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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Characterization and durability testing of plasma-sprayed zirconia-yttria and hafnia-yttria thermal barrier coatings. Part 1: Effect of spray parameters on the performance of several lots of partially stabilized zirconia-yttria powder

Initial experiments conducted on thermal barrier coatings prepared in the newly upgraded research plasma spray facility and the burner rig test facilities are discussed. Part 1 discusses experiments which establish the spray parameters for three baseline zirconia-yttria coatings. The quality of five similar coating lots was judged primarily by their response to burner rig exposure supplemented by data from other sources such as specimen characterizations and thermal diffusivity measurements. After allowing for burner rig variability, although there appears to be an optimum density (i.e., optimum microstructure) for maximum burner rig life, the distribution tends to be rather broad about the maximum. In Part 2, new hafnia-yttria-based coatings were evaluated against both baseline and alternate zirconia-yttria coatings. The hafnia-yttria coatings and the zirconia-yttria coatings that were prepared by an alternate powder vendor were very sensitive to plasma spray parameters, in that high-quality coatings were only obtained when certain parameters were employed. The reasons for this important observation are not understood. Also not understood is that the first of two replicate specimens sprayed for Part 1 consistently performed better than the second specimen. Subsequent experiments did not display this spray order affect, possibly because a chiller was installed in the torch cooling water circuit. Also, large changes in coating density were observed after switching to a new lot of electrodes. Analyses of these findings were made possible, in part, because of the development of a sensitive density measurement technique described herein in detail. The measured thermal diffusivities did not display the expected strong relationship with porosity. This surprising result was believed to have been caused by increased microcracking of the denser coatings on the stainless steel substrates.

Miller, Robert A.↗
NASA NTRS1993

Characterization and durability testing of plasma-sprayed zirconia-yttria and hafnia-yttria thermal barrier coatings. Part 2: Effect of spray parameters on the performance of several hafnia-yttria and zirconia-yttria coatings

This is the second of two reports which discuss initial experiments on thermal barrier coatings prepared and tested in newly upgraded plasma spray and burner rig test facilities at LeRC. The first report, part 1, describes experiments designed to establish the spray parameters for the baseline zirconia-yttria coating. Coating quality was judged primarily by the response to burner rig exposure, together with a variety of other characterization approaches including thermal diffusivity measurements. That portion of the study showed that the performance of the baseline NASA coating was not strongly sensitive to processing parameters. In this second part of the study, new hafnia-yttria coatings were evaluated with respect to both baseline and alternate zirconia-yttria coatings. The hafnia-yttria and the alternate zirconia-yttria coatings were very sensitive to plasma-spray parameters in that high-quality coatings were obtained only when specific parameters were used. The reasons for this important observation are not understood.

Miller, Robert A.↗
NASA NTRS1999

Fabrication and Performance of Zirconia Electrolysis Cells for Cabon Dioxide Reduction for Mars In Situ Resource Utilization Applications

Use of the Martian atmosphere (95% CO2) to produce oxygen (for propellant and life support) can significantly lower the required launch mass and dramatically reduce the total cost for Mars missions. Zirconia electrolysis cells are one of the technologies being considered for oxygen generation from carbon dioxide in Mars In Situ Resource Utilization (ISRU) production plants. The attractive features of the zirconia cell for this application include simple operation and lightweight, low volume system. A zirconia electrolysis cell is an all-solid state device, based on oxygen-ion conducting zirconia electrolytes, that electrochemically reduces carbon dioxide to oxygen and carbon monoxide. The cell consists of two porous electrodes (the anode and cathode) separated by a dense zirconia electrolyte. Typical zirconia cells contain an electrolyte layer which is 200 to 400 micrometer thick. The electrical conductivity requirement for the electrolyte necessitates an operating temperature of 9000 to 10000C. Recently, the fabrication of zirconia cells by the tape calendering has been evaluated. This fabrication process provides a simple means of making cells having very thin electrolytes (5 to 30 micrometers). Thin zirconia electrolytes reduce cell ohmic losses, permitting efficient operation at lower temperatures (8000C or below). Thus, tape-calendered cells provides not only the potential of low temperature operation but also the flexibility in operating temperatures. This paper describes the fabrication of zirconia cells by the tape calendering method and discusses the performance results obtained to date.

