Patent Description:
Ceramic matrix composites (CMCs) generally include a ceramic fiber reinforcement material embedded in a ceramic matrix material. The reinforcement material serves as the load-bearing constituent of the CMC in the event of a matrix crack, while the ceramic matrix protects the reinforcement material, maintains the orientation of its fibers, and serves to dissipate loads to the reinforcement material. Of particular interest to high-temperature applications, such as in gas turbines, are silicon-based composites, which include silicon carbide (SiC) as the matrix and/or reinforcement material.

Different processing methods have been employed in forming CMCs. For example, one approach includes chemical vapor infiltration (CVI). CVI is a process whereby a matrix material is infiltrated into a fibrous preform by the use of reactive gases at elevated temperature to form the fiber-reinforced composite. For example, conventional cloth based CMCs formed by CVI typically have a porosity between <NUM> percent and <NUM> percent, a fiber volume fraction between <NUM> percent and <NUM> percent, and an interlaminar tensile (ILT) strength between <NUM> MPa to <NUM>. 7MPa, i.e. between <NUM> ksi and <NUM> ksi, as measured by a standard <NUM> i.e. <NUM> inch diameter button pull test. CVI composite matrices typically have no free silicon phase, and thus have good creep resistance and the potential to operate at temperatures above <NUM> degrees Celsius i.e. <NUM>,<NUM> degrees Fahrenheit.

Another approach includes melt infiltration (MI), which employs molten silicon to infiltrate into a fiber-containing preform. For example, conventional unidirectional tape-based CMCs formed by MI typically have a porosity of below <NUM> percent, a fiber volume fraction between <NUM> percent and <NUM> percent, and an interlaminar tensile (ILT) strength between <NUM> MPa and <NUM> MPa (<NUM> ksi and <NUM> ksi). The matrix of MI composites contains a free silicon phase (i.e. elemental silicon or silicon alloy) that limits use of the CMC to below that of the melting point of the silicon or silicon alloy, or about <NUM> to <NUM> degrees Celsius (<NUM>,<NUM> degrees Fahrenheit to <NUM>,<NUM> degrees Fahrenheit). Moreover, the free silicon phase causes the MI SiC matrix to have relatively poor creep resistance.

Another approach employs a partial CVI process followed by an MI process, and is generally referred to as "slurry cast MI. " This approach usually yields an intermediate porosity between that of MI composites and CVI composites, generally of about <NUM> percent, a fiber volume fraction between <NUM> percent and <NUM> percent, an interlaminar tensile (ILT) strength between <NUM> MPa and <NUM> MPa (<NUM> ksi and <NUM> ksi), and also contains residual free silicon phase within the composite matrix. <CIT> discloses a process for manufacturing composite and laminates reinforced with continuous or long fibres for use as gas turbine components.

In a first aspect, there is provided a method according to claim <NUM>. In a second aspect, there is provided a method according to claim <NUM>. In a third aspect, there is provided a ceramic matrix composite article according to claim <NUM>.

The foregoing and other features, aspects and advantages of this disclosure will become apparent from the following detailed description of the various aspects of the disclosure taken in conjunction with the accompanying drawings, wherein:.

<FIG> illustrates a portion of a ceramic matrix composite (CMC) article <NUM> according to an embodiment of the present disclosure. CMC article <NUM> may include a ceramic fiber reinforcement material in a ceramic matrix material. As described in greater detail below, CMC article <NUM> is formed by a process resulting in CMC article <NUM> having a plurality of unidirectional arrays of fiber tows <NUM>, and a densified matrix <NUM>. Such a CMC article may be tailored to have improved properties such as, but not limited to, mechanical properties (e.g., interlaminar (ITL) strength and proportional limit (PL)), and oxidation resistance.

