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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 1,459 records · Page 81
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Self-evolving atomistic kinetic Monte Carlo simulations of defects in materials

The recent development of on-the-fly atomistic kinetic Monte Carlo methods has led to an increased amount attention on the methods and their corresponding capabilities and applications. In this review, the framework and current status of Self-Evolving Atomistic Kinetic Monte Carlo (SEAKMC) are discussed. SEAKMC particularly focuses on defect interaction and evolution with atomistic details without assuming potential defect migration/interaction mechanisms and energies. The strength and limitation of using an active volume, the key concept introduced in SEAKMC, are discussed. Potential criteria for characterizing an active volume are discussed and the influence of active volume size on saddle point energies is illustrated. A procedure starting with a small active volume followed by larger active volumes was found to possess higher efficiency. Applications of SEAKMC, ranging from point defect diffusion, to complex interstitial cluster evolution, to helium interaction with tungsten surfaces, are summarized. A comparison of SEAKMC with molecular dynamics and conventional object kinetic Monte Carlo is demonstrated. Overall, SEAKMC is found to be complimentary to conventional molecular dynamics, especially when the harmonic approximation of transition state theory is accurate. However it is capable of reaching longer time scales than molecular dynamics and it can be used to systematically increase the accuracy of other methods such as object kinetic Monte Carlo. Furthermore, the challenges and potential development directions are also outlined.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Dynamics in hard condensed matter probed by X-ray photon correlation spectroscopy: Present and beyond

Insight into the spatial ordering and dynamics of structural heterogeneity in materials is at the heart of understanding their structure and function. X-ray photon correlation spectroscopy (XPCS) measures the dynamic structure factor providing S(Q,t) information on the spontaneous low-energy dynamics intrinsic to many materials. Combined with in situ and in operando capabilities, XPCS provides unique insight into a variety of scientific areas, including phase separation in binary alloys, aging in metallic glasses, surface dynamics during growth, domain wall dynamics in ferroic complex oxides and charge and spin density wave motion in quantum materials. In conclusion, this review summarizes some recent XPCS work in these areas and discusses scientific opportunities that will be made possible with the many-fold increase in coherent flux provided by the world-wide construction and commissioning of X-ray sources based on multi-bend achromat (MBA) storage ring (SR) lattices and high repetition rate free electron lasers (FELs).

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2018

Biogeochemical controls on the speciation and aquatic toxicity of vanadium and other metals in sediments from a river reservoir

Effects of hydrologic variability on reservoir biogeochemistry are relatively unknown, particularly for less studied metals like vanadium (V). Further, few studies have investigated the fate and effects of sediment-associated V to aquatic organisms in hydrologically variable systems. Our primary objective was to assess effects of hydrologic manipulation on speciation and toxicity of V (range: 635 to 1620 mg kg- 1) and other metals to Hyalella azteca and Daphnia magna. Sediments were collected from a reservoir located in a former mining area and microcosm experiments were conducted to emulate 7-day drying and inundation periods. Despite high sediment concentrations, V bioavailability remained low with no significant effects to organism survival, growth, or reproduction. The lack of V toxicity was attributed to reduced speciation (III, IV), non-labile complexation, and sorption to Al/Fe/Mn-oxyhydroxides. Zinc (Zn) increased in surface and porewater with inundation, for some sediments exceeding the U.S. EPA threshold for chronic toxicity. While no effects of Zn to organism survival or growth were observed, Zn body concentrations were negatively correlated with H. azteca growth. Results from this study indicate that V bioavailability and environmental risk is dependent on V-speciation, and V is less influenced by hydrologic variability than more labile metals such as Zn.

