This invention relates to methods for producing an increased crystalline and dense coating. More particularly, this invention relates to a novel process for utilizing a modified laminar plasma plume regime to form increased crystalline and dense coatings in an as-sprayed condition without the use of auxiliary heating or a post heat treatment.
The components in the hot sections of gas turbine engines are exposed to increasingly harsh operating environments. The harsh operating environments can lead to degradation and damage of the turbine engines.
To remediate such damage, coatings are often applied to the surfaces of the gas turbine engines to provide thermal, environmental, or chemical protection. Of interest is the development of coatings to protect the surfaces of ceramic matrix composite (CMC) components from oxidation and volatilization in the presence of high temperature water vapor in a turbine gas stream. For example, when silicon carbide components are exposed to elevated temperatures in the presence of water vapor, the silicon carbide decomposes by oxidation and leads to eventual volatilization of the material in the form of silicon hydroxide species.
Environmental barrier coatings (EBC's) are commonly applied to surfaces of turbine engine components to provide water vapor barriers to the underlying component. EBC's are typically applied by thermal spray processes such as air plasma spray. During a conventional air plasma spray the coating is exposed to rapid cooling rates that lead to the retention of significant amounts of amorphous or other non-equilibrium phases. These retained phases are prone to volume transformations on heating and cooling (i.e., thermal cycling) of the component that can lead to cracking of the EBC on thermal cycling. The amorphous phase has a structure characterized by a highly disordered arrangement of atoms that lacks a periodic structure or crystal lattice. Non-equilibrium phases are phases that upon thermal exposure exhibit a rearrangement of the atoms to a lower energy configuration. When the coating is deposited in the amorphous phase, subsequent thermal exposure such as that provided in service, can lead to crystallization of the amorphous phase to equilibrium and non-equilibrium structures of the material. The crystallization process involves mass rearrangement of atoms in the material that can result in the evolution of significant stresses in the coating and the production of defects, cracking, delamination, and/or eventual spallation of the protective coating layer.
To increase performance of the coating, the amorphous structure can be crystallized before being put into service. Several methods have been developed to minimize or eliminate the development of stress and defects during the crystallization process of thermally sprayed EBCs. Primary among the methods used is the application of an extensive post-deposition heat treatment that allows the coating to slowly crystallize in such a way that the stresses induced during crystallization are evolved and then thermally annealed out of the coating in a single thermal exposure. These heat treatment schedules can take in excess of 50 hours and are costly.
Another method for the development of highly crystalline coatings is the application of auxiliary heating to a component during deposition. This method includes techniques such as applying the coating by plasma spray while the component is heated inside of a high temperature furnace and resistively or inductively heating the component during the deposition process. While these methods can provide the thermal energy needed to initiate crystallization during the plasma spray process, auxiliary heating can increase the cost of the deposition process. Additionally, auxiliary heating can limit the flexibility of the process to coat a wide range of part sizes and geometries as it forms non-uniform heating that produces local overheating and melting of part regions of complex geometries.
As a result, a coating process that provides the required thermal energy for crystallization during the plasma spray process without the use of auxiliary heating or post heat treatment would be desirable. Other advantages and applications of the present invention will become apparent to one of ordinary skill in the art.
In a first aspect of the present invention, a method of producing an improved dense and crystalline coating in an as-sprayed condition onto a substrate using a modified laminar plasma plume process, said modified laminar plasma plume process comprising the steps of: providing a cascade torch; establishing a coating process standoff distance of 3 inches or greater as measured from an outlet of the cascade torch to the substrate; generating a laminar plasma plume that contacts the substrate, wherein the laminar plasma plume is characterized as a substantially columnar shape-like structure along a longitudinal axis of the laminar plasma plume, the laminar plasma plume having a longitudinal length substantially equal to the coating process standoff distance; pre-heating the substrate with the laminar plasma plume to form a heated substrate; feeding powder particles; heating the powder particles to form molten powder particles; directing the molten powder particles from an outlet of the cascade torch into the laminar plasma plume; impinging the molten powder particles onto the heated substrate, and crystallizing the powder particles to form the improved dense and crystalline coating, said crystallizing occurring without the use of auxiliary heating or a post-heat treatment step.
