG. 3.

[0065] FIG. 11 illustrates a second step of a method for manufacturing the part according to the third example illustrated in FIG. 3.

[0066] FIG. 12 illustrates a third step of a method for manufacturing the part according to the third example illustrated in FIG. 3.

[0067] FIG. 13 illustrates a fourth step of a method for manufacturing the part according to the third example illustrated in FIG. 3.

DESCRIPTION OF THE EMBODIMENTS

[0068] The structure of several examples of coated parts 10, 20, 30 or 40 according to the invention will be described with reference to FIGS. 1 to 4. These parts 10-40 each comprise a metallic substrate 11, 21, 31 or 41 coated by a bonding layer 13, 23, 33 or 43 itself coated by a ceramic thermal barrier layer 15, 25, 35 or 45.

[0069] The metallic substrate 11-41 can be a superalloy, for example a nickel-based or cobalt-based superalloy. The bonding layer 13-43 can contain an alloy MCrAlY, with M designating nickel, cobalt or a nickel-cobalt combination, or a nickel aluminide. The bonding layer 13-43 can be in contact with the metallic substrate 11-41. The bonding layer 13-43 forms part of a thermal barrier which further comprises the ceramic layer 15-45 covering the bonding layer 13-43. The bonding layer 13-43 is present between the ceramic layer 15-45 and the metallic substrate 11-41. The ceramic layer 15-45 can be in contact with the bonding layer 13-43. The ceramic layer 15-45 can comprise zirconia, yttria stabilised zirconia referred to as “YSZ” or yttria partially stabilised zirconia referred to as “YPSZ” or a rare earth zirconate, such as gadolinium zirconate Gd.sub.2Zr.sub.2O.sub.7. The ceramic layer 15-45 can have a columnar structure. The assembly constituted by the substrate 11-41, the bonding layer 13-43 and the ceramic layer 15-45 is known per se.

[0070] FIGS. 1 to 4 represent the case of a thermal barrier consisting of only two layers, with a bonding layer 13-43 and a ceramic layer 15-45, but it does not depart from the scope of the invention when the thermal barrier comprises more than two layers, and for example more than two ceramic layers.

[0071] The various examples of coated parts 10-40, which are illustrated in FIGS. 1 to 4, differ in terms of the protective coating implemented.

[0072] Whichever the example considered, the protective coating covers the thermal barrier. The protective coating can be in contact with the thermal barrier. The protective coating can define the outer layer of the coating of the part 10-40, in other words the layer furthest from the metallic substrate 11-41.

[0073] The protective coating comprises a changing composition changing (i) either between a MAX phase PZ2 or PC2 in the first region 17, 27, 37 or 47 and Ti.sub.2AlC in the second region 19, 29, 39 or 49, or (ii) between a MAX phase PZ3 or PC3 in the first region 17-47 and Ti.sub.3AlC.sub.2 in the second region 19-49. The first region 17-47 is superimposed on the thermal barrier, The thermal barrier is between the metallic substrate 11-41 and the first region 17-47. The first region 17-47 can be in contact with the thermal barrier. In the formulas of the MAX phases PZ2, PC2, PZ3 and PC3, x is non-zero, equal to 1 or less than 1. The first region 17-47 can be in contact with the ceramic layer 15-45 of the thermal barrier. The second region 19-49 is superimposed on the first region 17-47. The first region 17-47 is located between the thermal barrier and the second region 19-49. The first region 17-47 is located between the ceramic layer 15-45 of the thermal barrier and the second region 19-49. The second region 19-49 can be in contact with the first region 17-47. The second region 19-49 is further away from the metallic substrate 11-41 than the first region 17-47.

[0074] Whichever example is considered, the thickness of the protective coating can be greater than or equal to 5 μm, for example between 5 μm and 500 μm, preferably between 5 μm and 50 μm. The thickness e.sub.1 of the first region 17-47 can be greater than or equal to 0.1 μm, for example between 0.1 μm and 50 μm. The thickness e.sub.2 of the second region 19-49 can be greater than or equal to 1 μm, for example between 1 μm and 50 μm. The protective coating can be porous or non-porous. In the case where the protective coating is porous, it can be advantageous to limit its porosity to a value less than or equal to 20% by volume.

