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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 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
NASA NTRS2020

DGEN Aeropropulsion Research Turbofan Source-Diagnostic Test: Experimental Setup and Acoustic-Data Structure

The experimental setup of, and available data from a recent core/combustor-noise source-diagnostic test utilizing a small turbofan engine are described. The 2019 test campaign continued the investigation of the core/combustor-noise component of aircraft-propulsor noise begun in an earlier baseline test, but with a more extensive acoustic-instrumentation layout. The purpose of both tests was to better understand the impact on civilian-transport airport-community noise from turbofan-combustor sources and thereby to lay the foundation for improved noise-prediction methods and noise-mitigation techniques. Simultaneous high-data-rate acoustic measurements were obtained using a circumferential sensor array at the core nozzle exit in conjunction with sideline and farfield microphone arrays. The test matrix contained engine operational points from engine idle to maximum power and was repeated for different circumferential and sideline array configurations, as well as for redundancy. The extensive data set (up to 93 channels of data and various configurations) allows the application of advanced source-separation and phased-array methods to elucidate not only the core-noise structure, but also the propagation characteristics of other propulsion noise sources. The present report provides a detailed description of the different test points, their associated instrumentation layouts, and the structure of the acquired data set. Results from various data analyses are reported separately.

Aeroacoustics↗
DOE OSTI2018

Mapping Catalytically Relevant Edge Electronic States of MoS 2

Molybdenum disulfide (MoS 2 ) is a semiconducting transition metal dichalcogenide that is known to be a catalyst for both the hydrogen evolution reaction (HER) as well as for hydro-desulfurization (HDS) of sulfur-rich hydrocarbon fuels. Specifically, the edges of MoS 2 nanostructures are known to be far more catalytically active as compared to unmodified basal planes. However, in the absence of the precise details of the geometric and electronic structure of the active catalytic sites, a rational means of modulating edge reactivity remain to be developed. Here in this paper we demonstrate using first-principles calculations, X-ray absorption spectroscopy, as well as scanning transmission X-ray microscopy (STXM) imaging that edge corrugations yield distinctive spectroscopic signatures corresponding to increased localization of hybrid Mo 4d states. Independent spectroscopic signatures of such edge states are identified at both the S L 2,3 and S K-edges with distinctive spatial localization of such states observed in S L 2,3 -edge STXM imaging. The presence of such low-energy hybrid states at the edge of the conduction band is seen to correlate with substantially enhanced electrocatalytic activity in terms of a lower Tafel slope and higher exchange current density. These results elucidate the nature of the edge electronic structure and provide a clear framework for its rational manipulation to enhance catalytic activity.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Structural Insights into the Mechanism of Carbapenemase Activity of the OXA-48 β-Lactamase

Carbapenem-hydrolyzing class D carbapenemases (CHDLs) are enzymes that produce resistance to the last-resort carbapenem antibiotics, severely compromising the available therapeutic options for the treatment of life-threatening infections. A broad variety of CHDLs, including OXA-23, OXA-24/40, and OXA-58, circulate in Acinetobacter baumannii , while the OXA-48 CHDL is predominant in Enterobacteriaceae . Extensive structural studies of A. baumannii enzymes have provided important information regarding their interactions with carbapenems and significantly contributed to the understanding of the mechanism of their carbapenemase activity. However, the interactions between carbapenems and OXA-48 have not yet been elucidated. We determined the X-ray crystal structures of the acyl-enzyme complexes of OXA-48 with four carbapenems, imipenem, meropenem, ertapenem, and doripenem, and compared them with those of known carbapenem complexes of A. baumannii CHDLs. In the A. baumannii enzymes, acylation by carbapenems triggers significant displacement of one of two conserved hydrophobic surface residues, resulting in the formation of a channel for entry of the deacylating water into the active site. We show that such a channel preexists in apo–OXA-48 and that only minor displacement of the conserved hydrophobic surface residues occurs upon the formation of OXA-48 acyl-enzyme intermediates. We also demonstrate that the extensive hydrophobic interactions that occur between a conserved hydrophobic bridge of the A. baumannii CHDLs and the carbapenem tails are lost in OXA-48 in the absence of an equivalent bridge structure. In conclusion, these data highlight significant differences between the interactions of carbapenems with OXA-48 and those with A. baumannii enzymes and provide important insights into the mechanism of carbapenemase activity of the major Enterobacteriaceae CHDL, OXA-48.

