Engineering topics
Publications and source records attributed to Opila, Elizabeth J..
A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a barium-strontium alumino silicate.
Advanced reusable launch vehicles will likely incorporate fiber-reinforced ceramic matrix composites (CMC's) in critical propulsion and airframe components. The use of CMC's is highly desirable to save weight, improve reuse capability, and increase performance. One of the candidate CMC materials is carbon-fiber-reinforced silicon carbide (C/SiC). In potential propulsion applications, such as turbopump rotors and nozzle exit ramps, C/SiC components will be subjected to a service cycle that includes mechanical loading under complex, high-pressure environments containing hydrogen, oxygen, and steam. Degradation of both the C fibers and the SiC matrix are possible in these environments. The objective of this effort was to evaluate the mechanical behavior of C/SiC in various environments relevant to reusable launch vehicle applications. Stress-rupture testing was conducted at the NASA Glenn Research Center on C/SiC specimens in air and steam-containing environments. Also, the oxidation kinetics of the carbon fibers that reinforce the composite were monitored by thermogravimetric analysis in the same environments and temperatures used for the stress-rupture tests of the C/SiC composite specimens. The stress-rupture lives obtained for C/SiC tested in air and in steam/argon mixtures are shown in the following bar chart. As is typical for most materials, lives obtained at the lower temperature (600 C) are longer than for the higher temperature (1200 C). The effect of environment was most pronounced at the lower temperature, where the average test duration in steam at 600 C was at least 30 times longer than the lives obtained in air. The 1200 C data revealed little difference between the lives of specimens tested in air and steam at atmospheric pressure.
Three silicon nitride materials were exposed to dry oxygen flowing at 0.44 cm/s at temperatures between 1200 and 1400 C. Reaction kinetics were measured with a continuously recording microbalance. Parabolic kinetics were observed. When the same materials were exposed to a 50% H2O - 50% O2 gas mixture flowing at 4.4 cm/s, all three types exhibited paralinear kinetics. The material is oxidized by water vapor to form solid silica. The protective silica is in turn volatilized by water vapor to form primarily gaseous Si(OH)4. Nonlinear least squares analysis and a paralinear kinetic model were used to determine both parabolic and linear rate constants from the kinetic data. Volatilization of the protective silica scale can result in accelerated consumption of Si3N4. Recession rates under conditions more representative of actual combustors are compared to the furnace data.
Current environmental barrier coatings (EBCs) for silicon-based ceramics consist of a bond coat and a top coat. Mullite bond coat modified by adding low CTE glass ceramics, such as BSAS (xBaO.1xSrO.Al2O3.2SiO2) or CAS (CaO.Al2O3.2SiO2), was developed in the NASA Enabling Propulsion Materials (EPM) Program. EBCs based on mullite+CAS bond coat were characterized using high steam thermal cycling test and high steam isothermal thermogravemitry (TGA) at 1225 C - 13,000 C. The Mullite+CAS bond coat showed far superior durability compared to mullite bond coat, due to enhanced crack resistance. A BSAS top coat provided further improved durability compared to EBCs with a yttria-stabilized zirconia (YSZ) top coat. Still further improvement in the durability was achieved by adding a silicon bond coat between the mullite and the substrate. However, the silicon/mullite+CAS/BSAS EBC showed inferior long-term durability compared to the current state-of-the art EBC (silicon/mullite+BSAS/BSAS EBC), presumably due to the higher CAS-silica chemical reactivity.
Two commercially available additive-containing silicon nitride materials were exposed in four environments which range in severity from dry oxygen at 1 atm pressure, and low gas velocity to an actual turbine engine. Oxidation and volatilization kinetics were monitored at temperatures ranging from 1066 to 1400 C. The main purpose of this paper is to examine the surface oxide morphology resulting from the exposures. It was found that the material surface was enriched in rare earth silicate phases in combustion environments when compared to the oxides formed on materials exposed in dry oxygen. However, the in situ formation of rare earth disilicate phases offered little additional protection from the volatilization of silica observed in combustion environments. It was concluded that externally applied environmental barrier coatings are needed to protect additive-containing silicon nitride materials from volatilization reactions in combustion environments. Introduction Si3N4 is proposed for use as components, such as vanes, in turbine applications. Tens of thousands of hours of life are needed for both land-based turbines and aeropropulsion applications. Additive-containing SisN4 materials are
Ultra-high temperature ceramic (UHTC) materials consisting of zirconium diboride or hafnium diboride plus silicon carbide offer a combination of properties that make them candidates for airframe leading edges on sharp-bodied reentry vehicles. These UHTC perform well in the environment for such applications, i.e. low pressure air. The purpose of this study was to examine three of these materials under conditions more representative of a propulsion environment, i.e. higher oxygen and total pressure. Results of stren$h and fracture toughness measurements, furnace oxidation, and thermal shock exposures are presented. The poor oxidation resistance of UHTCs is the predominant factor limiting their applicability to propulsion.
