Oxidation-resistant fiber coatings and related methods

Abstract

A method of manufacturing a coated reinforcing fiber for use in Ceramic Matrix Composites, the method comprising pre-oxidizing a plurality of silicon-based fibers selected from the group consisting of silicon carbide (SiC) fibers, silicon nitride (Si.sub.3N.sub.4) fibers, SiCO fibers, SiCN fibers, SiCNO fibers, and SiBCN fibers at between 700 to 1300 degrees Celsius in an oxidizing atmosphere to form a silica surface layer on the plurality of silicon-based fibers, forming a plurality of pre-oxidized fibers; applying a rare earth orthophosphate (REPO.sub.4) coating to the plurality of pre-oxidized fibers; and heating the plurality of REPO.sub.4 coated pre-oxidized fibers at about 1000-1500 degrees Celsius in an inert atmosphere to react the REPO.sub.4 with the silica surface layer to form a rare earth silicate or disilicate. The pre-oxidizing step may be 0.5 hours to about 100 hours. The heating step may be about 5 minutes to about 100 hours.

Claims

1. A method of manufacturing a coated reinforcing fiber for use in Ceramic Matrix Composites, the method comprising: pre-oxidizing a plurality of silicon-based fibers selected from the group consisting of SiCO fibers, SiCN fibers, SiCNO fibers, and SiBCN fibers at between 700 to 1300 degrees Celsius from between about in an oxidizing atmosphere to form a silica surface layer on the plurality of silicon-based fibers, forming a plurality of pre-oxidized fibers; applying a rare earth orthophosphate (REPO.sub.4) coating to the plurality of pre-oxidized fibers; and heating the plurality of REPO.sub.4 coated pre-oxidized fibers at about 1000-1500 degrees Celsius in an inert atmosphere to react the REPO.sub.4 with the silica surface layer to form a rare earth silicate, wherein the rare earth orthophosphate (REPO.sub.4) is selected from the group consisting of YPO.sub.4, ScPO.sub.4, CePO.sub.4, PrPO.sub.4, NdPO.sub.4, PmPO.sub.4, SmPO.sub.4, EuPO.sub.4, GdPO.sub.4, TbPO.sub.4, DyPO.sub.4, HoPO.sub.4, ErPO.sub.4, TmPO.sub.4, YbPO.sub.4, and LuPO.sub.4, or combinations thereof.

2. The method of claim 1, wherein the step of pre-oxidizing the plurality of fibers is from about 5 to 100 hours in one or more of atmospheric air, oxygen, water vapor, oxygen plasma, and CO.sub.2 gas.

3. The method of claim 1, wherein the step of applying a REPO.sub.4 coating is performed with one of a solution derived method, CVD, and PVD.

4. The method of claim 1, wherein a plurality of filaments is arranged in bundles of about 500 to about 5000 filaments.

5. The method of claim 4, wherein the bundles comprise a woven cloth or integrally woven preform.

6. The method of claim 1, wherein the REPO.sub.4 coating is about 50 nm to 5000 nm thick.

7. A method of manufacturing Ceramic Matrix Composites with an in-situ rare earth silicate-coated reinforcing fiber, the method comprising: pre-oxidizing a plurality of fibers, wherein the fibers are selected from the group consisting of SiCO fibers, SiCN fibers, SiCNO fibers, SiBCN fibers; coating the plurality of pre-oxidized fibers with a rare earth orthophosphate (REPO.sub.4), wherein the rare earth orthophosphate (REPO.sub.4) is selected from the group consisting of YPO.sub.4, ScPO.sub.4, CePO.sub.4, PrPO.sub.4, NdPO.sub.4, PmPO.sub.4, SmPO.sub.4, EuPO.sub.4, GdPO.sub.4, TbPO.sub.4, DyPO.sub.4, HoPO.sub.4, ErPO.sub.4, TmPO.sub.4, YbPO.sub.4, and LuPO.sub.4, or combinations thereof; forming a fiber tow, or fiber cloth preform with the REPO.sub.4 coated fibers; infiltrating the preform with a preceramic precursor with filler particles to form a Ceramic Matrix Composite; curing and pyrolizing the ceramic matrix composite; repeating the coating, infiltrating, curing and pyrolizing steps to increase ceramic matrix composite density; performing a heat treatment of the ceramic matrix composite in an inert environment of nitrogen or argon at about 1000-1500 degrees Celsius for about 5 minutes to about 100 hours to convert the REPO.sub.4 coatings on the fibers to rare earth disilicate coatings.

