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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Multilayer article having stabilized zirconia outer layer and chemical barrier layer

A multilayer article includes a substrate that includes at least one of a ceramic compound and a Si-containing metal alloy. An outer layer includes stabilized zirconia. Intermediate layers are located between the outer layer and the substrate and include a mullite-containing layer and a chemical barrier layer. The mullite-containing layer includes 1) mullite or 2) mullite and an alkaline earth metal aluminosilicate. The chemical barrier layer is located between the mullite-containing layer and the outer layer. The chemical barrier layer includes at least one of mullite, hafnia, hafnium silicate and rare earth silicate (e.g., at least one of RE.sub.2 SiO.sub.5 and RE.sub.2 Si.sub.2 O.sub.7 where RE is Sc or Yb). The multilayer article is characterized by the combination of the chemical barrier layer and by its lack of a layer consisting essentially of barium strontium aluminosilicate between the mullite-containing layer and the chemical barrier layer. Such a barium strontium aluminosilicate layer may undesirably lead to the formation of a low melting glass or unnecessarily increase the layer thickness with concomitant reduced durability of the multilayer article. In particular, the chemical barrier layer may include at least one of hafnia, hafnium silicate and rare earth silicate.

Lee, Kang N.↗
NASA NTRS2011

Kinetic Monte Carlo Simulation of Oxygen and Cation Diffusion in Yttria-Stabilized Zirconia

Yttria-stabilized zirconia (YSZ) is of interest to the aerospace community, notably for its application as a thermal barrier coating for turbine engine components. In such an application, diffusion of both oxygen ions and cations is of concern. Oxygen diffusion can lead to deterioration of a coated part, and often necessitates an environmental barrier coating. Cation diffusion in YSZ is much slower than oxygen diffusion. However, such diffusion is a mechanism by which creep takes place, potentially affecting the mechanical integrity and phase stability of the coating. In other applications, the high oxygen diffusivity of YSZ is useful, and makes the material of interest for use as a solid-state electrolyte in fuel cells. The kinetic Monte Carlo (kMC) method offers a number of advantages compared with the more widely known molecular dynamics simulation method. In particular, kMC is much more efficient for the study of processes, such as diffusion, that involve infrequent events. We describe the results of kinetic Monte Carlo computer simulations of oxygen and cation diffusion in YSZ. Using diffusive energy barriers from ab initio calculations and from the literature, we present results on the temperature dependence of oxygen and cation diffusivity, and on the dependence of the diffusivities on yttria concentration and oxygen sublattice vacancy concentration. We also present results of the effect on diffusivity of oxygen vacancies in the vicinity of the barrier cations that determine the oxygen diffusion energy barriers.

Good, Brian↗
NASA NTRS2011

Kinetic Monte Carlo Investigation of the Effects of Vacancy Pairing on Oxygen Diffusivity in Yttria-Stabilized Zirconia

Yttria-stabilized zirconia s high oxygen diffusivity and corresponding high ionic conductivity, and its structural stability over a broad range of temperatures, have made the material of interest for use in a number of applications, for example, as solid electrolytes in fuel cells. At low concentrations, the stabilizing yttria also serves to increase the oxygen diffusivity through the presence of corresponding oxygen vacancies, needed to maintain charge neutrality. At higher yttria concentration, however, diffusivity is impeded by the larger number of relatively high energy migration barriers associated with yttrium cations. In addition, there is evidence that oxygen vacancies preferentially occupy nearest-neighbor sites around either dopant or Zr cations, further affecting vacancy diffusion. We present the results of ab initio calculations that indicate that it is energetically favorable for oxygen vacancies to occupy nearest-neighbor sites adjacent to Y ions, and that the presence of vacancies near either species of cation lowers the migration barriers. Kinetic Monte Carlo results from simulations incorporating this effect are presented and compared with results from simulations in which the effect is not present.