A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a yttrium silicate.
A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a calcium alumino silicate.
A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a yttrium silicate.
A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a calcium alumino silicate.
Silicon-based ceramics are promising candidate structural materials for heat engines. The long-term stability of these materials to environmental degradation is dependent on the formation and retention of a protective SiO2 layer. It is well known that SiO2 forms stable volatile hydroxides in the presence of water vapor at elevated temperatures. Combustion conditions, which characteristically are at high velocities, contain significant water vapor pressures, and high temperatures tend to promote continuous formation of these hydroxides with resulting material degradation. For the degradation of silicon-based ceramics to be predicted, accurate thermodynamic data on the formation of silicon hydroxides are needed.
In this paper the oxidation behavior of ZrB2-20 vol% SiC is examined. Samples were exposed in stagnant air in a zirconia furnace (Deltech, Inc.) at temperatures of 1327, 1627, and 1927 C for ten ten-minute cycles. Samples were removed from the furnace after one, five, and ten cycles. Oxidized material was characterized by mass change when possible, x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). Oxidation kinetics, oxide scale development, and matrix recession were monitored as a function of time and temperature. Oxidation and recession rates of ZrB2 - 20 vol% SiC were adequately modeled by parabolic kinetics. Oxidation rates of this material are rapid, allowing only very short-term application in air or other high oxygen partial pressure environments.
Among the ultra-high temperature ceramics (UHTC) are a group of materials consisting of zirconium diboride or hafnium diboride plus silicon carbide, and in some instances, carbon. These materials offer a good combination of properties that make them candidates for airframe leading edges on sharp-bodied reentry vehicles. These UHTC perform well in the environment for such applications, i.e., air at low pressure. The purpose of this study was to examine three of these materials under conditions more representative of a propulsion environment, i.e., higher oxygen partial pressure and total pressure. Results of strength and fracture toughness measurements, furnace oxidation and high velocity thermal shock exposures are presented for ZrB2 plus 20 volume % SiC, ZrB2 plus 14 volume % SiC plus 30 volume % C, and SCS-9a SiC fiber reinforced ZrB2 plus 20 volume % SiC. The poor oxidation resistance of UHTCs is the predominant factor limiting their applicability to propulsion applications.
The formation of volatile silicon-hydroxide species from SiO2 in water containing atmospheres has been identified as a potentially important mode of degradation of Si-based ceramics. Availability of thermodynamic data for these species is a major problem. This study is part of an ongoing effort to obtain reliable, experimentally determined thermodynamic data for these species. The transpiration method was used to measure the pressure of Si-containing vapor in equilibrium with SiO2 (cristobalite) and Ar + H2O(g) with various mole fractions of water vapor, X(sub H2O), at temperatures ranging from 1000 to 1780 K. Enthalpies and entropies for the reaction, SiO2(s) + 2H2O(g) = Si(OH)4(g), were obtained, at X(sub H2O) = 0.15 and 0.37, from the variation of lnK with 1/T according to the 'second law method'. The following data were obtained: delta(H)deg = 52.9 +/- 3.7 kJ/mole and delta(S)deg = -68.6 +/- 2.5 J/mole K at an average temperature of 1550 K, and delta(H)deg = 52.5+/-2.0 kJ/mole and delta(S)deg= -69.7 +/- 1.5 J/moleK at an average temperature of 1384 K, for X(sub H2O)= 0.15 and 0.37, respectively. These data agree with results from the literature obtained at an average temperature of 1600 K, and strongly suggest Si(OH)4(g) is the dominant vapor species. Contradictory results were obtained with the determination of the dependence of Si-containing vapor pressure on the partial pressure of water vapor at 1187 and 1722 K. These results suggested the Si-containing vapor could be a mixture of Si(OH)4 + SiO(OH)2. Further pressure dependent studies are in progress to resolve these issues.
