Exploration of rare earth doped zirconia aerogels for high temperature aerospace applications
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Nathaniel Olson↗
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Advanced thermal barrier coating systems
Current state-of-the-art thermal barrier coating (TBC) systems consist of partially stabilized zirconia coatings plasma sprayed over a MCrAlY bond coat. Although these systems have excellent thermal shock properties, they have shown themselves to be deficient for a number of diesel and aircraft applications. Two ternary ceramic plasma coatings are discussed with respect to their possible use in TBC systems. Zirconia-ceria-yttria (ZCY) coatings were developed with low thermal conductivities, good thermal shock resistance and improved resistance to vanadium containing environments, when compared to the baseline yttria stabilized zirconia (YSZ) coatings. In addition, dense zirconia-titania-yttria (ZTY) coatings were developed with particle erosion resistance exceeding conventional stabilized zirconia coatings. Both coatings were evaluated in conjunction with a NiCr-Al-Co-Y2O3 bond coat. Also, multilayer or hybrid coatings consisting of the bond coat with subsequent coatings of zirconia-ceria-yttria and zirconia-titania-yttria were evaluated. These coatings combine the enhanced performance characteristics of ZCY with the improved erosion resistance of ZTY coatings. Improvement in the erosion resistance of the TBC system should result in a more consistent delta T gradient during service. Economically, this may also translate into increased component life simply because the coating lasts longer.
Dorfman, M. R.↗
Process Developed for Generating Ceramic Interconnects With Low Sintering Temperatures for Solid Oxide Fuel Cells
Solid oxide fuel cells (SOFCs) have been considered as premium future power generation devices because they have demonstrated high energy-conversion efficiency, high power density, and extremely low pollution, and have the flexibility of using hydrocarbon fuel. The Solid-State Energy Conversion Alliance (SECA) initiative, supported by the U.S. Department of Energy and private industries, is leading the development and commercialization of SOFCs for low-cost stationary and automotive markets. The targeted power density for the initiative is rather low, so that the SECA SOFC can be operated at a relatively low temperature (approx. 700 C) and inexpensive metallic interconnects can be utilized in the SOFC stack. As only NASA can, the agency is investigating SOFCs for aerospace applications. Considerable high power density is required for the applications. As a result, the NASA SOFC will be operated at a high temperature (approx. 900 C) and ceramic interconnects will be employed. Lanthanum chromite-based materials have emerged as a leading candidate for the ceramic interconnects. The interconnects are expected to co-sinter with zirconia electrolyte to mitigate the interface electric resistance and to simplify the processing procedure. Lanthanum chromites made by the traditional method are sintered at 1500 C or above. They react with zirconia electrolytes (which typically sinter between 1300 and 1400 C) at the sintering temperature of lanthanum chromites. It has been envisioned that lanthanum chromites with lower sintering temperatures can be co-fired with zirconia electrolyte. Nonstoichiometric lanthanum chromites can be sintered at lower temperatures, but they are unstable and react with zirconia electrolyte during co-sintering. NASA Glenn Research Center s Ceramics Branch investigated a glycine nitrate process to generate fine powder of the lanthanum-chromite-based materials. By simultaneously doping calcium on the lanthanum site, and cobalt and aluminum on the chromium site, we could sinter the materials below 1400 C. The doping concentrations were adjusted so that the thermal expansion coefficient matched that of the zirconia electrolyte. Also, the investigation was focused on stoichiometric compositions so that the materials would have better stability. Co-sintering and chemical compatibility with zirconia electrolyte were examined by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy (line scanning and dot map). The results showed that the materials bond well, but do not react, with zirconia electrolyte. The electric conductivity of the materials measured at 900 C in air was about 20 S/cm.
