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All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

Degradation of Yttria-Stabilized Zirconia in Molten Regolith Electrolysis Applications

The generation of oxygen from lunar resources is an enabling technology to support a sustained human presence on the lunar surface. Molten regolith electrolysis is a promising process for directly electrolyzing lunar regolith, which is primarily a mixture of oxide minerals. During electrolysis, metallic products (Fe, Si) are formed at the cathode and oxygen is produced at the anode. In order to perform electrolysis, the regolith must be molten to enable ionic transport of metallic cations and oxygen anions, requiring an operating temperature of 1600C. Common refractory oxide materials, such as Al2O3 and MgO, undergo rapid degradation due to the high operating temperature and contact with the corrosive molten regolith. This work investigates yttria-stabilized zirconia (YSZ) for molten regolith electrolysis applications. Corrosion studies are presented to elucidate the degradation mechanism of YSZ powders and crucibles exposed to lunar regolith simulants at 1600C. Two regolith simulants are used to represent regolith from the lunar maria (JSC-1A) and the lunar highlands (LHS-1). Degradation of YSZ in contact with regolith simulants is evaluated using SEM/EDS, XRD, and EBSD. Furthermore, a modified molten regolith electrolysis reactor is presented utilizing YSZ at the anode to enable facile collection of oxygen produced during electrolysis.

Kevin Yu↗
NASA NTRS1997

Single Crystal Fibers of Yttria-Stabilized Cubic Zirconia with Ternary Oxide Additions

Single crystal fibers of yttria (Y2O3)-stabilized cubic zirconia, (ZrO2) with ternary oxide additions were grown using the laser float zone fiber processing technique. Ternary additions to the ZrO2-Y2O3 binary system were studied aimed at increasing strength while maintaining the high coefficient of thermal expansion of the binary system. Statistical methods aided in identifying the most promising ternary oxide candidate (Ta2O5, Sc2O3, and HfO2) and optimum composition. The yttria, range investigated was 14 to 24 mol % and the ternary oxide component ranged from 1 to 5 mol %. Hafnium oxide was the most promising ternary oxide component based on 816 C tensile strength results and ease of fabrication. The optimum composition for development was 81 ZrO2-14 Y203-5 HfO2 based upon the same elevated temperature strength tests. Preliminary results indicate process improvements could improve the fiber performance. We also investigated the effect of crystal orientation on strength.

Ritzert, F. J.↗
NASA NTRS1978

Reactions of yttria-stabilized zirconia with oxides and sulfates of various elements

The reactions between partially stabilized zirconia, containing 8 weight-percent yttria, and oxides and sulfates of various elements were studied at 1200, 1300, and 1400 C for times to 800, 400, and 200 hours, respectively. These oxides and sulfates represent impurities and additives potentially present in gas turbine fuels or impurities in the turbine combustion air as well as the elements of the substrate alloys in contact with zirconia. Based on the results, these compounds can be classified in four groups: (1) compounds which did not react with zirconia (Na2SO4, K2SO4, Cr2O3, Al2O3 and NiO); (2) compounds that reached completely with both zirconia phases (CaO, BaO, and BaSO4); (3) compounds that reacted preferentially with monoclinic zirconia (Na2O, K2O, CoO, Fe2O3, MgO, SiO2, and ZnO); and (4) compounds that reacted preferentially with cubic zirconia (V2O5, P2O5).

Zaplatynsky, I.↗
NASA NTRS1984

High-temperature erosion of plasma-sprayed, yttria-stabilized zirconia in a simulated turbine environment

A series of rig calibration and high temperature tests simulating gas path seal erosion in turbine engines were performed at three impingement angles and at three downstream locations. Plasma sprayed, yttria stablized zirconia specimens were tested. Steady state erosion curves presented for 19 test specimens indicate a brittle type of material erosion despite scanning electron microscopy evidence of plastic deformation. Steady state erosion results were not sensitive to downstream location but were sensitive to impingement angle. At difference downstream locations specimen surface temperature varied from 1250 to 1600 C (2280 to 2900 F) and particle velocity varied from 260 to 320 m/s (850 to 1050 ft/s). The mass ratio of combustion products to erosive grit material was typically 240.