60 APPLIED LIFE SCIENCES↗
NASA NTRS2002

Foam Optics and Mechanics

The Foam Optics and Mechanics (FOAM) project will exploit the microgravity environment to more accurately measure the rheological and optical characteristics of wet aqueous foams. Using both rheology and laser light scattering diagnostics, the goal is to quantify the unusual elastic character of foams in terms of their underlying microscopic structure and dynamics. Of particular interest is determining how the elastic character vanishes, i.e., how the foam 'melts' into a simple viscous liquid, as a function of both increasing liquid content and increasing shear strain rate. The unusual elastic character of foams will be quantified macroscopically by measurement of the shear stress as a function of shear strain rate and of time following a step strain. Such data will be analyzed in terms of a yield stress, shear moduli, and dynamical time scales. Microscopic information about bubble packing and rearrangement dynamics, from which the macroscopic non-Newtonian properties ultimately arise, will be obtained non-invasively by multiple-light scattering: diffuse transmission spectroscopy (DTS) and diffusing wave spectroscopy (DWS). Quantitative trends with materials parameters, most importantly average bubble size and liquid content, will be sought in order to elucidate the fundamental connection between the microscopic structure and dynamics and the macroscopic rheology.

Durian, Douglas J.↗
DOE OSTI2016

Influence of Cu-doping on the structural and optical properties of CaTiO{sub 3} powders

Highlights: • Ca{sub 1−x}Cu{sub x}TiO{sub 3} powders were successfully synthesized via a polymeric precursor method. • Effects of Cu incorporated on the Ca-site into the CaTiO{sub 3} lattice as host matrix has been investigated. • The optical behavior reveals that the Ca{sub 1−x}Cu{sub x}TiO{sub 3} powders have potential applications in emerging technologies. - Abstract: Here, we report on the effect of chemical substitution on the structural and optical properties of Cu-doped CaTiO{sub 3} (CTO) polycrystalline powders synthesized by the polymeric precursor method. Our findings are discussed based on the structural order-disorder effects originating from the modification of the Ca{sub 1−x}Cu{sub x}TiO{sub 3} microcrystal matrix. These results may elucidate the compositional modulation and methods of controlling the structural design, as well as reveal the changes in the optical behavior of this system at an atomic level.

36 MATERIALS SCIENCE↗
DOE OSTI2025

In-situ/operando study of Cu-based nanocatalysts for CO 2 electroreduction using electrochemical liquid cell TEM

The structure of a nanocatalyst during electrocatalytic reactions often deviates from its pristine structure due to intrinsic properties, or physical and chemical adsorption at the catalytic surfaces. Taking Cu-based catalysts for CO 2 electroreduction reactions (CO 2 RR) as an example, they often experience segregation, leaching, and alloying during reactions. With the recent breakthrough development of high-resolution polymer electrochemical liquid cells, in-situ electrochemical liquid cell transmission electron microscopy (EC-TEM) alongside other advanced microscopy techniques, has become a powerful platform for revealing electrocatalysts restructuring at the atomic level. Considering the complex reactions involving electrified solid-liquid interfaces and catalyst structural evolution with intermediates, systematic studies with multimodal approaches are crucial. In this article, we demonstrate a research protocol for the study of electrocatalysts structural evolution during reactions using the in-situ EC-TEM platform. Using Cu and CuAg nanowire catalysts for CO 2 RR as model systems, we describe the experimental procedures and findings. We highlight the platform’s crucial role in elucidating atomic-scale pathways of nanocatalyst restructuring and identifying catalytic active sites, as well as avoiding potential artifacts to ensure unbiased conclusions. Using the multimodal characterization toolbox, we provide the opportunity to correlate the structure of a working catalyst with its performance. Finally, we discuss advancements as well as the remaining gap in elucidating the structural-performance relationship of working catalysts. We expect this article will assist in establishing guidelines for future investigations of complex electrochemical reactions, such as CO 2 RR and other catalytic processes, using the in-situ EC-TEM platform.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Bespoke Liquid/Liquid Interfaces (Final Technical Report)

