Patent Application
20200123069
The present disclosure is related generally to ceramic matrix composites (CMCs) and more particularly to a method of processing a CMC component.
Gas turbine engines include a compressor, combustor and turbine in flow series along a common shaft. Compressed air from the compressor is mixed with fuel in the combustor to generate hot combustion gases that rotate the turbine blades and drive the compressor. Improvements in the thrust and efficiency of gas turbine engines are linked to increasing turbine entry temperatures, which places a heavy burden on turbine blades.
Higher temperature requirements have led to the investigation and use of more heat resistant materials, including ceramic matrix composites (CMCs) in general and silicon carbide (SiC)-based CMCs in particular. Besides high temperature capability, CMCs generally exhibit low densities and low coefficients of thermal expansion. In some instances these CMC components may be employed alongside conventional metal (or metal alloy) components. For example, a metallic spar positioned inside a CMC airfoil, such as a CMC vane, may provide mechanical support and cooling air for the airfoil.
A challenge is avoiding potentially detrimental reactions at high temperatures between metallic elements (e.g., nickel and/or cobalt) in the metal component and unreacted elements (such as silicon) in the CMC component. Unreacted silicon remaining in the CMC component after melt infiltration with silicon or a silicon alloy may be referred to as “free” silicon. At high temperatures, the free silicon present in the CMC component may become highly mobile and diffuse into the metal component, leading to the formation of low melting-temperature phases and/or causing other problems.
A method of processing a ceramic matrix composite (CMC) component includes extracting silicon from a surface region of the CMC component such that free silicon is present in the surface region at a reduced amount of about 5 vol. % or less. The extraction comprises contacting the surface region with a wicking medium comprising an element reactive with silicon. The extraction is carried out at an elevated temperature prior to assembling the CMC component with a metal component.
A method of processing a CMC component to reduce diffusion when the CMC component is in contact with a metallic component at elevated temperatures, such as during operation in a gas turbine engine, is described.
Referring to the flow chart of
An assembly comprising the CMC component and a metal component may then be formed 104 where the surface region containing the reduced amount of free silicon is in contact with the metal component, and a metal-CMC interface is created. Due to the reduced amount of free silicon in the surface region, diffusion across the metal-CMC interface is inhibited at elevated temperatures. Thus, unwanted reactions between silicon and metallic elements in the metal component may be minimized or avoided altogether. Preferably, the amount of free silicon in the surface region is reduced to about 2 vol. % or less.
The CMC component may comprise a matrix reinforced with silicon carbide fibers, carbon fibers, alumina fibers, aluminosilicate fibers, and/or other ceramic fibers. The matrix may comprise silicon carbide, silicon nitride, silicon nitrocarbide, and/or other ceramic compounds. Typically, the fibers are silicon carbide fibers and the fiber preform is a silicon carbide fiber preform. A ceramic matrix composite that includes a matrix comprising silicon carbide and fibers comprising silicon carbide may be referred to as a silicon carbide/silicon carbide composite or SiC/SiC composite. As used herein, the term “silicon carbide” may refer broadly to the compound SiC as well as to other silicon-containing carbides.
The surface region subjected to the extraction may extend across all or only a portion of one or more surfaces of the CMC component. The surface region may be understood to extend to a depth into the CMC component of no more than about 125 microns, and in some cases no more than about 75 microns, or even shallower depths (e.g., no more than 25 microns). Depths beyond the surface region may be referred to as the “bulk” of the CMC component and may include higher amounts of free silicon relative to the surface region. For some applications, there may be multiple surface regions from which free silicon is extracted. In this disclosure, descriptions of the “surface region” are understood to apply to any or all of the surface regions of the CMC component from which silicon is extracted.
The wicking medium employed in the extraction may take the form of a porous material such as a felt or a powder that includes the reactive element, which may be, for example, carbon or a refractory metal such as molybdenum, niobium or tungsten. The felt may be fabricated from fibers, such as refractory metal (e.g., tungsten) fibers, carbon fibers, carbon nanotubes, and/or graphite fibers. The powder may comprise particles of any shape, including spherical, irregular, and/or elongated particles. Exemplary powders may comprise carbon black, carbon nanotubes, molybdenum particles, niobium particles, and/or tungsten particles. The CMC component may be partially or fully embedded in the powder to ensure direct contact between the surface region and the powders during extraction. When a felt is employed, the felt may be wrapped around part or all of the CMC component or otherwise secured thereto to ensure direct contact between the surface region and the felt during extraction.