In a second aspect of the present invention, a method of using a laminar plasma flow regime to create an improved dense and crystalline coating, comprising: providing a cascade torch, comprising a cathode and an anode, and one or more inner electrode inserts between the cathode and the anode to provide arc stability; establishing a predetermined coating process standoff distance as measured from an outlet of the cascade torch to a surface of the substrate; generating a laminar plasma plume that is defined, at least in part, by a longitudinal length along a longitudinal axis of the laminar plasma plume that extends from the outlet of the cascade torch to the substrate, wherein the laminar plasma plume is characterized as substantially columnar shape; pre-heating the surface of the substrate with the laminar plasma plume to a localized deposition spot temperature to form a heated substrate; introducing a powder material without substantially disrupting the laminar plasma plume; heating the powder particles to form molten powder particles; directing the molten powder particles from an outlet of the cascade torch into the laminar plasma plume and towards the heated substrate; impinging the molten powder particles onto the heated substrate, and crystallizing the powder particles to form the improved dense and crystalline coating, said crystallizing occurring without the use of auxiliary heating or a post-heat treatment step.
The invention may include any of the aspects in various combinations and embodiments to be disclosed herein.
The objectives and advantages of the invention will be better understood from the following detailed description of the preferred embodiments thereof in connection with the accompanying figures wherein like numbers denote same features throughout and wherein:
The objectives and advantages of the invention will be better understood from the following detailed description of the embodiments thereof in connection. The present disclosure relates to novel coating processes for producing improved coatings with increased crystallinity and density. The disclosure is set out herein in various embodiments and with reference to various aspects and features of the invention.
The relationship and functioning of the various elements of this invention are better understood by the following detailed description. The detailed description contemplates the features, aspects and embodiments in various permutations and combinations, as being within the scope of the disclosure. The disclosure may further be specified as comprising, consisting or consisting essentially of, any of such combinations and permutations of these specific features, aspects, and embodiments, or a selected one or ones thereof.
Prior to emergence of the present invention, a major challenge in the deposition of coatings by thermal spraying has been to develop a desired structure of the thermal spray coating using a process that is intrinsically non-equilibrium. In the case of materials systems such as the rare earth disilicate-based ceramics used for environmental barrier coatings, the relatively rapid cooling rates can trap the coating into undesirable metastable crystal structures including fully or partially amorphous coating structures. These resulting so-called “vitreous coatings” are then undesirably prone to crystallization to the equilibrium crystal structures upon high temperature service and eventually can lead to cracking and failure of the coating.
To overcome the above-mentioned challenges, the present invention offers a solution which is a notable departure from conventional plasma coating processes which utilize turbulent plasma plume flow regimes. In particular, the inventors have discovered that a laminar plasma plume with specific attributes as will be discussed, can be used to preheat the substrate to a sufficient temperature, followed by optimal introduction of powder particles into the in-tact laminar plasma plume without disruption of the laminar plasma plume. The particles are heated by the laminar plasma plume and accelerate towards the surface of the part or component to be coated. The term “laminar plasma plume” as used herein and throughout is intended to mean a plasma plume that is substantially isenthalpic along the radial axis of the torch, thereby leading to elimination or significant reduction of a radial gradient of the plasma parameters when compared to a traditional turbulent plasma plume. The thermal and kinetic energy supplied by the laminar plasma plume is capable of depositing a significantly dense and crystalline coating for a given application.
During this inventive process, by means of the relatively higher heat flux along the axis of the laminar plume in comparison to conventional processes, the coating and substrate are heated in a controlled manner to a temperature at or above the glass transformation temperature of the material being deposited. Creating and maintaining the glass transformation temperature is particularly important for the deposition of high-quality coatings of materials in which crystallization of the equilibrium phase has been historically suppressed by rapid cooling as is the case for rare earth disilicate and aluminosilicate environmental barrier coatings. Unlike conventional processes that utilize a turbulent plasma plume, the application of repeated directed heating of the substrate by the laminar plasma plume while the coating accumulates therealong ensures that during the deposition of each pass or layer of the thermally sprayed coating there exists the required thermal energy to cause both nucleation and growth of the crystals of the desired equilibrium phase, while limiting or eliminating the formation of amorphous phases in the coating. The use of a laminar plasma as specifically created by the present invention to possess certain characteristics reduces and/or eliminates the need for subsequent thermal processing of parts or components as a result of elimination or reduced amounts of amorphous phases or structures in the resultant coating. On the contrary, coatings produced by conventional plasma processes are significantly amorphous and undergo crystallization which occurs in service in a manner that causes the coating to damage.
An exemplary embodiment of the present invention will be discussed with respect to
A coating process standoff distance is established that is a minimum of 3 inches or greater. As used herein and throughout, the term “coating process standoff distance” is the distance measured from the outlet of the cascade torch 102 to the substrate 101 (e.g., turbine blade). In this regard, the substrate 101 to be coated is located at the approximate termination (i.e., distal end) of the laminar plasma plume 105 which is three inches or more from the outlet of the plasma torch 102.