The goal of DE-SC0001815 was to advance the basic science of liquid:liquid interface formation, to develop a deeper understanding of the mechanisms of phase separation and the essential relationships between solution composition, organization and dynamics that underlie the kinetic regime of solvent extraction. This included learning how interfacial organization and dynamics alters the properties of the primary coordination sphere of ions and the free energy of transport of ions complexes across a phase boundary. We relied primarily upon classical molecular dynamics studies to determine the equilibrium ensembles of these complex systems, but also utilized ab-initio MD and cluster-based density functional theory (DFT) calculations when more detailed investigation of the electronic structure was needed. We continued development of graph-theory based analyses to elucidate hierarchical correlations and expanded into geometric topology methods to quantify the collectively organized structures that can organize at a liquid/liquid interface during solute transport. One of the main conclusions was from the observation of two distinct mechanisms for solute transport - those that derive from amplifications of interfacial heterogeneity and surface roughness, and those wherein surface roughness has been dampened and instead collectively organized macrostructures work to bring solutes into the organic phase. It was our aim to create a concrete chemical model of the underlying driving forces behind interfacial primary and secondary structure formation and to map out the energetic features of solute transport so that tailored liquid/liquid can be developed that have characteristic kinetic features associated with mass transport.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2014

Strain tunable ferroelectric and dielectric properties of BaZrO{sub 3}

The crucial role of epitaxial (in-plane) strain on the structural, electronic, energetic, ferroelectric, and dielectric properties of BaZrO{sub 3} (BZO) is investigated using density-functional theory calculations. We demonstrate that the BZO crystal subjected to a critical compressive (or tensile) strain exhibits non-trivial spontaneous polarization that is higher than that of well-known ferroelectrics BaTiO{sub 3}, while the BZO crystal is essentially paraelectric in the absence of strain. The electronic structure and Born-effective-charge analyses elucidate that the strain-induced paraelectric-to-ferroelectric transition is driven by the orbital hybridization of d-p electrons between zirconium and oxygen. Through the strain-induced paraelectric-to-ferroelectric phase transition, the dielectric response of BZO is significantly enhanced by the in-plane strain. The tensile strain increases the in-plane dielectric constant by a factor of seven with respect to that without the strain, while the compression tends to enhance the out-of-plane dielectric response. Therefore, strain engineering makes BZO an important electromechanical material due to the diversity in ferroelectric and dielectric properties.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Effects of forcing time scale on the simulated turbulent flows and turbulent collision statistics of inertial particles

In this paper, we study systematically the effects of forcing time scale in the large-scale stochastic forcing scheme of Eswaran and Pope [“An examination of forcing in direct numerical simulations of turbulence,” Comput. Fluids 16, 257 (1988)] on the simulated flow structures and statistics of forced turbulence. Using direct numerical simulations, we find that the forcing time scale affects the flow dissipation rate and flow Reynolds number. Other flow statistics can be predicted using the altered flow dissipation rate and flow Reynolds number, except when the forcing time scale is made unrealistically large to yield a Taylor microscale flow Reynolds number of 30 and less. We then study the effects of forcing time scale on the kinematic collision statistics of inertial particles. We show that the radial distribution function and the radial relative velocity may depend on the forcing time scale when it becomes comparable to the eddy turnover time. This dependence, however, can be largely explained in terms of altered flow Reynolds number and the changing range of flow length scales present in the turbulent flow. We argue that removing this dependence is important when studying the Reynolds number dependence of the turbulent collision statistics. The results are also compared to those based on a deterministic forcing scheme to better understand the role of large-scale forcing, relative to that of the small-scale turbulence, on turbulent collision of inertial particles. To further elucidate the correlation between the altered flow structures and dynamics of inertial particles, a conditional analysis has been performed, showing that the regions of higher collision rate of inertial particles are well correlated with the regions of lower vorticity. Regions of higher concentration of pairs at contact are found to be highly correlated with the region of high energy dissipation rate.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Modes of Disorder in Poly(carbon monofluoride)

