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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Systematic computational study of oxide adsorption properties for applications in photocatalytic CO 2 reduction

While the adsorption properties of transition metal catalysts have been widely studied, leading to the discovery of various scaling relations, descriptors of catalytic activity, and well-established computational models, a similar understanding of semiconductor catalysts has not yet been achieved. In this work, we present a high-throughput density functional theory investigation into the adsorption properties of 5 oxides of interest to the photocatalytic CO 2 reduction reaction: TiO 2 (rutile and anatase), SrTiO 3 , NaTaO 3 , and CeO 2 . Using a systematic approach, we exhaustively identify unique surfaces and construct adsorption structures to undergo geometry optimizations. We then perform a data-driven analysis, which reveals the presence of weak adsorption energy scaling relations, the propensity of adsorbates of interest to interact with oxygen surface sites, and the importance of slab deformation upon adsorption. Our findings are presented in the context of experimental observations and in comparison to previously studied classes of catalysts, such as pure metals and tellurium-containing semiconductors, and reinforce the need for a comprehensive approach to the study of site-specific surface phenomena on semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

C/sic Life Prediction for Propulsion Applications

Accurate life prediction is critical to successful use of ceramic matrix composites (CMC). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and process made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC. Issues such as oxidation, steam and hydrogen effects on material behavior are discussed. Preliminary tests indicate that steam will aggressively remove SiC seal coat and matrix in line with past experience. The kinetics of water vapor reaction with carbon fibers is negligible at 600 C, but comparable to air attack at 1200 C. The mitigating effect of steam observed in fiber oxidation studies has also been observed in stress rupture tests. Detailed microscopy of oxidized specimens is being carried out to develop the oxidation model. Carbon oxidation kinetics are reaction controlled at intermediate temperatures and diffusion controlled at high temperatures (approximately 1000 C). Activation energies for T-300 and interface pyrolytic carbon were determined as key inputs to the oxidation model. Crack opening as a function of temperature and stress was calculated. Mechanical property tests to develop and verify the probabilistic life model are very encouraging except for residual strength prediction. Gage width is a key variable governing edge oxidation of seal coated specimens. Future efforts will include architectural effects, enhanced coatings, biaxial tests, and LCF. Modeling will need to account for combined effects.

Levine, Stanley R.↗
NASA NTRS2002

C/SIC Life Prediction for Propulsion Applications

Accurate life prediction is critical to successful use of ceramic matrix composites (CMC). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and progress made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC. Issues such as oxidation, steam and hydrogen effects on material behavior are discussed. Preliminary tests indicate that stream will aggressively remove SiC seal coat and matrix in line with past experience. The kinetics of water vapor reaction with carbon fibers is negligible at 600 C, but comparable to air attack at 1200 C. The mitigating effect of steam observed in fiber oxidation studies has also been observed in stress rupture tests. Detailed microscopy of oxidized specimens is being carried out to develop the oxidation model. Carbon oxidation kinetics are reaction controlled at intermediate temperatures and diffusion controlled at high temperatures (approx. 1000 C). Activation energies for T-300 and interface pyrolytic carbon were determined as key inputs to the oxidation model. Crack opening as a function of temperature and stress was calculated. Mechanical property tests to develop and verify the probabilistic life model are very encouraging except for residual strength prediction. Gage width is a key variable governing edge oxidation of seal coated specimens. Future efforts will include architectural effects, enhanced coatings, biaxial tests, and LCF. Modeling will need to account for combined effects.