Minh, N. Q.↗
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 NTRS2003

Scandia-and-Yttria-Stabilized Zirconia for Thermal Barriers

yttria in suitable proportions has shown promise of being a superior thermal- barrier coating (TBC) material, relative to zirconia stabilized with yttria only. More specifically, a range of compositions in the zirconia/scandia/yttria material system has been found to afford increased resistance to deleterious phase transformations at temperatures high enough to cause deterioration of yttria-stabilized zirconia. Yttria-stabilized zirconia TBCs have been applied to metallic substrates in gas turbine and jet engines to protect the substrates against high operating temperatures. These coatings have porous and microcracked structures, which can accommodate strains induced by thermal-expansion mismatch and thermal shock. The longevity of such a coating depends upon yttria as a stabilizing additive that helps to maintain the zirconia in an yttria-rich, socalled non-transformable tetragonal crystallographic phase, thus preventing transformation to the monoclinic phase with an associated deleterious volume change. However, at a temperature greater than about 1,200 C, there is sufficient atomic mobility that the equilibrium, transformable zirconia phase is formed. Upon subsequent cooling, this phase transforms to the monoclinic phase, with an associated volume change that adversely affects the integrity of the coating. Recently, scandia was identified as a stabilizer that could be used instead of, or in addition to, yttria. Of particular interest are scandia-and-yttria-stabilized zirconia (SYSZ) compositions of about 6 mole percent scandia and 1 mole percent yttria, which have been found to exhibit remarkable phase stability at a temperature of 1,400 C in simple aging tests. Unfortunately, scandia is expensive, so that the problem becomes one of determining whether there are compositions with smaller proportions of scandia that afford the required high-temperature stability. In an attempt to solve this problem, experiments were performed on specimens made with reduced proportions of scandia. The criterion used to judge these specimens was whether they retained the non-transformable tetragonal phase after a severe heat treatment of 140 hours at 1,400 C.

Mess, Derek↗
NASA NTRS1984

Overview of zirconia with respect to gas turbine applications

Phase relationships and the mechanical properties of zirconia are examined as well as the thermal conductivity, deformation, diffusion, and chemical reactivity of this refractory material. Observations from the literature particular to plasma-sprayed material and implications for gas turbine engine applications are discussed. The literature review indicates that Mg-PSZ (partially stabilized zirconia) and Ca-PSZ are unsuitable for advanced gas turbine applications; a thorough characterization of the microstructure of plasma-sprayed zirconia is needed. Transformation-toughened zirconia may be suitable for use in monolithic components.

Cawley, J. D.↗
DOE OSTI2024

Epitaxial Core/Shell Nanocrystals of (Europium-Doped) Zirconia and Hafnia

A careful design of the nanocrystal architecture can strongly enhance the nanocrystal function. So far, this strategy has faced a synthetic bottleneck in the case of refractory oxides. Here we demonstrate the epitaxial growth of hafnia shells onto zirconia cores and pure zirconia shells onto europium-doped zirconia cores. The core/shell structures are fully crystalline. Upon shelling, the optical properties of the europium dopant are dramatically improved (featuring a more uniform coordination and a longer photoluminescence lifetime), indicating the suppression of nonradiative pathways. These results launch the stable zirconium and hafnium oxide hosts as alternatives for the established NaYF 4 systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ab Initio Insights to Metal Passivation: Diffusion and Defect Formation in Amorphous Zirconia and Alumina

Metal passivation refers to the formation of protective oxide films on metals, which shield them from further corrosion and oxidation, playing a crucial role in maintaining their stability. The mesoscopic Point Defect Model has successfully predicted passivity as a steady state process where oxide growth from oxygen vacancies at the metal/film interface competes with oxide dissolution at the film/environment interface. In this work, informed by the Point Defect Model parameters, we use first-principles calculations to calculate defect formation and atomic diffusion in amorphous materials and correlate these descriptors with the behavior and growth of the oxide film. Focusing on amorphous zirconia and alumina, we demonstrate that defect formation energies exhibit significant variability in amorphous systems. In alumina, vacancies dominate, with cation and anion vacancies occurring at comparable concentrations. Diffusion calculations for stoichiometric amorphous alumina and zirconia, as well as oxygen-deficient zirconia, reveal faster diffusion in the oxygen-deficient case, highlighting the impact of defects on transport. Comparison of calculated self-diffusion coefficients for the dominant defect species with experimentally measured oxide thicknesses shows a clear correlation, suggesting that first-principles-derived diffusivity information can serve as a key descriptor for surface passivation film growth.

