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At least 1,027 records · Page 57

Three-dimensional ring current decay model

This work is an extension of a previous ring current decay model. In the previous work, a two-dimensional kinetic model was constructed to study the temporal variations of the equatorially mirroring ring current ions, considering charge exchange and Coulomb drag losses along drift paths in a magnetic dipole field. In this work, particles with arbitrary pitch angle are considered. By bounce averaging the kinetic equation of the phase space density, information along magnetic field lines can be inferred from the equator. The three-dimensional model is used to simulate the recovery phase of a model great magnetic storm, similar to that which occurred in early February 1986. The initial distribution of ring current ions (at the minimum Dst) is extrapolated to all local times from AMPTE/CCE spacecraft observations on the dawnside and duskside of the inner magnetosphere spanning the L value range L = 2.25 to 6.75. Observations by AMPTE/CCE of ring current distributions over subsequent orbits during the storm recovery phase are compared to model outputs. In general, the calculated ion fluxes are consistent with observations, except for H(+) fluxes at tens of keV, which are always overestimated. A newly invented visualization idea, designated as a chromogram, is used to display the spatial and energy dependence of the ring current ion differential flux. Important features of storm time ring current, such as day-night asymmetry during injection and drift hole on the dayside at low energies (less than 10 keV), are manifested in the chromogram representation. The pitch angle distribution is well fit by the function, J(sub o)(1 + Ay(sup n)), where y is sine of the equatorial pitch angle. The evolution of the index n is a combined effect of charge exchange loss and particle drift. At low energies (less than 30 keV), both drift dispersion and charge exchange are important in determining n.

Fok, Mei-Ching↗

From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis

Quantum chemistry in the form of density functional theory (DFT) calculations is a powerful numerical experiment for predicting intermolecular interaction energies. However, no chemical insight is gained in this way beyond predictions of observables. Energy decomposition analysis (EDA) can quantitatively bridge this gap by providing values for the chemical drivers of the interactions, such as permanent electrostatics, Pauli repulsion, dispersion, and charge transfer. These energetic contributions are identified by performing DFT calculations with constraints that disable components of the interaction. This review describes the second-generation version of the absolutely localized molecular orbital EDA (ALMO-EDA-II). The effects of different physical contributions on changes in observables such as structure and vibrational frequencies upon complex formation are characterized via the adiabatic EDA. Example applications include red- versus blue-shifting hydrogen bonds; the bonding and frequency shifts of CO, N 2 , and BF bound to a [Ru(II)(NH 3 ) 5 ] 2 + moiety; and the nature of the strongly bound complexes between pyridine and the benzene and naphthalene radical cations. Additionally, the use of ALMO-EDA-II to benchmark and guide the development of advanced force fields for molecular simulation is illustrated with the recent, very promising, MB-UCB potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stabilization of Dinuclear Rhodium and Iridium Clusters on Layered Titanate and Niobate Supports

Atomically dispersed organometallic clusters can provide well-defined nuclearity of active sites for both fundamental studies as well as new regimes of activity and selectivity in chemical transformations. More recently, dinuclear clusters adsorbed onto solid surfaces have shown novel catalytic properties resulting from the synergistic effect of two metal centers to anchor different reactant species. Difficulty in synthesizing, stabilizing, and characterizing isolated atoms and clusters without agglomeration challenges allocating catalytic performance to atomic structure. Here, we explore the stability of dinuclear rhodium and iridium clusters adsorbed onto layered titanate and niobate supports using molecular precursors. Both systems maintain their nuclearity when Statistical analysis of HAADF-STEM images revealed that rhodium and iridium dimers had mean cluster-to-cluster distances very similar to what is expected from a random distribution of atoms over a large area, indicating that they are dispersed without aggregation. The stability of dinuclear rhodium clusters supported on titanate nanosheets was also investigated by X-ray absorption fine structure (EXAFS), DRIFTS, and first-principles calculations. Both X-ray absorption spectroscopy and HAADF-STEM simulations, guided by density functional theory (DFT)-optimized structure models, suggested that rhodium dimers adsorb onto the nanosheets in an end-on binding mode that is stable up to 100 degrees C under reducing conditions. Finally, this study highlights that crystalline nanosheets derived from layered metal oxides can be used as model supports to selectively stabilize dinuclear clusters, which could have implications for heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Tracking of NiFe Smart Catalysts using In Situ X-Ray Absorption Spectroscopy for the Dry Methane Reforming Reaction