Zhong, Zhi-Min↗
Thermodynamic Assessment of the Y2o3-yb2o3-zro2 System
Yttria-zirconia (Y2O3-ZrO2) is the most widely used of the rare earth oxide-zirconia systems. There are numerous experimental studies of the phase boundaries in this system. In this paper, we assess these data and derive parameters for the solution models in this system. There is current interest in other rare earth oxide-zirconia systems as well as systems with several rare earth oxides and zirconia, which may offer improved properties over the Y2O3-ZrO2 system. For this reason, we also assess the ytterbia-zirconia (Yb2O3-ZrO2) and Y2O3-Yb2O3-ZrO2 system.
Jacobson, Nathan S.↗
Strength and Fracture Toughness of Solid Oxide Fuel Cell Electrolyte Material Improved
Solid oxide fuel cells (SOFC) are being developed for various applications in the automobile, power-generation, and aeronautics industries. Recently, the NASA Glenn Research Center has been exploring the possibility of using SOFC's for aeropropulsion under its Zero Carbon Dioxide Emission Technology (ZCET) Program. 10-mol% yttriastabilized zirconia (10YSZ) is a very good anionic conductor at high temperatures and is, therefore, used as an oxygen solid electrolyte in SOFC. However, it has a high thermal expansion coefficient, low thermal shock resistance, low fracture toughness, and poor mechanical strength. For aeronautic applications, the thin ceramic electrolyte membrane of the SOFC needs to be strong and tough. Therefore, we have been investigating the possibility of enhancing the strength and fracture toughness of the 10YSZ electrolyte without degrading its electrical conductivity to an appreciable extent. We recently demonstrated that the addition of alumina to zirconia electrolyte increases its strength as well as its fracture toughness. Zirconia-alumina composites containing 0 to 30 mol% of alumina were fabricated by hot pressing. The hot pressing procedure was developed and various hot pressing parameters were optimized, resulting in dense, crackfree panels of composite materials. Cubic zirconia and a-alumina were the only phases detected, indicating that there was no chemical reaction between the constituents during hot pressing at elevated temperatures. Flexure strength sf and fracture toughness K(sub IC) of the various zirconia-alumina composites were measured at room temperature as well as at 1000 C in air. Both properties showed systematic improvement with increased alumina addition at room temperature and at 1000 C. Use of these modified electrolytes with improved strength and fracture toughness should prolong the life and enhance the performance of SOFC in aeronautics and other applications.
Bansal, Narottam P.↗
Formulations for Stronger Solid Oxide Fuel-Cell Electrolytes
Tests have shown that modification of chemical compositions can increase the strengths and fracture toughnesses of solid oxide fuel-cell (SOFC) electrolytes. Heretofore, these solid electrolytes have been made of yttria-stabilized zirconia, which is highly conductive for oxygen ions at high temperatures, as needed for operation of fuel cells. Unfortunately yttria-stabilized zirconia has a high coefficient of thermal expansion, low resistance to thermal shock, low fracture toughness, and low mechanical strength. The lack of strength and toughness are especially problematic for fabrication of thin SOFC electrolyte membranes needed for contemplated aeronautical, automotive, and stationary power-generation applications. The modifications of chemical composition that lead to increased strength and fracture toughness consist in addition of alumina to the basic yttria-stabilized zirconia formulations. Techniques for processing of yttria-stabilized zirconia/alumina composites containing as much as 30 mole percent of alumina have been developed. The composite panels fabricated by these techniques have been found to be dense and free of cracks. The only material phases detected in these composites has been cubic zirconia and a alumina: this finding signifies that no undesired chemical reactions between the constituents occurred during processing at elevated temperatures. The flexural strengths and fracture toughnesses of the various zirconia-alumina composites were measured in air at room temperature as well as at a temperature of 1,000 C (a typical SOFC operating temperature). The measurements showed that both flexural strength and fracture toughness increased with increasing alumina content at both temperatures. In addition, the modulus of elasticity and the thermal conductivity were found to increase and the density to decrease with increasing alumina content. The oxygen-ion conductivity at 1,000 C was found to be unchanged by the addition of alumina.