58 GEOSCIENCES↗
DOE OSTI2024

Broadband Rotational Spectroscopy in Uniform Supersonic Flows: Chirped Pulse/Uniform Flow for Reaction Dynamics and Low Temperature Kinetics

ConspectusThe study of gas-phase chemical reactions at very low temperatures first became possible with the development and implementation of the CRESU (French acronym for Reaction Kinetics in Uniform Supersonic Flows) technique. CRESU relies on a uniform supersonic flow produced by expansion of a gas through a Laval (convergent-divergent) nozzle to produce a wall-less reactor at temperatures from 10 to 200 K and densities of 1016-1018 cm-3 for the study of low temperature kinetics, with particular application to astrochemistry. In recent years, we have combined uniform flows with revolutionary advances in broadband rotational spectroscopy to yield an instrument that affords near-universal detection for novel applications in photodissociation, reaction dynamics, and kinetics. This combination of uniform supersonic flows with chirped-pulse Fourier-transform microwave spectroscopy (Chirped-Pulse/Uniform Flow, CPUF) permits detection of any species with a modest dipole moment, thermalized to the uniform temperature of the gas flow, with isomer, conformer, and vibrational state specificity. In addition, the use of broadband, high-resolution, and time-dependent (microsecond time scale) micro- and mm-wave spectroscopy makes it an ideal tool for characterizing both transient and stable molecules, as well as studying their spectroscopy and dynamics.In this Account, we review recent advances made using the CPUF technique, including studies of photodissociation, radical-radical reaction dynamics, and low temperature kinetics. These studies highlight both the strength of universal and multiplexed detection and the challenges of coupling it to a high-density collisional environment. Product branching and product evolution as a function of time have been measured for astrochemically relevant systems, relying on the detailed characterization of these flow conditions via experiments and fluid dynamics simulations. In the photodissociation of isoxazole, an unusual heterocyclic molecule with a very low-energy conical intersection, we have identified 7 products in 5 reaction channels and determined the product branching, pointing to both direct and indirect pathways. We have also approached the same system from separated NO and C3H3 reactants to explore a broader range of the potential energy surface, demonstrating the power of multichannel branching measurements for complex radical-radical reactions. We determined the product branching in the C3H2 isomers in the photodissociation of the propargyl radical and identified the importance of a hydrogen atom catalyzed isomerization to the lowest energy cyclic form. This then motivated a study of direct D-H exchange reaction in radicals, in which we demonstrate that it is an important and overlooked pathway for deuterium fractionation in astrochemical environments. Recently, we have shown the measurement of low temperature kinetics inside an extended Laval nozzle, after which a shock-free secondary expansion to low temperature and density affords an ideal environment for detection by rotational spectroscopy. These results highlight the power and potential of the CPUF approach, and future prospects will also be discussed in light of these developments.

Dias, Nureshan↗
DOE OSTI2025

Sequential Dosing Strategies for Controlling Selectivity and Plasma-Phase Contributions in Plasma Catalysis

Plasma-assisted catalysis has advanced in recent years, particularly for transforming stable reactants at atmospheric pressure and ambient temperature. However, achieving a deeper understanding of the many plasma and catalytic contributions remains a significant goal, as improving product yield and selectivity in plasma catalysis depends on proper catalyst selection, which is often challenging due to the complex interplay between plasma-phase and plasma-surface reactions. A sequential methodology has emerged as a means to decouple the catalyst activity from plasma-phase reactions. In this approach, nonthermal plasma is used in one step to activate and/or convert a gas phase or surface bound reactant, while in a second step, the catalyst directs product formation under steady-state or temperature-programmed conditions. This review examines studies using this technique for reactions involving N 2 , CO 2 , and SO 2 , offering insights into reaction mechanisms and catalyst behavior/selection for these transformations. These systematic studies provide a framework that can be applied to other plasma-assisted reactions. We also highlight remaining questions, propose directions for future studies, and discuss the potential of applying this methodology to other reaction systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

General Effect of van der Waals Interactions on the Stability of Alkoxy Intermediates on Metal Surfaces

