ENCAPSULATED PARTICLES FOR MAINTAINING PARTICLE CHEMISTRY DURING PLASMA SPRAY APPLICATIONS

Abstract

Powder compositions are having core-shell structures for use in forming environmental barrier coatings (EBCs) and/or abradable coatings by atmospheric plasma spraying. The shell compositions and thicknesses are selected to provide inner core particle (silicate or phosphate particle) protection from the plasma and plume environments during atmospheric plasma spraying and avoid undesired modification to the particle chemistry during the deposition process. Shell coats can be designed to survive the plasma and plume environments during atmospheric plasma spraying. Alternatively, shell coats can be designed to be consumed during atmospheric plasma spraying.

Claims

1. A powder composition comprising: particles having a core-shell structure with an inner core particle and an outer particle shell wherein, in each case, the inner core particle is a Hf-silicate (HfSiO.sub.4), a Zr-silicate (ZrSiO.sub.4), a rare earth monosilicate (RE.sub.2SiO.sub.5), a rare earth disilicate (RE.sub.2Si.sub.2O.sub.7), or a rare earth phosphate (REPO.sub.4) particle, wherein RE is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu, and the outer particle shell provides protection of the inner core particle from plasma and plume environments during air plasma spraying.

2. A powder composition according to claim 1, wherein the outer shell has a composition and/or thickness such that at least part of the outer particle shell will survive air plasma spraying.

3. A powder composition according to claim 2, wherein the outer shell composition comprises a polymer, a metal, or a ceramic.

4. A powder composition according to claim 2, wherein the outer shell composition comprises polyester, poly(methyl methacrylate), Al, a rare earth metal, BN, Al.sub.2O.sub.3, or a rare earth oxide.

5. A powder composition according to claim 1, wherein the outer shell has a composition and/or thickness such that the outer particle shell is consumable during air plasma spraying.

6. A powder composition according to claim 5, wherein the outer shell composition comprises a polymer, a metal, or a ceramic.

7. A powder composition according to claim 5, wherein the outer shell composition comprises polyester, poly(methyl methacrylate), Si, or SiO.sub.2.

8. A powder composition according to claim 1, wherein the particles have a nominal diameter of 20 to 150 m.

9. A powder composition according to claim 1, wherein the outer shell of the particles has a thickness of 2-25 m.

10. A powder composition according to claim 1, wherein the outer shell makes up to 40 vol. % of the total volume of the particle.

11. A method of preparing a particulate composition comprising: preparing particles having a core-shell structure with an inner core particle and an outer shell wherein, in each case, the inner core particle is a Hf-silicate (HfSiO.sub.4), a Zr-silicate (ZrSiO.sub.4), a rare earth monosilicate (RE.sub.2SiO.sub.5), a rare earth disilicate (RE.sub.2Si.sub.2O.sub.7), or a rare earth phosphate (REPO.sub.4) particle, wherein RE is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu, and the outer shell provides protection of the inner core particle from plasma and plume environments during air plasma spraying; and subjecting said particles having a core-shell structure to air plasma spraying to produce a particulate composition wherein particles of the particulate composition optionally contain at least a portion of the outer shell of the particles having a core-shell structure.

12. A method for applying a silicate-based or phosphate-based coating to a substrate comprising: coating a substrate by subjecting a powder composition containing silicate or phosphate particles to air plasma spraying, wherein the particles have a core-shell structure comprising an inner core particle and an outer shell wherein, in each case, the inner core particle is a Hf-silicate (HfSiO.sub.4), a Zr-silicate (ZrSiO.sub.4), a rare earth monosilicate (RE.sub.2SiO.sub.5), a rare earth disilicate (RE.sub.2Si.sub.2O.sub.7), or a rare earth phosphate (REPO.sub.4) particle, wherein RE is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu, and the outer shell provides protection of the core particle from plasma and plume environments during air plasma spraying.

13. The method according to according to claim 12, wherein the outer shell has a composition and/or thickness such that at least part of the outer particle shell will survive air plasma spraying.

14. The method according to according to claim 13, wherein the outer shell composition comprises a polymer, a metal, or a ceramic.

15. The method according to according to claim 13, wherein the outer shell composition comprises polyester, poly(methyl methacrylate), Al, a rare earth metal, BN, Al.sub.2O.sub.3, or rare earth oxide.

16. The method according to according to claim 13, wherein the outer shell has a composition and/or thickness such that the outer particle shell is consumable during air plasma spraying.

17. The method according to according to claim 16, wherein the outer shell composition comprises a polymer, a metal, or a ceramic.

18. The method according to according to claim 16, wherein the outer shell composition comprises polyester, poly(methyl methacrylate), Si, or SiO.sub.2.

19. The method according to according to claim 13, wherein the particles have a nominal diameter of 20 to 150 m and/or the outer shell of the particles has a thickness of 2-25 m.