Hanschuh, R. F.↗
NASA NTRS1971

Factors affecting the thermal shock behavior of yttria stabilized hafnia based graphite and tungsten composites.

Hafnia-based composites containing either graphite or tungsten were investigated as rocket nozzle throat inserts in solid propellant rocket engines. The thermal shock resistance of these materials is considered in terms of macroscopic thermal conductivity, thermal expansion, modulus of elasticity, and compressive fracture stress. The effect of degree of hafnia stabilization, density, and graphite or tungsten content upon these parameters is discussed. The variation of the ratio of elastic modulus to compressive fracture stress with density and its effect upon thermal shock resistance of these materials are discussed in detail.

Lineback, L. D.↗
NASA NTRS1985

Destabilization of yttria-stabilized zirconia induced by molten sodium vanadate-sodium sulfate melts

The extent of surface destabilization of ZrO2 - 8 wt percent Y2O3 ceramic disks was determined after exposure to molten salt mixtures of sodium sulfate containing up to 15 mole percent sodium metavanadate (NaVO3) at 1173 K. The ceramic surface was observed to transform from the cubic/tetragonal to monoclinic phase, concurrent with chemical changes in the molten salt layer in contact with the ceramic. Significant attack rates were observed in both pure sulfate and metavanadate sulfate melts. The rate of attack was found to be quite sensitive to the mole fraction of vanadate in the molten salt solution and the partial pressure of sulfur trioxide in equilibrium with the salt melt. The observed parabolic rate of attack is interpreted to be caused by a reaction controlled by diffusion in the salt that penetrates into the porous layer formed by the destabilization. The parabolic rate constant in mixed sodium metavanadate - sodium sulfate melts was found to be proportional to the SO3 partial pressure and the square of the metavanadate concentration. In-situ Raman spectroscopic measurements allowed simultaneous observations of the ceramic phases and salt chemistry during the attack process.

Nagelberg, A. S.↗
NASA NTRS1991

Temperature dependence of hardness in yttria-stabilized zirconia single crystals

The temperature dependence of hardness and microcracking in single-crystal 9.5-mol pct-Y2O3-fully-stabilized cubic-ZrO2 was studied as a function of orientation. Crack lengths increased with increased temperature up to 500 C; above 800 C, no cracks were found, indicating an indentation brittle-to-ductile transition of about 800 C. The temperature dependence of hardness was reduced around 500 C. Etching studies to delineate the plastic zone around and below indents identified the operative slip systems. The role of dislocations and their interactions within the plastic zone on the hardness and indentation fracture behavior of cubic-ZrO2 are discussed.

Morscher, Gregory N.↗
NASA NTRS1997

Factors Influencing Residual Stresses in Yttria Stabilized Zirconia Thermal Barrier Coatings

To improve gas turbine and diesel engine performance using thermal barrier coatings (TBC's) requires an understanding of the factors that influence the in-service behavior of thermal barrier coatings. One of the many factors related to coating performance is the state of stress in the coating. The total stress state is composed of the stresses due to the in-service loading history and the residual stresses. Residual stresses have been shown to affect TBC life, the bond strength of thermal spray coatings, and the fatigue life of tungsten carbide coatings. Residual stresses are first introduced in TBC's by the spraying process due to elevated temperatures during processing and the difference in coefficients of thermal expansion of the top coat, bond coat, and substrate. Later, the residual stresses can be changed by the in-service temperature history due to a number of time and temperature dependent mechanisms, such as oxidation, creep, and sintering. Silica content has also been shown to affect sintering and the cyclic life of thermal barrier coatings. Thus, it is important to understand how the spraying process, the in-service thermal cycles, and the silica content can create and alter residual stresses in thermal barrier coatings.