As further described below, for example, pre-coated fiber tows, prepregging, ply layup, consolidation, and burnout may result in a cured preform for subsequent densification. A slurry may be used during prepregging, having for example a matrix precursor along with particulate fillers and pore formers such as polymeric pore formers to adjust the fiber spacing and pore size distribution and give a free-standing preform for CVI densification. After curing of the preform, e.g., pyrolysis of the matrix precursor and burnout of the pore formers, the cured preform can be densified using CVI alone, using a combination of a partial CVI followed by melt infiltration with silicon, silicon alloy or an oxide, such as rare-earth disilicates (RE<NUM>Si<NUM>O<NUM>), or using slurry infiltration prior to melt infiltration. Advantages of using tow-based unidirectional ply preforms may give more uniform pore structure for densification resulting in a more uniform CMC microstructure. Touching of fibers and continuous coatings may be eliminated, thereby improving mechanical properties and oxidation resistance of a CMC article. Such a technique of the present disclosure may be advantageous for application to silicon-bearing ceramic turbine components, for example, turbine blades, vanes, nozzles, shrouds, combustors, etc., and repairs thereof.

<FIG> illustrates a method <NUM> for forming ceramic matrix composite article <NUM> (<FIG>) in accordance with an embodiment of the present disclosure. In this exemplary embodiment, method <NUM> generally includes, at <NUM>, providing a shaped preform comprising a prepreg tape layup of unidirectional arrays of fiber tows, a matrix precursor, and a pore former, at <NUM> curing the shaped preform to pyrolyze the matrix precursor and burnout the pore former so that the shaped preform comprises the unidirectional arrays of fiber tows and a porous matrix skeleton having a monomodal pore size distribution, and at <NUM> subjecting the cured shaped preform to chemical vapor infiltration to densify the porous matrix skeleton so that the ceramic matrix composite article has a fiber volume fraction between <NUM> percent and <NUM> percent.

<FIG> illustrates an uncured shaped preform <NUM> fabricated from a plurality of prepreg layers <NUM> in the form of tape-like structures unidirectionally-aligned tows impregnated with a slurry <NUM> to create a generally two-dimensional laminate. The prepreg may be formed form, for example, a reinforcement material of a desired CMC and a slurry, which slurry may include a matrix precursor, a pore formers, particulate fillers, and a carrier, as described below. The slurry can be roll milled to deagglomerate and disperse the powders. The slurry can be infiltrated into the coated tows by passing the tows through a bath of the slurry. The tow can then be wound onto a drum and may include partial drying of the slurry such that a tape is formed. The tape can be removed from the drum and unidirectional preform plies can be cut to form the tape.

Materials for the tows may include silicon carbide (SiC) fibers, polycrystalline SiC fibers, or other suitable fiber. An example of a material suitable for the tows is HI-NICALON® from NGS Advanced Fibers Co. A suitable range for the diameters of the fibers is about five to about twenty micrometers, though fibers with larger and smaller diameters are also within the scope of this disclosure. The fibers may be preferably coated with materials such as a carbon or boron nitride interface layer (not shown) to impart certain desired properties to the CMC article, e.g., allows slippage between coating and the formed matrix material of the CMC article. A fiber tow, for example, may be a single bundle of about <NUM> individual fibers.

The slurry may include a matrix precursor such as organic or inorganic material that leaves char/residue after burnout such as pyrolysis or firing. In some embodiments, the matrix precursor may include a silicon containing precursor operable, as described below, for forming a porous silicon containing precursor such as silicon carbide in the cured preform. Examples of a matrix precursor include tetraethyl orthosilicate (TEOS), polycarbosilanes, polysilazanes, polysiloxanes, phenolics, and furanic compounds. A pore former may include a particle or other species that can remain present through a consolidation process but can be fugitive in the burnout or pyrolysis process resulting in a pore. Examples of a pore former can comprise polyethylene, polypropylene, polyamide, nylon, polytetrafluoroethylene (PTFE), polystyrene, polyvinyl acetate, polyvinyl alcohol, and/or cellulosic powders. Fillers may include an oxide or non-oxide particle or whisker that helps control shrinkage. Examples of a filler include SiC, B<NUM>C, SiO<NUM>, HfC, HfB<NUM>, ZrC, ZrB<NUM>, MoSi<NUM>, Si<NUM>N<NUM>, Al<NUM>O<NUM>, rare earth silicates, and rare earth silicides. A carrier may include organic or inorganic liquid that dissolves or carries the matrix precursor and other ingredients. Examples of a carrier include water, isopropanol, toluene, and acetone.