20. The method according to according to claim 13, wherein the outer shell makes up less than 40 vol. % of the total volume of the particle.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Implementations of the inventive concepts disclosed herein may be better understood when consideration is given to the following detailed description thereof. Such description make refers to the included drawings, which are not necessarily to scale, and which some features may be exaggerated and some features may be omitted or may be represented schematically in the interest of clarity. Like reference numerals in the drawings may represent and refer to the same or similar element, feature, or function. In the drawings:

[0032] FIG. 1 is a cross-sectional view of a core-shell particle having an inner core particle and an outer shell.

[0033] FIG. 2 is a cross-sectional view of an abradable coating prepared by air plasma spraying using core-shell articles of the present disclosure.

[0034] FIG. 3 is a depiction of an air plasma spraying deposition process.

DETAILED DESCRIPTION

[0035] Before explaining embodiments of the inventive concepts disclosed herein in detail, it is to be understood that the inventive concepts are not limited in their application to the details of construction and the arrangement of the components or steps or methodologies set forth in the following description or illustrated in the drawings. In the following detailed description of the embodiments of the inventive concepts, numerous specific details are set forth in order to provide a more thorough understanding of the inventive concepts. It will be apparent to one skilled in the art, however, having the benefit of the instant disclosure that the inventive concepts disclosed herein may be practiced without these specific details.

[0036] In general, embodiments of the present disclosure include providing a powder composition in which the particles of the powder have a core and shell structure comprising an inner core silicate or phosphate particle and an outer shell that provides protection for the inner core particle during air plasma spraying. The protective shell can be designed so as to be consumed during air plasma spraying or the protective shell can be designed so that at least a portion of the shell material survives air plasma spraying and is incorporated into the resultant coating produced by the air plasma spraying deposition process.

[0037] FIG. 1 depicts a particle having a core and shell structure in accordance with the present disclosure. The outer shell 10 can be made, for example, from polymers, metals, or ceramics. Inner core particle 20 is made from silicates or phosphates. While FIG. 1 shows a spherical inner core particle 20, this particle can actually be of irregular shape (e.g., having aspects ratios appreciably higher than 1). Similarly, while FIG. 1 shows the outer shell 10 uniformly surrounding the inner core particle 20, the shell coating can be non-uniform. Also, while an outer shell that completely surrounds the inner core particle can be desirable for protecting the inner core particle, partial shell coatings may be suitable in certain embodiments. In other words, the shell does not necessary need to fully engulf the core. Also, it is possible for the shell to be porous. Similarly, the core can also be porous.

[0038] Suitable silicate materials for the inner core particles are, for example, Hf-silicate (HfSiO.sub.4), Zr-silicate (ZrSiO.sub.4), rare earth monosilicates (RE.sub.2SiO.sub.5), and rare earth disilicates (RE.sub.2Si.sub.2O.sub.7), where RE is a rare earth metal selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Suitable phosphate materials for the inner core particles are, for example, rare earth phosphates (REPO.sub.4), where RE is a rare earth metal selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, for example, Lu, Yb, Er, Y, or Sc.

[0039] The outer shell can be made from various materials. Shell materials and shell thicknesses can be selected so as to provide the inner core particles with the desired protection from the plasma and plume environments during air plasma spraying. In some embodiments, the shell material and/or the thickness thereof are selected to provide a consumable outer shell, i.e., the outer shell is designed to be consumed during air plasma spraying while providing protection of the inner core particles. In other embodiments, the shell material and/or the thickness thereof are designed so that at least a portion of the shell material survives air plasma spraying and is incorporated into the resultant coating.

[0040] In some embodiments, the shell materials comprises a polymer such as polyester or poly(methyl methacrylate) (PMMA). Polymers with higher melting points like polyesters can be advantageous since lower melting point polymers may volatize too quickly during air plasma spraying. The shell material may also comprise a metal such as Al, a rare earth metal, or a refractory metal that decomposes quickly upon oxidation, e.g., Mo and Nb. Additionally, the shell material may comprise a ceramic that can decompose quickly during particle flight in plasma spraying such as BN, Al.sub.2O.sub.3, SiO.sub.2, or ceramics that are rich silica and/or phosphate, e.g., combinations of silica and/or phosphate with rare earth oxide(s), Hf oxide, or Zr oxide. For example, the ceramic can be a mixture containing up to 30 mol % rare earth oxide, Hf oxide, or Zr oxide, with the remainder being silica or phosphate. In still other embodiments, combinations of these materials can be used such as a combination of metal and ceramic.