The exsolution of nanoparticles from perovskite precursors has been explored as a route to synthesize catalysts with sinter or coke resistance. The characteristics of these exsolved nanoparticles are highly dynamic depending on the redox nature of the environment to which they are subjected. To develop their properties for thermo- and electrocatalytic applications, it is necessary to track the states and behavior of exsolved catalysts with in situ and ex situ characterization. In this study, we conduct in situ X-ray absorption spectroscopy (XAS) along with ex situ scanning transmission electron microscopy high-angle annular dark-field (STEM-HAADF) and energy-dispersive X-ray spectroscopy analysis of the parent perovskite oxide precursor, LaFe 0.8 Ni 0.2 O 3 , as its structure forms bimetallic NiFe nanoparticles and evolves in oxidative, reductive, and dry methane reforming environments. We develop a theory that NiFe exsolution is a function of the reduction potential where LaFe 0.8 Ni 0.2 O 3 transforms to NiFe alloy supported on LaO x -LaFeO x . The Ni starts to exsolve at 268 °C, while most Fe exsolves at 700 °C. During dry methane reforming conditions, most of the Fe is oxidized by CO 2 during the reaction and re-enters the perovskite as LaFeO 3 , while Ni remains on the surface as nanoparticles in the metallic state. During the oxidative regeneration phase, most of the Fe re-enters the bulk perovskite phase, while Ni is partially regenerated with a small percentage oxidized to large NiO nanoparticles. Finally, this study sheds light on the exsolution and regeneration of bimetallic alloy nanoparticles and the influence of the reaction conditions on their catalyst performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Universal scaling of weak localization in graphene due to bias-induced dispersion decoherence

The differential conductance of graphene is shown to exhibit a zero-bias anomaly at low temperatures, arising from a suppression of the quantum corrections due to weak localization and electron interactions. A simple rescaling of these data, free of any adjustable parameters, shows that this anomaly exhibits a universal, temperature- (T) independent form. According to this, the differential conductance is approximately constant at small voltages (V < kBT/e), while at larger voltages it increases logarithmically with the applied bias. For theoretical insight into the origins of this behaviour, which is inconsistent with electron heating, we formulate a model for weak-localization in the presence of nonequilibrium transport. According to this model, the applied voltage causes unavoidable dispersion decoherence, which arises as diffusing electron partial waves, with a spread of energies defined by the value of the applied voltage, gradually decohere with one another as they diffuse through the system. The decoherence yields a universal scaling of the conductance as a function of eV/kBT, with a logarithmic variation for eV/kBT > 1, variations in accordance with the results of experiment. Our theoretical description of nonequilibrium transport in the presence of this source of decoherence exhibits strong similarities with the results of experiment, including the aforementioned rescaling of the conductance and its logarithmic variation as a function of the applied voltage.

42 ENGINEERING↗

Characteristics of suprathermal H(+) and He(++) in plasmoids in the distant magnetotail

Rest frame distribution functions were obtained for suprathermal H(+) and He(2+) ions during 20 particle intensity increases that were observed in the distant magnetotail by ISEE-3. All of these increases were characterized by isotropic, approximately 100-keV electrons, preceded by beaming electrons and velocity-dispersed protons distributions whose signatures are typically associated with plasmoids. In each of the plasmoids, both H(+) and He(2+) are found to be convected tailward, with speeds that range from 200 to 1000 km/sec. The acceleration mechanism is found to depend on particle velocity, and it is established that the solar wind is a dominant plasma source. The plasmoids appear to be expanding at about 100 km/sec during their tailward propagation.