8. The method of claim 7, wherein the step of pre-oxidizing the plurality of fibers is from about 5 to 100 hours in one or more of atmospheric air, oxygen, water vapor, oxygen plasma, and CO.sub.2 gas.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the present invention and, together with a general description of the invention given above, and the detailed description of the embodiments given below, serve to explain the principles of the present invention.

(2) FIG. 1 presents a Scanning Electron Microscope micrograph of coated Nextel 610 (alumina) oxide fiber tows coated 5 times with LaPO.sub.4 using solution precursor method.

(3) FIGS. 2A-2B present Transmission Electron Microscope (TEM) micrographs of Nextel 720 (alumina-mullite) oxide fibers with LaPO.sub.4 (FIG. 2A) and CePO.sub.4 (FIG. 2B) coatings produced using the colloidal hydrated REPO.sub.4.Math.H.sub.2O sol method.

(4) FIGS. 3A-3B present TEM micrographs of Nextel 720 fibers with LaPO.sub.4 coatings produced using the colloidal hydrated LaPO.sub.4.Math.H.sub.2O (rhabdophane) sol method. FIG. 3A: 1 coat; FIG. 3B: 2 coats. Good control of the resulting LaPO.sub.4 coating thickness is demonstrated.

(5) FIG. 4 presents a TEM micrograph of a Nextel 720 fiber with (Y.sub.0.7La.sub.0.3)PO.sub.4 coating produced using mixed La—Y colloidal hydrated sols. The flexibility of the process in controlling the chemistry of the resulting REPO.sub.4 fiber coatings demonstrated. The composition was tailored to match the coefficient of thermal expansion of the coating to that of the fiber.

(6) FIGS. 5A-5E present examples of good control over the coating composition. Here SEM micrographs (FIGS. 5A-D) and EDS spectra (FIG. 5E) of (Gd.sub.0.4Dy.sub.0.6)PO.sub.4-coated Saphikon™ sapphire fiber are shown. The composition was tailored to take advantage of the xenotime-monazite phase transformation to achieve better coating compliance through transformation plasticity. The reaction to (Gd,Dy).sub.3Al.sub.5O.sub.12 garnet at the coating fiber interface is evident in the SEM micrograph FIG. 5C and the EDS spectrum in FIG. 5E.

(7) FIGS. 6A-6B are TEM micrographs depicting oxidized Tyranno SA SiC fiber with LaPO.sub.4 coating deposited using colloidal hydrated sol method (FIG. 6A) and the transformation of LaPO.sub.4 to La.sub.2Si.sub.2O.sub.7 after heat treatment in Ar at 1200 C. for 10 h (FIG. 6B).

(8) FIGS. 7A-7D show SEM micrographs of RE.sub.2Si.sub.2O.sub.7 coatings on SCS-0 SiC fibers: (FIGS. 7A, 7B) Y.sub.2Si.sub.2O.sub.7, 10 coats; (FIGS. 7C, 7D) Ho.sub.2Si.sub.2O.sub.7, 20 coats.

(9) FIGS. 8A-8B show SEM micrograph of silica fibers coated with YPO.sub.4 (6 coats) using the solution precursor method (FIG. 8A) and the x-ray diffraction spectrum demonstrating the conversion of YPO.sub.4 coating to Y.sub.2Si.sub.2O.sub.7 after heat treatment in argon at 1200° C. for 20 h (FIG. 8B).

(10) FIGS. 9A-9F compare the performance of uncoated fibers with two varieties of coated fibers in accordance with embodiments of the disclosed invention.