Good, Brian S.↗
NASA NTRS2009

Determination of Scattering and Absorption Coefficients for Plasma-Sprayed Yttria-Stabilized Zirconia Thermal Barrier Coatings at Elevated Temperatures

The temperature dependence of the scattering and absorption coefficients for a set of freestanding plasma-sprayed 8 wt% yttria-stabilized zirconia (8YSZ) thermal barrier coatings (TBCs) was determined at temperatures up to 1360 C in a wavelength range from 1.2 micrometers up to the 8YSZ absorption edge. The scattering and absorption coefficients were determined by fitting the directional-hemispherical reflectance and transmittance values calculated by a four-flux Kubelka Munk method to the experimentally measured hemispherical-directional reflectance and transmittance values obtained for five 8YSZ thicknesses. The scattering coefficient exhibited a continuous decrease with increasing wavelength and showed no significant temperature dependence. The scattering is primarily attributed to the relatively temperature-insensitive refractive index mismatch between the 8YSZ and its internal voids. The absorption coefficient was very low (less than 1 per centimeter) at wavelengths between 2 micrometers and the absorption edge and showed a definite temperature dependence that consisted of a shift of the absorption edge to shorter wavelengths and an increase in the weak absorption below the absorption edge with increasing temperature. The shift in the absorption edge with temperature is attributed to strongly temperature-dependent multiphonon absorption. While TBC hemispherical transmittance beyond the absorption edge can be predicted by a simple exponential decrease with thickness, below the absorption edge, typical TBC thicknesses are well below the thickness range where a simple exponential decrease in hemispherical transmittance with TBC thickness is expected. [Correction added after online publication August 11, 2009: "edge to a shorter wavelengths" has been updated as edge to shorter wavelengths."]

Eldridge, Jeffrey I.↗
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 NTRSDate not supplied

Optimizing Surfactant Templating of Yttria-stabilized Zirconia Aerogels for High-temperature Applications: Effect of Anionic & Nonionic Surfactant

Aerogels are useful thermal insulators due to low density, low thermal conductivity, and a tortuous path for solid conduction. However, the formulation must be optimized to increase thermal stability as drastic densification and surface area decrease is often exhibited after high-temperature exposure. Current research investigates yttria-stabilized zirconia (YSZ) aerogels for expected use between 600°C and 1000°C. We anticipate that new sol-gel chemistries will yield YSZ aerogels with retained mesoporous structure, increased surface area, and minimized shrinkage upon high-temperature exposure. This work investigates the anionic surfactant, sodium dodecyl sulfate (SDS), and the nonionic surfactant, Pluronic® P-123, as templating agents to prevent the collapse of the aerogel pore structure upon gelation and drying. To determine the effect of surfactant, characterization techniques such as nitrogen physisorption, x-ray diffraction, and scanning electron microscopy are used. By optimizing surfactant concentration, the thermal stability of YSZ aerogels can be enhanced, producing more efficient thermal insulators.

Rebecca C. Walker↗
NASA NTRSDate not supplied

Understanding thermal stability in doped zirconia aerogels for high temperature applications

The high porosities and low densities of ceramic aerogels offer outstanding insulative performance in applications where weight is a critical factor. The high surface-to-volume ratios and specific surface areas provide extremely low thermal conductivity, but also contribute to rapid densification of the pore structure at elevated temperatures. This densification diminishes their favorable properties and inhibits use of aerogels in high temperature applications. The purpose of this work is the establishment of a design framework for thermally stable, highly porous materials. Here we will review our recent studies on the effects of synthetic parameters and dopant chemistry on the evolution of zirconia-based aerogels. The structural evolution was studied to 1200 °C using nitrogen physisorption, scanning and transmission electron microscopy, and x-ray diffraction. The role of dopant identity and concentration in thermal stability was elucidated. In context of the design framework, dopant chemistry is an aggregate for many closely related material properties, each of which may contribute to aerogel structural evolution. To develop a truly predictive design framework for ceramic-based aerogels, systematic and comprehensive evaluation of thermodynamic and kinetic properties must be performed in conjunction with studies on structural evolution.

aerogel↗
NASA NTRSDate not supplied

Understanding Thermal Stability in Zirconia-Based Aerogels

For lightweight, thermal insulation needs above 1000ºC, the high surface to volume ratios of ceramic-based aerogels are practically unparalleled. Yet realizing the full potential of aerogel-based thermal protection systems requires not only increased thermal stability, but also a broadened menu of stabilizing mechanisms. Here we will review our recent efforts to understand the impact of synthetic parameters and dopant chemistry on the evolution of zirconia-based ceramics. A broad parametric window for thermal stability is established, in which the more sensitive variable of composition has been probed. However, dopant chemistry is actually an aggregate for many closely related material parameters including surface energy, enthalpy of formation, each of which may contribute uniquely to aerogel destabilization. A truly predictive design framework for ceramic-based aerogels requires further decoupling of these underlying properties through systematic and comprehensive evaluation of thermodynamic properties.

aerogel↗
NASA NTRSDate not supplied

Thermochemical Interactions of Yttria-Stabilized Zirconia and Molten Lunar Regolith Simulants

