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Opila, E. J.

Publications and source records attributed to Opila, E. J..

Stability of Materials in High Temperature Water Vapor: SOFC Applications

Solid oxide fuel cell material systems require long term stability in environments containing high-temperature water vapor. Many materials in fuel cell systems react with high-temperature water vapor to form volatile hydroxides which can degrade cell performance. In this paper, experimental methods to characterize these volatility reactions including the transpiration technique, thermogravimetric analysis, and high pressure mass spectrometry are reviewed. Experimentally determined data for chromia, silica, and alumina volatility are presented. In addition, data from the literature for the stability of other materials important in fuel cell systems are reviewed. Finally, methods for predicting material recession due to volatilization reactions are described.

Opila, E. J.↗

Integrated High Payoff Rocket Propulsion Technology (IHPRPT) SiC Recession Model

SiC stability and recession rates were modeled in hydrogen/oxygen combustion environments for the Integrated High Payoff Rocket Propulsion Technology (IHPRPT) program. The IHPRPT program is a government and industry program to improve U.S. rocket propulsion systems. Within this program SiC-based ceramic matrix composites are being considered for transpiration cooled injector faceplates or rocket engine thrust chamber liners. Material testing under conditions representative of these environments was conducted at the NASA Glenn Research Center, Cell 22. For the study described herein, SiC degradation was modeled under these Cell 22 test conditions for comparison to actual test results: molar mixture ratio, MR (O2:H2) = 6, material temperatures to 1700 C, combustion gas pressures between 0.34 and 2.10 atm, and gas velocities between 8,000 and 12,000 fps. Recession was calculated assuming rates were controlled by volatility of thermally grown silica limited by gas boundary layer transport. Assumptions for use of this model were explored, including the presence of silica on the SiC surface, laminar gas boundary layer limited volatility, and accuracy of thermochemical data for volatile Si-O-H species. Recession rates were calculated as a function of temperature. It was found that at 1700 C, the highest temperature considered, the calculated recession rates were negligible, about 200 m/h, relative to the expected lifetime of the material. Results compared favorably to testing observations. Other mechanisms contributing to SiC recession are briefly described including consumption of underlying carbon and pitting. A simple expression for liquid flow on the material surface was developed from a one-dimensional treatment of the Navier-Stokes Equation. This relationship is useful to determine under which conditions glassy coatings or thermally grown silica would flow on the material surface, removing protective layers by shear forces. The velocity of liquid flow was found to depend on the gas velocity, the viscosity of gas and liquid, as well as the thickness of the gas boundary layer and the liquid layer. Calculated flow rates of a borosilicate glass coating compared well to flow rates observed for this coating tested on a SiC panel in Cell 22.

Opila, E. J.↗

Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

T-300 carbon fibers and T-300 carbon fiber reinforced silicon carbide composites (C/SiC) were oxidized in flowing reduced oxygen partial pressure environments at a total pressure of one atmosphere (0.5 atm O2, 0.05 atm O2 and 0.005 atm O2, balance argon). Experiments were conducted at four temperatures (816deg, 1149deg, 1343deg, and 1538 C). The oxidation kinetics were monitored using thermogravimetric analysis. T-300 fibers were oxidized to completion for times between 0.6 and 90 h. Results indicated that fiber oxidation kinetics were gas phase diffusion controlled. Oxidation rates had an oxygen partial pressure dependence with a power law exponent close to one. In addition, oxidation rates were only weakly dependent on temperature. The C/SiC coupon oxidation kinetics showed some variability, attributed to differences in the number and width of cracks in the SiC seal coat. In general, weight losses were observed indicating oxidation of the carbon fibers dominated the oxidation behavior. Low temperatures and high oxygen pressures resulted in the most rapid consumption of the carbon fibers. At higher temperatures, the lower oxidation rates were primarily attributed to crack closure due to SiC thermal expansion, rather than oxidation of SiC since these reduced rates were observed even at the lowest oxygen partial pressures where SiC oxidation is minimal.