(11) FIGS. 10A-10E depict a portion of fiber reinforced SiC minicomposite and the thin silica film between the coated-fiber interface in accordance with embodiments of the disclosed invention.

(12) FIG. 11 presents normalized tensile strength of SiC/SiC composites with BN (BN) and Y.sub.2Si.sub.2O.sub.7 interface (Y.sub.2Si.sub.2O.sub.7) after oxidation in steam at 1000° C.

(13) It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific design features of the sequence of operations as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes of various illustrated components, will be determined in part by the particular intended application and use environment. Certain features of the illustrated embodiments have been enlarged or distorted relative to others to facilitate visualization and clear understanding. In particular, thin features may be thickened, for example, for clarity or illustration.

DETAILED DESCRIPTION OF THE INVENTION

(14) Ceramic materials are of interest for high temperature applications but are inherently brittle and may fail in a catastrophic manner. A known technique to improve the mechanical properties of ceramics includes reinforcement with high strength fibers to form CMCs. In order to realize the full benefits of fiber reinforcement, the matrix must transfer load to the fibers but become decoupled during fracture so that fibers remain intact and continue to bear a load. In SiC/SiC composites, the load transfer capabilities may be enhanced through boron nitride (BN) and carbon (C) fiber coatings.

(15) Generally, the fiber coating must be chemically and mechanically stable at high temperature in oxygenated environments. The coating must deflect cracks to maintain composite damage tolerance. While the aforementioned C and BN provide the requisite enhancement of physical properties, they are not oxidation resistant. This restricts the use of current SiC/SiC CMCs because they do not have adequate oxidation resistance at elevated temperatures (especially in the presence of water vapor). These limitations result in the degradation of the strength and toughness of SiC/SiC CMCs with C or BN interfaces after being exposed to an oxidizing operating environment.

(16) Such oxidation of fiber coatings is a major problem that has limited the widespread use of SiC/SiC composites. In use, the fiber coating becomes exposed to oxidizing environments when the ends of coated fibers are exposed to the surrounding oxygenated atmosphere. Also, when composite stress is above the proportional limit, the matrix cracks, allowing atmospheric oxygen to reach the fiber coatings. Both C and BN are prone to oxidation. Oxidation of carbon results in the formation of CO and CO.sub.2. This leaves a void between the fiber and the matrix, thus exposing the fiber side and the adjacent matrix to oxidation. This subsequently produce SiO.sub.2, which closes the gap between the fiber and the matrix. As a result, the matrix bonds strongly to the fibers, thus causing the composite to lose its damage tolerance. While the BN oxidation rate in dry air or oxygen is slower than carbon oxidation, in wet environments the oxidation rate of BN coatings is similar to carbon. Depending on temperature, the oxidation of BN results in the loss of BN, and the oxidation product (B.sub.2O.sub.3) volatilizes, leaving a gap. Subsequent formation of SiO.sub.2 at the interface causes the composite to lose its damage tolerance.

(17) To overcome these problems, the disclosure that follows will outline embodiments of a rare earth disilicate fiber coating, and related methods, for use with CMCs. The novel coating has been demonstrated to yield beneficial oxidation resistance, as compared to CMCs utilizing uncoated fibers or BN- and C-coated fibers. The addition of the inventive coated fibers yields improved environmental durability of ceramic matrix composites, herein demonstrated on SiC fiber reinforced silicon carbide matrix composites. A new process for obtaining a fiber coating is provided herein. The goal is to have pure disilicate coatings, because they are the most promising as an oxidation-resistant “weak interface” concept and also the most stable with SiC. The method disclosed herein supports the synthesis of disilicates, but monosilicates may result if the method's conditions are not adhered to.

(18) The following examples illustrate particular properties and advantages of some of the embodiments of the present invention. Furthermore, these are examples of reduction to practice of the present invention and confirmation that the principles described in the present invention are therefore valid but should not be construed as in any way limiting the scope of the invention.

