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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2023

Thermal Stability of M x O y Doped Zirconia Aerogels (M = Y, Yb, Gd, Ce, Ca) Studied Through 1200°C

The high porosities and low densities of ceramic aerogels offer outstanding insulative performance in applications where weight is a critical factor. The high surface area-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. This work contributes to a design framework for thermally stable aerogels via the study of dopant chemistry (Y, Yb, Gd, Ca, Ce) in zirconia aerogels. The structural evolution was studied to 1200°C using nitrogen physisorption, scanning 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 NTRS2001

Oxidative Recession, Sulfur Release, and Al203 Spallation for Y-Doped Alloys

Second-order spallation phenomena have been noted for Y-doped Rene'N5 after long term oxidation at 1150 degrees C. The reason for this behavior has not been conclusively identified. A mass equivalence analysis has shown that the surface recession resulting from oxidation has the potential of releasing about 0.15 monolayer of sulfur for every 1 mg/sq cm of oxygen reacted for an alloy containing 5 ppmw of sulfur. This amount is significant in comparison to levels that have been shown to result in first-order spallation behavior for undoped alloys. Oxidative recession is therefore speculated to be a contributing source of sulfur and second-order spallation for Y-doped alloys.

Smialek, James L.↗
DOE OSTI2022

Intrinsic ferroelectricity in Y-doped HfO 2 thin films

Ferroelectric HfO 2 -based materials hold great potential for the widespread integration of ferroelectricity into modern electronics due to their compatibility with existing Si technology. Earlier work indicated that a nanometre grain size was crucial for the stabilization of the ferroelectric phase. This constraint, associated with a high density of structural defects, obscures an insight into the intrinsic ferroelectricity of HfO 2 -based materials. Here we demonstrate that stable and enhanced polarization can be achieved in epitaxial HfO 2 films with a high degree of structural order (crystallinity). In this work, an out-of-plane polarization value of 50 μC cm –2 has been observed at room temperature in Y-doped HfO 2 (111) epitaxial thin films, with an estimated full value of intrinsic polarization of 64 μC cm –2 , which is in close agreement with density functional theory calculations. The crystal structure of films reveals the $Pca2_1$ orthorhombic phase with small rhombohedral distortion, underlining the role of the structural constraint in stabilizing the ferroelectric phase. Our results suggest that it could be possible to exploit the intrinsic ferroelectricity of HfO 2 -based materials, optimizing their performance in device applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Tiny Sc Allows the Chains to Rattle: Impact of Lu and Y Doping on the Charge-Density Wave in ScV 6 Sn 6

The kagome metals display an intriguing variety of electronic and magnetic phases arising from the connectivity of atoms on a kagome lattice. A growing number of these materials with vanadium–kagome nets host charge–density waves (CDWs) at low temperatures, including ScV 6 Sn 6 , CsV 3 Sb 5 , and V 3 Sb 2 . Curiously, only the Sc version of the RV 6 Sn 6 materials with a HfFe 6 Ge 6 -type structure hosts a CDW (R = Gd–Lu, Y, Sc). In this study, we investigate the role of rare earth size in CDW formation in the RV 6 Sn 6 compounds. Magnetization measurements on our single crystals of (Sc,Lu)V 6 Sn 6 and (Sc,Y)V 6 Sn 6 establish that the CDW is suppressed by substituting Sc by larger Lu or Y. Single-crystal X-ray diffraction reveals that compressible Sn–Sn bonds accommodate the larger rare earth atoms within loosely packed R–Sn–Sn chains without significantly expanding the lattice. We propose that Sc provides extra room in these chains crucial to CDW formation in ScV 6 Sn 6 . Our rattling chain model explains why both physical pressure and substitution by larger rare earth atoms hinder CDW formation despite opposite impacts on lattice size. Here, we emphasize the cooperative effect of pressure and rare earth size by demonstrating that pressure further suppresses the CDW in a Lu-doped ScV 6 Sn 6 crystal. Our model not only addresses why a CDW only forms in the RV 6 Sn 6 materials with tiny Sc but also advances our understanding of why unusual CDWs form in the kagome metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Epitaxial Er-doped Y 2 O 3 on silicon for quantum coherent devices