An electrical power supply (not shown) is operably connected to supply power to the cascade torch 102. A plasma gas 104 is supplied into the inlet of cascades torch 102. The plasma gas 104 is ionized within the torch 102 to produce a laminar plasma plume 105. The laminar plasma plume 105is substantially isenthalpic along the radial axis of the torch 102 (
The laminar plasma plume 105 pre-heats the substrate to a temperature that is at or above a glass transition temperature of the resultant coating to be deposited. Of particular significance and benefit is the elimination of auxiliary heating sources when pre-heating the substrate 101. By keeping the substrate 101 and the coating built-up thereon at or above the glass transition temperature, conditions favoring crystal formation of the resultant formation are established. Specifically, the powder particles 106 upon impinging the substrate 101 undergo a cooling rate that is suitable to reduce or minimize formation of amorphous phases in comparison to a coating produced by a turbulent plasma plume of
With the substrate 101 preheated with laminar plasma plume 105, and the laminar plasma plume 105 structurally in-tact with its distal end touching the substrate 101, the powder particles can now be introduced. Hopper 103 can introduce the powder particles 106 into the laminar plume 105. One example of a configuration for introducing the powder is shown in
The powder particles 106 are heated within the laminar plasma plume 105 such that substantially all of the particles 106 become molten. The powder particles 106 in such molten state are accelerated towards the substrate 101. The power particles impinge the substrate 101 and crystallize to form a resultant coating with increased crystallinity and density. The integrity of the laminar plasma plume 105 is maintained during the formation of the coating. Additionally, the laminar plasma plume 105 remains in contact with the substrate 101 to ensure that the coating accumulating onto the substrate 101 is sufficiently heated and maintained at a temperature at or above the glass transition temperature of the resultant coating. The resultant coating possesses sufficient crystallinity such that no post-heat treatment or auxiliary heating is required.
A high level block flow diagram representative of the key steps of the of the present invention in one aspect and as described hereinabove with respect to process 100 is shown in
Various improved coatings with increased crystallinity and density can be produced using the techniques of the present invention. For example, in another embodiment of the present invention, it has been found that by using a high enthalpy plasma torch in a laminar flow regime at relatively long standoff distances in comparison to conventional turbulent plasma flow processes (
The laminar plasma plume 105 as utilized by the present invention is created with specific power and thermal heat transfer characteristics favorable for creating the improved coatings, as will now be described with respect to
The laminar plasma plume 105 is defined, at least in part, by a longitudinal length along a longitudinal axis of the laminar plasma plume 105 that extends from the outlet of the cascade torch 102 to the substrate 101. The longitudinal length remains substantially constant during the process 100 and is substantially equal to the standoff distance, which is 3 inches at minimum or greater. The laminar plasma plume 105 can be further characterized as columnar-like in structure as can be seen in
On the contrary, referring to
The characteristics of the laminar plasma plume 105 as created by the present invention collectively contribute to form a localized deposition spot temperature of the heated substrate 101 that is greater than a corresponding localized deposition spot temperature created by a conventional plasma turbulent plasma plume of
While the preferred embodiments of the process have been set forth above, the following examples are intended to provide a basis for comparison of the present invention, with other coating processes, but they are not to be construed as limiting the invention. X-ray diffraction and optical microscopy images of as-sprayed coating cross sections deposited by the present invention were performed and compared to the same for coatings produced by conventional state of the art technology as described in the Examples below.
A conventional turbulent plasma plume as shown in
X-ray diffraction data was obtained on the coating and the results reported in
The optical microscopy images at a magnification 200X of the coating was obtained and is shown at
A laminar plasma plume process as shown in
X-ray diffraction data was obtained on the coating and the results reported in
The optical microscopy images at a magnification of 200X of the coating was obtained and is shown at
While it has been shown and described what is considered to be certain embodiments of the invention, it will, of course, be understood that various modifications and changes in form or detail can readily be made without departing from the spirit and scope of the invention. It is, therefore, intended that this invention is not limited to the exact form and detail herein shown and described, nor to anything less than the whole of the invention herein disclosed and hereinafter claimed.
This application claims the benefit of International Application No. PCT/US2020/050168, filed on Sep. 10, 2020, which claimed the benefit of U.S. Provisional Application Ser. No. 62/899,871, filed on Sep. 13, 2019, which are incorporated herein by reference.
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/US20/50168 | 9/10/2020 | WO |
Number | Date | Country | |
---|---|---|---|
62899871 | Sep 2019 | US |