[0041] The inclusion or exclusion of shell materials in the final coating may be desirable to enhance or preserve, respectively, properties of the final coating. For example, in some embodiments, the particles are designed to provide abradable coatings. In such embodiments, it can be advantageous to select shell materials and/or shell thicknesses such that at least a portion of the outer shell survives air plasma spraying. The incorporation of the shell materials, e.g., polyester or YPO.sub.4, into the final coating can enhance the abradability thereof. Suitable shell materials for powders intended to provide abradable coatings include polymers (e.g., polyester, poly(methyl methacrylate) (PMMA)), metals (e.g., Al, rare earth metal), and ceramics (e.g., BN, Al.sub.2O.sub.3, a mixture of silica or phosphate and rare earth oxide(s)).

[0042] In some embodiments, the particles are designed to provide a layer for use in an EBC coating. In such embodiments, it may be advantageous to select shell materials and/or shell thicknesses such that the outer shell is consumed (e.g., volatized) during air plasma spraying. In such cases, the inclusion of shell material in the final coating may adversely impact the desired properties of the final coating. Suitable shell materials for providing EBC layers include polymers (e.g., polyester, poly(methyl methacrylate) (PMMA)) and ceramics (e.g., SiO.sub.2).

[0043] Particle size for the core and shell particles can vary widely. In general, the total particle (core and shell) have a nominal diameter of greater than 15 m and less than 200 m, for example, 20 to 150 m or 20 to 60 m.

[0044] As noted above, the shell thickness can be varied to provide the desired level of protection for the inner core particle, and depending on whether it is desirable to have shell material incorporated into the final coating. Further, the shell thickness will depend on the selected shell material, for example, polyester shells could be relatively thick whereas silica shells could be relatively thin (e. g., around 1 m). For example, in some embodiments the outer shell can have a thickness of 2-25 m, for example, 2-10 m. In some embodiments, the outer shell makes up to 40 vol. % of the total volume of the particle. In some embodiments, the outer shell makes up 5 to 20 vol. % of the total volume of the particle. In general, the overall thickness (shell plus core) is greater than 15 m and less than 200 m.

[0045] In some embodiments, the inner core particle is a Hf-silicate (HfSiO.sub.4) or Zr-silicate (ZrSiO.sub.4) particle. In other embodiments, the inner core particle is a rare earth monosilicate (RE.sub.2SiO.sub.5) or rare earth disilicate (RE.sub.2Si.sub.2O.sub.7), e.g. Yb.sub.2SiO.sub.5 and Yb.sub.2Si.sub.2O.sub.7. Still, in other embodiments, the inner core particle is a rare earth phosphate (REPO.sub.4), e.g., YPO.sub.4.

[0046] By way of example, for abradable coating the shell and core particles according to the present disclosure can have cores selected from HfSiO.sub.4, ZrSiO.sub.4, Yb.sub.2Si.sub.2O.sub.7, ScPO.sub.4, YbPO.sub.4, and YPO.sub.4, and shells selected from SiO.sub.2, polyester, a silica-rich mixture with HfSiO.sub.4, ZrSiO.sub.4, or Yb.sub.2Si.sub.2O.sub.7, a phosphate-rich mixture with YPO.sub.4, a metal, and BN. For EBC coatings the shell and core particles can have cores selected from HfSiO.sub.4, ZrSiO.sub.4, Yb.sub.2Si.sub.2O.sub.7, and YPO.sub.4, and shells selected from SiO.sub.2, polyester, a silica-rich mixture with HfSiO.sub.4, ZrSiO.sub.4, or Yb.sub.2Si.sub.2O.sub.7, and a phosphate-rich mixture with YPO.sub.4.

[0047] The shell coating can be applied to the core particles using various methods. For example, the shell coatings can be applied by solvent coating, cladding, slurry processing, or thermal spraying.

[0048] Regarding a method aspect of the present disclosure, in some embodiments the method comprises applying a coating to a substrate by air plasma spraying using powders containing core and shell particles as described above. For example, the method can comprise coating a CMC substrate, such as SiC based CMCs (e.g., an SiC/SiC CMC), with an EBC coating or an abradable coating using powders containing core and shell particles as described above. In other embodiments, the method comprises applying an abradable coating to a substrate intended for use as a seal in a gas turbine engine wherein the seal will come into contact with rotor blade tips.

[0049] In some embodiments, the method is performed so that at least a portion of the outer shell materials survive the plasma and plume environment during the atmospheric plasma spraying and these shell materials are incorporate into the resultant coating. In other embodiments, the method is performed so that the outer shell are consumed (e.g., volatized) in the plasma and plume environment during the atmospheric plasma spraying so as to prevent these shell materials from being incorporated into the resultant coating.

[0050] When using particles without protective coatings, the plasma and plume environments formed during the atmospheric plasma spraying can cause the silicate or phosphate particles to undergo volatilization leading to changes in the particle chemistry and ultimately regions of undesirable chemistry in the final coating. The presence of the shell coating inhibits particle volatilization.

