Mullite Coatings on SiC and C/C–Si–SiC Substrates Characterized by Infrared Spectroscopy

Mullite (3Al₂O₃·2SiO₂) coatings on SiC substrates and SiC precoated carbon/carbon composite (C/C-Si-SiC) substrates were produced by pulsed laser deposition (PLD) using pressed mullite powder targets. The layers can be characterized efficiently by IR reflection spectroscopy in the spectral range between 650 and 5000 cm⁻¹. The deposited coatings turn into mullite upon oxidation in air at temperatures between 1400° and 1600°C. Fabry-Perot interferences indicate a high quality and homogeneity of the mullite coating/SiC substrate interface. Amorphous SiO₂ gradually forms during prolonged heating or at higher temperatures.     

Ultra-High-Temperature Ceramic Coatings for Oxidation Protection of Carbon–Carbon Composites

Carbon–carbon (C–C) composites are attractive materials for hypersonic flight vehicles but they oxidize in air at temperatures >500°C and need thermal protection systems to survive aerothermal heating. We investigated using multilayers of high-temperature ceramics such as ZrB₂ and SiC to protect C–C against oxidation. Our approach combines pretreatment and processing steps to create continuous and adherent high-temperature ceramic coatings from infiltrated preceramic polymers. We tested our protective coatings at temperatures above 2600°C at the National Solar Thermal Testing Facility using controlled cold-wall heat flux profiles reaching a maximum of 680 W/cm².     

Preparation of Metal Ruthenates by Spray Pyrolysis

Submicrometer crystalline metal ruthenate powders with perovskite structure, MRuO₃ (M = Sr, La), and pyrochlore structure, M₂Ru₂O_{7- x} (0.5 < x < 1; M = Bi, Pb, Y, Eu, Gd, Tb, Dy, Ho, Er, Tm), were prepared by spray pyrolysis using metal nitrates and glycolates under an oxygen-gas atmosphere at temperatures up to 1100°C. Submicrometer-sized solid single crystals (SrRuO₃), submicrometer-sized hollow spheres consisting of nanocrystallites (pyrochlore rare-earth ruthenates, Bi₂Ru₂O₇, and Pb₂Ru₂O_6.5 below 1000°C), and nanometer-sized particles (Pb_2.31Ru_1.69O_6.5 and Bi-Pb-O above 1000°C) were observed. Particle formation proceeded by intraparticle reaction and intraparticle reaction followed by evaporation of volatile metal oxides to form metal oxide vapors followed by condensation and reaction to form particles. The former was observed for systems where no volatile metal oxides were formed, whereas the latter occurred for the Pb-Ru-O and Bi-Ru-O systems, where volatile metal oxides, such as Bi₂O, PbO, and RuO _x could occur. Particle morphology depended strongly on precursor properties. Submicrometer-sized single-crystal SrRuO₃ particles could be formed from the metal nitrates but not from Sr(NO₃)₂ and ruthenium glycolate, which gave hollow polycrystalline particles. In general, crystallite size could be controlled by varying precursor properties and reactor temperature, with higher temperatures giving larger crystallite sizes.     

Chemical Considerations in Carbon-Fiber/Oxide-Matrix Composites

Thermochemical calculations are performed to evaluate the chemical compatibility of oxides with carbon at temperatures of the order of 1650°C and to evaluate the implications of carbon oxidation. These calculations indicate that Al₂O₃, BeO, Y₂O₃, and Ce₂O₃ are stable with carbon provided there are no cracks or pores for CO gas to escape. In the presence of cracks or interconnected pores, both the direct reduction of oxides with carbon as well as the oxidation of carbon can proceed rapidly. The calculations also indicate that even in the absence of such cracks the oxidation of carbon can generate high enough CO partial pressures to degrade the composite properties by formation of CO gas bubbles or of cracks in the oxide. The results of these calculations are confirmed by conducting experiments on samples of pyrolytic and vitreous carbon disks hot-pressed within Al₂O₃ and Y₂O₃disks and exposing them in argon and oxygen environments at 1650–1800°C. An oxidation model is then proposed that includes thermodynamic and kinetic considerations as well as creep behavior of oxides. The model quantitatively predicts the times required to initiate the formation of gas bubbles and qualitatively considers the factors influencing the growth rate of bubbles and formation of cracks.     