Rare-earth ions have incomplete 4f shells and possess narrow optical intra-4f transitions due to shielding from electrons in the 5s and 5p orbitals, making them good candidates for solid-state optical quantum memory. The emission of Er 3+ in the telecom C-band (1530 nm – 1565 nm) makes it especially attractive for this application. In order to build practical, scalable devices, the REI needs to be embedded in a non-interacting host material, preferably one that can be integrated with silicon. In this paper, we show that Er 3+ can be isovalently incorporated into epitaxial Y 2 O 3 thin films on Si (111). We report on the synthesis of epitaxial, single-crystalline Er:Y 2 O 3 on Si with a narrow inhomogeneous linewidth in the photoluminescence spectra, 5.1 GHz (<100 mK) and an optical excited state lifetime of 8.1 ms. The choice of Y 2 O 3 was driven by its low nuclear spin and small lattice mismatch with Si. Using photoluminescence (PL) and electron paramagnetic resonance, we show that Er 3+ substitutes for Y in the crystal lattice. The role of interfacial SiO x , diffusion of silicon into the film, and the effect of buffer layers on inhomogeneous PL linewidth are examined. We also find that the linewidth decreased monotonically with film thickness but surprisingly exhibits no correlation with the film crystalline quality as measured by the x-ray rocking curve scans suggesting other factors at play that limit the inhomogeneous broadening in Y 2 O 3 films.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Magnetic properties of Lu and Y doped Ce-Fe-B magnets

The growing demand for Nd2Fe14B magnets is exacerbating the current critical materials shortage. To reduce the amount of critical material in Nd2Fe14B magnets, chemical substitutions have been used and shown to improve the magnetic behavior, such as the Curie Temperature TC, anisotropy field Ha, and saturation magnetization MS.

Bretana, Alex↗
NASA NTRS1991

High-T sub c fluorine-doped YBa2Cu3O(y) films on ceramic substrates by screen printing

Thick films of fluorine-doped YBa2Cu3O(y) were screen printed on highly polished alumina, magnesia spinel, strontium titanate, and yttria-stabilized zirconia (YSZ) substrates. They were annealed at 1000 C and soaked in oxygen at 450 C, followed by slow cooling to room temperature. The films were characterized by electrical resistivity measurements as a function of temperature and x-ray diffraction. The film on YSZ showed the best characteristics with a T sub c (onset) of 91 K, T sub c (R equals 0) of 88.2 K, and a transition width, delta T sub c (10-90 percent), of approximately 1.7 K. The film adhesion, probably controlled by interdiffusion of cations between the film and the substrate, was good in all cases except on strontium titanate where the film completely detached from the substrate.

Bansal, Narottam P.↗
NASA NTRSDate not supplied

Development of Luminescence Lifetime-Based Surface Temperature Mapping for Environmental Barrier Coatings

Luminescence lifetime-based temperature mapping for thermal barrier coatings (TBCs) has been previously demonstrated up to temperatures approaching 1200 °C. Advantages of this method include insensitivities to reflected radiation and emissivity uncertainties. Because of a push towards greater efficiency turbine engine operation using higher turbine inlet temperatures, there is an ongoing movement from TBC-coated superalloy turbine engine components to SiC/SiC ceramic matrix composite components protected by environmental barrier coatings (EBCs). The useful application of luminescence lifetime-based temperature mapping to EBCs requires a significant increase in high temperature capability from below 1200 °C up into the 1300 to 1500 °C temperature range where the much higher background thermal radiation is a challenging issue. In addition, the luminescing sensing layer must exhibit thermochemical compatibility with the EBC. To meet these requirements, Er-doped Y 2 SiO 5 was selected as the luminescing sensor layer material both for its enhanced temperature sensitivity above 1300 °C and its compatibility with rare-earth disilicate EBC topcoats. Both localized spot temperature measurements as well as luminescence lifetime imaging-based temperature mapping were demonstrated up to 1560 °C for Er-doped Y 2 SiO 5 disks. In addition, temperature mapping capability was demonstrated from a 15 µm thick Er-doped Y 2 SiO 5 layer at the surface of a Sc 2 Si 2 O 7 based EBC topcoat. Both localized spot and temperature mapping by luminescence lifetime imaging were demonstrated up to 1380 °C (upper temperature limit of this slurry-based layered EBC) with excellent suppression of background thermal radiation and no degradation of the Er-doped Y 2 SiO 5 temperature sensing surface layer. The source of the novel enhanced temperature sensitivity above 1300 °C will be discussed as well as a path towards compatibility between sensing layer and EBC topcoat to higher temperatures.

temperature measurement↗
DOE OSTI2023

Improving Proton Conductivity by Navigating Proton Trapping in High Scandium-Doped Barium Zirconate Electrolytes

Proton-conducting oxides are used in intermediate-temperature (300 °C < T < 700 °C) applications of fuel cells, electrolyzers, membrane reactors, hydrogen pumps, and sensors. The proton conductivity of doped ABO 3 perovskites is partly dependent on the proton concentration and hence on the level of material hydration. However, how the material hydration ability is affected by differences in doping is not fully understood. Here, we show the prospect of proton trapping and detrapping that influences material hydration and dehydration. The proton-trapping influence is significant for Sc-doped BaZrO 3 compared to Y-doped BaZrO 3 . Here, our work offers a perspective to understand how defect interaction/associations influence the hydration ability of proton-conducting oxides. Furthermore, positron annihilation lifetime spectroscopy was revealed to be a valuable technique for studying the proton-trapping phenomena and the defect chemistry of dense proton conductors. Density functional theory calculations also showed that a high hydration level in Sc-doped BaZrO 3 boosts proton migration. In contrast, the effect of boosting the proton migration due to increased hydration is limited for Y-doped BaZrO 3 . This effect, in turn, might explain the trend of conductivity with dopant concentration in doped BaZrO 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