(19) Yttrium disilicate coatings were formed on Hi-Nicalon type S™ fibers (or generally, silicon carbide fibers), using a three stage coating process. 1) Hi-Nicalon type S™ fibers were oxidized at 1000° C. for 0.5 hours to 20 hours in laboratory air to form a thin silica surface layer. 2) YPO.sub.4 coatings were then applied to the pre-oxidized Hi-Nicalon type S™ fibers. 3) Coated fibers were heated at about 1200° C. for about 10 hours in argon to react the YPO.sub.4 coating with the silica surface layer to form yttrium disilicate. The coatings were characterized by X-ray diffraction, SEM, and TEM.

(20) All Si-based fibers will have their own oxidation kinetics and thermal stability. The objective is to prepare pre-oxidized fibers having a suitable SiO.sub.2 thickness while limiting adverse effects on the fiber strength. For some fibers, fiber strength may even be improved slightly after oxidation. Each type of fiber will have its own optimal pre-oxidation regime, which may be established experimentally, but the general principles, including methods of oxidation, remain the same.

(21) In some embodiments of the disclosed invention, certain parameters may be varied to meet design objectives, while still yielding acceptable performance. By way of example and not limitation, in some embodiments, the plurality of silicon carbide fibers may be pre oxidized from about 0.5 hours to about 100 hours in atmospheric air, and the preoxidized YPO.sub.4 coated fibers may be heated from about 1000° C. to about 1500° C. for about 10 hours to about 20 hours.

(22) In some embodiments of the disclosed invention, the step of pre-oxidizing the plurality of fibers may be conducted in an atmosphere of one or more of oxygen, water vapor, oxygen plasma, and CO.sub.2 gas.

(23) In some embodiments of the disclosed invention, a plurality of silicon-based fibers selected from the group consisting of silicon nitride (Si.sub.3N.sub.4) fibers, SiCO fibers, SiCN fibers, SiCNO fibers, and SiBCN fibers may be used in place of silicon carbide fibers, using pre-oxidizing and heat treatment parameters within the limits described above.

(24) In some embodiments of the disclosed invention, the fibers may be selected from the group consisting of non-Si based fibers, such carbon fibers, boron nitride fibers, boron carbide fibers, metal boride fibers, metal carbide fibers, or oxide ceramic fibers. These fibers do not contain Si, and unlike Si-based fibers a surface silica layer cannot be formed on them by oxidation. Thus, for these fibers other methods of SiO.sub.2 deposition may be used, e.g. a solution derived method, CVD, and PVD, forming a plurality of silica coated ceramic fibers.

(25) In a solution derived method, silica coatings on fibers may be deposited using tetraethoxysilane (TEOS) or other commercially available sol-gel precursors.

(26) Alternatively, silica gel, [Si(OH).sub.4], may be formed by hydrolysis and polycondensation of tetraethoxysilane (TEOS) in isopropanol or ethanol media with water added in a ratio from 1 to 20 mol H.sub.2O to 1 mol of TEOS and an acid or a base catalyst:
Si(OC.sub.2H.sub.5).sub.4+4H.sub.2O.fwdarw.Si(OH).sub.4+4C.sub.2H.sub.5OH

(27) After hydrolysis, the Si(OH).sub.4 dispersion in isopropanol or ethanol may be used for fiber coatings.

(28) Alternatively, amorphous SiO.sub.2 nano-sized particles may be formed by heat treating Si(OH).sub.4:
Si(OH).sub.4.fwdarw.SiO.sub.2+2H.sub.2O

(29) The SiO.sub.2 nanoparticles are then re-dispersed in water or ethanol and used for fiber coating.

(30) In a CVD method, SiO.sub.2 films may be deposited using a variety of CVD techniques, such as low temperature CVD, plasma-enhanced CVD (PECVD), medium or low pressure CVD, atmospheric CVD, or photo-induced CVD. Various precursor chemistries for SiO.sub.2 deposition have been reported, including tetraethylorthosilicate (TEOS)-O.sub.2, TEOS-O.sub.3, SiH.sub.4—O.sub.2, SiH.sub.4—N.sub.2O, and more.