High-Temperature Cermets: I, Compatibility

The stability of refractory oxides (Y₂O₃,-stabilized HfO₂ and ZrO₂, Tho₂, CeO₂), carbides (HfC, NbC, TaC, and ZrC), borides (NbB₂ and TaB₂), and HfN was determined in combination with the Groups VIA and VIIA refractory metals and combinations thereof. Thermodynamic calculations were made to predict stability up to 2500°K between the ceramic oxides and carbides in contact with Mo, Re, and W. Reaction studies were conducted between the ceramics and the Groups VIA and VIIA refractory metals in vacuum and in helium to 2750°C. The Mo-40 wt% Re, Re, and W were stable in contact with the carbides, nitrides, and oxides to 2450°C with two exceptions. These occurred when CeO₂ reacted with W at 1700°C and Mo-40 wt% Re reacted with WC. The Mo-40 wt% Re and Re also reacted with the NbB₂ and TaB_a above 2200°C to form very hard single-phase compounds.     

Reaction-Rate Studies of Thorium-Uranium Dicarbides in Moist Air

A number of arc-melted or sintered thorium or uranium carbides were reacted in moist air at 30° and 50° C. The initial reactions appeared to follow a simple linear rate law, the thorium-containing carbides being about ten times more reactive than UC₂. Initial rate constants at 50° C based on bulk particle surface area were 0.25 μg per cm²per second for UC₂ and 2.78 pg per cm²per second for ThC₂. Rate constants for mixed, thorium and uranium carbides fell between these values. The reaction produced both gaseous and solid products. Solid reaction products consisted of thorium or uranium oxides and condensed hydrocarbons; the oxides could be hydrated. The gaseous products were principally aliphatic hydrocarbons and hydrogen.     

Volatile Metal Oxide Evaporation during Aerosol Decomposition

The role of particle evaporation during synthesis of volatile metal oxide powders (Bi₂O₃, MoO₃, PbO, and V₂O₅) by aerosol decomposition (spray pyrolysis) in a heated flow reactor was investigated. Solid particles (0.1–0.6 (Am) of predominantly β-Bi₂O₃ were formed with smooth spherical shape at all reactor temperatures (673–1173 K) employed. Solid MoO₃ particles (0.1–1.2 μm) produced at low temperatures (673–773 K) had a roughly spherical or faceted morphology and at high temperatures (873 K) had a platelike or layered structure. Solid V₂O₅ particles produced at low temperatures (573–673 K) were spherical and at high temperatures (973–1073 K) were platelike. The PbO particles were solid and spherical for all temperatures studied (773°–1073°C). Evaporative losses of up to 100% to the reactor walls were observed for all the metal oxides, due to their substantial vapor pressures. The evaporative losses were modeled by considering simultaneous particle evaporation and mass transfer of the metal oxide vapor to the reactor walls. The calculations indicated that, for most of these volatile metal oxides, evaporative losses were limited by diffusional transport of the vapor to the reactor walls and that evaporative losses occur when the vapor pressure of the oxides in the reactor is above 10^-5-10^-3 mm Hg.     

Phase Equilibria in the Hafnia–Yttria–Lanthana System

The HfO₂–Y₂O₃–La₂O₃ system was studied in the wide range of temperatures (1250°–2800°C) and concentrations by methods of X-ray analysis at 20°C, petrography, differential thermal analysis in helium at temperatures to 2500°C, thermal analysis in air using a solar furnace at temperatures to 3000°C, and electron microprobe X-ray analysis. The complete phase diagram was constructed. The liquidus and solidus projections, crystallization paths for the alloys, isothermal (1250°, 1600°, and 1900°C) and polythermal sections are presented. The structure of the boundary binary systems defines the phase equilibria in the ternary system. No ternary compounds were found. Ternary solid-solution regions were determined based on constituent oxides and intermediate phases.     