[0075] The features of the protective coating that are applicable whichever example of the part is considered have just been described. The features specific to each of the examples illustrated in FIGS. 1 to 4 will now be described.

[0076] In the case of the part 10 illustrated in FIG. 1, the second region 19 defines the outer surface S of the part 10. In this example, the first region 17 comprises a MAX phase PZ2, PC2, PZ3 or PC3 with x less than 1. Hence, the MAX phase of the first region 17 comprises both titanium and chromium, or titanium and zirconium. In the case of FIG. 1, this MAX phase results from diffusion between deposited elements which results in a protective coating consisting of a single and same layer comprising the first region and the second region.

[0077] The example of part 20 illustrated in FIG. 2 only differs from part 10 in that the protective coating further comprises an additional protective layer 22 covering the second region 29 and comprising a MAX phase of formula Ti.sub.2AlC and in that the second region 29 comprises a MAX phase Ti.sub.3AlC.sub.2 and the first region 27 comprises a MAX phase PZ3 or PC3. Here, the additional protective layer 22 defines the outer surface S of the part 20. The additional protective layer 22 can be in contact with the second region 29.

[0078] The example of part 30 illustrated in FIG. 3 comprises the first 37 and second 39 regions in the form of distinct layers. As will be repeated below in connection with FIGS. 10 to 13, the forming of the first region does not result here from a diffusion of zirconium or chromium in a MAX phase Ti.sub.2AlC or Ti.sub.3AlC.sub.2, rather the materials corresponding to the desired phases in the first 37 and second 39 regions have been deposited directly. The example of FIG. 3 further comprises an intermediate layer 34 of zirconium or a zirconium alloy, or chromium or a chromium alloy present on the thermal barrier. The intermediate layer 34 is located between the ceramic layer 35 of the thermal barrier and the first region 37. This intermediate layer 34 is deposited first, in order to avoid any risk of degradation of the thermal barrier during the depositing of the layers forming the first 37 and second 39 regions. The io thickness e.sub.3 of the intermediate layer 34 can be less than or equal to 20 μm, for example between 2 μm and 10 μm.

[0079] The example of part 40 illustrated in FIG. 4 only differs from part 30 according to the third example in that the protective coating further comprises an additional protective layer 42 covering the second region 49 and comprising a MAX phase of formula Ti.sub.2AlC and in that the second region 49 comprises a MAX phase Ti.sub.3AlC.sub.2 and the first region 47 comprises a MAX phase PZ3 or PC3. Here, the additional protective layer 42 defines the outer surface S of the part 40. The additional protective layer 42 can be in contact with the second region 49. The part 40 also comprises an intermediate layer 44 having the same properties as the layer 34 described above.

[0080] A possible application will now be described for the coated part according to the invention in the context of incorporation in a turbomachine, with reference to FIGS. 5 and 6.

[0081] FIG. 5 illustrates a coated turbomachine blade 100 constituting a possible example of a coated part according to the invention. In the example of FIG. 5, the metallic substrate defines a turbomachine blade which comprises an aerofoil 101, a root 102 formed by a portion with the greatest thickness, for example with a bulb-shaped cross-section, extended by a shank 103, an inner platform 110 located between the shank 103 and the aerofoil 101 and an outer platform or shroud 120 in the vicinity of the free end of the aerofoil.

[0082] FIG. 6 illustrates the incorporation of the turbomachine blade 100 in a turbomachine wheel 200. FIG. 6 illustrates a turbomachine wheel 200 comprising a hub 130 on which are mounted a plurality of blades 100, each blade 100 having a root 102 formed by a thickest portion, for example with a bulb-shaped cross-section, which is engaged in a corresponding housing 131 arranged on the periphery of the hub 130 and an aerofoil 101. The wheel 200 also includes a plurality of blade shroud elements 120 mounted on each of the blades 100.