Gloeckler, G.↗

The Influence of Smoke Particle Properties and Cabin Characteristics on Smoke Detection in Lunar Gravity

Spacecraft fires pose a threat to the success of future Lunar, Martian, and deep space exploration missions. As NASA plans to return humans to the Moon in the next decade, novel mission requirements will present new fire safety challenges. For example, materials that are fire resistant on Earth are expected to burn under planned habitat conditions (elevated oxygen concentrations and reduced cabin pressure) and partial gravity (0.16g). Optimal smoke detector placement will depend on a combination of buoyant plume velocities, induced by partial gravity, and Environmental Control and Life Support Systems (ECLSS) parameters, including particle filtration rates, supply and return placement within the cabin, and forced air velocities. These ECLSS parameters must also address the need for rapid Lunar dust removal, as Lunar dust exposure poses a risk to crew health and hardware functionality. Here, we present progress toward a computational fluid dynamics model to evaluate smoke transport in a Lunar habitat. Recent work has demonstrated that if air supplies are placed on ceilings and returns on the floor, a buoyant smoke layer at the ceiling may disperse over the order of minutes even under low forced flow conditions. We expand upon these results to examine the influence of different supply and return configurations on smoke plume development. Additionally, we also address differences in the transport of smoke particles and Lunar dust by varying particle parameters like size, density, and shape factor. Finally, we discuss ongoing and future experimental efforts to measure smoke particle properties and transport under partial gravity, elevated oxygen, and reduced pressure conditions.

Claire Fortenberry↗

Regulating Catalytic Properties and Thermal Stability of Pt and PtCo Intermetallic Fuel-Cell Catalysts via Strong Coupling Effects between Single-Metal Site-Rich Carbon and Pt

Developing low platinum-group-metal (PGM) catalysts for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs) for heavy-duty vehicles (HDVs) remains a great challenge due to the highly demanded power density and long-term durability. Here, this work explores the possible synergistic effect between single Mn site-rich carbon (Mn SA -NC) and Pt nanoparticles, aiming to improve intrinsic activity and stability of PGM catalysts. Density functional theory (DFT) calculations predicted a strong coupling effect between Pt and MnN 4 sites in the carbon support, strengthening their interactions to immobilize Pt nanoparticles during the ORR. The adjacent MnN 4 sites weaken oxygen adsorption at Pt to enhance intrinsic activity. Well-dispersed Pt (2.1 nm) and ordered L1 2 -Pt 3 Co nanoparticles (3.3 nm) were retained on the Mn SA -NC support after indispensable high-temperature annealing up to 800 °C, suggesting enhanced thermal stability. Both PGM catalysts were thoroughly studied in membrane electrode assemblies (MEAs), showing compelling performance and durability. The Pt@Mn SA -NC catalyst achieved a mass activity (MA) of 0.63 A mg Pt –1 at 0.9 V iR-free and maintained 78% of its initial performance after a 30,000-cycle accelerated stress test (AST). The L1 2 -Pt 3 Co@Mn SA -NC catalyst accomplished a much higher MA of 0.91 A mg Pt –1 and a current density of 1.63 A cm –2 at 0.7 V under traditional light-duty vehicle (LDV) H 2 –air conditions (150 kPa abs and 0.10 mg Pt cm –2 ). Furthermore, the same catalyst in an HDV MEA (250 kPa abs and 0.20 mg Pt cm –2 ) delivered 1.75 A cm –2 at 0.7 V, only losing 18% performance after 90,000 cycles of the AST, demonstrating great potential to meet the DOE targets.