Oxygen produced from lunar resources through in-situ resource utilization (ISRU) is critical to maintaining a permanent human presence on the lunar surface. Molten regolith electrolysis and carbothermal reduction are two promising ISRU techniques for generating oxygen directly from lunar regolith, which is primarily a mixture of oxide minerals; however, both processes require operating temperatures of 1600C to melt lunar regolith and dissociate the molten oxides. These conditions limit the use of many oxide refractory materials, such as Al2O3 and MgO, due to rapid degradation resulting from reactions between the refractory materials and molten lunar regolith. Yttria-stabilized zirconia (YSZ) is a promising refractory oxide to provide containment of molten regolith while demonstrating limited reactivity. This work focuses on corrosion studies of YSZ powders and dense YSZ crucibles in contact with molten lunar mare and highlands regolith simulants at 1600C. The interactions between YSZ and molten regolith are characterized using SEM/EDS, XRD, and EBSD with an emphasis on elemental and microstructural analysis to assess reactivity and degradation of YSZ. Due to lunar regolith’s similar composition to calcium-magnesium-aluminosilicates (CMAS) and YSZ’s usage as a thermal barrier coating, these interactions can serve to inform YSZ/CMAS behavior by simulating cases of elevated CMAS/YSZ ratios and for higher than intended gas turbine temperatures.

Kevin Yu↗
NASA NTRS2024

Thermochemical Interactions Between Yttria-Stabilized Zirconia and Molten Lunar Regolith Simulants

Oxygen produced through in-situ resource utilization (ISRU) is critical to maintaining a permanent human presence on the lunar surface. Molten regolith electrolysis and carbothermal reduction are two promising ISRU techniques for generating oxygen directly from lunar regolith, which is primarily a mixture of oxide minerals; however, both processes require operating temperatures of 1600 C to melt lunar regolith and dissociate the molten oxides. These conditions limit the use of many oxide refractory materials, such as Al2O3 and MgO, due to rapid degradation resulting from reactions between the refractory materials and molten lunar regolith. Yttria-stabilized zirconia (YSZ) is shown here to be a promising refractory oxide to provide containment of molten regolith while demonstrating limited reactivity. This work focuses on corrosion studies of YSZ powders and dense YSZ crucibles in contact with molten lunar maria and highlands regolith simulants at 1600 C. The interactions between YSZ and molten regolith are characterized using SEM/EDS, XRD, and EBSD. A FactSage thermochemical model is created to compare with the experimental results. These combined analyses suggest that lunar maria regolith will degrade YSZ faster than lunar highlands regolith due to the lower viscosity of the maria regolith. The feasibility of long-term molten regolith containment with YSZ is discussed based on the YSZ powder and crucible results.

Kevin Yu↗
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↗
DOE OSTI2023

Fuel cell and electrolyzer hotbox module using conductive zirconia stacks

Modular pressurized hotbox for use and substitution in a variety of pressurized electrochemical applications to include reversible solid oxide electrolyzer and fuel cells, energy storage systems, renewable fuel production, solid-state hydrogen pumping and liquefaction, and oxygen transport membranes. This is enabled by mixed electronic and ionic conducting compositions of vanadia-yttria and vanadia-calcia stabilized zirconia and a dry powder method of manufacture for ceramic core stacks.

McLarty, Dustin↗
DOE OSTI2023

Reconstructing Oxygen-Deficient Zirconia with Ruthenium Catalyst on Atomic-Scale Interfaces toward Hydrogen Production

Downsizing a catalyst nanoparticle (NP) to a single atom (SA) has proven to be highly effective in increasing catalytic activity and decreasing the amount of catalyst required for various electrochemical reactions. However, insufficient stability of the single-atom site catalysts (SACs) is still a significant challenge for their practical application. Here, SACs firmly bound to stable metal oxide NPs are proposed to dramatically increase the electrochemical activity and stability of SA-based catalysts for hydrogen evolution reaction (HER). Starting from a Ru-infiltrated, Zr-based metal-organic framework (MOF), the tetragonal zirconium oxide (ZrO 2-x ) NPs-embedded carbon matrix is fabricated as support through facile pyrolysis. Simultaneously, Ru SAs as active sites are well dispersed on the surface of ZrO 2-x NPs due to the generation of oxygen vacancies in the tetragonal ZrO 2-x . Finally, the Ru-ZrO 2-x SAC exhibits a 4–5 times higher mass activity than commercial Pt and Ru catalysts and superior durability due to strong metal-support interaction (SMSI) between Ru atoms and ZrO 2-x substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Selective dehydra-decyclization of cyclic ethers to conjugated dienes over zirconia