Levine, Stanley R.↗
DOE OSTI2025

Symmetry breaking forms split-off flat bands in quantum oxides controlling metal versus insulator phases

The crystal structure used as input to electronic structure calculation of conventionally bonded solids consists primarily of the standard crystallographic degrees of freedom. Quantum solids sometimes have additional microscopic degrees of freedom (m-DOF) nested within the crystallographic structure. These might include local motifs including positional (Peierls dimers, deformed octahedra, Jahn-Teller distortions), magnetic (local moment configurations) and dipolar (local ferroelectric configurations). Such motifs can be observed experimentally via local probes that avoid averaging, and theoretically as distinct total energy lowering features relative to more simplified “average crystallographic structures”. Here we examine the ability of electronic structure methods independent of strong correlation physics to explain the broad phenomenology of metal-insulator selectivity in quantum oxides by energy-lowering symmetry breaking. We do this by avoiding the restriction of considering only (i) electron-electron interactions in a fixed unresponsive lattice—as done in Mott strong correlation explanations—allowing, however, (ii) local positional and magnetic motifs that coexist within a crystallographic landscape. We find in a broad range of quantum oxides with different symmetry breaking modes the formation of split-off flat bands that can also control metallic versus insulating characteristics. The split-off band effect is common to magnetic and non-magnetic materials, including both binary and ternary oxides. One finds that when such local symmetry breaking motifs are considered in mean-field-like (e.g. density functional theory) electronic structure calculations of quantum oxides, they explain many of the observed trends in metal vs insulator phases discussed otherwise in prior literature via strong correlation in symmetry unbroken view.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1994

Theoretical Study of the Nitric Oxide epsilon and 1100 A Bands

Potential-energy curves, transition-moment functions, Einstein Alpha coefficients and radiative lifetimes associated with the Rydberg state of nitric oxide are calculated in large Gaussian basis sets employing internally contracted MRCI from state-averaged CASSCF wave functions. Computationally, a strong sensitivity of the results to the choice of the CASSCF active space is seen, and careful examination of this behavior gives insight into matters related to the treatment of weakly occupied orbitals, which is a consideration in any study Rydberg excited states. The epsilon system transition-moment function and radiative lifetimes are in disagreement with another calculation in the literature, but reasons for the discrepancies are examined, and the present results are determined to be more accurate.

Sheehy, Jeffrey A.↗
NASA NTRS2010

Highly porous and mechanically strong ceramic oxide aerogels

Structurally stable and mechanically strong ceramic oxide aerogels are provided. The aerogels are cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions. The functional groups can be hydroxyl groups, which are native to ceramic oxides, or they can be non-hydroxyl functional groups that can be decorated over the internal surfaces of the ceramic oxide network. Methods of preparing such mechanically strong ceramic oxide aerogels also are provided.

Leventis, Nicholas↗
NASA NTRS2012

Highly porous and mechanically strong ceramic oxide aerogels

Structurally stable and mechanically strong ceramic oxide aerogels are provided. The aerogels are cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions. The functional groups can be hydroxyl groups, which are native to ceramic oxides, or they can be non-hydroxyl functional groups that can be decorated over the internal surfaces of the ceramic oxide network. Methods of preparing such mechanically strong ceramic oxide aerogels also are provided.

Leventis, Nicholas↗
DOE OSTI2026

Restricted Partition Function Semiclassical Transition State Theory (RPF-SCTST): Applications to Reactions Involving Hydrogen Cyanide, Hydrogen Peroxide, and Formaldehyde Oxide

We demonstrate the efficiency of the numerical calculation of thermal semiclassical transition state theory (SCTST) rates across several representative chemical reactions using the restricted partition function (RPF)─viz a function that depends only on the imaginary action associated with a reaction. Here, we treat the potential energy surfaces (PESs) through fourth order expansions around the saddle point and integrate the Hamiltonian up to second order in employing vibrational perturbation theory. We apply this formalism to uni- and bimolecular reactions with different─though relatively high─barrier heights to uncover the influence of the barrier properties, minimal energies, and separability of the rotational motion on rate constants and tunneling corrections. Although all modes are coupled within the RPF, we found in our numerical examples that the rotational component in the absence of significant rotational distortions can be separated from the vibrational contributions. Moreover, a classical treatment of the rotational contribution is adequate over the temperature range from approximately 100 to 1000 K. We also found that the choice of DFT basis set can lead to variations in rate constants of up to an order of magnitude. Lastly, different schemes for counting eligible energy levels result in rate constants that differ by no more than a factor of 2, with the remaining discrepancies attributed to the treatment of near-convergent levels in perturbation theory.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