25 ENERGY STORAGE↗

Effect of crystallite geometries on electrochemical performance of porous intercalation electrodes by multiscale operando investigation

Lithium-ion batteries are yet to realize their full promise because of challenges in the design and construction of electrode architectures that allow for their entire interior volumes to be reversibly accessible for ion storage. Electrodes constructed from the same material and with the same specifications, which differ only in terms of dimensions and geometries of the constituent particles, can show surprising differences in polarization, stress accumulation and capacity fade. Here, using operando synchrotron X-ray diffraction and energy dispersive X-ray diffraction (EDXRD), we probe the mechanistic origins of the remarkable particle geometry-dependent modification of lithiation-induced phase transformations in V2O5 as a model phase-transforming cathode. A pronounced modulation of phase coexistence regimes is observed as a function of particle geometry. Specifically, a metastable phase is stabilized for nanometre-sized spherical V2O5 particles, to circumvent the formation of large misfit strains. Spatially resolved EDXRD measurements demonstrate that particle geometries strongly modify the tortuosity of the porous cathode architecture. Greater ion-transport limitations in electrode architectures comprising micrometre-sized platelets result in considerable lithiation heterogeneities across the thickness of the electrode. These insights establish particle geometry-dependent modification of metastable phase regimes and electrode tortuosity as key design principles for realizing the promise of intercalation cathodes. Designing electrode architectures for Li-ion batteries that can be reversibly accessible for ion storage can be challenging. Using operando techniques the mechanistic origin of lithiation-induced phase transformations in a V2O5 model cathode is now clarified.

Luo, Yuting↗

Roadmap on exsolution for energy applications

Over the last decade, exsolution has emerged as a powerful new method for decorating oxide supports with uniformly dispersed nanoparticles for energy and catalytic applications. Due to their exceptional anchorage, resilience to various degradation mechanisms, as well as numerous ways in which they can be produced, transformed and applied, exsolved nanoparticles have set new standards for nanoparticles in terms of activity, durability and functionality. In conjunction with multifunctional supports such as perovskite oxides, exsolution becomes a powerful platform for the design of advanced energy materials. In the following sections, we review the current status of the exsolution approach, seeking to facilitate transfer of ideas between different fields of application. We also explore future directions of research, particularly noting the multi-scale development required to take the concept forward, from fundamentals through operando studies to pilot scale demonstrations.

25 ENERGY STORAGE↗

Simultaneous type-I and type-II phase matching for second-order nonlinearity in integrated lithium niobate waveguide

Second-order optical nonlinearity is widely used for both classical and quantum photonic applications. Due to material dispersion and phase matching requirements, the polarization of optical fields is pre-defined during the fabrication. Only one type of phase matching condition is normally satisfied, and this limits the device flexibility. Here, we demonstrate that phase matching for both type-I and type-II second-order optical nonlinearity can be realized simultaneously in the same waveguide fabricated from thin-film lithium niobate. This is achieved by engineering the geometry dispersion to compensate for the material dispersion and birefringence. The simultaneous realization of both phase matching conditions is verified by the polarization dependence of second-harmonic generation. Correlated photons are also generated through parametric down conversion from the same device. This work provides a novel approach to realize versatile photonic functions with flexible devices.

Briggs, Ian↗

Dispersion characteristics for wide slotlines on low-permittivity substrates

A spectral-domain Galerkin method is used to calculate the dispersion characteristics of wide slotlines on low-permittivity substrates that are electrically thin. The range of parameters covered are d/lambda sub 0 = 0.006-0.06, W/lambda sub 0 = 0.005-2.0, and epsilon sub r = 2.22, 3.0, 3.8, and 9.8. The choice of expansion and testing functions makes possible the extraction of the asymptotic form of the infinite integrals, resulting in a computationally efficient solution. The agreement between calculated and measured slot wavelengths on narrow and wide slots is generally within 2.0 percent over 2-6 GHz.