Bansal, Narottam P.↗
High temperature furnace modeling and performance verifications
A two dimensional conduction/radiation problem for an alumina crucible in a zirconia heater/muffle tube enclosing a liquid iron sample was solved numerically. Variations in the crucible wall thickness were numerically examined. The results showed that the temperature profiles within the liquid iron sample were significantly affected by the crucible wall thicknesses. New zirconia heating elements are under development that will permit continued experimental investigations of the zirconia furnace. These elements have been designed to work with the existing furnace and have been shown to have longer lifetimes than commercially available zirconia heating elements. The first element has been constructed and tested successfully.
Smith, James E., Jr.↗
Superplastic forming of ceramic insulation
Superplasticity has been demonstrated in many fine-grained structural ceramics and ceramic composites, including yttria-stabilized tetragonal zirconia polycrystal (YTZP), alumina, and Al2O3-reinforced zirconia (Al2O3/YTZ) duplex composites and SiC-reinforced Si3N4. These superplastic ceramics obviously offer the potential benefit of forming net shape or near net shape parts. This could be particularly useful for forming complicated shapes that are difficult to achieve using conventional forming techniques, or require elaborate, subsequent machining. In the present study, we successfully demonstrated the following: (1) superplastic 3Y-TXP and 20 percent Al2O3/YTZ composite have for the first time been successfully deformed into hemispherical caps via a biaxial gas-pressure forming technique; (2) no experimental difficulty was encountered in applying the required gas pressures and temperatures to achieve the results, thus, it is certain that higher rates of deformation than those presented in this study will be possible by using the current test apparatus at higher temperatures and pressures; and (3) an analytical model incorporating material parameters, such as variations during forming in the strain rate sensitivity exponent and grain growth-induced strain hardening, is needed to model accurately and therefore precisely control the biaxial gas-pressure forming of superplastic ceramics. Based on the results of this study, we propose to fabricate zirconia insulation tubes by superplastic extrusion of zirconia polycrystal. This would not only reduce the cost, but also improve the reliability of the tube products.
Nieh, T. G.↗
Blood Pump Bearing System
Methods and apparatus are provided for a blood pump bearing system within a pump housing to support long-term high-speed rotation of a rotor with an impeller blade having a plurality of individual magnets disposed thereon to provide a small radial air gap between the magnets and a stator of less than 0.025 inches. The bearing system may be mounted within a flow straightener, diffuser, or other pump element to support the shaft of a pump rotor. The bearing system includes a zirconia shaft having a radiused end. The radiused end has a first radius selected to be about three times greater than the radius of the zirconia shaft. The radiused end of the zirconia shaft engages a flat sapphire endstone. Due to the relative hardness of these materials a flat is quickly produced during break-in on the zirconia radiused end of precisely the size necessary to support thrust loads whereupon wear substantially ceases. Due to the selection of the first radius, the change in shaft end-play during pump break-in is limited to a total desired end-play of less than about 0.010 inches. Radial loads are supported by an olive hole ring jewel that makes near line contact around the circumference of the shaft to support high speed rotation with little friction. The width of olive hole ring jewel is small to allow heat to conduct through to thereby prevent heat build-up in the bearing. A void defined by the bearing elements may fill with blood that then coagulates within the void. The coagulated blood is then conformed to the shape of the bearing surfaces.