Opila, E. J.↗

Oxidation and Volatilization of Silica-Formers in Water Vapor

At high temperatures SiC and Si3N4 react with water vapor to form a silica scale. Silica scales also react with water vapor to form a volatile Si(OH)4 species. These simultaneous reactions, one forming silica and the other removing silica, are described by paralinear kinetics. A steady state, in which these reactions occur at the same rate, is eventually achieved, After steady state is achieved, the oxide found on the surface is a constant thickness and recession of the underlying material occurs at a linear rate. The steady state oxide thickness, the time to achieve steady state, and the steady state recession rate can all be described in terms of the rate constants for the oxidation and volatilization reactions. In addition, the oxide thickness, the time to achieve steady state, and the recession rate can also be determined from parameters that describe a water vapor-containing environment. Accordingly, maps have been developed to show these steady state conditions as a function of reaction rate constants, pressure, and gas velocity. These maps can be used to predict the behavior of silica formers in water-vapor containing environments such as combustion environments. Finally, these maps are used to explore the limits of the paralinear oxidation model for SiC and Si3N4

Opila, E. J.↗

High Temperature Corrosion of Silicon Carbide and Silicon Nitride in Water Vapor

Silicon carbide (SiC) and silicon nitride (Si3N4) are proposed for applications in high temperature combustion environments containing water vapor. Both SiC and Si3N4 react with water vapor to form a silica (SiO2) scale. It is therefore important to understand the durability of SiC, Si3N4 and SiO2 in water vapor. Thermogravimetric analyses, furnace exposures and burner rig results were obtained for these materials in water vapor at temperatures between 1100 and 1450 C and water vapor partial pressures ranging from 0.1 to 3.1 atm. First, the oxidation of SiC and Si3N4 in water vapor is considered. The parabolic kinetic rate law, rate dependence on water vapor partial pressure, and oxidation mechanism are discussed. Second, the volatilization of silica to form Si(OH)4(g) is examined. Mass spectrometric results, the linear kinetic rate law and a volatilization model based on diffusion through a gas boundary layer are discussed. Finally, the combined oxidation and volatilization reactions, which occur when SiC or Si3N4 are exposed in a water vapor-containing environment, are presented. Both experimental evidence and a model for the paralinear kinetic rate law are shown for these simultaneous oxidation and volatilization reactions.

Opila, E. J.↗

Water Vapor Effects on Silica-Forming Ceramics

Silica-forming ceramics such as SiC and Si3N4 are proposed for applications in combustion environments. These environments contain water vapor as a product of combustion. Oxidation of silica-formers is more rapid in water vapor than in oxygen. Parabolic oxidation rates increase with the water vapor partial pressure with a power law exponent value close to one. Molecular water vapor is therefore the mobile species in silica. Rapid oxidation rates and large amounts of gases generated during the oxidation reaction in high water vapor pressures may result in bubble formation in the silica and nonprotective scale formation. It is also shown that silica reacts with water vapor to form Si(OH)4(g). Silica volatility has been modeled using a laminar flow boundary layer controlled reaction equation. Silica volatility depends on the partial pressure of water vapor, the total pressure, and the gas velocity. Simultaneous oxidation and volatilization reactions have been modeled with paralinear kinetics.

Opila, E. J.↗

Thermodynamics of Si-C-O system

The Si-C-O predominance diagram, in conjunction with a free-energy minimum of the gas phase, has been used to explain several observations in the reactions of SiC and/or carbon with SiO2. In the predominance diagram, the axes are chosen as the primary activity units for carbon and oxygen. The predominance diagram shows only the stable condensed phases SiO2, SiC, carbon, and silicon. It also shows the isobars for SiO(g) and CO(g), which are the primary gas-phase species. Only the thermodynamics of the system is considered. The observations explained include the general adjustment of carbon-rich SiC to a free-energy minimum on the SiC/SiO2 coexistence line and the inability to form free silicon from SiO2 and carbon, except at very high temperatures.

Jacobson, N. S.↗