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Opila, Elizabeth J.

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

67 records · Page 4

SiC Recession Due to SiO2 Scale Volatility Under Combustion Conditions: Thermodynamics and Gaseous Diffusion Model - Part 2

In combustion environments, volatilization of SiO2 to Si-O-H(g) species is a critical issue. Available thermochemical data for Si-O-H(g) species were used to calculate boundary layer controlled fluxes from SiO2. Calculated fluxes were compared to volatilization rates Of SiO2 scales grown on SiC which were measured in Part 1 of this paper. Calculated volatilization rates were also compared to those measured in synthetic combustion gas furnace tests. Probable vapor species were identified in both fuel-lean and fuel-rich combustion environments based on the observed pressure, temperature and velocity dependencies as well as the magnitude of the volatility rate. Water vapor is responsible for the degradation of SiO2 in the fuel-lean environment. Silica volatility in fuel-lean combustion environments is attributed primarily to the formation of Si(OH)4(g) with a small contribution of SiO(OH)2(g).

Opila, Elizabeth J.↗

Volatile Si-O-H Species in Combustion Environments

The formation of volatile Si-O-H species from silica occurs in water-vapor containing environments such as combustion environments. In this paper the pressure and temperature dependence of known Si-O-H species are surveyed. Trends based on the number of water molecules incorporated in the Si-O-H species are identified. Larger molecules (more OH groups) tend to have a higher pressure dependence and lower temperature dependence. These trends are then used to identify possible unknown species observed in high pressure fuel-rich combustion environments.

Opila, Elizabeth J.↗

Oxidation of Chemically-Vapor-Deposited Silicon Carbide in Carbon Dioxide

Chemically-vapor-deposited silicon carbide (CVD SiC) was oxidized in carbon dioxide (CO2) at temperatures of 1200-1400 C for times between 96 and 500 h at several gas flow rates. Oxidation weight gains were monitored by thermogravimetric analysis (TGA) and were found to be very small and independent of temperature. Possible rate limiting kinetic mechanisms are discussed. Passive oxidation of SiC by CO2 is negligible compared to the rates measured for other oxidants that are also found in combustion environments, oxygen and water vapor.

Opila, Elizabeth J.↗

Volatile Reaction Products From Silicon-Based Ceramics in Combustion Environments Identified

Silicon-based ceramics and composites are prime candidates for use as components in the hot sections of advanced aircraft engines. These materials must have long-term durability in the combustion environment. Because water vapor is always present as a major product of combustion in the engine environment, its effect on the durability of silicon-based ceramics must be understood. In combustion environments, silicon-based ceramics react with water vapor to form a surface silica (SiO2) scale. This SiO2 scale, in turn, has been found to react with water vapor to form volatile hydroxides. Studies to date have focused on how water vapor reacts with high-purity silicon carbide (SiC) and SiO2 in model combustion environments. Because the combustion environment in advanced aircraft engines is expected to contain about 10-percent water vapor at 10-atm total pressure, the durability of SiC and SiO2 in gas mixtures containing 0.1- to 1-atm water vapor is of interest. The reactions of SiC and SiO2 with water vapor were monitored by measuring weight changes of sample coupons in a 0.5-atm water vapor/0.5-atm oxygen gas mixture with thermogravimetric analysis.

Opila, Elizabeth J.↗

Paralinear Oxidation of CVD SiC in Water Vapor

The oxidation kinetics of CVD SiC were monitored by thermogravimetric analysis (TGA) in a 50% H2O/50% O2 gas mixture flowing at 4.4 cm/s for temperatures between 1200 and 1400 C. Paralinear weight change kinetics were observed as the water vapor oxidized the SiC and simultaneously volatilized the silica scale. The long-term degradation rate of SiC is determined by the volatility of the silica scale. Rapid SiC surface recession rates were estimated from these data for actual aircraft engine combustor conditions.

Opila, Elizabeth J.↗

The Oxidation of CVD Silicon Carbide in Carbon Dioxide

Chemically-vapor-deposited silicon carbide (CVD SiC) was oxidized in carbon dioxide (CO2) at temperatures of 1200-1400 C for times between 100 and 500 hours at several gas flow rates. Oxidation weight gains were monitored by thermogravimetric analysis (TGA) and were found to be very small and independent of temperature. Possible rate limiting kinetic laws are discussed. Oxidation of SiC by CO2 is negligible compared to the rates measured for other oxidants typically found in combustion environments: oxygen and water vapor.

Opila, Elizabeth J.↗

Mass Spectrometric Identification of Si-O-H(g) Species from the Reaction of Silica with Water Vapor at Atmospheric Pressure

A high-pressure sampling mass spectrometer was used to detect the volatile species formed from SiO2 at temperatures between 1200C and 1400C in a flowing water vapor/oxygen gas mixture at 1 bar total pressure. The primary vapor species identified was Si(OH)4. The fragment ion Si(OH)3+,' was observed in quantities 3 to 5 times larger than the parent ion Si(OH)4+. The Si(OH)3+ intensity was found to have a small temperature dependence and to increase with the water vapor partial pressure as expected. In addition, SiO(OH)+ believed to be a fragment of SiO(OH)2, was observed. These mass spectral results were compared to the behavior of silicon halides.