High-Temperature Properties of Mixed α'/β'-SiAlON Materials

The mechanical behavior of mixed α'/β'-SiAlON materials was studied at elevated temperatures. Two different α'/β'-SiAlON compositions along the Si₃N₄-Y₂O₃9AlN composition line in the Si₃N₄-Al₂O₃AlN-YN3AlN plane (α'-SiAlON plane) were prepared using three different raw-material mixtures. Six different materials were obtained with significantly lower values in α'-SiAlON than expected. The high-temperature properties of the materials studied were influenced strongly by the chemical composition (α' content and grain-boundary phase) of the SiAlONs. A high content of α'-SiAlON was beneficial in terms of creep behavior of the materials. The same materials, however, were characterized by a considerably degradated fracture behavior at elevated temperatures in air because of a crack-growth process enhanced by the poor oxidation resistance of these materials. It was concluded that, despite some superior features of the materials studied, a long-term application of mixed α'/β'-SiAlON materials at 1400°C in air is problematical. A combination of all properties required for such applications was not observed. For that reason, it is suggested that the real high-temperature potential of these materials in air should be limited to temperatures <1300°C.     

Oxidation Resistance of Alumina–Titanium Nitride and Alumina–Titanium Carbide Composites

The presence of TiC or TiN paritcles in an Al₂O₃ matrix affects the thermal stability of the composites in oxidizing environments. In isothermic oxidation tests at 700°, 800°, 900°, 1000°, and 1100°C for up to 20 h, two different oxidation regimes have been observed at T < 900°C and at 900°C ≤ T ≤ 1100°C. At low temperatures ( T < 900°C), the oxidation follows a phase-boundary reaction; the reaction product initially consists of aggregates of submicrometer needlelike TiO₂ rutile crystals that subsequently grow and coalesce. When a continuous TiO₂ rutile layer is formed ( T ≥ 900°C), the oxidation kinetics change to parabolic, and the diffusion of O₂ through a thick TiO₂ layer is proposed as the governing step.     

Contamination Effects on Interfacial Porosity during Cyclic Oxidation of Mullite-Coated Silicon Carbide

Plasma-sprayed mullite (3Al₂O₃2SiO₂) and mullite/yttria-stabilized zirconia (mullite/YSZ) dual-layer coatings have been developed to protect silicon-based ceramics from environmental attack. The mullite/SiC system develops interfacial pores during cyclic oxidation. The development of pores at the mullite/sintered SiC interface in air has been investigated as a function of the purity of mullite at 1230°–1350°C in an atmospheric-pressure furnace. The silica scale is readily contaminated by impurities of alkali or alkaline-earth metal oxides from the mullite coating. The contamination enhances oxidation and reduces the scale viscosity by forming alkali or alkaline-earth metal silicates. The porosity increases as the temperature and contamination increase and decreases as the purity of the mullite increases.     

Measurement of Oxygen Diffusion in Dy2O3 and Gd2O3 by Studying High-Temperature Oxidation of the Metals

Studies of the oxidation of Gd and Dy at P _O2's from 10^−0.3 to 10^−14.5 atm and temperatures from 727° to 1327°C indicate both semiconducting and ionic-conducting domains in the sesquioxides formed. At higher temperatures, where dense coarsegrained oxide layers developed, the rate of oxidation in the high- P ₀₂ semiconducting domain yielded oxygen diffusion coefficients in Dy₂O₃ in excellent agreement with literature values derived from oxidation of partially reduced oxide single crystals. Under the same conditions, the oxidation of Gd yielded oxygen diffusion coefficients in cubic Gd₂O₃ which are considerably below literature values for monoclinic single-crystal Gd₂O₃. At lower temperatures, porous scales were formed, and apparent diffusion coefficients derived from oxidation rates show a smaller temperature dependence than the high-temperature data. At low P _O2, the oxides behave as ionic conductors, and metal oxidation rates result in estimates of the electronic contribution to the electrical conductivity of the order of 10⁻⁶ to 10⁻⁷Ω⁻¹ cm⁻¹.     