The critical role of noncovalent van der Waals (vdW) interactions in determining the relative thermodynamic stability of alkoxy intermediates has been demonstrated for the Cu(110) surface using a combination of experiment and theory. The results may be significant for the selectivity control of copper-based reactions of alcohols. Previous examination of this effect on Au(110) was also extended to include higher molecular weight alcohols; on Cu(110) and Au(110) the hierarchy for the strength of binding of the alkoxys was found to be the same within experimental accuracy, with alkoxy species of greater chain length being more stable. The equilibrium constants governing the competition of alcohol pairs for binding sites of the alkoxys are also similar on the two surfaces. These results reveal the generality of such vdW effects. In conclusion, this work expands the understanding of the role of vdW interactions on the binding efficacy of key reactive intermediates on metal surfaces, a key factor in the rational design of complex and selective catalytic processes.

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

Modeling Profiles of Micrometeorological Variables in a Tropical Premontane Rainforest Using Multi-Layered CLM (CLM-ML)

This study updates the multi-layered Community Land Model (CLM-ml) for hillslopes and compares predictions from against observations collected in tropical montane rainforest, Costa Rica. Modifications are made in order to capture a wider array of vertical leaf area distributions, predict CO 2 profiles, account for soil respiration, and adjust wind forcings for difficult topographic settings. Test results indicate that the modified multi-layer CLM model can successfully replicate the shape of various micrometeorological profiles (humidity, CO 2 , temperature, and wind speed) under the canopy. In the single-layer models (CLM4.5 and CLM5), excessive day-to-night differences in leaf temperature and leaf wetness were originally noted, but CLM-ml significantly improved these issues, decreasing the amplitudes of diurnal cycles by 67% and 47%. Sub-canopy considerations, such as canopy shapes and turbulent transfer parameters, also played a significant role in model performance. More importantly, unlike single layer models, the results that CLM-ml produces can be compared to variables measured within the canopy to provide far more detailed diagnostic information. Further observations and model developments, aimed at reflecting surface heterogeneity, will be necessary to adequately capture the complexity and the features of the tropical montane rainforest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Advancing Cross-Disciplinary Understanding of Land-Atmosphere Interactions

The evolution of disciplinary silos and increasingly narrow disciplinary boundaries have together resulted in one-sided approaches to the study of land-atmosphere interactions—a field that requires a bi-directional approach to understand the complex feedbacks and interactions that occur. The integration of surface flux and atmospheric boundary layer measurements is therefore essential to advancing our understanding. The Land-Atmosphere 2021 workshop (held virtually, June 10-11, 2021) involved almost 300 participants from around the world and promoted cross-discipline collaboration by way of talks from invited speakers, moderated discussions, breakout sessions, and a virtual poster session. The workshop focused on five main theme areas: “big picture” overview, instrumentation and remote sensing, modeling, water, and aerosols and clouds. In talks and breakout groups, there were frequent calls for more AmeriFlux sites to be instrumented for boundary layer height measurements, and for the development of some “super sites” where profiling instruments would be deployed. There was further agreement on the need for the standardization of various datasets. There was also a consensus that funding agencies need to be willing to support the sorts of large projects (including associated instrumentation) which can drive interdisciplinary work. Early-career scientists, in particular, expressed enthusiasm for working across disciplinary boundaries but noted that there need to be more financial support and training opportunities so they would be better prepared for interdisciplinary work. Investment in these career development opportunities would enable today's cohort of early-career scientists to advance the frontiers of interdisciplinary work over the next couple of decades.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Universal linear intensity transformations using spatially incoherent diffractive processors