It is preferred that the pore size of the felt is in a range from about about 10 microns to about 100 microns, or from about 10 microns to about 50 microns, which may prevent an excessive wicking rate that can lead to undesired porosity in the bulk of the CMC. Similarly, the particle size of the powder may be less than about 100 microns and is typically at least about 10 microns, such as in a range from about 10 microns to about 50 microns, or from about 10 microns to about 100 microns.
The extraction may be carried out at a temperature in a range from about 1380° C. to about 1450° C., or from about 1380° C. to about 1430° C. The temperature is selected based on the melting temperature of silicon and its alloys. Silicon liquefies at 1414° C., but alloys of silicon may have reduced melting temperatures (e.g., as low as about 1380° C.); thus, extraction of silicon from a CMC that has been melt-infiltrated with a silicon alloy may occur at a somewhat lower temperature. A CMC component, such as a SiC/SiC CMC component, has a much higher temperature resistance and can withstand the extraction without degradation. A time duration for the extraction is typically from about 5 min to about 20 min. The extraction process may be carried out in air or in a controlled environment, such as a vacuum or inert gas atmosphere.
The silicon extraction may result in porosity or roughness within the surface region. While roughness at the surface of the CMC component may be beneficial (e.g., for adhesion of an environmental barrier coating), porosity in the bulk of the CMC is generally undesirable and may detrimentally affect the mechanical properties of the component. Consequently, as mentioned above, it is important to control the extraction rate such that free silicon is removed only from the surface region. In addition to selecting the porosity or particle size of the wicking medium to be within a preferred range, a thin coating of boron nitride (BN) may be applied to the surface of the CMC component prior to extraction. Because the contact angle or wetting angle between boron nitride and silicon is very high, the BN coating may help to reduce the extraction rate and allow for easy removal of the wicking medium after extraction. Typically, the BN coating is applied by spraying to a thickness of 25 microns or less (e.g., from about 1 micron to about 25 microns).
Another option is to process the surface of the fiber preform to minimize the amount of free silicon remaining at the surface after melt infiltration. In such a case, the extraction may be carried out on a modified surface having, at the outset, a reduced amount of free silicon. Accordingly, referring to the flow chart of
The surface modification process 108 may include applying a surface formulation comprising a resin and/or a preceramic polymer to a surface of a fiber preform, preferably a rigidized fiber preform. The surface formulation may have a viscosity low enough to promote flow over the surface, but high enough to prevent excessive penetration into the fiber preform such that, upon melt infiltration, the surface of the CMC component is selectively modified. Preferably, the viscosity of the surface formulation may lie in a range from about 300 cp to about 1000 cp. The surface formulation may be applied to the surface of the fiber preform by brushing, dipping, spraying, or another method.
After application of the surface formulation, a curing step may be carried out to immobilize and/or harden the formulation, thereby forming a surface coating on the preform. The curing may involve heating the surface formulation to an elevated temperature in a range from 150° C. to about 400° C., or exposing the preform to light or a chemical curing agent. Typically, the curing may take place over a time period of about 1 min to about 60 min.
The surface formulation may include other components as needed (e.g., to control viscosity) in addition to the resin and/or the preceramic polymer. The resin may be a high char-yielding resin, such as a phenolic resin, where char yield may be understood to refer to the percent solids (primarily or exclusively carbon) remaining after pyrolysis, as discussed below. The preceramic polymer may comprise an organosilicon polymer and/or an inorganic silicon polymer. For example, the preceramic polymer may comprise polycarbosilane and/or polysiloxane, each of which may be converted to silicon carbide upon heating to a suitable pyrolysis temperature.