Delayed Alumina Scale Spallation on Rene'n5+y: Moisture Effects and Acoustic Emission

The single crystal superalloy Rene'N5 (with or without Y-doping and hydrogen annealing) was cyclically oxidized at 1150 C for 1000 hours. After considerable scale growth (>= 500 hours), even the adherent alumina scales formed on Y-doped samples exhibited delayed interfacial spallation during subsequent water immersion tests, performed up to one year after oxidation. Spallation was characterized by weight loss, the amount of spalled area, and acoustic emission response. Hydrogen annealing (prior to oxidation) reduced spallation both before and after immersion, but without measurably reducing the bulk sulfur content of the Y-doped alloys. The duration and frequency of sequential, co-located acoustic emission events implied an interfacial crack growth rate at least 10(exp -3) m/s, but possibly higher than 10(exp 2) m/s. This is much greater than classic moisture-assisted slow crack growth rates in bulk alumina (10(exp -6) to 10(exp -3) m/s), which may still have occurred undetected by acoustic emission. An alternative failure sequence is proposed: an incubation process for preferential moisture ingress leads to a local decrease in interfacial toughness, thus allowing fast fracture driven by stored strain energy.

Smialek, James L.↗
NASA NTRS1995

(abstract) All Epitaxial Edge-geometry SNS Devices with Doped PBCO and YBCO Normal Layers

We will present our results on tapered-edge-geometry SNS weak link fabricated from c-axis oriented base-, counterelectrode and normal layers using a variety of processing conditions. To date, we have employed a variety of different normal materials (Co-doped YBCO, Y-doped PBCO, Ca-doped PBCO). We have been examining the junction fabrication process in detail and we will present our methods. In particular, we have been examining both epitaxial and non-epitaxial milling mask overlayers and we will present a comparison of both methods. These devices behave similar to the expectations of the resisively shunted junction model and conventional SNS proximity effect models but with some differences which will be discussed. We will present the detailed systematics of our junctions including device parameters versus temperature, rf and dc magnetic response for the various processing conditions.

epitaxial doped PBCO YBCO junction fabrication mil↗
DOE OSTI2021

Modeling the performance and faradaic efficiency of solid oxide electrolysis cells using doped barium zirconate perovskite electrolytes

Y-doped BaZrO 3 (BaZr 1 x Y x O 3 δ , or “BZY”), a proton-conducting ceramic featuring high bulk conductivity and good chemical stability, is a promising electrolyte material for solid oxide electrolysis cells. Further doping with Ce and/or Yb (creating materials “BCZY” and “BCZYYb”) can improve conductivity and sintering properties, but at significant penalty to cells’ faradaic efficiency (FE). Studies have proposed that reduction of lattice Ce can occur in the hydrogen electrode, which consumes some hydrogen produced by the hydrogen evolution reaction, leading to decreased FE. Despite studies suggesting this phenomenon, the mechanism is largely unknown. In this work, we developed a multiphysics model to study the transport of multiple defect species and the performance of BZY, BCZY, and BCZYYb, capturing the tradeoff between enhanced performance at the cost of FE for BCZY and BCZYYb electrolytes compared to BZY. We also found that increasing the water content of the anode gas supply lowers the current output of the cell but results in better FE. The model, which uses several parameters previously unavailable in the literature, was validated to experiments varying temperature, steam water content, and electrolyte material, as well as two performance metrics (performance curves and FE). Results verify and explain observed trends, informing future work on Ce-doped BZY electrolytes.

08 HYDROGEN↗
NASA NTRSDate not supplied

Environmental Barrier Coating Surface Temperature Mapping Using a Compatible Er-Doped Sc 2 SiO 5 Temperature-Sensing Layer