ZrO 2 provides high selectivity (>90%) to conjugated pentadienes through the dehydra-decyclization of C-5 cyclic ethers, even at high conversions. 1,3-Pentadiene was the major product in both reaction of 2-methyltetrahydrofuran and tetrahydropyran over ZrO 2 . The reaction of 3-methyltetrahydrofuran produced nearly stoichiometric amounts of isoprene. Other catalysts, including TiO 2 , γ-Al 2 O 3 , and H-ZSM-5, were generally much less selective and produced a mixture of diene isomers. A combination of TPD and steady-state measurements revealed that both piperylenes are exclusively produced through primary catalytic pathways from 2-methyltetrahydrofuran, avoiding any isomerization once formed. First-principle calculations on ZrO 2 imply the presence of an energetically favored, surface isomerization of ring-opened intermediates to conjugated alkenolates that selectively dehydrate to conjugated dienes, providing high selectivity to the desired products. Finally, the stabilization of the conjugated alkenolate is key for understanding the ability of ZrO 2 to selectively produce conjugated dienes from cyclic ethers, without the need for the thermo-limited diene isomerization.

1,3 -pentadiene↗
DOE OSTI2024

3D Ferroelectric Phase Field Simulations of Polycrystalline Multi‐Phase Hafnia and Zirconia Based Ultra‐Thin Films

Abstract HfO 2 – and ZrO 2 –based ferroelectric thin films have emerged as promising candidates for the gate oxides of next‐generation electronic devices. Recent work has experimentally demonstrated that a tetragonal/orthorhombic (t/o‐) phase mixture with partially in‐plane polarization can lead to negative capacitance (NC) stabilization. However, there is a discrepancy between experiments and the theoretical understanding of domain formation and domain wall motion in these multi‐phase, polycrystalline materials. Furthermore, the effect of anisotropic domain wall coupling on NC has not been studied so far. Here, 3D phase field simulations of HfO 2 – and ZrO 2 –based mixed‐phase ultra‐thin films on silicon are applied to understand the necessary and beneficial conditions for NC stabilization. It is found that smaller ferroelectric grains and a larger angle of the polar axis with respect to the out‐of‐plane direction enhances the NC effect. Furthermore, it is shown that theoretically predicted negative domain wall coupling even along only one axis prevents NC stabilization. Therefore, it is concluded that topological domain walls play a critical role in experimentally observed NC phenomena in HfO 2 – and ZrO 2 –based ferroelectrics.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Ultrahigh temperature in situ transmission electron microscopy based bicrystal coble creep in zirconia I: Nanowire growth and interfacial diffusivity

This study demonstrates novel in situ transmission electron microscopy-based microscale single grain boundary Coble creep experiments used to grow nanowires through a solid-state process in cubic ZrO 2 between ≈ 1200 °C and ≈ 2100 °C. Experiments indicate Coble creep drives the formation of nanowires from asperity contacts during tensile displacement, which is confirmed by phase field simulations. The experiments also facilitate efficient measurement of grain boundary diffusivity and surface diffusivity. 10 mol% Sc 2 O 3 doped ZrO 2 is found to have a cation grain boundary diffusivity of $D_{gb} = (0.056 ± 0.05)exp (\frac{-380,000±41,000}{RT})m^2 s^{-1}$, and $D_s = (0.10 ± 0.27)exp(\frac{-380,000 ± 28,000}{RT}) m^2 s^{-1}$.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ultrahigh temperature in situ transmission electron microscopy based bicrystal coble creep in Zirconia II: Interfacial thermodynamics and transport mechanisms

This work uses a combination of stress dependent single grain boundary Coble creep and zero-creep experiments to measure interfacial energies, along with grain boundary point defect formation and migration volumes in cubic ZrO 2 . These data, along with interfacial diffusivities measured in a companion paper are then applied to analyzing two-particle sintering. The analysis presented here indicates that the large activation volume, v * = v f + v m primarily derives from a large migration volume and suggests that the grain boundary rate limiting defects are delocalized, possibly due to electrostatic interactions between charge compensating defects. The discrete nature of the sintering and creep process observed in the small-scale experiments supports the hypothesis that grain boundary dislocations serve as sources and sinks for grain boundary point defects and facilitate strain during sintering and Coble creep. Model two-particle sintering experiments demonstrate that initial-stage densification follows interface reaction rate-limited kinetics.

36 MATERIALS SCIENCE↗