(31) In a PVD method, pure or doped silica layers can be deposited using planar or rotating cylindrical magnetron by cathode reactive sputtering with either radiofrequency (RF) or direct current (DC) power with pure Si or doped Si targets in Ar/O.sub.2 plasma at low (2 μbar) or atmospheric pressure, or SiO target in Ar plasma at the base pressure of 2×10.sup.−3 Pa. The coatings may be applied either at room temperature or elevated temperatures.

(32) In another embodiment of the PVD method, silica layers may be deposited by electron beam evaporation from a SiO source in vacuum or SiO.sub.2 source under oxygen pressure of between 10.sup.−5 and 3×10.sup.−4 mbar. Evaporation from SiO source at pressure of 2×10.sup.−3 Pa. by resistive heating may also be used

(33) The rare-earth orthophosphate (REPO.sub.4) coating may be applied to tows, or bundles of fibers, using a solution-derived method, to include heteroprecipitation. The coating may be used in conjunction with tows ranging from about 500 filaments to about 5000 filaments. Some embodiments may demand complete coverage of all filaments in the tow, while other embodiments will establish a user-selected minimum coverage threshold to achieve performance goals.

(34) For purposes of clarity, a filament is considered equivalent to a fiber. A bundle is a plurality of filaments or fibers. A tow is an untwisted bundle of continuous filaments. Yarn, on the other hand, comprises twisted bundles of filaments, and the filaments may not necessarily be, and most often are not, continuous through the entire length of the yarn bundle.

(35) The REPO.sub.4 coating may also be applied to woven cloths. Some embodiments may result in complete coverage of all filaments in the woven cloth, while other embodiments will establish a user-selected minimum coverage threshold to achieve performance goals.

(36) In some embodiments of the disclosed invention, the step of applying an REPO.sub.4 coating may be performed with one of a solution derived method, Chemical Vapor Deposition (CVD), or Physical Vapor deposition (PVD).

(37) The solution derived methods include but may not be limited to: (1) using solution precursors; (2) using colloidal hydrated REPO.sub.4.Math.H.sub.2O sols; and (3) using colloidal REPO.sub.4 sols.

(38) In a solution precursor process, the precursors in the solution react to form REPO.sub.4 directly on the fiber surface. Examples of solution precursors that form REPO.sub.4 are: (a) trimethyl phosphate as the phosphorous source and RE nitrate [RE(NO.sub.3).sub.3] as the rare earth source, and (b) phytic acid as the phosphorous source and RE(NO.sub.3).sub.3 as the RE source.

(39) For colloidal coatings (using colloidal hydrated REPO.sub.4.Math.H.sub.2O sols or using colloidal REPO.sub.4 sols), hydrated REPO.sub.4.Math.H.sub.2O particles are first formed by precipitating reaction:
RE(NO.sub.3).sub.3+H.sub.3PO.sub.4═REPO.sub.4.Math.H.sub.2O+3HNO.sub.3

(40) The REPO.sub.4.Math.H.sub.2O particles are dispersed in either water or ethanol and used for fiber coating. Fiber coatings using colloidal hydrated REPO.sub.4.Math.H.sub.2O particles are converted to REPO.sub.4 by heat treating in air at about 600° C. (using colloidal hydrated REO.sub.4.Math.H.sub.2O sols).

(41) Alternatively, REPO.sub.4 nano-sized particles can be formed by heat treating REPO.sub.4.Math.H.sub.2O particles at about 600° C. The REPO.sub.4 particles are then re-dispersed in water or in ethanol and used for fiber coating (using colloidal REPO.sub.4 sols).

(42) Turning attention to the Scanning Electron Microscopy (SEM) image in FIG. 1, it shows LaPO.sub.4 coated Nextel 610 (alumina) oxide fiber tows coated using solution precursor method. Nearly complete and relatively uniform coverage is achieved.