Phase Relations in the System UO2-UO3– Y2O3

The phase relations in the system U02-U03-Yz03, particularly in the Y203-rich region, were examined by X-ray and chemical analyses of reacted powders heated at temperatures up to 1700°C in H₂, CO₂-CO₂ and air. Four phases were identified in the system at temperatures between 1000° and 1700°C: U308, face-centered cubic solid solution, body-centered cubic solid solution, and a rhombohedral phase of composition (U,Y)₇O₂ ranging from 52.5 to 75 mole % Y₂O₃. The rhombohedral phase oxidized to a second rhombohedral phase with a nominal composition (U,Y), at temperatures below 1000°C. This phase transformed to a face-centered cubic phase after heating in air above 1000° C. The solubility of UO, in the body-centered cubic phase is about 14 mole % between 1000° and 1700°C but decreases to zero as the uranium approaches the hexavalent oxidation state. The solubility of Yz03 in the face-centered cubic solid solution ranges from 0 to 50 mole % Y2O3 under reducing conditions and from 33 to 60 mole % Y2O3 under oxidizing conditions at 1000°C. At temperatures above 1000° C, the face-centered cubic solid solution is limited by a filled fluorite lattice of composition (U,Y)O₂. For low-yttria content, oxidation at low temperatures (<300°C) permits additional oxygen to be retained in the structure to a composition approaching (U,Y)O_2.25 A tentative ternary phase diagram for the system UO₂-UO₃-Y₂O₃ is presented and the change in lattice parameter and in cell volume for the solid-solution phases is correlated with the composition.     

Novel CO2 Absorbents Using Lithium-Containing Oxide

We have discovered a series of lithium-containing oxides that immediately react with ambient carbon dioxide (CO₂) up to 700°C. The products react and return reversibly to the oxides at a temperatures higher than about 700°C. The absorption capacity surpasses that of other CO₂ absorbents by a factor of 10. Utilizing these absorbents, the possibility of a CO₂ separation system that operates at around 500°C is proposed. It is generally believed that a CO₂ separation process operable at temperatures higher than 500°C has the special benefit of a small energy penalty. Moreover, the absorption also proceeds at ambient temperature in the atmospheric environment. This property offers the possibility of many other applications, such as air cleaners or cartridges. Therefore, we think these materials have the potential to make a valuable contribution to the realization of CO₂ emission control.     

Phase Relations in the Ternary Systems Nd─B─N, Sm─B─N, and Gd─B─N

Phase relations and phase stabilities have been derived for the ternary systems RE─B─N (RE = Nd, Sm, or Gd) at elevated temperatures (1400°C and above) by means of X-ray powder analysis. Under the experimental conditions selected, various ternary compounds are found to be stable: Nd₃B₂N₄ with the Ce₃B₂N₄ type and (Nd,Sm,Gd)BN₂ with the PrBN₂ type. Phase equilibria at 1400°C and under 10⁵ Pa of argon are mainly characterized by the incompatibility of the RE metals Nd, Sm, and Gd with BN due to the competing equilibria between the RE tetraborides and the RE mononitrides. Each of the ternary compounds, however, is found to be in a two-phase equilibrium with hex -BN. Because of the different thermodynamic stabilities within the various structure series of ternary rare-earth boron nitrides RE₃B₂N₄ and REBN₂, the compound Nd₃B₂N₄ is observed only at temperatures below 1800°C and under 10⁵ Pa of Ar, whereas GdBN₂ is found to be stable only at temperatures above 1400°C under a partial pressure of 10⁵ Pa of N₂.     

Preparation of Tungsten Cobalt Carbides and Oxide via an Organometallic Heterobimetallic Complex as a Single-Source Precursor

Tungsten cobalt carbides and oxides can be obtained via a single-step pyrolysis of an organometallic single-source precursor (eta⁵-C₅H₅)(CO)₃WCo(CO)₄ (1). Pyrolysis of 1 in an oxygen atmosphere produced WCoO₄ at 600°C. In a nitrogen atmosphere W₆Co₆C was obtained when 1 was heated at 700°C. However, under vacuum, the pyrolysis of 1 produced the other phase-W₃Co₃C-at 700°C. Both carbides were contaminated with graphitic carbon, as indicated by their ESCA spectra. Powders that were obtained by using these procedures had particle sizes of up to 100 µm. Micrography showed that the particles were porous, which indicated outgassing during pyrolysis.     