McGrann, Roy T. R.↗
NASA NTRSDate not supplied

The Influence of Yttria Content on the Thermal Stability of Yttria-Stabilized Zirconia Aerogels

Aerogels demonstrate extraordinarily low thermal conductivity and low density, presenting a promising form of lightweight insulation for aerospace applications. The primary challenge is stabilization of the highly porous structure at temperatures to 1200 °C. Upon collapse of the pore structure, the favorable thermal properties and low density are diminished. Yttria-stabilized zirconia (YSZ) aerogels are synthesized to investigate the effect of composition on morphology, phase behavior, and thermal stability (specific surface area, pore size distribution). This work demonstrates the improvement in thermal stability of zirconia aerogels with increased yttria content. To develop insight on the influence of structure on thermal stability, the effects of water content and solids loading are studied and in elucidation of the mechanism by which yttria stabilizes the pore structure. With an improved understanding of aerogel structure and performance, metal oxide aerogels can be developed to withstand the extreme environments of space exploration.

Nathaniel Olson↗
NASA NTRS1997

Plasma-Sprayed Refractory Oxide Coatings on Silicon-Base Ceramics

Silicon-base ceramics are promising candidate materials for high temperature structural applications such as heat exchangers, gas turbines and advanced internal combustion engines. Composites based on these materials are leading candidates for combustor materials for HSCT gas turbine engines. These materials possess a combination of excellent physical and mechanical properties at high temperatures, for example, high strength, high toughness, high thermal shock resistance, high thermal conductivity, light weight and excellent oxidation resistance. However, environmental durability can be significantly reduced in certain conditions such as when molten salts, H2 or water vapor are present. The oxidation resistance of silicon-base materials is provided by SiO2 protective layer. Molten salt reacts with SiO2 and forms a mixture of SiO2 and liquid silicate at temperatures above 800C. Oxygen diffuses more easily through the chemically altered layer, resulting in a catastrophic degradation of the substrate. SiC and Si3N4 are not stable in pure H2 and decompose to silicon and gaseous species such as CH4, SiH, SiH4, N2, and NH3. Water vapor is known to slightly increase the oxidation rate of SiC and Si3N4. Refractory oxides such as alumina, yttria-stabilized zirconia, yttria and mullite (3Al2O3.2SiO2) possess excellent environmental durability in harsh conditions mentioned above. Therefore, refractory oxide coatings on silicon-base ceramics can substantially improve the environmental durability of these materials by acting as a chemical reaction barrier. These oxide coatings can also serve as a thermal barrier. The purpose of this research program has been to develop refractory oxide chemical/thermal barrier coatings on silicon-base ceramics to provide extended temperature range and lifetime to these materials in harsh environments.

Tewari, Surendra↗
NASA NTRS1981

Microstructure and mechanical properties of bulk yttria-partially-stabilized zirconia

A commercially available bulk 4.5 mole percent yttria-(Y2O3) partially stabilized zirconia (PSZ) was studied by light microscopy, X-ray analysis, microhardness measurement, and fracture toughness testing. The growth of the precipitates and the phase transformations were studied as a function of aging in air at 1500 C. Aging curves were constructed for both the as received and the solution annealed and quenched materials; the curves showed hardness peaks at 1397 and 1517 Kg/sq mm respectively. The rectangular plate shaped tetragonal precipitates were found to have a 110 habit plane. A total of twelve different types of tetragonal precipitates were found. Grinding of the Y2O3 PSZ into powder did not cause a significant amount of metastable tetragonal precipitates to transform into the monoclinc phase, thus indicating that transformation toughening is not a significant mechanism for the material.

Valentine, P. G.↗
NASA NTRS2004

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.↗
NASA NTRS1981

Microstructure and mechanical properties of bulk yttria-partially-stabilized zirconia

A commercially available bulk 4.5 mole percent yttria-Y2O3)-partially-stabilized zirconia (PSZ) was studied by light microscopy, X-ray analysis, microhardness measurement, and fracture toughness testing. The growth of the precipitates and the phase transformations were studied as a function of aging in air at 1500 C. Aging cuves were constructed for both the as-received and the solution-annealed-and-quenched materials; the curves showed hardness peaks at 1397 and 1517 kg/sq mm, respectively. A total of twelve different types of tetragonal precipitates were found. The rectangular plate-shaped tetragonal precipitates were found to have a (110) habit plane. Grinding of the Y2O3 PSZ into powder did not cause a significant amount of metastable tetragonal precipitates to transform into the monoclinic phase, thus indicating that transformation toughening is not a significant mechanism for the material. The fracture toughness of the aged and of the unaged solution-annealed-and-quenched PSZ was found to be between 2 and 3 MN/cu m/2.

