Measuring the Wear and Abrasion Resistance of Air Plasma Sprayed Aluminum Oxide for Lunar Exploration
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Lunar Habitation↗
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Ambient Aging of Epitaxial and Polycrystalline Rhenium Thin Films
Extending the lifetime of superconducting qubits requires materials that are resistant to surface oxidation. Rhenium has emerged as one such promising candidate that forms a sub-nanometer oxide. Grain boundaries are known to promote material degradation, and thus, we compare epitaxial (single crystal, no grain boundaries) and polycrystalline (many grain boundaries) rhenium thin films after three years of ambient environmental exposure. Epitaxial rhenium remained free of undesired particles, while polycrystalline rhenium developed surface oxide crystallites. Surface characterization using scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy reveals localized oxygen and nitrogen enrichment, together with a Re⁷⁺ oxidation state in the polycrystalline surface particles, consistent with the proposed formation of ammonium perrhenate. Epitaxial rhenium demonstrated greater resistance to aging and oxidation, making it a more promising candidate for superconducting qubits. Ongoing cleaning and XPS depth profiling will further determine the identity and origin of the surface crystallites.
Wiacek, Wiktoria [Fermilab]↗
Ambient Aging of Epitaxial and Polycrystalline Rhenium Thin Films
Extending the lifetime of superconducting qubits requires materials that are resistant to surface oxidation. Rhenium has emerged as one such promising candidate that forms a sub-nanometer oxide. Grain boundaries are known to promote material degradation, and thus we compared epitaxial (single crystal, no grain boundaries) and polycrystalline (many grain boundaries) rhenium thin films after three years of ambient environmental exposure. Epitaxial rhenium remained free of undesired particles, while polycrystalline rhenium developed surface oxide crystallites. Surface characterization using scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy reveals localized oxygen and nitrogen enrichment together with a Re⁷⁺ oxidation state in the polycrystalline surface particles, consistent with the proposed formation of ammonium perrhenate. Epitaxial rhenium demonstrated greater resistance to aging and oxidation, making it a more promising candidate for superconducting qubits. Ongoing cleaning and XPS depth profiling will further determine the identity and origin of the surface crystallites.
Wiacek, Wiktoria [William Rainey Harper Coll.]↗
Literature survey on oxidations and fatigue lives at elevated temperatures
Nickel-base superalloys are the most complex and the most widely used for high temperature applications such as aircraft engine components. The desirable properties of nickel-base superalloys at high temperatures are tensile strength, thermomechanical fatigue resistance, low thermal expansion, as well as oxidation resistance. At elevated temperature, fatigue cracks are often initiated by grain boundary oxidation, and fatigue cracks often propagate along grain boundaries, where the oxidation rate is higher. Oxidation takes place at the interface between metal and gas. Properties of the metal substrate, the gaseous environment, as well as the oxides formed all interact to make the oxidation behavior of nickel-base superalloys extremely complicated. The important topics include general oxidation, selective oxidation, internal oxidation, grain boundary oxidation, multilayer oxide structure, accelerated oxidation under stress, stress-generation during oxidation, composition and substrate microstructural changes due to prolonged oxidation, fatigue crack initiation at oxidized grain boundaries and the oxidation accelerated fatigue crack propagation along grain boundaries.
Liu, H. W.↗
Invited Review Paper in Commemoration of Over 50 Years of Oxidation of Metals: Addressing the Role of Water Vapor on Long-Term Stainless Steel Oxidation Behavior
In the past 20 years, it has become clear that the long-term exposure of chromia-forming austenitic stainless steels to air containing ~ 10 vol% water vapor at 650–800 °C significantly increases the Cr consumption rate compared to laboratory air. However, a similar acceleration does not occur in 100% steam because O 2 is not available to form volatile CrO 2 (OH) 2 . As the research has shown, this accelerated Cr loss is particularly important for thin-walled components like gas turbine recuperators. Typically, conventional austenitic stainless steels exhibit accelerated attack (i.e., rapid formation of Fe-rich oxide nodules), while higher alloyed steels resist this type of degradation until the alloy surface becomes Cr depleted. The development of strategies and solutions for this issue are reviewed. Model Fe–Cr–Ni alloys have been used to study composition effects on this behavior. For example, increasing the Mn content up to ~ 4 wt% was not beneficial, but increasing the Ni content improved oxidation resistance in this environment. However, at 650–700 °C even highly alloyed steels showed surface Cr depletion at alloy grain boundaries resulting in Fe-rich oxide nodule formation. The path forward for this issue will require more refined mechanistic understanding and increased used of modeling to develop better application-specific lifetime models to identify the most cost-effective alloy solutions.
