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Embedded High-Temperature Sensors: Enhancing Thermoelectrical Performance with Refractory Composites Gradient Layers
To monitor the stability of various energy and manufacturing systems, sensors capable of operating at temperatures exceeding 1000 °C in diverse environments for extended durations are essential. However, under harsh conditions, degradation of sensing materials is a concern that can be controlled by embedding the sensors into refractory oxides. Doped-LaCrO3 based composites are excellent candidates for high-temperature sensing applications due to their good thermoelectrical properties. However, chemical reactivity between the conductive phase and the refractory oxides can decrease the performance of the sensors. In this work, it was devised gradient-type protective layers safeguarding conductive phases within embedded thermocouples, which were fabricated and characterized by X-Ray Diffraction for phase development analysis, Scanning Electron Microscopy and Energy-dispersive X-ray spectroscopy for microstructure and cationic interdiffusion kinetics, long-term thermoelectric testing was completed up to 1400 °C. The enhanced performance of these novel sensors addresses a critical limitation, rendering them viable for long-term high-temperature applications.
Regenerative Performance of the NASA Symmetrical Solid Oxide Fuel Cell Design
The NASA Glenn Research Center is developing both a novel cell design (BSC) and a novel ceramic fabrication technique to produce fuel cells predicted to exceed a specific power density of 1.0 kW/kg. The NASA Glenn cell design has taken a completely different approach among planar designs by removing the metal interconnect and returning to the use of a thin, doped LaCrO3 interconnect. The cell is structurally symmetrical. Both electrodes support the thin electrolyte and contain micro-channels for gas flow-- a geometry referred to as a bi-electrode supported cell or BSC. The cell characteristics have been demonstrated under both SOFC and SOE conditions. Electrolysis tests verify that this cell design operates at very high electrochemical voltage efficiencies (EVE) and high H2O conversion percentages, even at the low flow rates predicted for closed loop systems encountered in unmanned aerial vehicle (UAV) applications. For UAVs the volume, weight and the efficiency are critical as they determine the size of the water tank, the solar panel size, and other system requirements. For UAVs, regenerative solid oxide fuel cell stacks (RSOFC) use solar panels during daylight to generate power for electrolysis and then operate in fuel cell mode during the night to power the UAV and electronics. Recent studies, performed by NASA for a more electric commercial aircraft, evaluated SOFCs for auxiliary power units (APUs). System studies were also conducted for regenerative RSOFC systems. One common requirement for aerospace SOFCs and RSOFCs, determined independently in each application study, was the need for high specific power density and volume density, on the order of 1.0 kW/kg and greater than 1.0 kW/L. Until recently the best reported performance for SOFCs was 0.2 kW/kg or less for stacks. NASA Glenn is working to prototype the light weight, low volume BSC design for such high specific power aerospace applications.
Doping Effects on Multivalence States, Electronic Structure, and Optical Band Gap in LaCrO 3 under Varied Atmospheres: An Integrated Experimental and Density Functional Theory Study
Doping effects on the valence state, electronic structure, and optical band and the effects on electrical conductivity were studied on the doped lanthanum chromite (LaCrO 3 ) system. The specific compositions studied were La 1–x Ca x CrO 3 (LCCx), La 1–x Sr x CrO 3 (LSCx), and La 0.8 Sr 0.2 Cr 1–x Mn x O 3 (LSCMx) (0.1 ≤ x ≤ 0.4). The powders were synthesized using a modified Pechini sol–gel method, and the ceramic samples were densified using a reactive sintering method resulting in densities >96% theoretical. X-ray photoelectron spectroscopy (XPS) was completed to characterize the defect states and cationic valence compensation as a result of divalent (Ca 2+ or Sr 2+ ) and trivalent (Mn 3+ ) substitutions. XPS was completed for samples tested in oxidizing and reducing atmospheres (up to 1500 °C), which provided insights into the oxidation state transitions induced by the Ca 2+ and Sr 2+ dopants. The work notably demonstrated, for the first time, the oxidation/reduction transitions of Cr 4+ to Cr 3+ in Sr 2+ /Mn 3+ co-doped samples under reducing atmospheres. Reflectance UV–vis spectrophotometry optical band gap measurements were also completed for the same materials; a decrease in the optical band gap (2.81–3.12 eV) was shown with increased substitution, suggesting electronic structure modifications in the LaCrO 3 perovskite. Density functional theory calculations validated experimental trends, predicting a diminishing band gap with a rising dopant concentration. The transition in Cr oxidation states was attributed to the presence of divalent/trivalent cations. These findings contribute some insights into methods to tune the LaCrO 3 electrical properties for various low- and high-temperature applications.
Volatile products from the interaction of KCl(g) with Cr2O3 and LaCrO3 in oxidizing environments
Cooled target collection techniques and high pressure mass spectrometric sampling were used to measure the relative rates of oxidative vaporization and to identify the volatile products emanating from samples of chromia and Mg-doped lanthanum chromite. The materials were exposed to partial pressures of KCl with and without H2O in one atmosphere of slowly flowing oxygen at elevated temperatures. Chromia and fresh samples of lanthanum chromite exhibited enhanced rates of oxidative vaporization upon exposure to these reactants. Mass spectrometric identification showed that the enhancements resulted from the heterogeneous formation of complex molecules of the type KCl sub 1,2,3 CrO3 and KOH sub l,2 CrO3. Lanthanum chromite that had undergone prolonged oxidative vaporization exhibited no enhanced oxidation upon exposure to the reactants.
Mg-perovskite/silicate melt partition coefficients in the CMS system at 2430 C and 226 Kbars
The partitioning of elements among lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements has been reported, and these results as well as interpretations based on them have generated controversy. The first set of direct measurements on a synthetic system in the CaO-MgO-SiO2 (CMS) is reported. An experiment was conducted at Stony Brook, using the USSA-2000 split sphere anvil apparatus. An experiment in the CMS system doped with oxides of Al, Ti, Sc, and Sm and run at a nominal temperature of 2380 C and pressure of 226 kbars is reported. Nominal temperatures were measured with a W 3 percent Re/W 25 percent Re thermocouple. The hot spot temperature, where the liquidus is located, is estimated to be at 2430 C. A 10 mm MgO octahedron was used in concert with 4 mm truncation edge lengths on the WC cubes. The sample was contained in a Re capsule which was inserted into a LaCrO3 furnace. Pressure was calibrated at 2000 C. Run duration was approximately 3 minutes. The charge was mounted in epoxy and analyzed using a CAMECA SX-50 electron microprobe. Standard operating conditions were employed, although counting time for the less abundant elements was increased to improved counting statistics. The melt is unquenchable, and forms a dendritic intergrowth of quench crystals and residual melt. It was analyzed using a 30 micron raster. The structural identity of the Mg-perovskite phase was confirmed using x ray microdiffractometry. The results of the investigation are presented.