After curing, the surface coating may be pyrolyzed to convert the resin to carbon and/or the preceramic polymer to silicon carbide. The pyrolysis may be carried out at a temperature in a range from about 850° C. to about 1300° C. in an ambient (e.g., air) or controlled environment (e.g., vacuum or inert gas). Due to the pyrolysis of the surface coating, the surface of the preform may include a layer of carbon and/or silicon carbide. Upon melt infiltration with silicon or a silicon alloy, the carbon may be converted to silicon carbide, and the silicon carbide already at the surface of the preform may help to prevent any unreacted silicon from access to the surface of the CMC component.
Also or alternatively, it may be advantageous to modify the morphology of the surface of the CMC component to include a number of discrete, raised surface features (“surface bumps”) which limit the extent of contact between the CMC component and the metallic component. The surface bumps include the surface region described above. To produce the raised surface features, the fiber preform may be modified during chemical vapor infiltration (CVI) as described below such that surface bumps are formed upon melt infiltration.
Prior to CVI, a fiber preform having a predetermined shape may be positioned with tooling having holes facing one or more surfaces of the fiber preform. In other words, the fiber preform may be placed adjacent to or in contact with the tooling, which may serve to hold the shape of the fiber preform during deposition of a matrix material, or “rigidization.” As would be known by the skilled artisan, the fiber preform is typically formed in a predetermined geometry (e.g., an airfoil shape) from a stack or arrangement of plies each comprising a woven or nonwoven arrangement of fibers or fiber tows.
Once the fiber preform and the tooling are properly positioned, a sufficient clamping pressure may be applied to the tooling to force portions of the one or more surfaces of the fiber preform into the holes, thereby forming protruded regions of the fiber preform. As the clamping pressure is applied, the fiber preform is exposed to gaseous reagents at an elevated temperature, and the matrix material, such as silicon carbide, is deposited on the fiber preform. This deposition process may be referred to as CVI. The gaseous reagents may be delivered through the holes in the tooling. A rigidized preform including surface protrusions at locations opposite to the holes in the tooling is thus formed.
The tooling may include one or more flow passages in fluid communication with the holes for transport of the gaseous reagents to the fiber preform. In the other words, the fiber preform may be exposed to the gaseous reagents by flowing the gaseous reagents through the one or more flow passages and out the holes. Due to the high temperatures employed during CVI, the tooling may be fabricated from a material such as graphite.
As would be known to the skilled artisan, the gaseous reagents employed in the process may include a reaction precursor and a carrier gas and may depend on the matrix material to be formed. In one example, where the matrix material includes silicon carbide, the gaseous reagents may include methyltrichlorosilane (CH3SiCl3; reaction precursor) and hydrogen gas (H2; carrier gas). During the chemical reaction, methyltrichlorosilane may decompose to form solid SiC and gaseous hydrochloric acid (HCl), the former of which is deposited on the fiber preform while the latter is removed by entrainment in the carrier gas. Other gaseous reagents suitable for forming silicon carbide or other matrix materials may also or alternatively be employed.
The holes may be uniformly spaced apart on a surface of the tooling, or they may have an irregular arrangement. Edges of the holes may be rounded or sloped. Typically, the holes have a width or diameter (“size”) in a range from about 0.1 in (0.25 cm) to about 0.5 in (1.3 cm). Preferably, the holes have a size larger than a width or diameter of the fiber tows to ensure that portions of the fiber preform can be forced into the holes. Also to facilitate formation of the protruded regions, the clamping pressure is typically high enough to force portions of the fiber preform into the holes, but not so high that individual fibers within the fiber tows are damaged. For example, the clamping pressure may lie in a range from about 10 psi (69 kPa) to about 100 psi (690 kPa), or from about 50 psi (345 kPa) to about 100 psi (690 kPa). There may be additional holes in the tooling intended for delivery of the gaseous reagents that are not relied on for formation of the protruded regions. These additional holes may be smaller in width or diameter than the holes used to form the protruded regions. In other words, the additional holes may be smaller than the width or diameter of the fiber tows.