Aber, Gregory S.↗
Blood Pump Bearing System
An apparatus is provided for a blood pump bearing system within a pump housing to support long-term highspeed rotation of a rotor with an impeller blade having a plurality of individual magnets disposed thereon to provide a small radial air gap between the magnets and a stator of less than 0.025 inches. The bearing system may be mounted within a flow straightener, diffuser, or other pump element to support the shaft of a pump rotor. The bearing system includes a zirconia shaft having a radiused end. The radiused end has a first radius selected to be about three times greater than the radius of the zirconia shaft. The radiused end of the zirconia shaft engages a flat sapphire endstone. Due to the relative hardness of these materials a flat is quickly produced during break-in on the zirconia radiused end of precisely the size necessary to support thrust loads whereupon wear substantially ceases. Due to the selection of the first radius, the change in shaft end-play during pump break-in is limited to a total desired end-play of less than about 0.010 inches. Radial loads are supported by an olive hole ring jewel that makes near line contact around the circumference of the Ir shaft to support big speed rotation with little friction. The width of olive hole ring jewel is small to allow heat to conduct through to thereby prevent heat build-up in the bearing. A void defined by the bearing elements may fill with blood that then coagulates within the void. The coagulated blood is then conformed to the shape of the bearing surfaces.
Aber, Gregory S.↗
Separation of Carbon Monoxide and Carbon Dioxide for Mars ISRU-Concepts
Solid oxide electrolyzers, such as electrolysis cells utilizing yttria-stabilized zirconia, can produce oxygen from Mars atmospheric carbon dioxide and reject carbon monoxide and unreacted carbon dioxide in a separate stream. The oxygen-production process has been shown to be far more efficient if the high-pressure, unreacted carbon dioxide can be separated and recycled back into the feed stream. Additionally, the mass of the adsorption compressor can be reduced. Also, the carbon monoxide by-product is a valuable fuel for space exploration and habitation, with applications from fuel cells to production of hydrocarbons and plastics. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU. Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, respectively. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU, Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, Research needs for the design shown are as follows: (1) The best adsorbent for the process must be determined. (2) Adsorption isotherms must be measured, both for pure components and mixtures. (3) Mathematical modeling must be performed to provide a solid framework for design. (4) The separation system must be constructed and tested. (5) System integration must be studied.
LeVan, M. Douglas↗
Method for Providing a Jewel Bearing for Supporting a Pump Rotor Shaft
Methods for a blood pump bearing system within a pump housing to support long-term high-speed rotation of a rotor with an impeller blade having a plurality of individual magnets disposed thereon to provide a small radial air gap between the magnets and a stator of less than 0.025 inches. The bearing system may be mounted within a flow straightener, diffuser, or other pump element to support the shaft of a pump rotor. The bearing system includes a zirconia shaft having a radiused end. The radiused end has a first radius selected to be about three times greater than the radius of the zirconia shaft. The radiused end of the zirconia shaft engages a flat sapphire endstone. Due to the relative hardness of these materials a flat is quickly produced during break-in on the zirconia radiused end of precisely the size necessary to support thrust loads whereupon wear substantially ceases. Due to the selection of the first radius, the change in shaft end-play during pump break-in is limited to a total desired end-play of less than about 0.010 inches. Radial loads are supported by an olive hole ring jewel that makes near line contact around the circumference of the shaft to support high speed rotation with little friction. The width of olive hole ring jewel is small to allow heat to conduct through to thereby prevent heat build-up in the bearing. A void defined by the bearing elements may fill with blood that then coagulates within the void. The coagulated blood is then conformed to the shape of the bearing surfaces.
Gregory S Aber↗
Sintering and Interface Strain Tolerance of Plasma-Sprayed Thermal and Environmental Barrier Coatings
Ceramic thermal and environmental barrier coatings will be more aggressively designed to protect gas turbine engine hot section SiC/SiC Ceramic Matrix Composite (CMC) components in order to meet future engine higher fuel efficiency and lower emission goals. A coating system consisting of a zirconia-based oxide topcoat (thermal barrier) and a mullite/BSAS silicate inner coat (environmental barrier) is often considered a model system for the CMC applications. However, the coating sintering, and thermal expansion mismatch between the zirconia oxide layer and the silicate environmental barrier/CMC substrate will be of major concern at high temperature and under thermal cycling conditions. In this study, the sintering behavior of plasma-sprayed freestanding zirconia-yttria-based thermal barrier coatings and mullite (and/or barium-strontium-aluminosilicate, i.e., BSAS) environmental barrier coatings was determined using a dilatometer in the temperature range of 1200-1500 C. The effects of test temperature on the coating sintering kinetics were systematically investigated. The plasma-sprayed zirconia-8wt.%yttria and mullite (BSAS) two-layer composite coating systems were also prepared to quantitatively evaluate the interface strain tolerance of the coating system under thermal cycling conditions based on the dilatomentry. The cyclic response of the coating strain tolerance behavior and interface degradation as a function of cycle number will also be discussed.