Farnell, Mackinzie S. [University of California, B↗
NASA NTRS1976

Durability of zirconia thermal-barrier ceramic coatings on air-cooled turbine blades in cyclic jet engine operation

Thermal barrier ceramic coatings of stabilized zirconia over a bond coat of Ni Cr Al Y were tested for durability on air cooled turbine rotor blades in a research turbojet engine. Zirconia stabilized with either yttria, magnesia, or calcia was investigated. On the basis of durability and processing cost, the yttria stabilized zirconia was considered the best of the three coatings investigated.

Liebert, C. H.↗
NASA NTRS1985

Microstructural aspects of zirconia thermal barrier coatings

Various combination of plasma-sprayed bond coatings and zirconia ceramic coatings on a nickel-based superalloy substrate were tested by static thermal exposure at 1200 C and cyclic thermal exposure to 1000 C. The bond coats were based on Ni-Cr-Al alloys with additions of rare earth elements and Si. The ceramic coats were various ZrO2-Y2O3 compositions, of which the optimum was found to be ZrO2-8.9 wt percent Y2O3. Microstructural analysis showed that resistance to cracking during thermal exposure is strongly related to deleterious phase changes. Zones depleted of Al formed at the bond coat/ceramic coat interface due to oxidation and at the bond coat/substrate interface due to interdiffusion, leading eventually to breakdown of the bond coat. The 8.9 percent Y2O3 coating performed best because the as-sprayed metastable tetragonal phase converted slowly into the low-Y2O3 tetragonal plus high-Y2O3 cubic-phase mixture, so that the deleterious monoclinic phase was inhibited from forming. Failure appeared to start with the formation of circumferential cracks in the zirconia, probably due to compressive stresses during cooling, followed by the formation of radial cracks due to tensile stresses during heating. Cracks appeared to initiate at the Al2O3 scale/bond coat interface and propagate through the zirconia coating. Comparisons were made with the behavior of bulk ZrO2-Y2O3 and the relationship between the microstructure of the tetragonal phase and the phase diagram. A separate investigation was also made of the ZrO2-Al2O3 interface.

Mitchell, T. E.↗
NASA NTRS1988

Oxygen separation from air using zirconia solid electrolyte membranes

Air separation using a zirconia solid electrolyte membrane is a possible alternative source of oxygen. The process of zirconia oxygen separation is reviewed, and an oxygen plant concept using such separation is described. Potential cell designs, stack designs, and testing procedures are examined. Fabrication of the materials used in a zirconia module as well as distribution plate design and fabrication are examined.

Suitor, J. W.↗
NASA NTRS1989

Thermodynamic properties of some metal oxide-zirconia systems

Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.

Jacobson, Nathan S.↗
NASA NTRS1995

Thermal conductivity of zirconia thermal barrier coatings

Thermal barrier coatings (TBC's) applied to the hot gas components of turbine engines lead to enhanced fuel efficiency and component reliability. Understanding the mechanisms which control the thermal transport behavior of the TBC's is of primary importance. Physical vapor description (PVD) and plasma spraying (PS) are the two most commonly used coating techniques. These techniques produce coatings with unique microstructures which control their performance and stability. The PS coatings were applied with either standard power or hollow sphere particles. The hollow sphere particles yielded a lower density and lower thermal conductivity coating. The thermal conductivity of both fully and partially stabilized zirconia, before and after thermal aging, will be compared. The thermal conductivity of the coatings permanently increase upon being exposed to high temperatures. These increases are attributed to microstructural changes within the coatings. Sintering of the as fabricated plasma sprayed lamellar structure is observed by scanning electron microscopy of coatings isothermally heat treated at temperatures greater than 1100 C. During this sintering process the planar porosity between lamella is converted to a series of small spherical pores. The change in pore morphology is the primary reason for the observed increase in thermal conductivity. This increase in thermal conductivity can be modeled using a relationship which depends on both the temperature and time of exposure. Although the PVD coatings are less susceptible to thermal aging effects, preliminary results suggest that they have a higher thermal conductivity than PS coatings, both before and after thermal aging. The increases in thermal conductivity due to thermal aging for partially stabilized plasma sprayed zirconia have been found to be less than for fully stabilized plasma sprayed zirconia coatings. The high temperature thermal diffusivity data indicates that if these coatings reach a temperature above 1100 C during operation, they will begin to lose their effectiveness as a thermal barrier.