Janaswamy, R.↗

Morphological and physical characteristics of the Virgo Cluster - First results from the Las Campanas photographic survey

Preliminary results are presented of a photographic survey of the Virgo cluster to the faintest convenient limit of the Las Campanas du Pont 2.5 m reflector, performed in order to study the complexity of both the surface and velocity distributions within the central 6 degree radius region. The survey is described and the resulting Catalog is discussed, and the frequency of galaxy types found and listed in the Catalog is described. The physical properties of the dwarfs are summarized, and luminosity functions are given separately for each morphological type. The progressive change of (MBT) faintward along the morphological sequence from Sc I through Sm and Im types is shown, leading to a calibration of the de Vaucouleurs Lambda luminosity index and a determination of its intrinsic dispersion. The preliminary results on the distribution of galaxies of all types in the two principal subclustering regions found are summarized, and the velocity distributions over the face of the 6 degree core are discussed for the various galaxy types.

Sandage, A.↗

Modeling, Monitoring and Fault Diagnosis of Spacecraft Air Contaminants

Control of air contaminants is a crucial factor in the safety considerations of crewed space flight. Indoor air quality needs to be closely monitored during long range missions such as a Mars mission, and also on large complex space structures such as the International Space Station. This work mainly pertains to the detection and simulation of air contaminants in the space station, though much of the work is easily extended to buildings, and issues of ventilation systems. Here we propose a method with which to track the presence of contaminants using an accurate physical model, and also develop a robust procedure that would raise alarms when certain tolerance levels are exceeded. A part of this research concerns the modeling of air flow inside a spacecraft, and the consequent dispersal pattern of contaminants. Our objective is to also monitor the contaminants on-line, so we develop a state estimation procedure that makes use of the measurements from a sensor system and determines an optimal estimate of the contamination in the system as a function of time and space. The real-time optimal estimates in turn are used to detect faults in the system and also offer diagnoses as to their sources. This work is concerned with the monitoring of air contaminants aboard future generation spacecraft and seeks to satisfy NASA's requirements as outlined in their Strategic Plan document (Technology Development Requirements, 1996).

Ramirez, W. Fred↗

WGM-Resonator/Tapered-Waveguide White-Light Sensor Optics

Theoretical and experimental investigations have demonstrated the feasibility of compact white-light sensor optics consisting of unitary combinations of (1) low-profile whispering-gallery-mode (WGM) resonators and (2) tapered rod optical waveguides. These sensors are highly wavelength-dispersive and are expected to be especially useful in biochemical applications for measuring absorption spectra of liquids. These sensor optics exploit the properties of a special class of non-diffracting light beams that are denoted Bessel beams because their amplitudes are proportional to Bessel functions of the radii from their central axes. High-order Bessel beams can have large values of angular momentum. In a sensor optic of this type, a low-profile WGM resonator that supports modes having large angular momenta is used to generate high-order Bessel beams. As used here, "low-profile" signifies that the WGM resonator is an integral part of the rod optical waveguide but has a radius slightly different from that of the adjacent part(s).

Stekalov, Dmitry↗

Batch Effect Correction Methods for NASA GeneLab Transcriptomic Datasets

RNA sequencing (RNA-seq) data from space biology experiments promise to yield invaluable insights into the effects of spaceflight on terrestrial biology. However, sample numbers from each study are low due to limited crew availability, hardware, and space. To increase statistical power, spaceflight RNA-seq datasets from different missions are often aggregated together. However, this can introduce technical variation or "batch effects", often due to differences in sample handling, sample processing, and sequencing platforms. Several computational methods have been developed to correct for technical batch effects, thereby reducing their impact on true biological signals. In this study, we combined 7 mouse liver RNA-seq datasets from NASA GeneLab (part of the NASA Open Science Data Repository) to evaluate several common batch effect correction methods (ComBat and ComBat-seq from the sva R package, and Median Polish, Empirical Bayes, and ANOVA from the MBatch R package). We quantitatively evaluated the ability of these methods to correct for technical batch variables in space biology RNA-seq data using the following criteria: BatchQC, principal component analysis, dispersion separability criterion, log fold change correlation, and differential gene expression analysis. Each batch variable / correction method combination was then assessed using a custom scoring approach to identify the optimal correction method for the combined dataset, by geometrically probing the space of all allowable scoring functions to yield an aggregate volume-based scoring measure. Finally, we describe the way in which the GeneLab multi-study analysis and visualization portal will allow users to examine the presence or absence of batch effects using multiple metrics. If the user chooses to perform batch effect correction, the scoring approach described here can be implemented to identify the optimal correction method to use for their specific combined dataset prior to analysis.