Zhu, Dongming↗
Kinetic Monte Carlo Simulation of Cation Diffusion in Low-K Ceramics
Low thermal conductivity (low-K) ceramic materials are of interest to the aerospace community for use as the thermal barrier component of coating systems for turbine engine components. In particular, zirconia-based materials exhibit both low thermal conductivity and structural stability at high temperature, making them suitable for such applications. Because creep is one of the potential failure modes, and because diffusion is a mechanism by which creep takes place, we have performed computer simulations of cation diffusion in a variety of zirconia-based low-K materials. The kinetic Monte Carlo simulation method is an alternative to the more widely known molecular dynamics (MD) method. It is designed to study "infrequent-event" processes, such as diffusion, for which MD simulation can be highly inefficient. We describe the results of kinetic Monte Carlo computer simulations of cation diffusion in several zirconia-based materials, specifically, zirconia doped with Y, Gd, Nb and Yb. Diffusion paths are identified, and migration energy barriers are obtained from density functional calculations and from the literature. We present results on the temperature dependence of the diffusivity, and on the effects of the presence of oxygen vacancies in cation diffusion barrier complexes as well.
Good, Brian↗
Constraining the Temperature of Impact Melt from the Mistastin Lake Impact Structure Using Zircon Crystal Structures
Impact melt is a product of hyper-velocity impact events formed by the instantaneous melting of near-surface target rocks. Constraining the temperature of impact melt is vital to understanding its prograde heating and cooling history, which can have implications for inferring the environment of early Earth ~4.0 billion years ago when microbial life potentially arose. To date, only one datum on the initial impact melt temperature has been derived by Timms et al. These authors studied zirconia microstructures and crystallographic orientations that revealed the former presence of cubic zirconia, found in a black impact glass at the Mistastin Lake impact structure, Canada. The presence of cubic zirconia indicates a minimum temperature for the impact melt of >2370°C from the dissociation temperature of zircon to cubic zirconia and liquid SiO2. With only one temperature datum, it is still difficult to constrain the entire temperature range experienced during the impact melting process; from its instantaneous formation to thermal equilibrium with the “cold” clasts collected along the crater floor and walls. In addition, obtaining a temperature value from only one type of impactite limits the inferred temperature range, because each impactite experiences a different cooling history. In this study, we present a preliminary investigation of 61 zircon crystals, 14 of which are similar to those studied by Timms et al., from the Mistastin Lake impact structure. To acquire a more accurate temperature profile representative of impact melt, zircon crystals were collected from different types of impactites containing impact melt, including additional samples of the black impact glass studied by Timms et al.