(43) FIG. 2 shows Transmission Electron Microscopy (TEM) images of Nextel 720 (alumina-mullite) oxide fibers with LaPO.sub.4 and CePO.sub.4 coatings produced using the colloidal hydrated REPO.sub.4.Math.H.sub.2O sols method.

(44) FIG. 3 shows Transmission Electron Microscopy (TEM) images of Nextel 720 fibers with LaPO.sub.4 coatings produced using the colloidal hydrated LaPO.sub.4.Math.H.sub.2O (rhabdophane) sols method. The two images demonstrate that the method allows good control of the resulting LaPO.sub.4 coating thickness by varying the number of rhabdophane coats applied.

(45) Moving on to FIG. 4, it shows a Transmission Electron Microscopy (TEM) image of a Nextel 720 fiber with (Y.sub.0.7, La.sub.0.3)PO.sub.4 coating produced using mixed La—Y colloidal hydrated sols. The composition was targeted to match the coefficients of thermal expansion (CTE) of the fiber and the coating. This example demonstrates the flexibility of the process in controlling the chemistry of the resulting REPO.sub.4 fiber coatings.

(46) FIG. 5 shows Scanning Electron Microscopy (SEM) micrographs and EDS spectra of (Gd.sub.0.4Dy.sub.0.6)PO.sub.4-coated Saphikon™ sapphire fiber. Here the composition was tailored to take advantage of the xenotime-monazite phase transformation to achieve better coating compliance through transformation plasticity. The coatings were produced using mixed colloidal hydrated sols. This is another example that demonstrates the flexibility of the process in controlling the chemistry of the resulting REPO.sub.4 fiber coatings.

(47) FIG. 6 shows TEM micrographs of oxidized Tyranno SA SiC fiber with LaPO.sub.4 coating deposited using colloidal hydrated sol method and the transformation of LaPO.sub.4 to La.sub.2Si.sub.2O.sub.7 after heat treatment in Ar at 1200 C. for 10 h.

(48) In an Electron Beam Physical Vapor Deposition (EB-PVD) process, the REPO.sub.4 coatings may be deposited onto fibers heated to temperatures from about 600° C. to 1100° C. in a vacuum chamber at pressures between 10.sup.−5 and 10.sup.−4 Torr with an electron gun and a REPO.sub.4 target prepared by hot-pressing from stoichiometric REPO.sub.4 powder produced in a manner described above.

(49) In a Laser Ablation PVD process, the REPO.sub.4 coatings may be deposited onto fibers at temperatures from room temperature to about 730° C. using a pulsed laser to evaporate the target material.

(50) Alternatively, REPO.sub.4 coatings may be deposited onto the fibers or fiber preform using a Combustion Chemical Vapor Deposition (CCVD) method. As an example of this process, thin LaPO.sub.4 coatings were deposited on 3M Nextel 610 fibers using soluble precursors. The precursors dissolved in an organic solvent were nebulized into flowing oxidant (oxygen or air) and combusted in the flame directed at the fibers, forming a crystalline LaPO.sub.4 coating. Continuous fiber tows may be coated with the tows continuously fed through the flame. To improve efficiency and uniformity, multiple flames from multiple directions may be used. Different flammable organic solvents, such as xylene, ethanol, and toluene may be used.

(51) The REPO.sub.4 coating may be applied with a coating thickness from about 50 nm to about 5000 nm, and the inert atmosphere may comprise an argon or nitrogen atmosphere.

(52) Another method of forming yttrium silicate coatings in-situ during fabrication of SiC/SiC ceramic matrix composites with Y.sub.2Si.sub.2O.sub.7 coated SiC fibers includes infiltrating YPO.sub.4 coated fibers with StarFire® SMP-10 SiC precursor or StarFire® SMP-10 SiC precursor loaded with 1 μm SiC particles to form SiC/SiC composites. SiC particles were used as a filler to reduce shrinkage and cracking of the matrix during pyrolysis. The composites were cured at about 250° C. for 3 hours in an Ar or N inert gas environment below 3 atm, e.g. 1 atm, or under vacuum below 0.1 atm, and then pyrolyzed at temperatures above 800° C. for 1 hour in argon with a heating rate of 1° C. to 10° C. per minute such that the pre-ceramic polymer is converted from a polymer state to an amorphous ceramic. The process of infiltration and pyrolysis may be repeated one to five times to improve the composite density. Composites were given a final heat treatment in argon at about 1200° C. for a total time of about 10 hours to densify the matrix and to convert the YPO.sub.4 coatings to yttrium silicate.