[0083] FIGS. 1 to 6 which have just been described relate to examples of possible structures for the coated parts according to the invention. The description of FIGS. 7 to 13 which will follow, attempts to describe the aspect relating to the manufacture of such coated parts.

[0084] FIGS. 7 to 9 relate to the manufacture of the example of part 10 of FIG. 1. The starting material comprises the metallic substrate 11, the bonding layer 13 and the ceramic layer 15 (FIG. 7). The protective coating is then formed by first depositing a layer 14 of zirconium or a zirconium alloy, or a layer 14 of chromium or a chromium alloy on the ceramic layer 15 (FIG. 8). The layer 14 can be deposited in contact with the ceramic layer 15. A second MAX phase of formula Ti.sub.2AlC or Ti.sub.3AlC.sub.2 is then deposited on the layer 14, Various techniques can be used to deposit the layer 14 and the second MAX phase. A spray technique can be used, for example thermal spraying, or vapour phase deposition, for example physical vapour deposition (PVD). Examples of usable techniques include: cold spray, atmospheric plasma spraying (APS), suspension plasma spraying (SPS), solution precursor plasma spraying (SPPS), powder-route high velocity oxygen fuel spraying (HVOF), powder-route high velocity air fuel spraying (HVAF), liquid-route high velocity suspension flame spray (HVSFS), electron-beam physical vapor deposition (EB-PVD), high power impulse magnetron sputtering (HiPIMS), the sol-gel route or electrophoresis. As indicated above, when the second MAX phase is deposited at high temperature, as is the case, for example, in a thermal spraying process, the zirconium or chromium of the layer 14 diffuses into the second MAX phase during the step of depositing the latter. The diffusion of the zirconium or chromium into the second MAX phase can be performed by imposing a temperature greater than or equal to 900° C., for example between 900° C. and 1200° C.

[0085] The layer 14 has the same nature as the intermediate layer 34 or 44 mentioned above and thus avoids any risk of degradation of the underlying thermal barrier during the step of depositing the protective coating (avoids any risk of erosion of the thermal barrier by sprayed particles). In addition to this, in the particular case of FIG. 1, the layer 14 is also used in the case of the part 10 of FIG. 1 in order to obtain the first region 17 having a mixed MAX phase based on zirconium and titanium, or on chromium and titanium, by diffusion of the deposited elements.

[0086] At the end of the diffusion of the zirconium or chromium into the second MAX phase, the part 10 is obtained having a protective coating having the first region 17 and the second region 19 (FIG. 9). The method can be continued by depositing an additional protective layer 22, if this is desired, in order to obtain the part 20 according to FIG. 2.

[0087] FIGS. 10 to 13 relate to the case of the part 30 of FIG. 3 for which there is no need to use a phenomenon of diffusion of the deposited elements in order to form the first region 37. The method starts with a starting material comprising metallic substrate 31, bonding layer 33 and ceramic layer 35. The zirconium-based or chromium-based intermediate layer 34 is then deposited on the ceramic layer 35. As indicated above, this intermediate layer 34 makes it possible, in particular, to avoid any risk of degradation of the underlying thermal barrier during the step of depositing the protective coating, Then, the desired materials for constituting the first and second regions are deposited directly on this intermediate layer 34. The techniques mentioned above can be used to deposit each of the layers 34, 37 and 39. According to this example, the zirconium-based or chromium-based intermediate layer 34 is located in the finished coated part obtained after forming the protective coating, Of course, if it is desired, an additional protective layer 42 can be formed.

[0088] Once the part is coated, before the first use, a pre-oxidation heat treatment can be performed beforehand at a temperature between 950° C. and 1100° C. in order to form the protective alumina layer. Alternatively, this alumina layer can be formed in situ during the operation in an oxidising environment.