Poly(carbon monofluoride), or (CF) n , is a layered fluorinated graphite material consisting of nanosized platelets. In this work, we present experimental multidimensional solid-state NMR spectra of (CF)n, supported by density functional theory (DFT) calculations of NMR parameters, which overhauls our understanding of structure and bonding in the material by elucidating many ways in which disorder manifests. We observe strong 19 F NMR signals conventionally assigned to elongated or “semi-ionic” C–F bonds and find that these signals are in fact due to domains where the framework locally adopts boat-like cyclohexane conformations. We calculate that C–F bonds are weakened but are not elongated by this conformational disorder. Exchange NMR suggests that conformational disorder avoids platelet edges. We also use a new J-resolved NMR method for disordered solids which provides molecular-level resolution of highly fluorinated edge states. Strings of consecutive difluoromethylene groups at edges are relatively mobile. Topologically distinct edge features, including zigzag edges, crenellated edges, and coves are resolved in our samples by solid-state NMR. Disorder should be controllable in a manner dependent on synthesis, affording new opportunities for tuning the properties of graphite fluorides.

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

Facet-dependent structure and dissociation of water at pristine IrO 2 /water interfaces

Understanding the microscopic structure of water at metal oxide interfaces is crucial for advancing electrocatalysis. IrO 2 , specifically, has shown exceptional activity for electrochemical water oxidation, but we currently lack a fundamental understanding of how the surface structure of IrO 2 impacts water reactivity. In this work, we developed a machine learning potential trained to first-principles accuracy for modeling IrO 2 /water interfaces across different facets: (110), (100), (101), and (001). Using extensive machine learning molecular dynamics simulations, we investigated the spontaneous dissociation of water molecules at these interfaces. Our results reveal a distinct dissociation probability trend: (110) > (100) ≈ (101) > (001), which we attribute primarily to the reaction thermodynamics of surface water dissociation. A strong correlation is observed between the surface Ir–O bond distances and the dissociation probabilities, highlighting the role of surface geometry in modulating reactivity. As a consequence, the interfacial solvation structures and hydrogen bonding environments are dynamically tuned by the varying water dissociation capabilities across facets. This work elucidates how water dissociation energetics depend on surface orientation and interfacial structure, offering atomistic insights into manipulating reaction chemistry at electrocatalytic interfaces.

organic↗
NASA NTRS2011

Solar Cycle Fine Structure and Surface Rotation from Ca II K-Line Time Series Data

Analysis of three and a half decades of data from the NSO/AFRL/Sac Peak K-line monitoring program yields evidence for four components to the variation: (a) the solar cycle, with considerable fine structure and a quasi-periodicity of 122.4 days; (b) a stochastic process, faster than (a) and largely independent of it, (c) a quasi-periodic signal due to rotational modulation, and of course (d) observational errors (shown to be quite small). Correlation and power spectrum analyses elucidate periodic and aperiodic variation of these chromospheric parameters. Time-frequency analysis is especially useful for extracting information about differential rotation, and in particular elucidates the connection between its behavior and fine structure of the solar cycle on approximately one-year time scales. These results further suggest that similar analyses will be useful at detecting and characterizing differential rotation in stars from stellar light-curves such as those being produced at NASA's Kepler observatory.

Scargle, Jeff↗
DOE OSTI2025

First-Principles Simulations Correlating X-ray Absorption Spectroscopy Features to Point Defects in h -BN

Hexagonal boron nitride (h-BN) is a promising material for a range of emerging applications in electronics, quantum information technology, and energy storage. Soft X-ray absorption spectroscopy (XAS) is powerful to reveal atomic details of BN, especially in the presence of defects. However, correlating XAS spectral features with specific defect types remains elusive. In this Letter, we report B K-edge XAS measurements of sputter-deposited turbostratic h-BN films and use a combination of first-principles spectroscopic simulations and analysis of detailed electronic structure and local charge transfer characteristics to elucidate their unique spectroscopic features. Our results show that the two main defect-related peaks, between the main π* resonances of h-BN and B2O3, as typically observed in BN films deposited by energetic condensation or bombarded with energetic ions, are associated with electronic states of H-passivated B atoms bonded to one and two oxygen impurity atoms, respectively. These conclusions hold significant implications for applications relying on defect-mediated properties of h-BN.