In Situ Observation of Domain Wall Lateral Creeping in a Ferroelectric Capacitor

As a promising candidate for next-generation nonvolatile memory devices, ferroelectric oxide films exhibit many emergent phenomena with functional applications, making understanding polarization switching and domain evolution behaviors of fundamental importance. However, tracking domain wall motion in ferroelectric oxide films with high spatial resolution remains challenging. Here, in this study, an in situ biasing approach for direct atomic-scale observations of domain nucleation and sideways motion is presented. By accurately controlling the applied electric field, the lateral translational speed of the domain wall can decrease to less than 2.2 Å s −1 , which is observable with atomic resolution STEM imaging. In situ observations on a capacitor structured PbZr 0.1 Ti 0.9 O 3 /La 0.7 Sr 0.3 MnO 3 heterojunction demonstrate the unique creeping behavior of a domain wall under a critical electric field, with the atomic structure of the creeping domain wall revealed. Moreover, the evolution of the metastable domain wall forms an elongated morphology, which contains a large proportion of charged segments. Phase-field simulations unveil the competition between gradient, elastic, and electrostatic energies that decide this unique domain wall creeping and morphology variation. This work paves the way toward a complete fundamental understanding of domain wall physics and potential modulations of domain wall properties in real devices.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A Density Functional Theory (DFT) Study on the Effect of Chlorine in the Magnesium Zinc Oxide (MZO) Front Interface for Cadmium Telluride (CdTe) Thin Film Solar Cells

Cadmium telluride photovoltaics has benefitted greatly from the cadmium chloride treatment which causes a remarkable improvement in cell efficiencies. This work investigates the effect of elemental chlorine at the interface between the magnesium zinc oxide front contact and the cadmium telluride absorber in such a device. Band alignment including band bending and interface states and its role in potential charge carrier transport is the key feature studied. It is seen that a small amount of chlorine is leads to a more desirable band alignment. Higher concentrations of chlorine result in unfavorable band characteristics.

14 SOLAR ENERGY↗
DOE OSTI2021

Octahedral rotations in Ruddlesden-Popper layered oxides under pressure from first principles

The combination of reduced dimensionality and tunable structural distortions in layered perovskite oxides makes these materials ideal platforms for designing novel properties and functionalities. One example is hybrid improper ferroelectricity in n = 2 Ruddlesden-Popper oxides, where the combination of a layered crystal structure and rotations of the metal-oxide octahedra break symmetry and induce a polarization. Precisely controlling the octahedral rotation distortions, for example by the application of hydrostatic pressure, provides a pathway to tune and optimize the properties of these materials. Here we combine group theoretic methods, density functional theory calculations, and Landau theory analysis to investigate how octahedral rotations respond to pressure in the hybrid improper ferroelectrics Sr 3 Zr 2 O 7 , Ca 3 Ti 2 O 7 , and Sr 3 Sn 2 O 7 . We find that factors that are known to control the pressure response of ABO 3 perovskites—the formal charge of the A- and B-site cations, tolerance factor, and B-site chemistry—also impact the pressure response of these layered perovskites. We also show that coupling between the octahedral rotation and strain order parameters plays a key role in determining the overall pressure response. Despite some similarities, we find that these layered perovskites display a distinct pressure response compared to their ABO 3 perovskite analogs. By identifying trends and underlying mechanisms that control octahedral rotations in Ruddlesden-Popper oxides under pressure, this work lays the foundation for tailoring the structure and properties of these materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Water vapor oxidation of SiC layer in surrogate TRISO fuel particles