Dinwiddie, R. B.↗
NASA NTRS1995

Thermal conductivity of zirconia thermal barrier coatings

Thermal barrier coatings (TBC's) applied to the hot gas components of turbine engines lead to enhanced fuel efficiency and component reliability. Understanding the mechanisms which control the thermal transport behavior of the TBC's is of primary importance. Physical vapor deposition (PVD) and plasma spraying (PS) are the two most commonly used coating techniques. These techniques produce coatings with unique microstructures which control their performance and stability. The PS coatings were applied with either standard powder or hollow sphere particles. The hollow sphere particles yielded a lower density and lower thermal conductivity coating. The thermal conductivity of both fully and partially stabilized zirconia, before and after thermal aging, will be compared. The thermal conductivity of the coatings permanently increases upon exposed to high temperatures. These increases are attributed to microstructural changes within the coatings. Sintering of the as-fabricated plasma sprayed lamellar structure is observed by scanning electron microscopy of coatings isothermally heat treated at temperatures greater than 1100 C. During this sintering process the planar porosity between lamella is converted to a series of small spherical pores. The change in pore morphology is the primary reason for the observed increase in thermal conductivity. This increase in thermal conductivity can be modeled using a relationship which depends on both the temperature and time of exposure. Although the PVD coatings are less susceptible to thermal aging effects, preliminary results suggest that they have a higher thermal conductivity than PS coatings, both before and after thermal aging. The increases in thermal conductivity due to thermal aging for partially stabilized plasma sprayed zirconia have been found to be less than for fully stabilized plasma sprayed zirconia coatings. The high temperature thermal diffusivity data indicate that if these coatings reach a temperature above 1100 C during operation, they will begin to lose their effectiveness as a thermal barrier.

Dinwiddie, R. B.↗
NASA NTRS2003

Processing of Alumina-Toughened Zirconia Composites

Dense and crack-free 10-mol%-yttria-stabilized zirconia (10YSZ)-alumina composites, containing 0 to 30 mol% of alumina, have been fabricated by hot pressing. Release of pressure before onset of cooling was crucial in obtaining crack-free material. Hot pressing at 1600 C resulted in the formation of ZrC by reaction of zirconia with grafoil. However, no such reaction was observed at 1500 C. Cubic zirconia and -alumina were the only phases detected from x-ray diffraction indicating no chemical reaction between the composite constituents during hot pressing. Microstructure of the composites was analyzed by scanning electron microscopy and transmission electron microscopy. Density and elastic modulus of the composites followed the rule-of-mixtures. Addition of alumina to 10YSZ resulted in lighter, stronger, and stiffer composites by decreasing density and increasing strength and elastic modulus.

Bansal, Narottam P.↗
DOE OSTI2025

Structural Templation of MOF-Derived Zirconia Nanoparticles

Templated synthesis is an important avenue for the development and synthesis of porous materials, as it provides a high level of control over the resulting structure. However, this control is difficult to achieve at the atomic level for poorly crystalline or noncrystalline materials, such as metal–organic framework (MOF)-derived carbons. We report the carbonization of three zirconium-based MOFs with different framework and inorganic building unit structures to form zirconia nanoparticles in a carbon matrix. Using a combination of X-ray diffraction, X-ray total scattering, and transmission electron microscopy, we found that the extended Zr-oxo chains of MIL-140C-bpy facilitate the formation of larger and more ordered zirconia nanoparticles. In contrast, the discrete Zr 6 -oxo clusters of UiO-67-bpy and Zr-ABTC result in smaller and differently structured nanoparticles.

metal-organic framework↗
NASA NTRS2024

Post-Synthetic Modification of Yttria-Stabilized Zirconia Aerogels with Silica Coatings for Enhanced Thermal Stability

Maintaining high surface area and porosity at high temperatures is important when considering aerogels for use in thermal management systems. The mesoporous structure of aerogels results in extremely low thermal conductivity, making them lightweight, high performance insulating materials. Maintaining these properties requires innovative routes to suppress sintering and pore collapse as use temperatures rise. The current work aims to improve the pore structure stability of yttria-stabilized zirconia aerogels by the addition of a SiO 2 coating. The functionalization of surface hydroxyl groups by the addition of SiO 2 is hypothesized to mitigate condensation reactions, which are a driving force for shrinkage and pore structure collapse. Zirconia aerogels with 0, 10 and 30 mol% yttria (YO 1.5 ) additions were coated in a tetraethyl orthosilicate (TEOS) solution and exposed to temperatures up to 1200°C. Crystal structure, pore structure, and aerogel morphology were investigated to understand changes in aerogel thermal stability. The SiO 2 coating exhibited a greater influence on pore stability over yttria concentration, with specific surface area of the coated aerogels being twice that of the uncoated aerogels up to 1000°C. However, the presence of the SiO 2 coating promoted rapid sintering and densification at 1200°C, establishing an upper use temperature for SiO 2 and a need to develop other coating chemistries.

aerogel↗