chemical structure↗
DOE OSTI2016

Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy

The solution structures of highly active Ir water-oxidation catalysts are elucidated herein by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by 1 H and 17 O NMR, EPR, resonance Raman and UV–vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Beyond Badger’s Rule: The Origins and Generality of the Structure–Spectra Relationship of Aqueous Hydrogen Bonds

The structure of hydrogen bonded networks is intimately intertwined with their dynamics. Despite the incredibly wide range of hydrogen bond strengths encountered in water clusters, ion-water clusters and liquid water, we demonstrate that the previously reported correlation between the change in the equilibrium bond length of the hydrogen bonded OH covalent bond and the corresponding shift in its harmonic frequency in water clusters is much more broadly applicable. Surprisingly, this correlation describes the ratios for both the equilibrium OH bond length/harmonic frequency, and the vibrationally averaged bond length/anharmonic frequency in water, hydronium water and halide water clusters. Consideration of harmonic and anaharmonic data leads to a correlation of -19 ± 1 cm -1 /0.001 Å. The basic nature of this correlation is further confirmed through the analysis of ab initio Molecular Dynamics (AIMD) trajectories for liquid water. We show that this simple correlation for both harmonic and anharmonic systems can be modeled by the response of an OH bond to an external field. Treating the OH bond as a Morse oscillator, we develop analytic expressions, which relate the ratio of the shift in the vibrational frequency of the hydrogen-bonded OH bond to the shift in OH bond length, to parameters in the Morse potential and the ratio of the first and second derivatives of the field-dependent projection of the dipole moment of water onto the hydrogen-bonded OH bond. Based on our analysis, we develop a protocol for reconstructing the AIMD spectra of liquid water from the sampled distribution of the OH bond lengths. Our conclusions elucidate the origins of the relationship between the molecular structure of the fleeting hydrogen-bonded network and the ensuing dynamics, which can be probed by vibrational spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Precipitation Hardening in Ferroelectric Ceramics

Domain wall motion in ferroics, similar to dislocation motion in metals, can be tuned by well-concepted microstructural elements. In demanding high-power applications of piezoelectric materials, the domain wall motion is considered as a lossy hysteretic mechanism that should be restricted. Current applications for so-called hard piezoelectrics are abundant and hinge on the use of an acceptor-doping scheme. However, this mechanism features severe limitations due to enhanced mobility of oxygen vacancies at moderate temperatures. By analogy with metal technology, the authors present here a new solution for electroceramics, where precipitates are utilized to pin domain walls and improve piezoelectric properties. Through a sequence of sintering, nucleation, and precipitate growth, intragranular precipitates leading to a fine domain structure are developed as shown by transmission electron microscopy, piezoresponse force microscopy, and phase-field simulation. This structure impedes the domain wall motion as elucidated by electromechanical characterization. As a result, the mechanical quality factor is increased by ≈50% and the hysteresis in electrostrain is suppressed considerably. This is even achieved with slightly increased piezoelectric coefficient and electromechanical coupling factor. This novel process can be smoothly implemented in industrial production processes and is accessible to simple laboratory experimentation for microstructure optimization and implementation in various ferroelectric systems.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Effect of Surface Terminations on the Initial Stages of TiO 2 Deposition on Functionalized Silicon

As atomic layer deposition (ALD) emerges as a method to fabricate architectures with atomic precision, emphasis is placed on understanding surface reactions and nucleation mechanisms. ALD of titanium dioxide with TiCl 4 and water has been used to investigate deposition processes in general, but the effect of surface termination on the initial TiO 2 nucleation lacks needed mechanistic insights. Here, this work examines the adsorption of TiCl 4 on Cl–, H–, and HO– terminated Si(100) and Si(111) surfaces to elucidate the general role of different surface structures and defect types in manipulating surface reactivity of growth and non-growth substrates. The surface sites and their role in the initial stages of deposition are examined by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Density functional theory (DFT) computations of the local functionalized silicon surfaces suggest oxygen-containing defects are primary drivers of selectivity loss on these surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