Accurate surface temperature-mapping capabilities in the 1300 to 1500 °C range are needed for SiC/SiC ceramic matrix composites protected by environmental barrier coatings (EBCs) under testing in turbine engine environment facilities. The strong background thermal radiation at these higher temperatures is a challenging issue. Er-doped Y 2 SiO 5 was previously shown to be capable of achieving luminescence lifetime-based temperature mapping up to 1560 °C as a standalone material. However, compatibility issues between an Er-doped Y 2 SiO 5 surface temperature sensing layer and an underlying Sc 2 Si 2 O 7 -based EBC topcoat limited temperature mapping of the EBC surface to a maximum of 1380 °C. Therefore, an Er-doped Sc 2 SiO 5 temperature sensing layer has been subsequently developed with better compatibility with the Sc2Si2O7-based EBC topcoat. Localized spot temperature measurements as well as luminescence lifetime imaging-based temperature mapping were demonstrated up to 1535 °C from a 15 µm thick Er-doped Sc 2 SiO 5 layer at the surface of a Sc2Si2O7-based EBC topcoat, a significant improvement over the Er-doped Y2SiO5 layer 1380 °C temperature sensing limit. No degradation of the Er-doped Sc 2 SiO 5 temperature sensing surface layer was observed.

temperature measurement↗
NASA NTRS1990

Microstructure and magnetization of doped Y-Ba-Ca-O materials prepared by melt quench and post annealing method

Y-Ba-Cu-O bulk materials prepared using the melt quench and post annealing method were shown to have very high maximum as well as remanent magnetization. Studies were carried out on materials prepared using this method which deviate from the Y:Ba:Cu = 1:2:3 stoichiometry. In one series of materials, only the stoichiometry was changed, in particular by introducing an excess of yttrium. In other cases, dopants including several rare earths were introduced. Effects of variations in composition on microstructure and phase evolution are discussed, as well as effects on the magnetic susceptibility and on the magnetization. The results show that doped materials can exhibit improvements in magnetic properties. Furthermore, the use of dopants sheds light on the role of defect sites in flux pinning.

Hojaji, H.↗
DOE OSTI2022

Modified Calcium Manganites for Thermochemical Energy Storage Applications

CaAl 0.2 Mn 0.8 O 3-δ (CAM28) and CaTi 0.2 Mn 0.8 O 3-δ (CTM28) are perovskite metal oxides developed for high-temperature thermochemical energy storage (TCES) applications, e.g., in support of air Brayton power generation. Previous reports for these compounds focus on the equilibrium non-stoichiometry (δ) as a function of temperature and oxygen partial pressure (pO 2 ) and the endotherm (or exotherm) accompanying changes in δ resulting from thermal reduction (or re-oxidation). Herein, we report results for elemental substitution and doping (Al, Co, Fe, La, Sr, Ti, Y, Zn, and Zr) of calcium manganites (CM) that establish the preference for CAM28 and CTM28. Techniques employed include conventional (screening and equilibrium) and ballistically heated multi-cycle thermogravimetric analysis (TGA), conventional and high temperature ( in-situ ) X-ray diffraction (XRD), and differential scanning calorimetry (DSC). Forward-looking results for A-site Y-doped materials, e.g., Ca 0.9 Y 0.1 MnO 3-δ (CYM910), establish a route to increasing the reduction enthalpy relative to CAM28 and CTM28, albeit at the expense of increased reduction temperatures and raw materials costs. A thermodynamic model presented for CAM28, but extendable to related materials, provides values for the reaction enthalpy and extent of reduction as a function of temperature and oxygen partial pressure for use in design efforts. Taken as a whole, the results support the choice of Al-doped CaMnO 3-δ as a low-cost material for TCES in a high temperature air Brayton application, but point the way to achieving higher stored energy densities that could lead to overall cost savings.

Miller, James E.↗
DOE OSTI2024

Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Solid-oxide electrolyzer cells (SOECs) based on a yttria-stabilized zirconia (YSZ) oxide electrolyte produce hydrogen from water with the assistance of excess thermal energy; however, Sr diffusion within the Gd-doped CeO 2 (GDC) barrier layer during processing or operation can lead to the formation of unwanted secondary phases such as SrO and SrZrO 3 . Here, to establish and compare the degree of impact of these phases on SOEC performance, we conduct first-principles calculations to study their bulk oxide conductivities and compare them to that of the YSZ electrolyte. We find that SrO has a low conductivity arising from the poor mobility and low concentration of mobile oxygen vacancies, and its presence in SOECs should therefore be avoided. SrZrO 3 also has a lower oxide conductivity than YSZ; however, this discrepancy is primarily due to lower vacancy concentrations rather than low mobility. We find that sufficient levels of Y-doping on the Zr site can increase oxygen vacancy concentrations in SrZrO 3 to achieve an oxide ionic conductivity on par with that of YSZ, thereby mitigating any potential deleterious effect on transport performance. Energy-dispersive X-ray spectroscopy confirms that Y is the most common minority element present in SrZrO 3 forming near the GDC–YSZ interface, alleviating concerns regarding the impact of SrZrO 3 on device performance. These results from our combined computational–experimental analysis can inform future engineering strategies designed to limit the detrimental effects of Sr-induced secondary phase formation on SOEC performance.

08 HYDROGEN↗