36 MATERIALS SCIENCE↗
Using In-Situ Deposition of Metallic Thin Films on Mars to Monitor Atmospheric H20
We describe the use of a novel sensor, designed to characterize the reactive nature of the Martian atmosphere, to also characterize the instantaneous abundance of atmospheric H,O. The sensor deposits, in situ, a thin silver film onto a sapphire substrate and monitors oxidation by measuring resistance of the Ag film during both deposition and subsequent oxidation [1,2]. . The evaporation source is placed in the center of a hollow, open-ended tube. On flash heating the source, evaporated metallic silver rapidly reacts with oxidizing gases in the tube, depositing on the tube walls as a resisitive Ag oxide film. Unoxidized silver deposits over the Ag oxides, once the oxidizing gases in the vicinity of the source have been consumed. Since the ends of the tube are open, atmospheric gases in the tube cause a time delay as the evaporated silver initially reacts with the available O2, and H2O; once oxidizing gases in the tube are significantly depleted, a silver film closes the chemiresistor circuit. In principle this operation mode provides a repeatable measure of the variable H2O abundance, since O2, levels are constant in the atmosphere. To explore the utility of the instrument as an H2O sensor, predict its behavior, and identify possible failure modes, we developed a numerical model of the instrument, and exercised it for Mars conditions. The model predicts the behavior of the electrical circuit, the temperature dependence of resistivity for each component, and the resultant Joule heating. The model balances Joule heating against radiation, sensible heat loss to ambient CO2, and, latent heat loss from sublimating Ag. The flux of Ag atoms from the source is tracked continuously. In the gas phase, the number density of Ag, O2, and H2O is calculated, along with their reaction rates on collision. The model suggests that Ag substantially depletes H2O only near the center of the tube. The model supports the hypothesis that the onset of high conductivity between the A u electrodes is a function of the H2O abundance in the ambient gas, but only to a limit; when H2O abundances are buffered at or above 240K (an H2O abundance that would not have occurred on Mars), metallic Ag never deposits in excess of Ago, and the circuit does not close. A significant difference in the Mars simulation is that the Ag source sublimates more quickly, primarily because of differences in sensible heat fluxes from the source. This allows subsequent heating of the W filament used to support the Ag source. Had the originally-designed experimental sequence been carried out on Mars, the filament might have melted, making subsequent investigations impossible.
Zent, A. P.↗
Solid State oxygen Sensor Development
To anticipate future long-duration mission needs for life support sensors, we explored the feasibility of using thin-film metal-oxide semiconductors. The objective of this task was to develop gas sensors for life support applications which would be suitable for long-duration missions. Metal oxides, such as ZnO, SnO2, and TiO2 have been shown to react with oxygen molecules. Oxygen lowers the metal oxide's electrical resistance. Critical to the performance is the application of the oxide in a thin film on an inert substrate: the thinner the film, the more readily the oxygen penetration and hence the more rapid and sensitive the sensor. Metal oxides are not limited to oxygen detection, rather, oxides offer detection and quantification applications to the complete range of gases of interest, not only for life support systems, but for propellants as well.
Cheung, Jeffery T.↗
Thermal Shock Behavior of Single Crystal Oxide Refractive Concentrators for High Temperatures Solar Thermal Propulsion
Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium-aluminum-garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) have been considered as refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermal mechanical reliability of the oxide components in severe thermal environments during space mission sun/shade transitions is of great concern. In this paper, critical mechanical properties of these oxide crystals are determined by the indentation technique. Thermal shock resistance of the oxides is evaluated using a high power CO, laser under high temperature-high thermal gradients. Thermal stress fracture behavior and failure mechanisms of these oxide materials are investigated under various temperature and heating conditions.
Zhu, Dongming↗
Pigmented coating resists thermal shock
Coating pigment composed of zinc oxide and potassium silicate resists the effects of thermal shock and long exposure to direct sunlight.
Harada, Y.↗
Communication—Reduction of DC Resistance of Ni-Rich Lithium Transition Metal Oxide Cathode by Atomic Layer Deposition
A coating using Atomic layer deposition (ALD) of Al 2 O 3 was applied to Ni-rich lithium transition metal oxide cathode material. This ALD coating reduces the DC resistance (DCR) and increases the cycling performance of the Ni-rich cathode. Additionally, the reduced DCR comes from decreased solid electrolyte interphase (SEI) resistance on the anode, which is attributed to reduced transition metal deposition. This is due to the ALD coating preventing the direct contact between the cathode and the electrolyte, and therefore inhibits transition metal dissolution. This study suggests the promise of using ALD coating to reduce the DCR of Ni-rich cathode materials.
25 ENERGY STORAGE↗
Elevated temperature mechanical behavior of monolithic and SiC whisker-reinforced silicon nitrides
The mechanical behavior of a 30 volume percent SiC whisker reinforced silicon nitride and a similar monolithic silicon nitride were measured at several temperatures. Measurements included strength, fracture toughness, crack growth resistance, dynamic fatigue susceptibility, post oxidation strength, and creep rate. Strength controlling defects were determined with fractographic analysis. The addition of SiC whiskers to silicon nitride did not substantially improve the strength, fracture toughness, or crack growth resistance. However, the fatigue resistance, post oxidation strength, and creep resistance were diminished by the whisker addition.