(53) In further embodiments of the disclosed invention, certain parameters may be varied to meet design objections, while still yielding acceptable performance. By way of example and not limitation, in some embodiments, composites may be cured at from about 150° C. to about 400° C. for a period ranging from about 5 min to about 5 hours.

(54) Likewise, the composites may be pyrolyzed at a temperature from about 400° C. to about 1500° C. for a period ranging from about 0.5 hour to about 10 hours. Re-pyrolyzing may be performed between temperatures from about 800° C. to about 1500° C. for a period from about 0.5 hour to about 10 hours.

(55) Final heat treatment of the composites may be performed at a temperature ranging from about 1000° C. to about 1500° C. for a period between about 5 hours to about 15 hours to densify the matrix and to convert the YPO.sub.4 coatings to yttrium silicate.

(56) The ceramic precursor may include SiC or other ceramic particles that are inert with respect to the preceramic polymer precursor. Preceramic polymers may be loaded with up to 55 vol % of the inert ceramic particles, with the preferred embodiment being between 10 vol. % and 35 vol %. The particles may have a mean diameter from about 0.1 μm to about 10 μm, while some embodiments may use particles having a mean diameter of about 1 μm. In other embodiments, a mixture of particles with bimodal or more complex particle size distributions may be used, which may allow a higher total solids loading of the precursor. The inert environment may include an argon or nitrogen inert atmosphere.

(57) Composites with no coatings were made and used as a control for comparison, and each of the composites was tested for tensile strength. Although the average tensile strength of coated fibers pre-oxidized for about 20 hours and about 0.5 hours and heat treated at about 1200° C. for about 10 hours in argon was reduced by 10% and 30% respectively (Table 1), the average tensile strengths of the composites made from the coated fibers were 2 to 3 times stronger than composites formed with uncoated fibers (Table 2). The following tables provide details with respect to the observed performance.

(58) TABLE-US-00001 TABLE 1 Tensile strength (GPa) of Hi-Nicalon type S ™ fibers heat treated in argon at 1200° C. for 10 hours: Preoxidized - 20 h Preoxidized - 0.5 h Control (no coating) 2.6 ± 0.24 2.8 ± 0.25 YPO.sub.4 Coating 2.5 ± 0.17 2.0 ± 0.23

(59) TABLE-US-00002 TABLE 2 Tensile strength (MPa) of Hi-Nicalon type S ™ reinforced SiC composites with and without yttrium silicate interface coatings: Control (no coating) Preoxidized - 20 h Preoxidized - 0.5 h 200 ± 80 380 ± 70 500 ± 110

(60) FIGS. 7A-7D show scanning electron micrographs of RE.sub.2Si.sub.2O.sub.7 coatings deposited on SCS-0 SiC fibers using the method described in the present invention. These micrographs demonstrate the flexibility of the method in controlling both the chemistry and the thickness of the RE.sub.2Si.sub.2O.sub.7 coatings by selecting the appropriate precursors and varying the number of coats applied: Y.sub.2Si.sub.2O.sub.7, 10 coats (FIGS. 7A-7B) and Ho.sub.2Si.sub.2O.sub.7, 20 coats (FIGS. 7C-7D).

(61) FIGS. 8A-8B show scanning electron micrograph (FIG. 8A) of silica fibers coated with YPO.sub.4 (6 coats) using the solution precursor method and the x-ray diffraction spectrum (FIG. 8B) demonstrating the conversion of YPO.sub.4 coating to Y.sub.2Si.sub.2O.sub.7 after heat treatment in argon at 1200° C. for 20 h.