Tolometti, G. D.↗
TEMPERATURE CONSTRAINT OF THE MISTASTIN LAKE IMPACT STRUCTURE IMPACT MELT ROCKS
Impact melt is a product of hypervelocity cratering events formed by the instantaneous melting of near-surface target rocks. The temperatures of impact melt upon formation are believed to be superheated, vastly exceeding the liquidus temperature of igneous rocks formed via endogenic processes. However, quantitative understanding of the formation and duration of superheated temperatures remains incomplete. To date, only one datum on the hottest post-shock temperature (>2370 °C) has been derived by Timms et al. (2017) [1]. These authors studied the microstructures and crystallographic orientations preserved within a rim of vermicular ZrO2 of a zircon grain entrained within impact glass at the Mistastin Lake impact structure, Canada. Diagnostic crystallographic orientation indicated the presence of cubic zirconia, requiring a minimum temperature for the impact melt of >2370°C from the dissociation of zircon to cubic zirconia and liquid SiO2. With only one temperature datum, it cannot be stated whether the temperature of the impact melt sheet was homogenous across the entire structure or if the thermal history of the melt varied with spatial distribution. In this study, we present a preliminary investigation of 70 zircon grains, 22 of which exhibit rims of vermicular ZrO2 dissociation textures, similar to those studied by Timms et al. (2017). To acquire a more accurate temperature profile representative of impact melt, zircon crystals were collected from different types of impact melt bearing units, including additional samples of the impact glass studied by Timms et al. (2017). Of the 22 zircon grains with dissociation textures, at least 4 grains in the impact glass show diagnostic evidence of pre-existing cubic zirconia, and 1 grain from a glass-bearing breccia exhibits granular zircon textures, possible evidence of a transition from high-P to high-T conditions. These results show the heterogeneous post-shock temperature distribution of superheated impact melt within the Mistastin impact structure. [1] Timms, N.E., Erickson, T.M., Zanetti, M.R., Pearce, M.A., Cayron, C., Cavosie, A.J., Reddy, S.M., Wittmann, A. and Carpenter, P.K., 2017. Cubic zirconia in> 2370° C impact melt records Earth's hottest crust. Earth and Planetary Science Letters, 477, pp.52-58.
rock↗
Thermal Conductivity and Erosion Durability of Composite Two-Phase Air Plasma Sprayed Thermal Barrier Coatings
To enhance efficiency of gas turbines, new thermal barrier coatings (TBCs) must be designed which improve upon the thermal stability limit of 7 wt% yttria stabilized zirconia (7YSZ), approximately 1200 C. This tenant has led to the development of new TBC materials and microstructures capable of improved high temperature performance. This study focused on increasing the erosion durability of cubic zirconia based TBCs, traditionally less durable than the metastable t' zirconia based TBCs. Composite TBC microstructures composed of a low thermal conductivity/high temperature stable cubic Low-k matrix phase and a durable t' Low-k secondary phase were deposited via APS. Monolithic coatings composed of cubic Low-k and t' Low-k were also deposited, in addition to a 7YSZ benchmark. The thermal conductivity and erosion durability were then measured and it was found that both of the Low-k materials have significantly reduced thermal conductivities, with monolithic t' Low-k and cubic Low-k improving upon 7YSZ by approximately 13 and approximately 25%, respectively. The 40 wt% t' Low-k composite (40 wt% t' Low-k - 60 wt% cubic Low-k) showed a approximately 22% reduction in thermal conductivity over 7YSZ, indicating even at high levels, the t' Low-k secondary phase had a minimal impact on thermal in the composite coating. It was observed that a mere 20 wt% t' Low-k phase addition can reduce the erosion of a cubic Low-k matrix phase composite coating by over 37%. Various mixing rules were then investigated to assess this non-linear composite behavior and suggestions were made to further improve erosion durability.
Rare earth zirconia↗
Significance of thermal contact resistance in two-layer thermal-barrier-coated turbine vanes
The importance of thermal contact resistance between layers in heat transfer through two layer, plasma sprayed, thermal barrier coatings applied to turbine vanes was investigated. Results obtained with a system of NiCrAlY bond and yttria stabilized zirconia ceramic show that thermal contact resistance between layers is negligible. These results also verified other studies which showed that thermal contact resistance is negligible for a different coating system of NiCr bond calcia stabilized zirconia ceramic. The zirconia stabilized ceramic thermal conductivity data scatter presented in the literature is ?20 to -10 percent about a curve fit of the data. More accurate predictions of heat transfer and metal wall temperatures are obtained when the thermal conductivity values are used at the ?20 percent level.
Liebert, C. H.↗