Abstract Under spatially coherent light, a diffractive optical network composed of structured surfaces can be designed to perform any arbitrary complex-valued linear transformation between its input and output fields-of-view (FOVs) if the total number ( N ) of optimizable phase-only diffractive features is ≥~2 N i N o , where N i and N o refer to the number of useful pixels at the input and the output FOVs, respectively. Here we report the design of a spatially incoherent diffractive optical processor that can approximate any arbitrary linear transformation in time-averaged intensity between its input and output FOVs. Under spatially incoherent monochromatic light, the spatially varying intensity point spread function ( H ) of a diffractive network, corresponding to a given, arbitrarily-selected linear intensity transformation, can be written as H ( m , n ; m ′, n ′) = | h ( m , n ; m ′, n ′)| 2 , where h is the spatially coherent point spread function of the same diffractive network, and ( m , n ) and ( m ′, n ′) define the coordinates of the output and input FOVs, respectively. Using numerical simulations and deep learning, supervised through examples of input-output profiles, we demonstrate that a spatially incoherent diffractive network can be trained to all-optically perform any arbitrary linear intensity transformation between its input and output if N ≥ ~2 N i N o . We also report the design of spatially incoherent diffractive networks for linear processing of intensity information at multiple illumination wavelengths, operating simultaneously. Finally, we numerically demonstrate a diffractive network design that performs all-optical classification of handwritten digits under spatially incoherent illumination, achieving a test accuracy of >95%. Spatially incoherent diffractive networks will be broadly useful for designing all-optical visual processors that can work under natural light.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Ordering, flexibility and frustration in arrays of porphyrin nanorings

The regular packing of atoms, molecules and nanoparticles provides the basis for the understanding of structural order within condensed phases of matter. Typically the constituent particles are considered to be rigid with a fixed shape. Here we show, through a combined experimental and numerical study of the adsorption of cyclic porphyrin polymers, nanorings, on a graphite surface, that flexible molecules can exhibit a rich and complex packing behaviour. Depending on the number of porphyrin sub-units within the nanoring we observe either a highly ordered hexagonal phase or frustrated packing driven by directional interactions which for some arrangements is combined with the internal deformation of the cyclic polymer. Frustration and deformation occur in arrays of polymers with ten sub-units since close packing and co-alignment of neighbouring groups cannot be simultaneously realised for nanorings with this internal symmetry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Bottom-up design of de novo thermoelectric hybrid materials using chalcogenide resurfacing

Hybrid organic/inorganic thermoelectric materials based on conducting polymers and inorganic nanostructures have been demonstrated to combine both the inherently low thermal conductivity of the polymer and the superior charge transport properties (high power factors) of the inorganic component. While their performance today still lags behind that of conventional inorganic thermoelectric materials, solution-processable hybrids have made rapid progress and also offer unique advantages not available to conventional rigid inorganic thermoelectrics, namely: (1) low cost fabrication on rigid and flexible substrates, as well as (2) engineering complex conformal geometries for energy harvesting/cooling. While the number of reports of new classes of viable hybrid thermoelectric materials is growing, no group has reported a general approach for bottom-up design of both p- and n-type materials from one common base. Thus, unfortunately, the literature comprises mostly of disconnected discoveries, which limits development and calls for a first-principles approach for property manipulation analogous to doping in traditional semiconductor thermoelectrics. Here, molecular engineering at the organic/inorganic interface and simple processing techniques are combined to demonstrate a modular approach enabling de novo design of complex hybrid thermoelectric systems. Here, we chemically modify the surfaces of inorganic nanostructures and graft conductive polymers to yield robust solution processable p- and n-type inorganic/organic hybrid nanostructures. Our new modular approach not only offers researchers new tools to perform true bottom-up design of thermoelectric hybrids, but also strong performance advantages as well due to the quality of the designed interfaces. For example, we obtain enhanced power factors in existing (by up to 500% in Te/PEDOT:PSS) and novel (Bi 2 S 3 /PEDOT:PSS) p-type systems, and also generate water-processable and air-stable high performing n-type hybrid systems (Bi 2 Te 3 /PEDOT:PSS), thus highlighting the potency of our ex situ strategy in opening up new material options for thermoelectric applications. Finally, this strategy establishes a unique platform with broad handles for custom tailoring of thermal and electrical properties through hybrid material tunability and enables independent control over inorganic material chemistry, nanostructure geometry, and organic material properties, thus providing a robust pathway to major performance enhancements.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Hybrid plasmonic Au–TiN vertically aligned nanocomposites: a nanoscale platform towards tunable optical sensing