Under accidental conditions for high temperature gas-cooled reactors (HTGR), the SiC layer in tri-structural-isotropic (TRISO) fuel particles can be exposed to water vapor. In this study, oxidation behaviors of surrogate TRISO fuel particles were investigated in a He-20 vol% water vapor mixed atmosphere at temperatures up to 1600 °C. The growth of the crystalline oxide passivation layer with cracks and pores followed a parabolic law with time, where the maximum was 2.3 μm at 1600 °C. The oxide layer and the SiC surface under the oxide became flattened with increasing temperature, as a function of the silica viscosity and the diffusion path of water vapor. Volatilization of the oxide layer was analyzed using a mechanistic model that an inert gas in oxidizing atmospheres could influence the magnitude of volatilization. The fracture load and strength of the oxidized and thinned SiC layer were numerically estimated to decrease from 2.27 to 1.69 N and from 317 to 299 MPa, respectively, with the SiC thickness decrease from 35 to 32 μm. This prediction indicates that the oxidized SiC layer should retain fission products. Additionally, the mechanical integrity of each layer in the TRISO fuel particle after oxidation was evaluated. The results in this work provide important data for the safety analysis of accidental scenarios in HTGRs.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Nucleation and growth of molybdenum disulfide grown by thermal atomic layer deposition on metal oxides

To enable greater control over thermal atomic layer deposition (ALD) of molybdenum disulfide (MoS 2 ), here we report studies of the reactions of molybdenum hexafluoride (MoF 6 ) and hydrogen sulfide (H 2 S) with metal oxide substrates from nucleation to few-layer films. In situ quartz crystal microbalance experiments performed at 150, 200, and 250 °C revealed temperature-dependent nucleation behavior of the MoF 6 precursor, which is attributed to variations in surface hydroxyl concentration with temperature. In situ Fourier transform infrared spectroscopy coupled with ex situ x-ray photoelectron spectroscopy (XPS) indicated the presence of molybdenum oxide and molybdenum oxyfluoride species during nucleation. Density functional theory calculations additionally support the formation of these species as well as predicted metal oxide to fluoride conversion. Residual gas analysis revealed reaction by-products, and the combined experimental and computational results provided insights into proposed nucleation surface reactions. With additional ALD cycles, Fourier transform infrared spectroscopy indicated steady film growth after ~13 cycles at 200 °C. XPS revealed that higher deposition temperatures resulted in a higher fraction of MoS 2 within the films. Deposition temperature was found to play an important role in film morphology with amorphous films obtained at 200 °C and below, while layered films with vertical platelets were observed at 250 °C. Finally, these results provide an improved understanding of MoS 2 nucleation, which can guide surface preparation for the deposition of few-layer films and advance MoS 2 toward integration into device manufacturing.

36 MATERIALS SCIENCE↗
NASA NTRS2023

Estimates of Permeability of Water in Rare Earth Silicates Using the Modified Theory of Deal and Grove

The salient elements of the theory of oxide growth under an environmental barrier are reviewed. In addition, the results from steam oxidation tests recently conducted on environmental barrier coated specimens are reported. The oxide thickness between the coating and substrate are reported as a function of time. Also, the results from previously conducted steam oxidation tests are reviewed. An approach to estimate the permeability of water through the various coating systems using the oxide thickness versus time measurements and the theory of oxide growth is demonstrated. Although the steam oxidation tests may have been performed under disparate conditions, the approach allows one to rank the protection efficiency of the various coating systems against substrate oxidation on an equivalent basis.

environmental barrier coatings↗
DOE OSTI2022

Oxidative Self-Assembly of Au/Ag/Pt Alloy Nanoparticles into High-Surface Area, Mesoporous, and Conductive Aerogels for Methanol Electro-oxidation