The size (e.g., width or diameter) of the surface bumps formed on the CMC component may be comparable in size or larger than the holes employed in the tooling. An increased size is possible due to the addition of material to the fiber preform (via CVI and melt infiltration) after the initial formation of the protruded regions. The height of the surface bumps is typically at least about 0.015 in (0.04 cm) and may lie in a range from about 0.005 in (0.01 cm) to about 0.03 in (0.08 cm). The surface bumps may include the matrix material and/or portions of the fibers.
Typically, densification to form the final composite is achieved in a melt infiltration step that follows CVI; however, it is possible to achieve densification by depositing a sufficient amount of matrix material during CVI such that a further melt infiltration step is not required. In such a case, the surface protrusions formed as described above via CVI may be understood to be the surface bumps of the CMC component.
In one example, the metal component is a metallic spar and the CMC component is a CMC airfoil (e.g., a vane for a gas turbine engine) formed with internal surface bumps. The metallic spar may provide mechanical support to the CMC vane and feed cooling air to an internal surface of the CMC vane. In this case, the predetermined shape of the fiber preform is an airfoil shape, and the fiber preform comprises an internal cavity. The tooling includes internal tooling positioned within the internal cavity and external tooling placed external to the fiber preform, where the internal tooling comprises holes facing internal surfaces of the fiber preform. A clamping force sufficient to force portions of the internal surfaces of the fiber preform into the holes is applied, thereby forming internal protruded regions of the fiber preform. During the application of the clamping force, the fiber preform is exposed to gaseous reagents at an elevated temperature, and a matrix material is deposited on the fiber preform to form a rigidized preform. The external tooling may include the additional holes mentioned above that are employed for delivery of the gaseous reagents and not relied on for formation of the protruded regions.
After CVI, the internal and external tooling is removed, and the rigidized preform may be infiltrated with a melt for densification. Typically, a slurry infiltration step precedes melt infiltration, as is known in the art. Thus, a CMC airfoil including internal surface bumps is formed. When an assembly is formed from the CMC airfoil (e.g., a vane) and the metallic spar, only the internal surface bumps of the CMC airfoil are in contact with the metallic spar. Thus, diffusion of free silicon from the CMC airfoil to the metallic spar at elevated temperatures, such as during operation of a gas turbine engine, may be diminished or avoided altogether.
Another means of minimizing diffusion across the CMC-metal interface may comprise, prior to forming the assembly, depositing an isolation layer or diffusion barrier comprising a material non-reactive with silicon on the metal component. For example, the isolation layer may comprise an aluminide such as CoAl. Any residual silicon in the surface region not removed by the approaches described above may be prevented by the isolation layer from reacting with the metal component during high temperature exposure.
The method of processing a CMC component described herein may further comprise other conventional steps in CMC fabrication, such as laying up of plies to form a fiber preform having a predetermined shape, and/or application of a fiber interphase coating such as boron nitride to the fiber preform prior to rigidization. A rigidized fiber preform may be formed by applying a matrix material to the fiber preform during a CVI process. The rigidized fiber preform may be infiltrated with a slurry comprising silicon carbide particles in a liquid carrier into the SiC fiber preform. The slurry may further include reactive elements such as carbon that can react with the molten silicon or silicon alloy during melt infiltration, thereby reducing free silicon in the bulk of the CMC component.
To clarify the use of and to hereby provide notice to the public, the phrases “at least one of <A>, <B>, . . . and <N>” or “at least one of <A>, <B>, . . . <N>, or combinations thereof” or “<A>, <B>, . . . and/or <N>” are defined by the Applicant in the broadest sense, superseding any other implied definitions hereinbefore or hereinafter unless expressly asserted by the Applicant to the contrary, to mean one or more elements selected from the group comprising A, B, . . . and N. In other words, the phrases mean any combination of one or more of the elements A, B, . . . or N including any one element alone or the one element in combination with one or more of the other elements which may also include, in combination, additional elements not listed.
Although considerable detail with reference to certain embodiments has been described, other embodiments are possible. The spirit and scope of the appended claims should not be limited, therefore, to the description of the preferred embodiments contained herein. All embodiments that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.
Furthermore, the advantages described above are not necessarily the only advantages, and it is not necessarily expected that all of the described advantages will be achieved with every embodiment.