Stability of Molybdenum Disilicide in Combustion Gak Environments

The stability of MoSi₂ in combustion gas at 1370° and 1600°C was evaluated using SOLGASMIX-PV thermodynamic modeling, periodic weight measurements, and characterization via XRD, SEM, EDS, and image analysis. Passive oxidation occurred at both temperatures. During an initial stage of exposure, specimen surfaces oxidized to form MoO_3(g) and amorphous SiO₂ via reduction of CO₂ and H₂O. After a short time (<6.5 min at 1370°C, <1 min at 1600°C), the oxidation mechanism switched; Mo₅Si₃ and amorphous SiO₂ formed as oxidation products. The first mechanism esulted in the formation of 46.1 vol% at 1370°C and 42.6 vol% at 1600°C of the amorphous silica surface coating. The attainment of a near-terminal weight gain implied silica formation was limited by H₂O and CO₂ diffusion through the silica coating.     

Oxidation Behavior and Flexural Strength of Aluminum Nitride Exposed to Air at Elevated Temperatures

The oxidation behavior of a sintered aluminum nitride containing 3 wt% Y₂O₃ as a sintering aid was investigated. Samples were exposed to air at elevated temperatures for times up to 100 h. The weights of the samples were continuously monitored during exposure at various temperatures and humidity levels. The effects of oxidation on room-temperature flexural strength were also determined, and correlated to the observed weight changes of the samples. At temperatures 1200°C, linear weight gains were observed. However, at temperatures above 1200°C, the weight gains became parabolic with respect to exposure time. The oxidation rates were significantly increased by water vapor in the air. The oxidation products were found by X-ray analysis to be a mixture of Al₂O₃ and 5A1₂O₃·3Y₂O₃. The oxide layer formed on the surface was severely cracked because of the thermal expansion mismatch between the oxide layer and the substrate. The cracks initiated in the oxide layer and propagated into the substrate, resulting in severe reduction in the room-temperature flexural strength of the material. When exposed to ambient air for more than 50 h at temperatures greater than 1100°C, the strengths of the samples decreased to less than half that of the as-received material.     

Method for Production of α-Alumina Whiskers via Vapor-Liquid-Solid Deposition

α-alumina (α-Al₂O₃, corundum) fibers exhibit high thermal and chemical stability, as well as good mechanical properties, even at high temperatures. Such characteristics make them good candidates for use in composites. Nevertheless, very few methods of producing α-Al₂O₃ fibers are available. In the present work, we describe a method that uses aluminum pieces deposited on SiO₂ powder, in an argon atmosphere, at temperatures in the range 1300°–1600°C. The α-Al₂O₃ fibers are obtained via vapor-liquid-solid deposition. The novel addition of nickel and cobalt (or their oxides) allows the use of temperatures >1500°C, resulting in improved fiber production. We demonstrate that the metals do not contaminate the fibers produced in this way. Finally, we also estimate the tensile strength of the Al₂O₃ fibers produced through this method.     

Microstructure and Short-Term Oxidation of Hot-Pressed Si3N4/ZrO2(+Y2O3) Ceramics

Composite ceramic materials based on Si₃N₄ and ZrO₂ stabilized by 3 mol% Y₂O₃ have been formed using aluminum isopropoxide as a precursor for the Al₂O₃ sintering aid. Densification was carred out by hot-pressing at temperatures in the range 1650° to 1800°C, and the resulting micro-structures were related to mechanical properties as well as to oxidation behavior at 1200°C. Densification at the higher temperatures resulted in a fibrous morphology of the Si₃N₄ matrix with consequent high room-temperature toughness and strength. Decomposition of the ZrO₂ grains below the oxidized surface during oxidation introduced radial stresses in the subscalar region, and from the oxidation experiments it is suggested that the ZrO₂ incorporated some N during densification.