Advanced launch systems (e.g., Reusable Launch Vehicle and other Shuttle Class concepts, Rocket-Based Combine Cycle, etc.), and interplanetary vehicles will very likely incorporate fiber reinforced ceramic matrix composites (CMC) in critical propulsion components. The use of CMC is highly desirable to save weight, to improve reuse capability, and to increase performance. CMC candidate applications are mission and cycle dependent and may include turbopump rotors, housings, combustors, nozzle injectors, exit cones or ramps, and throats. For reusable and single mission uses, accurate prediction of life is critical to mission success. The tools to accomplish life prediction are very immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for a variety of space propulsion applications. This paper describes an approach to satisfy the need to develop an integrated life prediction system for CMC that addresses mechanical durability due to cyclic and steady thermomechanical loads, and takes into account the impact of environmental degradation.
SiC is proposed for structural applications in high pressure, high temperature. high gas velocity environments of turbine and rocket engines. These environments are typically composed of complex gas mixtures containing carbon dioxide, oxygen, water vapor, and nitrogen. It is known that the primary oxidant for SiC in these environments is water vapor.
The oxidation kinetics of CVD SiC were measured by thermogravimetric analysis (TGA) in a 4H2 (central dot) 12H2O (central dot) 10CO (central dot) 7CO2 (central dot) 67N2 gas mixture flowing at 0.44 cm/s at temperatures between 1300 and 1450 C in fused quartz furnace tubes at I atm total pressure. The SiC was oxidized to form solid SiO2. At less than or = 1350 C, the SiO2 was in turn volatilized. Volatilization kinetics were consistent with the thermodynamic predictions based on SiO formation. These two simultaneous reactions resulted in overall paralinear kinetics. A curve fitting technique was used to determine the linear and parabolic rate constants from the paralinear kinetic data. Volatilization of the protective SiO2 scale resulted in accelerated consumption of SiC. Recession rates under conditions more representative of actual combustors were estimated from the furnace data.
The requirements for hot-gas-path materials in gas turbine engines are demanding. These materials must maintain high strength and creep resistance in a particularly aggressive environment. A typical gas turbine environment involves high temperatures, rapid gas flow rates, high pressures, and a complex mixture of aggressive gases. Figure 26.1 illustrates the requirements for components of an aircraft engine and critical issues [1]. Currently, heat engines are constructed of metal alloys, which meet these requirements within strict temperature limits. In order to extend these temperature limits, ceramic materials have been considered as potential engine materials, due to their high melting points and stability at high temperatures. These materials include oxides, carbides, borides, and nitrides. Interest in using these materials in engines appears to have begun in the 1940s with BeO-based porcelains [2]. During the 1950s, the efforts shifted to cermets. These were carbide-based materials intended to exploit the best properties of metals and ceramics. During the 1960s and 1970s, the silicon-based ceramics silicon carbide (SiC) and silicon nitride (Si3N4) were extensively developed. Although the desirable high-temperature properties of SiC and Si3N4 had long been known, consolidation of powders into component-sized bodies required the development of a series of specialized processing routes [3]. For SiC, the major consolidation routes are reaction bonding, hot-pressing, and sintering. The use of boron and carbon as additives which enable sintering was a particularly noteworthy advance [4]. For Si3N4 the major consolidation routes are reaction bonding and hot pressing [5]. Reaction-bonding involves nitridation of silicon powder. Hot pressing involves addition of various refractory oxides, such as magnesia (MgO), alumina (Al2O3), and yttria (y2O3). Variations on these processes include a number of routes including Hot Isostatic Pressing (HIP), gas-pressure sintering, sinter-HIPing, and Encapsulation-HIPing. It is important to note that each process involves the addition of secondary elements, which later were shown to dramatically influence oxidation and corrosion behavior. As dense bodies of silicon-based ceramics became more readily available, their desirable high temperature properties were confirmed. These materials retained strength to very high temperatures (i.e. 1300-1400 C). Further, they were lightweight and made from abundant materials. SiC and Si3N4 therefore emerged as leading ceramic candidates for components in heat engines, designed to operate at higher temperatures for better performance and fuel efficiency. The first US programs for ceramics in heat engines have been reviewed [6]. Selected programs on ceramic engine parts are summarized here in regard to their contributions to understanding the corrosion behavior of a heat engine environment.