Valentine, P. G.↗
NASA NTRS2014

Multilayer Thermal Barrier Coating (TBC) Architectures Utilizing Rare Earth Doped YSZ and Rare Earth Pyrochlores

To allow for increased gas turbine efficiencies, new insulating thermal barrier coatings (TBCs) must be developed to protect the underlying metallic components from higher operating temperatures. This work focused on using rare earth doped (Yb and Gd) yttria stabilized zirconia (t' Low-k) and Gd2Zr2O7 pyrochlores (GZO) combined with novel nanolayered and thick layered microstructures to enable operation beyond the 1200 C stability limit of current 7 wt% yttria stabilized zirconia (7YSZ) coatings. It was observed that the layered system can reduce the thermal conductivity by approximately 45 percent with respect to YSZ after 20 hr of testing at 1316 C. The erosion rate of GZO is shown to be an order to magnitude higher than YSZ and t' Low-k, but this can be reduced by almost 57 percent when utilizing a nanolayered structure. Lastly, the thermal instability of the layered system is investigated and thought is given to optimization of layer thickness.

Thermal Barrier Coating↗
NASA NTRS2021

Microwave Photoelasticity: Exploiting Multiple Resonances to Measure Stress Changes within Yttria-Partially-Stabilized-Zirconia

The NASA Glenn Research Center is developing non-destructive-testing (NDT) methods to enable the measurement of stresses embedded in optically opaque materials using microwave radiation in a free-space quasi-optical system. This methodology tracks microwave resonances observed in reflected scattering parameters extracted from materials under load. In this paper, we report the successful measurement of the stress-optic-coefficient of bulk yttria-partially stabilized zirconia (YTZP) ceramic of C = 1.42 x 10-4 ± 6.65 x 10-6 (1/GPa), across W-Band (80-100 GHz), and determined that this result is independent of sample thickness. The primary goal of this research is to establish a methodology to quantify and assess the life expectancy of ceramic thermal and environmental barrier coating (TBCs/EBCs). Bulk YTZP samples can undergo multiple resonances within a contiguous measurement bandwidth, each corresponding to an integer multiple wave number ∝. This allows for the acquisition and analysis of multiple stress measurement points within a single sample. As an additional benefit, one can approximate the refractive index of YTZP across a wide bandwidth by observing multiple resonances produced by a set of samples with varying thicknesses. Using this approach, the refractive index of bulk YTZP was found to be n = 5.80 ± 0.043 across the 85-115 GHz frequency band.

Seth W. Waldstein↗
NASA NTRS2003

Lower-Conductivity Thermal-Barrier Coatings

Thermal-barrier coatings (TBCs) that have both initial and post-exposure thermal conductivities lower than those of yttria-stabilized zirconia TBCs have been developed. TBCs are thin ceramic layers, generally applied by plasma spraying or physical vapor deposition, that are used to insulate air-cooled metallic components from hot gases in gas turbine and other heat engines. Heretofore, yttria-stabilized zirconia (nominally comprising 95.4 atomic percent ZrO2 + 4.6 atomic percent Y2O3) has been the TBC material of choice. The lower-thermal-conductivity TBCs are modified versions of yttria-stabilized zirconia, the modifications consisting primarily in the addition of other oxides that impart microstructural and defect properties that favor lower thermal conductivity.

Miller, Robert A.↗
NASA NTRS1976

Ceramic thermal-barrier coatings for cooled turbines

Coating systems consisting of a plasma sprayed layer of zirconia stabilized with either yttria, magnesia or calcia over a thin alloy bond coat have been developed, their potential was analyzed and their durability and benefits evaluated in a turbojet engine. The coatings on air cooled rotating blades were in good condition after completing as many as 500 two-minute cycles of engine operation between full power at a gas temperature of 1644 K and flameout, or as much as 150 hours of steady state operation on cooled vanes and blades at gas temperatures as high as 1644 K with 35 start and stop cycles. On the basis of durability and processing cost, the yttria stabilized zirconia was considered the best of the three coatings investigated.

Liebert, C. H.↗