Salem, Jonathan A.↗
Preliminary study of cyclic thermal shock resistance of plasma-sprayed zirconium oxide turbine outer air seal shrouds
Several experimental concepts representing potential high pressure turbine seal material systems were subjected to cyclic thermal shock exposures similar to those that might be encountered under severe engine start-up and shut-down sequences. All of the experimental concepts consisted of plasma-sprayed yttria stabilized ZrO2 on the high temperature side of the blade tip seal shroud. Between the ZrO2 and a cooled, dense metal backing, various intermediate layer concepts intended to mitigate thermal stresses were incorporated. Performance was judged on the basis of the number of thermal shock cycles required to cause loss of seal material through spallation. The most effective approach was to include a low modulus, sintered metal pad between the ZrO2 and the metallic backing. It was also found that reducing the density of the ZrO2 layer significantly improved the performance of specimens with plasma-sprayed metal/ceramic composite intermediate layers.
Bill, R. C.↗
Measuring Wear and Abrasive Resistance of Air Plasma Sprayed Aluminum Oxide Coatings for Lunar Exploration
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Lunar Dust↗
Air-stable, earth-abundant molten chlorides and corrosion-resistant containment for chemically-robust, high-temperature thermal energy storage for concentrated solar power
A dramatic reduction in man-made CO 2 emissions could be achieved if the cost of electricity generated from concentrated solar power (CSP) plants could become competitive with fossil-fuel-derived electricity. The solar heat-to-electricity conversion efficiency of CSP plants may be significantly increased (and the associated electricity cost decreased) by operating CSP turbines with inlet temperatures ≥750 °C instead of ≤550 °C, and by using thermal energy storage (TES) at ≥750 °C to allow for rapidly dispatchable and/or continuous electricity production. Unfortunately, earth-abundant MgCl 2 -KCl-based liquids currently being considered as low-cost media for large-scale, high-temperature TES are susceptible to oxidation in ambient air, with associated undesired changes in liquid composition and enhanced corrosion of metal alloys in pipes and tanks containing such liquids. In this paper, alternative high-temperature, earth-abundant molten chlorides that are resistant to oxidation in ambient air are identified via thermodynamic calculations. Here, the oxidation resistance, and corrosion-resistant containment, of such molten chlorides at 750 °C are then demonstrated. Such an air-tolerant strategy, involving chemically-robust, low-cost TES media paired with effective containment materials, provides a critical advance towards the higher-temperature operation of, and lower-cost electricity generation from, CSP plants.
14 SOLAR ENERGY↗
Experimental studies and applications of vanadium oxides.
The electrical and electrochemical properties of V-5 and V-7 vanadium oxides were investigated. The effects of pressure, temperature and moisture on the bulk resistivity of the oxides in powder, sintered, and crystalline form were determined, and the static and dynamic volt-ampere characteristics were obtained. Sintered samples tested showed better electrical stability than the compressed powder samples. Two types of commercially available vanadium pentoxide were heat-treated to obtain various crystalline oxide forms which were mounted on alumina substrates and terminated by thick-film conductors for making electrical connections. Indications are that these materials could have applications as sensors, critical-temperature resistors, high-speed switches, and temperature-compensation elements in hybrid microelectronic circuits.
Williams, L., Jr.↗
Microstructural Characterization of Ion Irradiated ODS MA956 Alloy
Oxide Dispersion Strengthened (ODS) alloys are considered as promising nuclear materials for the next generation advanced nuclear reactors due to their improved elevated temperature mechanical properties and radiation damage resistance. MA956 is a commercial ODS alloy with superior oxidation resistance and creep strength at elevated temperatures. The improved properties for ODS alloys can be attributed to the presence of dispersed nanosized oxide particles. These oxide particles can act as barriers to dislocation motion and provide additional sinks and sites for point defect recombination. Hence, their stability can greatly affect the properties of the irradiated ODS alloys. Besides, irradiation will induce defects into the ODS alloys, and these defects can develop further as irradiation dose increases. Furthermore, the defects propagation can significantly undermine the mechanical properties of the bulk materials, resulting in irradiation hardening and lower ductility. Therefore, it is necessary to have a good understanding of the defect’s evolution with irradiation. Hence, efforts are ongoing to understand the effect of ion irradiation on ODS MA956 with emphasis on oxide particles and evolution of defects as a function of dose (2.5, 50 and 100 dpa).
07 ISOTOPE AND RADIATION SOURCES↗
Removable preheater elements improve oxide induction furnace
Heat and corrosion resistant preheater elements are used in oxide induction furnaces to raise the temperature to the level for conducting electricity. These preheater elements are then removed and the induction coil energized.
Leipold, M. H.↗