Tunable plasmonic structure at the nanometer scale presents enormous opportunities for various photonic devices. In this work, we present a hybrid plasmonic thin film platform: i.e., a vertically aligned Au nanopillar array grown inside a TiN matrix with controllable Au pillar density. Compared to single phase plasmonic materials, the presented tunable hybrid nanostructures attain optical flexibility including gradual tuning and anisotropic behavior of the complex dielectric function, resonant peak shifting and change of surface plasmon resonances (SPRs) in the UV-visible range, all confirmed by numerical simulations. Lastly, the tailorable hybrid platform also demonstrates enhanced surface plasmon Raman response for Fourier-transform infrared spectroscopy (FTIR) and photoluminescence (PL) measurements, and presents great potentials as designable hybrid platforms for tunable optical-based chemical sensing applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Liquid ToF-SIMS revealing the oil, water, and surfactant interface evolution

Bilge water from ships is regarded as a major pollutant in the marine environment. Bilge water exists in a stable oil-in-water (O/W) emulsion form. However, little is known about the O/W liquid–liquid (l–l) interface. Traditional bulk characterization approaches are not capable of capturing the chemical changes at the O/W l–l interface. Although surfactants are deemed essential in droplet formation, their roles in bilge water stabilization have not been fully revealed. We have utilized novel in situ chemical imaging tools including in situ scanning electron microscopy (SEM) and in situ time-of-flight secondary ion mass spectrometry (ToF-SIMS) to study the evolving O/W interface using a NAVY bilge model for the first time. The droplet size distribution (DSD) does not change significantly without the addition of X-100 surfactants under static or rocking conditions. Both the oil components and the water clusters are shown to evolve over time at the O/W droplet interface by in situ liquid SIMS imaging. Of particular interest to droplet stabilization, the contribution of surfactants to the aged bilge droplets becomes more significant as the droplet size increases. The higher mass surfactant component does not appear on the droplet surface immediately while many lower mass surfactants are solvated inside the droplet. We have provided the first three-dimensional images of the evolving O/W interface and demonstrated that in situ surface chemical mapping is powerful enough to reveal the complex and dynamic l–l interface in the liquid state. Our observational insights suggest that surfactants are important in mediating droplet growth and facilitating effective separation of bilge water emulsion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Parametric dependencies of resonant layer responses across linear, two-fluid, drift-MHD regimes

Non-axisymmetric magnetic fields arising in a tokamak either by external or internal perturbations can induce complex non-ideal MHD responses in their resonant surfaces while remaining ideally evolved elsewhere. This layer response can be characterized in a linear regime by a single parameter called the inner-layer Δ, which enables outer-layer matching and the prediction of torque balance to non-linear island regimes. In this work, we follow strictly one of the most comprehensive analytic treatments including two-fluid and drift MHD effects and keep the fidelity of the formulation by incorporating the numerical method based on the Riccati transformation when quantifying the inner-layer Δ. The proposed scheme reproduces not only the predicted responses in essentially all asymptotic regimes but also with continuous transitions as well as improved accuracies. In particular, the Δ variations across the inertial regimes with viscous or semi-collisional effects have been further resolved, in comparison with additional analytic solutions. The results imply greater shielding of the electromagnetic torque at the layer than what would be expected by earlier work when the viscous or semi-collisional effects can compete against the inertial effects, and also due to the intermediate regulation by kinetic Alfvén wave resonances as rotation slows down. These are important features that can alter the non-axisymmetric plasma responses including the field penetration by external fields or island seeding process in rotating tokamak plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Arctic tundra shrubification: a review of mechanisms and impacts on ecosystem carbon balance

Abstract Vegetation composition shifts, and in particular, shrub expansion across the Arctic tundra are some of the most important and widely observed responses of high-latitude ecosystems to rapid climate warming. These changes in vegetation potentially alter ecosystem carbon balances by affecting a complex set of soil–plant–atmosphere interactions. In this review, we synthesize the literature on (a) observed shrub expansion, (b) key climatic and environmental controls and mechanisms that affect shrub expansion, (c) impacts of shrub expansion on ecosystem carbon balance, and (d) research gaps and future directions to improve process representations in land models. A broad range of evidence, including in-situ observations, warming experiments, and remotely sensed vegetation indices have shown increases in growth and abundance of woody plants, particularly tall deciduous shrubs, and advancing shrublines across the circumpolar Arctic. This recent shrub expansion is affected by several interacting factors including climate warming, accelerated nutrient cycling, changing disturbance regimes, and local variation in topography and hydrology. Under warmer conditions, tall deciduous shrubs can be more competitive than other plant functional types in tundra ecosystems because of their taller maximum canopy heights and often dense canopy structure. Competitive abilities of tall deciduous shrubs vs herbaceous plants are also controlled by variation in traits that affect carbon and nutrient investments and retention strategies in leaves, stems, and roots. Overall, shrub expansion may affect tundra carbon balances by enhancing ecosystem carbon uptake and altering ecosystem respiration, and through complex feedback mechanisms that affect snowpack dynamics, permafrost degradation, surface energy balance, and litter inputs. Observed and projected tall deciduous shrub expansion and the subsequent effects on surface energy and carbon balances may alter feedbacks to the climate system. Land models, including those integrated in Earth System Models, need to account for differences in plant traits that control competitive interactions to accurately predict decadal- to centennial-scale tundra vegetation and carbon dynamics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Spectral near-field thermal emission extraction by optical waveguides

As far-field thermal emission is limited by blackbody radiation, the significant enhancement of thermal radiation in the near-field plays a vital role in a variety of applications such as infrared sensing, radiation cooling, and thermophotovoltaics. Yet the techniques of exporting the near-field signal to the far field are still not mature, typically relying on complex instrumentation capable of being applied only to the surfaces of model systems and structures. Here we develop an efficient method of extracting near-field thermal radiation to the far field by integrating a nanoscale thermal emitter with a high-index optical waveguide. By directly depositing the emitter onto the optical waveguide, it requires no vacuum gap and enables efficient coupling of near-field thermal radiation into propagating wave-guided modes. A single-mode planar waveguide incorporated with an indium-tin oxide (ITO) film as a thermal emitter is theoretically investigated to prove the feasibility of thermal extraction. The Wiener-chaos expansion method is applied to directly calculate the thermal radiation from the emitter-waveguide system. We experimentally demonstrate the fidelity of the optical-waveguide-assisted near-field thermal extraction by measuring the emission spectrum of an ITO-coated optical fiber and comparing with theoretical predictions. Our experimental demonstration in conjunction with the direct simulation paves the way for effectively extracting near-field thermal radiation with applications in chemical sensing, infrared imaging, and near-field thermal energy management.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Enormous electron-electron scattering in the filled-cage cubic compound B a 10 T i 24 B i 39

Cubic intermetallic compound Ba 10 Ti 24 Bi 39 has a Ba 6 Bi 16 polyhedral cage with a Bi guest atom encapsulated inside. The compound can be formulated as Ba 5 Ti 12 Bi$_{19+x}$ when $x$ signifies the extra Bi atoms filling cages. It crystallizes in a complex noncentrosymmetric cubic structure in space group $P-43m$ with cell parameter $a = 12.6787(4)Å$. The guest Bi atoms distribute diffusely in the cages and seem to play a role in stabilizing the crystal structure. The magnetic susceptibility of this compound shows a weak temperature dependence with a positive slope coefficient. The charge transport properties as a function of temperature exhibit two competing components which are in charge of positive and negative magnetoresistances. Electronic band-structure calculations reveal the complex multiband hybridization of Ti/Bi orbitals near the Fermi surface, which may play a role in the enormous electron-electron scattering in this material evidenced by the large Kadowaki-Woods ratio.

36 MATERIALS SCIENCE↗