(62) Turning attention to FIGS. 9A-9F, SEM fractography showed no crack deflection and no fiber pullout for the composites without coatings (FIGS. 9A-9B). Crack deflection at the fiber coating interface was observed for composites containing yttrium silicate coatings (FIGS. 9C-9F).

(63) TEM characterization confirmed the presence of α-Y.sub.2Si.sub.2O.sub.7 at the fiber-matrix interface depicted in FIGS. 10A-10E.

(64) SiC/SiC composites with BN and Y.sub.2Si.sub.2O.sub.7 fiber coatings were exposed to steam at 1000° C. for 10, 50, and 100 h and their tensile strengths were measured and compared. FIG. 11 presents normalized tensile strengths (composite strength after exposure to steam normalized to the as-fabricated strength) of SiC/SiC composites with BN (BN) and Y.sub.2Si.sub.2O.sub.7 interface (Y.sub.2Si.sub.2O.sub.7—CB and Y.sub.2Si.sub.2O.sub.7-G) after oxidation in steam at 1000° C. For SiC/SiC composites with Y.sub.2Si.sub.2O.sub.7 interphase, the relative strength increased by 10-20% after 10 h exposure. At longer exposures of 50 to 100 hours the relative strength decreased gradually, but the composites still retained ˜90% of their original strength after 100 h exposure. In contrast, the composites with BN interphase experienced a severe drop of strength already after 10 h exposure to steam. Furthermore, the mini-composites with BN interphase retained only ˜20% of their initial as-fabricated strength after 10 h exposure and 10% after exposure for 50 and 100 h.

(65) While the experimental results, above, are directed to particular examples of oxidation resistant fiber coatings, it is noted that embodiments of the disclosed invention are applicable to all rare earth disilicates and monosilicates. Alternative embodiment examples include disilicates and monosilicates of other rare earth orthophosphates, e.g. scandium, yttrium, lutetium, ytterbium, terbium, erbium, holmium, dysprosium, gadolinium, and europium, or combinations thereof.

(66) In some embodiments of the disclosed invention, the REPO.sub.4 coating may have. an applied thickness from about 50 nm to about 1000 nm. To facilitate complete conversion of REPO.sub.4 to RE.sub.2Si.sub.2O.sub.7, the ratio of the REPO.sub.4 coating thickness to the thickness of the underlying silica layer on the fiber surface should not exceed ˜0.9. Preferably, a 25 to 100 nm silica layer should remain on the fiber surface after complete conversion of REPO.sub.4 to RE.sub.2Si.sub.2O.sub.7. The ratio of the final RE.sub.2Si.sub.2O.sub.7 coating thickness to the fiber diameter may be from about 0.005 to about 0.5. The RE.sub.2Si.sub.2O.sub.7 interface coating will have a thickness exceeding the surface roughness amplitude of the fiber by a factor of 2-10 to facilitate fiber pull-out.

(67) The optimal thickness of the actual interface coating (e.g. RE.sub.2Si.sub.2O.sub.7, BN, C, etc.) will depend on a number of parameters, including the fiber surface roughness, coating compliance, elastic properties and thermal conductivity of the CMC constituents, thermal expansion mismatch, fiber strength, etc. The optimal coating thickness is also a function of coating thickness uniformity, which is typically much better for CVD methods than for solution-derived methods, and thus may be process-dependent. In addition, it may be application dependent. Beyond that, the coating thickness needs to be kept to a minimum. A large volume fraction of the coating in the composite may negatively affect other essential composite properties, such as modulus, interlaminar shear strength, thermal conductivity, thermal expansion, etc.

(68) Improved environmental stability and structural properties resulting from the claimed and disclosed invention are particularly suited for use in turbine and scram jet engine components, other hot-section components and exhaust section components for high performance military aircraft, thermal protection systems on hypersonic vehicles, high efficiency low emission land based power-generation turbines, radiant burners, and high temperature filters in power plants or hazardous waste disposal facilities.

(69) While the present invention has been illustrated by a description of one or more embodiments thereof and while these embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and method, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept.