Monazite Coatings on Fibers: II, Coating without Strength Degradation

Washed and unwashed rhabdophane (LaPO₄· x H₂O) sols were used to apply monazite coatings to 3M Nextel 720 and 610 fibers. This precursor was designed to minimize stress corrosion from gaseous decomposition products at high temperature. The coatings were heat-treated in-line at 900°–1300°C, in air, using a continuous vertical coater with immiscible liquid displacement. Coatings were characterized by optical microscopy, scanning electron microscopy, and transmission electron microscopy. The sol was characterized with light-scattering and zeta-potential measurements. Precursor phase evolution was studied with differential thermal analysis/thermogravimetric analysis and X-ray diffractometry. The washed sol had a higher pH and lower weight loss than the unwashed sol. The as-coated fibers were tensile tested, along with coated fibers heat-treated in air at 1200°C for 100 h. The precursor was slightly phosphate-rich, and this excess phosphate reacted with alumina in the fiber to occasionally make very small (<10 nm) pockets of AlPO₄ at the coating–fiber interface after 100 h at 1200°C. Both washed and unwashed sols made coated fibers with higher tensile strengths than those of coated fibers made from other precursors, and the washed sol may actually have slightly increased fiber strength when in-line heat treatments at <1200°C were used. A small amount of AlPO₄ may also have helped seal preexisting flaws. Degradation mechanisms during fiber coating are discussed in this paper.     

Zirconia–Silica–Carbon Coatings on Ceramic Fibers

Precursors for zircon–carbon mixtures were made to coat fibers for ceramic-matrix composites. Precursors were characterized using XRD, TGA, and DTA. Zircon formed from vanadium- or lithium-doped precursors after heat treatments at ≥900°C in air, but it did not form at 1200°–1400°C in argon when large amounts of carbon were added. Some precursors were used to coat Nextel™ 720 and Hi-Nicalon™ fibers. The coatings were characterized using SEM and TEM, and coated-fiber tensile strengths were measured. Although zircon formed in powders, only tetragonal-zirconia–silica mixed phases formed in fiber coatings at 1200°C in air. Loss of vanadium oxide flux to the fibers may have caused the lack of conversion to zircon. The strengths of the coated fibers were severely degraded after heat treatment at ≥1000°C in air, but not in argon. The coated fibers were compared with zirconia–carbon-coated fibers made using similar methods. Mechanisms for fiber strength degradation are discussed.     

Porous Yttrium Aluminum Garnet Fiber Coatings for Oxide Composites

A porous oxide fiber coating was investigated for Nextel^™ 610 fibers in an alumina matrix. Polymeric-solution-derived yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) with a fugitive carbon phase was used to develop the porous fiber coating. Ultimate tensile strengths of tows and minicomposites following heat treatments in argon and/or air were used to evaluate the effect of the porous fiber coating. The porous YAG fiber coatings did not reduce the strength of the tows when heated in argon, and they degraded tow strength by only ∼20% after heating in air at 1200°C for 100 h. Minicomposites containing porous YAG-coated fibers were nearly twice as strong as those containing uncoated fibers. However, after heating at 1200°C for 100 h, the porous YAG coatings densified to >90%, at which point they were ineffective at protecting the fibers, resulting in identical strengths for minicomposites with and without a fiber coating.     

Monazite Coatings on SiC Fibers I: Fiber Strength and Thermal Stability

Commercially available SiC fibers were coated with monazite (LaPO₄) using a continuous vertical coater at 1100°C. Coated fibers were heat treated in dry air, argon, and laboratory air at 1200°C for 1–20 h. The tensile strengths of uncoated and coated fibers were measured and evaluated before and after heat treatment. Fiber coating did not degrade SiC fiber strength, but heat treatment afterwards caused significant degradation that correlated with silica scale thickness. Possible strength degradation mechanisms for the coated fibers are discussed. Coating morphology, microstructure, and SiC oxidation were observed with scanning electron microscopy and transmission electron microscopy. Monazite reacted with SiC to form lanthanum silicate (La₂Si₂O₇) in argon, but was stable with SiC in air. Despite the large coefficient of thermal expansion difference between monazite and SiC, micron thick monazite coatings did not debond from most types of SiC fibers. Possible explanations for the thermomechanical stability of the monazite fiber coatings are discussed.     

Spherical Rhabdophane Sols. II: Fiber Coating

A rhabdophane (LaPO₄·nH₂O) sol with fine spherical particles was used to coat Nextel™ 720 fiber tows continuously with monazite (LaPO₄). The coatings are compared with those made previously from rod-shaped particles. The coated fibers were heat-treated at 1000°–1300°C for 1, 10, and 100 h. The effect of heat treatment temperature and time on coating microstructure was characterized by scanning electron microscopy and transmission electron microscopy, and the strengths of the coated fibers were measured after coating and heat treatment. Grain shapes and grain growth rates were measured. Coating thickness uniformity was quantified by a fit to a truncated extreme-value distribution. Coating hermeticity was evaluated by analysis of grain growth rates. The spherical particles promote more rapid coating densification and local hermeticity, but introduce problems with sintering shrinkage cracking that are not present in coatings derived from rod-shaped particles.     

Effect of coating deposition temperature on monazite coated fiber

Monazite (LaPO₄) was continuously coated on 3M Nextel^™ 720 fiber tows with an ethanolic precursor using hexadecane for immiscible liquid displacement. Coating deposition temperatures were varied from 900 to 1300°C. Fibers coated at 900°C were heat-treated up to 100 h at 1200°C. Coated fibers were characterized by analytical TEM, and tensile strengths were measured by single filament tensile tests. The monazite precursor was characterized by X-ray, DTA/TGA, and mass spectrometry. Microstructure evolution was complex and may have involved recrystallization of large defective grains into smaller grains and then subsequent growth of these grains, along with coarsening of porosity. After 100 h at 1200°C there was significant roughening of the coating–fiber interface, with facetting of alumina grains in the fiber and some lanthanum segregation to these facetted boundaries. Spheroidization of thin coatings was also observed. Tensile strength of coated fiber decreased with increasing deposition temperature and with time at temperature after deposition. Possible reasons for the strength decrease are discussed.     

Continuous Coating of Oxide Fiber Tows Using Liquid Precursors: Monazite Coatings on Nextel 720™

Seven different aqueous or ethanolic precursors were used to continuously coat monazite (LaPO₄) on Nextel 720™ fiber tows. Immiscible liquid displacement was used to minimize bridging of coating between filaments. Precursor viscosities, densities, and concentrations were measured, and solids were characterized by DTA/TGA and X-ray. Coatings were cured in-line at 1200°-1400°C and characterized for thickness, microstructure, and composition by optical microscopy, SEM, and TEM. Tensile strengths of the coated fibers varied with the precursor used and were 25% to >50% lower than those of the as-received fiber. The coating stoichiometry and coating thickness of a particular precursor did not correlate with tensile strength. Median coating thicknesses were typically ∼50–100 nm for precursors with 40–80 g/L monazite, much larger than thicknesses predicted by theory for 12 mm diameter monofilaments. There were significant thickness variations from filament to filament, but usually little variation in composition or microstructure. Amorphous AlPO₄ layers formed from phosphate-rich precursors. Factors that could affect coating characteristics and tensile strength reduction were discussed.     

Effect of Yttrium Aluminum Garnet Additions on Alumina-Fiber-Reinforced Porous-Alumina-Matrix Composites

The effects of incorporating yttrium aluminum garnet (YAG) into a porous alumina matrix reinforced with Nextel 610 alumina fibers were investigated. Composites with various amounts of YAG added to the matrix were prepared to determine its effect on retained tensile strengths after heating to 1100° and 1200°C. Strengths of YAG-containing composites were slightly lower than those of an all-alumina-matrix composite after heating for 5 h to 1100°C. However, after heating for 5 or 100 h at 1200°C, all the YAG-containing composites displayed greater strengths and greater strains to failure than the all-alumina composite. At the higher temperature, the presence of YAG is believed to inhibit the densification of the matrix, which helps to maintain higher levels of porosity and weaker interparticle bonding that allows for crack-energy dissipation within the matrix. A reduction in grain growth of the fibers by the presence of segregated Y was also observed, which may also contribute to higher fiber strength, thereby increasing the retained strengths of the YAG-containing composites.     

Precipitation Coating of Monazite on Woven Ceramic Fibers: II. Effect of Processing Conditions on Coating Morphology and Strength Retention of Nextel™ 610 and 720 Fibers

Woven cloths of Nextel^™ 610 and 720 fibers were coated with monazite by precipitation. The cloths were first saturated with concentrated precursor solutions, and then submerged in warm water to initiate precipitation onto the fiber surfaces. Coatings were characterized by scanning electron microscopy, and transmission electron microscopy; thermogravimetric analysis was performed on LaPO₄ owders precipitated in solution under the same conditions as the coatings were deposited. Coating thickness distributions were measured and analyzed. Coated fiber strength was measured following heat treatment for 2 h at 1200°C. Processing conditions which retain a substantial fraction of the uncoated fiber strength are identified, and are discussed in the context of current understanding of strength degradation in coated fibers. Strength retention of coated Nextel^™ 610 fibers following heat treatment was broadly insensitive to precursor solution chemistry and was more strongly affected by intercoat firings which govern the final coating microstructure. For fixed processing conditions, more strength degradation was observed in Nextel^™ 720 due to higher residual stresses in the fiber.     

Two Phase Monazite/Xenotime 30LaPO4–70YPO4 Coating of Ceramic Fiber Tows

Equiaxed yttrium–lanthanum phosphate nanoparticles (Y_0.7,La_0.3)PO₄·0.7H₂O were made and used to continuously coat Nextel^™ 720 fiber tows. The particles were precipitated from a mixture of yttrium and lanthanum citrate chelate and phosphoric acid (H₃PO₄), and characterized with differential thermal analysis and thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. The coated fibers were heat treated at 1000°–1300°C for 1, 10, and 100 h. Coating grain growth kinetics and coated fiber strengths were determined and compared with equiaxed La-monazite coatings. The relationships between coating porosity, coating hermeticity, and coated fiber strength are discussed.     

Effect of Thermal Exposures on the Strengths of Nextel™ 550 and 720 Filaments

The effects of thermal exposure on the strengths of Nextel™ 550 and 720 tows, bare and coated with carbon, were determined by room-temperature tensile testing of single filaments extracted from tows that had been exposed to different thermal environments (i.e., air or vacuum) at temperatures from 550° to 1400°C. The results help define the allowable composite processing conditions when using these tows. A 28% drop in the strength of Nextel 550 filaments occurred after a thermal exposure at 1100°C for 2 h in air. After an exposure of 1300°C/2 h/air, a strength degradation of ∼47% resulted. Filaments exposed above 1100°C under vacuum showed more severe strength degradation than filaments exposed in air. The observed strength degradation may stem from a combination of phase transformations of the alumina, the onset of mullite crystallization, and/or exaggerated mullite grain growth. Strength after heat treatment under vacuum at 1050° and 1150°C did not deteriorate as rapidly as after heat treatment under vacuum between 950° and 1050°C or between 1150° and 1250°C. This may be a result of the competition between healing of flaws by the amorphous silica and its evaporation (leading to an increase in its viscosity or loss) and/or densification of the filaments. Nextel 720 filaments exhibited about 9% strength loss after an exposure at 1100°C/2 h/air. The filaments maintained 75% of their strength after a 1300°C/2 h/air heat treatment. The observed strength degradation may stem from thermal grooving, grain growth, and/or annealing of the mullite subgrain boundaries. Thermal exposure of >10 h at 1300°C was required to produce measurable grain growth. Strength loss between 1200° and 1300°C (air heat treatment) was not as great as between 1100° and 1200°C or 1300° and 1400°C.     

Thermal Degradation of Fiber Coatings in Mullite-Fiber-Reinforced Mullite Composites

The thermal degradation behavior of single-layer BN and of double-layer BN/SiC chemically vapor-deposited fiber coatings in mullite-fiber-reinforced mullite composites was investigated by means of transmission electron microscopy after processing and heat treatment of the composites at 1000°, 1200°, and 1300°C for 6 h in air. The single-layer BN coatings were ˜0.7 mu m thick and consisted of turbostratic BN with (0001) basal planes lying parallel to the surfaces of the fibers plus nanosized areas that had no preferential orientation. This microstructure remained unchanged up to 1000°C; however, distinct coarsening of the randomly oriented BN crystallites occurred in the temperature range of 1000°-1200°C. The single-layer BN coatings were stable against oxidation, up to 1200°C. At higher temperatures, degradation of the coatings via oxidation occurred. Double-layer BN/SiC coating systems consisted of BN that was 0.08 mu m thick and SiC layers that were 0.16 mu m thick and deposited onto the mullite fibers. The turbostratic BN was highly anisotropic and did not undergo any microstructural change, up to 1300°C. The outer SiC layer of the double-layer coating system improved the oxidation resistance of BN in the 1200°-1300°C temperature range, despite a partial oxidation of SiC to SiO₂.     

Continuous aluminum oxide-mullite-hafnium oxide composite ceramic fibers with high strength and thermal stability by melt-spinning from polymer precursor

Continuous aluminum oxide-mullite-hafnium oxide (AMH) composite ceramic fibers were obtained by melt-spinning and calcination from polymer precursor that synthesized by hydrolysis of the aluminum isopropoxide, dimethoxydimethylsilane and hafnium alkoxide. Due to the fine diameter of 8–9 µm, small grain size of less than 50 nm and the composite crystal texture, the highest tensile strength of AMH ceramic fibers was 2.01 GPa. And the AMH ceramic fibers presented good thermal stability. The tensile strength retention was 75.48% and 71.49% after heat treatment at 1100 °C and 1200 °C for 0.5 h respectively, and was 61.57% after heat treatment at 1100 °C for 5 h. And the grain size of AMH ceramic fibers after heat treatment was much smaller than that of commercial alumina fibers even when the heat treatment temperature was elevated to 1500 °C, benefited by the grain size inhibition of monoclinic-HfO₂ (m-HfO₂) grains distributed on the boundary of alumina and mullite grains.     

Thermal Stability of Air Plasma Spray and Solution Precursor Plasma Spray Thermal Barrier Coatings

Yttria-stabilized zirconia (7YSZ) thermal barrier coatings (TBCs) were produced by conventional air plasma spray (APS) and solution precursor plasma spray (SPPS) processes. Both TBCs were isothermally heat treated from 1200° to 1500°C for 100 h. Changes in the phase content, microstructure, and hardness were investigated. The nontransformable tetragonal ( t ') phase is the predominant phase in both the as-sprayed APS and SPPS TBCs. APS and SPPS coatings exhibit similar thermal stability behavior such as densification rate, hardness increase, and grain coarsening rate. Both the as-received and heat-treated APS and SPPS TBCs show a bimodal pore size distribution with nano- and micro-size pores. After 1400°C/100 h heat treatment, equiaxed grains replace the columnar structure in APS TBCs and the splat structure disappears. Vertical cracks remain after the 1500°C/100 h exposure in SPPS TBCs. The monoclinic phase appears in APS TBCs after a 1400°C/100 h exposure and in SPPS coatings after a 1500°C/100 h exposure.     

Effect of Yttria and Yttrium-Aluminum Garnet on Densification and Grain Growth of Alumina At 1200°–1300°C

Densification and grain growth of alumina were studied with yttria or yttrium-aluminum garnet (YAG) additives at the relatively low temperatures of 1200°–1300°C. Yttria doping was found to inhibit densification and grain growth of alumina at 1200°C and, depending on dopant level, had a lesser effect at 1300°C. At 1200°C, yttria inhibits densification more than it hinders grain growth. The rate of grain growth increases faster with temperature than the rate of densification. Alumina-YAG particulate composites were difficult to sinter, yielding relative densities of only 65% and 72% after 100 h at 1200° and 1300°C, respectively. Pure YAG compacts exhibited essentially no densification for times up to 100 h at 1300°C.     