Lauren M. Sanders↗

Characterization of CO2 Binding on Alkaline Metal Oxide Sorbents and DFMs for Combined Capture and Conversion

As the world endures environmental crises associated with climate change and the rise of atmospheric CO2 concentrations from anthropogenic CO2 emission, carbon capture and utilization (CCU) technologies are increasingly necessary. Reactive carbon capture (RCC) technologies, in which capture and conversion of CO2 occur in a single reactor, are more energetically and economically attractive by avoiding the need to purify, compress, and transport the captured CO2. To this end, the development of dual function materials (DFM) that enable CO2 capture and conversion to useful C1 products, namely (1) methane, (2) CO, and (3) methanol, are attractive near-term targets for commercial CCU processes for renewable fuels and chemicals. DFM are composed of sorbents and catalysts co-dispersed on the same high surface area carrier. The sorbent component allows for selective capture of CO2 from a gas stream and the catalyst component subsequently performs the in-situ conversion of the adsorbed CO2 upon introduction of a reactive gas (typically H2). The survey of DFM formulations reveals a variety of sorbent+catalyst combinations of interest. There is, however, a lack of depth in fundamental understanding of how the CO2 binds to these materials and how the subsequent reaction mechanisms are affected, which are critical features for the development of next-generation materials with improved performance. To this end, we will describe in this work the CO2 binding characteristics of established and/or new DFM and their sorbent-only counterparts. The surface CO2 binding mechanism and capture capacity will be probed using techniques such as in-situ DRIFTS, operando TGA, and CO2 chemisorption.

alkaline oxides↗

Desalinating a Real Hyper-Saline Pre-Treated Produced Water via Direct-Heat Vacuum Membrane Distillation

Membrane distillation (MD) is an emerging thermal desalination technology capable of desalinating waters of any salinity. During typical MD processes, the saline feedwater is heated and acts as the thermal energy carrier; however, temperature polarization (as well as thermal energy loss) contributes to low distillate fluxes, low single-pass water recovery and poor thermal efficiency. An alternative approach is to integrate an extra thermal energy carrier as part of the membrane and/or module assembly, which can channel externally provided heat directly to the membrane-feedwater interface and/or along the feed channel length. This direct-heat delivery has been demonstrated to increase single-pass water recovery and enhance the overall thermal efficiency. We developed a bench-scale direct-heated vacuum MD (DHVMD) process to desalinate pre-treated oil and gas "produced water" with an initial total dissolved solids of 115,500 ppm at a feed temperature ranging between 24 and 32 degrees C. We evaluated both water flux and specific energy consumption (SEC) as a function of water recovery. The system achieved a 50% water recovery without significant scaling, with an average flux >6 kg m-2 hr-1 and a SEC as low as 2,530 kJ kg-1. The major species of mineral scales (i.e., NaCl, CaSO4, and SrSO4) that limited the water recovery to 68% were modeled in terms of thermodynamics and identified by scanning electron microscopy and energy-dispersive X-ray spectroscopy. In addition, we further developed and employed a physics-based process model to estimate temperature, salinity, water transport and energy flows for full-scale vacuum MD and DHVMD modules. Model results show that a direct-heat input rate of 3,600 W can increase single-pass water recovery from 2.1% to 3.1% while lowering the thermal SEC from 7,800 kJ kg-1 to 6,517 kJ kg-1 in an unoptimized module. Finally, the scaling up potential of DHVMD process is briefly discussed.

brine↗