Opila, Elizabeth J.↗

Environmental Effects on Non-oxide Ceramics

Non-oxide ceramics such as silicon carbide (SiC) and silicon nitride (Si3N4) are promising materials for a wide range of high temperature applications. These include such diverse applications as components for heat engines, high temperature electronics, and re-entry shields for space vehicles. Table I lists a number of selected applications. Most of the emphasis here will be on SiC and Si3N4. Where appropriate, other non-oxide materials such as aluminum nitride (AlN) and boron nitride (BN) will be discussed. Proposed materials include both monolithic ceramics and composites. Composites are treated in more detail elsewhere in this volume, however, many of the oxidation/corrosion reactions discussed here can be extended to composites. In application these materials will be exposed to a wide variety of environments. Table I also lists reactive components of these environments.It is well-known that SiC and Si3N4 retain their strength to high temperatures. Thus these materials have been proposed for a variety of hot-gas-path components in combustion applications. These include heat exchanger tubes, combustor liners, and porous filters for coal combustion products. All combustion gases contain CO2, CO, H2, H2O, O2, and N2. The exact gas composition is dependent on the fuel to air ratio or equivalence ratio. (Equivalence ratio (EQ) is a fuel-to-air ratio, with total hydrocarbon content normalized to the amount of O2 and defined by EQ=1 for complete combustion to CO2 and H2O). Figure 1 is a plot of equilibrium gas composition vs. equivalence ratio. Note that as a general rule, all combustion atmospheres are about 10% water vapor and 10% CO2. The amounts of CO, H2, and O2 are highly dependent on equivalence ratio.

Jacobson, Nathan S.↗

Volatile Hydroxide Species of Common Protective Oxides and their Role in High Temperature Corrosion

Thermodynamic data for volatile hydroxides and oxyhydroxides formed from the reaction of water vapor with Cr2O3, SiO2, A12O3, Y2O3,. and ZrO2 were assembled. The volatile species formed at temperatures between 800 and 2200K in model combustion environments containing 10% water vapor and 10% oxygen at 1 and 10 bar total pressure were calculated using free energy minimization techniques. Assuming an acceptable maximum vapor pressure limit for volatile species of 10 bar, an upper use temperature for these oxides was determined at 1 and 10 bar total pressure. The dependence of these volatile species on both water vapor and oxygen pressure was determined.

Opila, Elizabeth J.↗

Durability of Silica-Protected Ceramics in Combustion Atmospheres

This overview of oxidation and corrosion effects on silica-protected ceramics and composites is divided into two parts: (1) External effects and (2) Internal effects. In regard to the first part, the literature indicates silica the best of the common protective oxides in pure oxygen. However in actual applications, there are four major degradation routes which must be considered: (1) Formation of SiO(g); (2) water vapor enhancement of oxidation rate of Si(OH)4 volatiles; (3) low level metal cation enhancement of oxidation rate; and (4) molten salt and slag corrosion. Several protective coating concepts have been discussed, which may minimize these effects. Internal effects deal with a microcrack providing a path for oxygen ingress to the oxygen sensitive fiber and fiber coating. This is a critical area of study for theses materials. Possible solutions involve a fluid glass to fill the cracks and/or oxygen getting along the walls of the crack.

Jacobson, Nathan S.↗

Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

Opila, Elizabeth J.↗

Oxygen Tracer Diffusion in LA(z-x) SR(X) CUO(4-y) Single Crystals

The tracer diffusion of O-18 in La(2-x)Sr(x)CuO(4-y) single crystals (x = 0 to 0.12) has been measured from 400 to 700 C in 1 atm of oxygen using SIMS analysis. Evidence for diffusion by a vacancy mechanism was found at low strontium contents. Oxygen diffusivities for x greater than or = 0.07 were depressed by several orders of magnitude below the diffusivity for undoped La2CuO(4+/-y). The observed effects of strontium doping on oxygen diffusivity are discussed in terms of defect chemical models. The decreasing oxygen diffusivity with increasing strontium was attributed to the ordering of oxygen vacancies at large defect concentrations. A diffusion anisotropy D(sub ab)/D(sub c) of nearly 600 was also found at 500 C.

OXYGEN DIFFUSIVITY↗

Ceramic Matrix Composites (CMC) Life Prediction Development

Advanced launch systems will very likely incorporate fiber reinforced ceramic matrix composites (CMC) in critical propulsion and airframe components. The use of CMC will save weight, increase operating margin, safety and performance, and improve reuse capability. For reusable and single mission use, accurate life prediction is critical to success. The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many applications. This paper describes an approach and progress made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation.

Levine, Stanley R.↗