The particles included in the pore former include a monomodal particle size distribution for a collection of particles which have a single clearly discernable maxima on a particle size distribution curve as compared to a collection of particles having a bimodal particle size distribution having two clearly discernable maxima on a particle size distribution curve, or a for a collection of particles having a multimodal particle size distribution of three or more clearly discernable maxima on a particle size distribution curve. The particles included in a pore former include a median size in the range of from <NUM> micrometer to <NUM> micrometers, may include a median size in the range of from about <NUM> micrometer to about <NUM> micrometers, may include a median size in the range of from about <NUM> micrometer to about <NUM> micrometers, and/or may include a median size in the range of from about <NUM> micrometers to about <NUM> micrometers. Prior to passing the tows through a bath of the slurry, the slurry including the matrix precursor, the pore formers, the particulate fillers, and the carrier may be combined and mixed until a uniform mixture is obtained with the pore formers having a uniform spacial distribution.

The plurality of plies of the resulting prepregs are laid-up or stacked into a desired pattern and shape, and typically arranged so that tows of the prepreg layers are oriented parallel, transverse (e.g., perpendicular), or at an angle relative to other tows of the prepreg layers in other plies. The plurality of layers may typically undergo consolidation or debulking while subjected to applied pressure and an elevated temperature, such as in a vacuum or in and autoclave or localized application of pressure and heat.

The consolidated plurality of stacked plies is subjected to burnout such as pyrolysis or heated in vacuum or in an inert or a reactive atmosphere in order to decompose the matrix precursor, to form a ceramic or ceramic char, and where the pore former is, for example, volatilized, and produces a porous preform for chemical vapor infiltration, resulting in cured preform <NUM> illustrated in <FIG>. The resulting porosity of precursor matrix has a predominantly monomodal pore size distribution and predominantly uniform spacial distribution. For example, the local maxima in the pore size distribution of the cured porous silicon-containing precursor is between about <NUM> micrometer to about <NUM> micrometers, about <NUM> micrometers to about <NUM> micrometers, about <NUM> micrometer to about <NUM> micrometers, and/or about <NUM> micrometers to about <NUM> micrometers. The cured preform may have a volume porosity of about <NUM> percent to about <NUM> percent.

The cured preform is then subject to chemical vapor infiltration, such as with a gaseous source of silicon carbide supplied externally. The gaseous silicon carbide source infiltrates into the porosity, reacts to deposit SiC on the internal pore surfaces of the porous layer to form a densified silicon carbide matrix of CMC article <NUM> as shown in <FIG>, and may contain no free Si metal. An appropriate chemical vapor infiltration gas may include methyl-trichlorosilane, dimethyl-dichlorosilane, silane + methane, tetrachlorosilane + methane, and other suitable gases.

The resulting porosity of CMC article <NUM> has a monomodal pore size distribution. The median pore size of the CVI-densified CMC article is <NUM> micrometers to <NUM> micrometers, or <NUM> micrometers to about <NUM> micrometers. CMC article <NUM> may have a volume porosity of about <NUM> percent to about <NUM> percent. The CMC article may have a uniform spacial distributed fiber volume percentage. For example, the CMC article may have a fiber volume of between about <NUM> percent and about <NUM> percent. In other embodiments, a CMC article may be tailored to have different fiber volume throughout the CMC based on the layup and tape prepregs. For example, CMC article may include at least one first portion having a first fiber volume percentage and at least one second portion having a second fiber volume percentage different from said first fiber volume percentage.