[0051] The inner core particles used in the method are, for example, Hf-silicate (HfSiO.sub.4), Zr-silicate (ZrSiO.sub.4), rare earth monosilicates (RE.sub.2SiO.sub.5), rare earth disilicates (RE.sub.2Si.sub.2O.sub.7), or rare earth phosphates (REPO.sub.4), where RE is a rare earth metal selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. the materials used for the outer shell in the method are, for example, polymers such as polyester or poly(methyl methacrylate) (PMMA), metals such as Al or a rare earth metal, or ceramics such as BN, Al.sub.2O.sub.3, or silica-rich mixture with HfSiO.sub.4, ZrSiO.sub.4, or Yb.sub.2Si.sub.2O.sub.7. It is also possible to use combinations of these materials as the shell materials.

[0052] FIG. 2 shows a cross section of a CMC substrate 50 having an abradable coating 60 applied thereto using the core and shell particles described herein using atmospheric plasma spraying. The inner core particles 1 become to some degree molten during the atmospheric plasma spraying process and are deposited onto the substrate as so-called splats. In the embodiment of FIG. 2, at least a portion of the shell material 10 survives the atmospheric plasma spraying process and is incorporated into the final coating. Also, the coating has a certain porosity represented by pores 70. This porosity enhances the abradability of the coating.

[0053] For example, the porosity can be 20% or higher. In some embodiments, the porosity can be up to 50% Further, porosity can be adjusted through the incorporation of auxiliary agents in the coating such as a polymer particles. For example, a fugitive material can be incorporated into the abradable coating and then subsequently baked out to provide a desired porosity.

[0054] As noted above, the selection of shell materials and shell thicknesses can be used to adjust desired properties of the final coating. Additionally, parameters associated with atmospheric plasma spraying such as gas flow rates, powder feed rate, and current can be used to adjust temperature and particle velocity which in turn can be used to vary the formation of the final coating on the substrate.

[0055] As shown in FIG. 3, an air plasma spray torch or air plasma spray gun 100 has an anode 110 and a cathode 120. An electric arc is created between cathode 110 and an anode 120. Gas flowing through passageway 130 is forced to flow through the electric arc which generates a high temperature plasma jet 140 which is discharged from the torch/gun via nozzle 150. The shell and core particles are introduced via inlet 160 into the jet 140 resulting in at least partial consumption of the outer shell. The particles are directed towards the substrate where they form a coating 180. FIG. 1 shows the shell and core particles introduced via injector 160 into the jet 140 as a cross flow after the jet has existed the nozzle 150. Alternatively, the monociliate shell and core particles can be introduced via an inlet 190 into the jet 140 at the nozzle 150, i.e., as the jet is existing the nozzle.

[0056] In an exemplary embodiment of a method aspect of the present disclosure, in a plasma spray device a plasma formation gas (e.g., argon) is made to flow through between an anode and a cathode separated by a flow channel. Applying a voltage to the anode and cathode causes the flowing plasma formation gas to form a plasma. A plasma jet is discharged from a plasma spray nozzle and a powder composition containing particles having a core-shell structure are injected into the plasma jet. The particles have a Zr-silicate inner core and a PMMA outer shell. During particle flight through the plasma jet, at least a portion of the PMMA shell is consumed and the Zr-silicate inner core becomes at least partially molten. The at least partially molten particles are deposited on the surface of a CMC substrate.

[0057] Generally, the powder compositions and methods described herein can be advantageous in terms of preserving the silicate/phosphate chemistry of the particles. Such preservation of chemistry can in turn result in maximizing material performance for the resultant coatings.

[0058] For EBC coatings, using the shell and core particles of the present disclosure can aid in the formation of coatings that exhibit little or no cracking, and reduce the number of oxide particles subject to volatilization of silica/phosphate, thereby preserving the silicate/phosphate chemistry. Further, using the shell and core particles of the present disclosure can yield coatings having a significant retention of crystalline phase (e.g., more than 95%).

[0059] For abradable systems, using the shell and core particles of the present disclosure can yield coatings with distinct features such as splat like pores formed by the residual shell (e.g., polymer) and lower levels of pure crystalline phase compared to the EBC coatings (e.g., 80% or less).

[0060] The corresponding structures, material, acts, and equivalents of all means or steps plus function elements in the claims below are intended to include any structure, material, or act for performing the function in combination with other claimed elements are specifically claimed. The description of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill without departing from the scope and spirit of the invention. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for embodiments with various modifications as are suited to the particular use contemplated.

[0061] Modifications and equivalents may be made to the features of the claims without departing from the spirit or scope of the invention. Thus, it is intended that the present invention covers the modifications and variations disclosed above provided that these changes come within the scope of the claims and their equivalents.