High-Temperature Stability of Lanthanum Orthophosphate (Monazite) on Silicon Carbide at Low Oxygen Partial Pressures

The stability of lanthanum orthophosphate (LaPO₄) on SiC was investigated using a LaPO₄-coated SiC fiber at 1200°–1400°C at low oxygen partial pressures. A critical oxygen partial pressure exists below which LaPO₄ is reduced in the presence of SiC and reacts to form La₂O₃ or La₂Si₂O₇ and SiO₂ as the solid reaction products. The critical oxygen partial pressure increases from ∼0.5 Pa at 1200°C to ∼50 Pa at 1400°C. Above the critical oxygen partial pressure, a thin SiO₂ film, which acts as a reaction barrier, exists between the SiC fiber and the LaPO₄ coating. Continuous LaPO₄ coatings and high strengths were obtained for coated fibers that were heated at or below 1300°C and just above the critical oxygen partial pressure for each temperature. At temperatures above 1300°C, the thin LaPO₄ coating becomes morphologically unstable due to free-energy minimization as the grain size reaches the coating thickness, which allows the SiO₂ oxidation product to penetrate the coating.     

Residual Stress and Microstructural Evolution in Tantalum Oxide Coatings on Silicon Nitride

Due to its coefficient of thermal expansion (CTE) and phase stability up to 1360°C, tantalum oxide (Ta₂O₅) was identified and investigated as a candidate environmental barrier coating for silicon nitride-based ceramics. Ta₂O₅ coatings were plasma sprayed onto AS800, a silicon nitride ceramic from Honeywell International, and subjected to static and cyclic heat treatments up to 1200°C in air. Cross-sections from coated and uncoated substrates were polished and etched to reveal the effect of heat treatments on microstructure and grain size. As-sprayed coatings contained vertical cracks that healed after thermal exposure. Significant grain growth that was observed in the coatings led to microcracking due to the anisotropic CTE of Ta₂O₅. High-energy X-ray diffraction was used to determine the effect of heat treatment on residual stress and phases. The uncoated substrates were found to have a surface compressive layer before and after thermal cycling. Coating stresses in the as-sprayed state were found to be tensile, but became compressive after heat treatment. The microcracking and buckling that occurred in the heat-treated coatings led to stress relaxation after long heat treatments, but ultimately would be detrimental to the function of the coating as an environmental barrier by affording open pathways for volatile species to reach the underlying ceramic.     

Precipitation Coating of Rare-Earth Orthophosphates on Woven Ceramic Fibers—Effect of Rare-Earth Cation on Coating Morphology and Coated Fiber Strength

Monazite (La, Ce, Nd, and GdPO₄) and xenotime (Tb, Dy, and YPO₄) coatings were deposited on woven Nextel^™ 610 and 720 fibers by heterogeneous precipitation from a rare-earth citrate/phosphoric acid precursor. Coating phases and microstructure were characterized by SEM and TEM, and coated fiber strength was measured after heat treatment at 1200°C for 2 h. Coated fiber strength increased with decreasing ionic radius of the rare-earth cation in the monazite and xenotime coatings, and correlates with the high-temperature weight loss and the densification rate of the coatings. Dense coatings with trapped porosity and high weight loss at a high temperature degrade fiber strength the most. The degradation is consistent with stress corrosion driven by thermal residual stress from coating precursor decomposition products trapped in the coating at a high temperature.     

Evolution of Texture in Rhabdophane-Derived Monazite Coatings

Microstructure and texture development of fiber coatings of rhabdophane-sol-derived monazite was studied. As-deposited textures and orientation relationships during phase transformations were determined by TEM. Monazite coatings had a crystallographic texture relict from that of as-deposited rhabdophane, with layers of rod-shaped particles that changed orientation by 90° across layers. Heat treatment at 1200°C of minicomposites with these coated fibers caused considerable monazite grain coarsening, and disappearance of the texture.     

Effectiveness of Monazite Coatings in Oxide/Oxide Composites after Long-Term Exposure at High Temperature

The effectiveness of monazite (LaPO₄) in providing an oxidation-resistant weak fiber/matrix interface was evaluated in a fiber roving/thin coating/ceramic-matrix composite with >20% fiber volume fraction. Nextel™ 610/monazite/alumina composites were fabricated and tensile tested after isothermal exposures of up to 1000 h. Some strength loss was seen after short-term exposures (1100°–1200°C/5–250 h); however, no further loss was observed after 1000 h at 1200°C. Conversely, control samples containing uncoated fiber displayed >70% strength losses after only 5 h at 1200°C. Fiber pullout was seen in monazite-containing samples even after 1000 h at 1200°C. Debonding was predominantly in the coating or at either the fiber/coating or coating/matrix interface. Push-out testing confirmed the weakness of the monazite coating interface.