Those skilled in the art will appreciate that the teachings of this disclosure are also applicable to other CMC material combinations, and that such combinations are within the scope of this disclosure. Suitable materials for use in the chemical vapor infiltration process may include silicon carbide, silicon nitride, silicon oxynitride, silicon oxy-carbide, silicon dioxide, aluminum nitride, aluminum oxide, boron carbide, zirconium carbide, hafnium carbide, zirconium diboride, hafnium diboride, molybdenum silicides, and other suitable material.

Testing of CMC articles formed in accordance with the technique of the present disclosure, including monomodal pore size distribution, showed interlaminar tensile (ILT) strength values of <NUM> to <NUM> ksi (<NUM> to <NUM> MPa) for CMCs with <NUM>/<NUM> architecture and a fiber volume fraction of about <NUM> percent ([<NUM>:<NUM>]<NUM> architecture, <NUM>" thick) to <NUM> percent ([<NUM>:<NUM>]<NUM> architecture, <NUM>" thick), which are significantly higher than the ILT values for conventional CVI composites made from woven fibers, and are comparable to, or better than, typical values for MI-type ceramic composites.

<FIG> shows a schematic representation of the microstructure of a conventional CVI composite preform made with woven fibers. The cross-over of the fiber tows in the weave pattern tend to compress the tows into tight bundles. Also, due to the surface roughness of the woven fiber cloth, the fiber plies tend to pack inefficiently. The microstructure of the conventional CVI preform thus has two distinct types of porosity; the first being the small inter-fiber pores within the fiber tows, and the second being the larger inter-tow pores caused by the weaving pattern and the dis-registry of this pattern at the ply boundaries.

<FIG> shows an idealized representation of the pore size distributions for CVI preforms and final densified composites made using the conventional woven fiber-based CVI approach and by the technique of the present disclosure. The two populations of pores illustrated in <FIG> and described in the previous paragraph lead to a bimodal or multimodal pores size distribution for the conventional woven fiber CVI preforms. By using the process outlined in the current invention, and described in <FIG>, a preform microstructure as shown in <FIG> is obtained, which has a monomodal pore size distribution. Following densification via CVI or a combination of CVI and MI processes, the amount of porosity is reduced and the means of the peaks in the pore size distributions may be shifted, but the multimodal or monomodal nature of the distributions is retained. It is the larger pores, e.g. above <NUM> micrometers in size, that are primarily responsible for limiting the interlaminar tensile strength and proportional limit strength of conventional cloth-based CVI composites. Composites made by the present disclosure eliminate, or minimize, the amount of this undesirable large porosity, resulting in the improved interlaminar tensile strengths cited.

The present inventors' work indicates that, for a specimen of constant thickness, the interlaminar tensile (ILT) strength is inversely related to the fiber volume fraction, as long as the fibers remain homogenously dispersed within the matrix and as long as the porosity remains predominantly monomodal. On the other hand, the ultimate tensile strength (UTS) and the proportional limit (PL) are directly related to the fiber volume fraction.

Therefore, an optimum balance of properties for a specific application may include CMC articles in accordance with the present disclosure having fiber volumes of <NUM> percent to <NUM> percent compared to fiber volumes of <NUM> percent to <NUM> percent normally used for conventional CVI composites. In some embodiments as noted above, portions of a ceramic matrix composite article may have different of fiber volume percentages based on the desired properties of the different portions of the ceramic matrix composite article. For example, some ceramic matrix composite articles may have portions or regions that have a lower fiber volume percentage compared to other portions or regions that have a higher fiber volume percentage.

<FIG> illustrates a method <NUM> for forming ceramic matrix composite articles in accordance with an embodiment of the present disclosure. In this exemplary embodiment, method <NUM> generally includes, at <NUM> coating fiber tows, at <NUM> prepregging the tows to form prepreg tape, and at <NUM> cutting the prepreg tape and laying up an uncured preform for forming the article. At <NUM>, the preform is consolidated such as in an autoclave under heat and pressure. At <NUM>, the preform is subject to a burn-out process so that, for example, the resulting preform has a monomodal pore size distribution. At <NUM>, the cured perform is subjected to chemical vapor infiltration to densify the cured preform to form a finished ceramic matrix composite articles at <NUM>. A ceramic matrix composite articles formed by method <NUM> may have an optimized range of interlaminar (ILT) strength and proportional limit (PL) with a fiber volume of between <NUM> percent and <NUM> percent, and a volume porosity of about <NUM> percent to about <NUM> percent. The ceramic matrix of the ceramic matrix composite may have a monomodal pore size distribution with a median pore size of about <NUM> micrometer to about <NUM> micrometers. The ceramic matrix of the ceramic matrix composite may have a uniform spacial pore distribution. Such a ceramic matrix composite article may be advantageous for application to silicon-bearing ceramic turbine components, for example, turbine blades, vanes, nozzles, shrouds, combustors, etc., and repairs thereof.

In the chemical vapor infiltration (CVI) process, a matrix material such as silicon carbide is infiltrated into a fibrous preform by the use of reactive gases at elevated temperature. Generally, limitations introduced by having reactants diffuse into the preform and by-product gases diffusing out of the perform result in relatively high residual porosity of between about <NUM> percent and about <NUM> percent in the composite. In the forming of the CMCs using CVI, the inner portion of the composite formed by CVI typically has a higher porosity than the porosity of the outer portion. The CVI composite matrices typically have no free silicon phase, good creep resistance and the potential to operate at temperatures above <NUM> degrees Celsius, i.e. <NUM>,<NUM> degrees Fahrenheit.

<FIG> illustrates a method <NUM> for forming ceramic matrix composite articles in accordance with an embodiment of the present disclosure. In this exemplary embodiment, method <NUM> generally includes, at <NUM> coating fiber tows, at <NUM> prepregging the tows to form prepreg tape, and at <NUM> cutting the prepreg tape and laying up an uncured preform for forming the article. At <NUM>, the preform is consolidated such as in an autoclave under heat and pressure. At <NUM>, the preform is subject to a burn-out process so that, for example, the preform matrix has a monomodal pore size distribution. At <NUM>, the cured perform is subjected to a chemical vapor infiltration to densify the cured preform resulting in a volume porosity of about <NUM> percent to about <NUM> percent. Further densification may occur at <NUM> with melt infiltration process to form a finished ceramic matrix composite articles at <NUM>. The melt infiltration may include silicon, silicon alloy, a silicide, an oxide, or a combination thereof. In method <NUM>, the step of chemical vapor infiltration may be a partial or full chemical vapor infiltration compared to the chemical vapor infiltration process of method <NUM> (<FIG>). A ceramic matrix composite articles formed by method <NUM> may have a volume porosity of less than about <NUM> percent. The ceramic matrix of the ceramic matrix composite may have a monomodal pore size distribution with a median pore size of about <NUM> micrometers to about <NUM> micrometers. The ceramic matrix of the ceramic matrix composite may have a uniform spacial pore distribution. Such a ceramic matrix composite article may be advantageous for application to silicon-bearing ceramic turbine components, for example, turbine blades, vanes, nozzles, shrouds, combustors, etc., and repairs thereof.

<FIG> illustrates a method <NUM> for forming ceramic matrix composite articles in accordance with an embodiment of the present disclosure. In this exemplary embodiment, method <NUM> generally includes, at <NUM> coating fiber tows, at <NUM> prepregging the tows to form prepreg tape, and at <NUM> cutting the prepreg tape and laying up an uncured preform for forming the article. At <NUM>, the preform is consolidated such as in an autoclave under heat and pressure. At <NUM>, the preform is subject to a burn-out process so that, for example, the preform matrix has a monomodal pore size distribution. At <NUM>, the cured perform is subjected to chemical vapor infiltration to densify the cured preform. Further, densification may be occur at <NUM> by application of a slurry cast followed at <NUM> by melt infiltration to form a finished ceramic matrix composite articles at <NUM>. The slurry cast may include silicon carbide, silicon nitride, molybdenum silicides, boron carbide, HfC, ZrC, HfB2, ZrB2, rare earth silicates, and the melt infiltration may include silicon, silicon alloys, silicides, oxide, or combinations thereof. A ceramic matrix composite articles formed by method <NUM> may have a volume porosity of less than about <NUM> percent. The ceramic matrix of the ceramic matrix composite has a monomodal pore size distribution with a median pore size of <NUM> micrometers to <NUM> micrometers. The ceramic matrix of the ceramic matrix composite may have a uniform spacial pore distribution. Such a ceramic matrix composite article may be advantageous for application to silicon-bearing ceramic turbine components, for example, turbine blades, vanes, nozzles, shrouds, combustors, etc., and repairs thereof.

The further densification in methods <NUM> and <NUM> using melt infiltration may result in ceramic matrix composite articles that are fully dense, e.g., having generally zero, or less than about <NUM> or less that about <NUM> percent by volume residual porosity. This very low porosity gives the composite desirable mechanical properties, such as a high proportional limit strength and interlaminar tensile and shear strengths, high thermal conductivity and good oxidation resistance. The matrices may have a free silicon phase (i.e. elemental silicon or silicon alloy) that may limits the use temperature of the ceramic matrix composite articles to below that of the melting point of the silicon or silicon alloy, or about <NUM> to <NUM> degrees Celsius, i.e. about <NUM>,<NUM> degrees Fahrenheit to <NUM>,<NUM> degrees Fahrenheit. The free silicon phase may result in a lower creep resistance compared to densification solely by chemical vapor infiltration.

It is to be understood that the above description is intended to be illustrative, and not restrictive. For example, the above-described embodiments (and/or aspects thereof) may be used in combination with each other. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the various embodiments without departing from their scope. While the dimensions and types of materials described herein are intended to define the parameters of the various embodiments, they are by no means limiting and are merely exemplary. Many other embodiments will be apparent to those of skill in the art upon reviewing the above description. The scope of the various embodiments should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. In the appended claims, the terms "including" and "in which" are used as the plain-English equivalents of the respective terms "comprising" and "wherein. " Moreover, in the following claims, the terms "first," "second," and "third," etc. are used merely as labels, and are not intended to impose numerical requirements on their objects. Also, the term "operably" in conjunction with terms such as coupled, connected, joined, sealed or the like is used herein to refer to both connections resulting from separate, distinct components being directly or indirectly coupled and components being integrally formed (i.e., one-piece, integral or monolithic).

While the disclosure has been described in detail in connection with only a limited number of embodiments, it should be readily understood that the disclosure is not limited to such disclosed embodiments. Additionally, while various embodiments have been described, it is to be understood that aspects of the disclosure may include only some of the described embodiments. Accordingly, the disclosure is not to be seen as limited by the foregoing description, but is only limited by the scope of the appended claims.

Claim 1:
A method (<NUM>) for forming a ceramic matrix composite article (<NUM>), the method (<NUM>) comprising:
providing (<NUM>) a shaped preform comprising a prepreg tape layup of unidirectional arrays of fiber tows (<NUM>), a matrix precursor, and a pore former, wherein the pore former includes particles having a monomodal particle size distribution with a median size in a range of <NUM> micrometer to <NUM> micrometers;
curing (<NUM>) the shaped preform to pyrolyze the matrix precursor and burnout the pore former so that the shaped preform comprises the unidirectional arrays of fiber tows (<NUM>) and a porous matrix skeleton having a monomodal pore size distribution, wherein a median of the monomodal pore size distribution of the cured preform is between <NUM> micrometers and <NUM> micrometers; and
subjecting (<NUM>) the cured shaped preform to chemical vapor infiltration to densify the porous matrix skeleton so that the ceramic matrix composite article (<NUM>) has a fiber volume fraction between <NUM> percent and <NUM> percent and a matrix having a monomodal pore size distribution with a median pore size of <NUM> micrometer to <NUM> micrometers.