The ability to assemble nanoparticles (NPs) into functional nanostructures is critical for the advancement of nanoscience. However, common assembling techniques utilize organic ligands or biomolecules, which are detrimental for charge transport and interparticle coupling, which impede the efficient integration of low-dimensional properties. Herein, we report a methodology for the self-supported assembly of ultra-small (3-6 nm) Au/Ag/Pt alloy NPs into large, free-standing alloy superstructures (aerogels) that exhibit direct NP connectivity, high surface area (125 ± 0.43 to142 ± 0.93 m 2 /g) and mesoporosity (21.6 ± 2.2 nm), and superior electrocatalytic activity for methanol oxidation reaction (MOR). Precursor Au/Ag/Pt alloy NPs and hydrogels were synthesized via stepwise galvanic replacement reaction (GRR) of the glutathione (GSH)-coated Ag NPs, followed by oxidative removal of the surfactant ligands. The composition of alloy aerogels was tuned by varying the oxidant/GSH molar ratio, which governs the extent of Ag dealloying with in-situ generated HNO 3 and increases the exposure of Au and Pt on the aerogel surface. The alloy aerogels exhibit superior MOR mass activity, which is 21.4 and 2.5 times higher than those of the precursor NPs and commercial Pt (40 wt.%)/C electrocatalysts, respectively. The MOR surface-specific activity (MOR-SSA) of the aerogels was improved by >17% when the Pt content was increased from 22.4% to 31.2%. The aerogels exhibit improved electronic conductivity, enhanced tolerance for carbonaceous byproducts, and maintained ~94% of the initial MOR activity at -0.3 V for 24 h in an alkaline medium. In conclusion, the interconnected porous superstructure of the aerogel provides a facile conduit for molecules to reach the pristine active surface whereas the presence of oxophilic Au promotes the dissociative adsorption of methanol, enabling the Au/Ag/Pt alloy aerogel a high efficiency, durable electrocatalyst for next generation of energy conversion studies.

36 MATERIALS SCIENCE↗
DOE OSTI2022

2D materials-assisted heterogeneous integration of semiconductor membranes toward functional devices

Heterogeneous integration techniques allow the coupling of highly lattice-mismatched solid-state membranes, including semiconductors, oxides, and two-dimensional materials, to synergistically fuse the functionalities. The formation of heterostructures generally requires two processes: the combination of crystalline growth and a non-destructive lift-off/transfer process enables the formation of high-quality heterostructures. Although direct atomic interaction between the substrate and the target membrane ensures high-quality growth, the strong atomic bonds at the substrate/epitaxial film interface hinder the non-destructive separation of the target membrane from the substrate. Alternatively, a 2D material-coated compound semiconductor substrate can transfer the weakened (but still effective) surface potential field of the surface through the 2D material, allowing both high-quality epitaxial growth and non-destructive lift-off of the grown film. This Perspective reviews 2D/3D heterogeneous integration techniques, along with applications of III–V compound semiconductors and oxides. Here, the advanced heterogeneous integration methods offer an effective method to produce various freestanding membranes for stackable heterostructures with unique functionalities that can be applied to novel electrical, optoelectronic, neuromorphic, and bioelectronic systems.

2D materials↗
DOE OSTI2021

An antisite defect mechanism for room temperature ferroelectricity in orthoferrites

Single-phase multiferroic materials that allow the coexistence of ferroelectric and magnetic ordering above room temperature are highly desirable, motivating an ongoing search for mechanisms for unconventional ferroelectricity in magnetic oxides. Here, we report an antisite defect mechanism for room temperature ferroelectricity in epitaxial thin films of yttrium orthoferrite, YFeO 3 , a perovskite-structured canted antiferromagnet. A combination of piezoresponse force microscopy, atomically resolved elemental mapping with aberration corrected scanning transmission electron microscopy and density functional theory calculations reveals that the presence of Y Fe antisite defects facilitates a non-centrosymmetric distortion promoting ferroelectricity. This mechanism is predicted to work analogously for other rare earth orthoferrites, with a dependence of the polarization on the radius of the rare earth cation. Our work uncovers the distinctive role of antisite defects in providing a mechanism for ferroelectricity in a range of magnetic orthoferrites and further augments the functionality of this family of complex oxides for multiferroic applications.

36 MATERIALS SCIENCE↗