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At least 307 records · Page 17

Chemo-Mechanically Driven In Situ Hierarchical Structure Formation in Mixed Conductors (Final Technical Report)

This document is the Final Technical Report for the Early Career project DE-SC0018963. Essential materials for energy technologies tend to exhibit “hierarchical” functions – they perform multiple, inter-related tasks at different locations, across disparate length and time scales. To best support this heterogeneous function, there is a fundamental need to understand and direct formation of corresponding tailored hierarchical architectures. In particular, a wide variety of applications, from energy conversion and storage to sensing and gas separation, rely on oxide mixed ionic and electronic conductors (MIECs). These critical ceramic materials catalyze reactions at their surfaces and selectively transport both ionic and electronic species in the bulk. Ideally, MIECs should adopt hierarchical structures with 1) high surface areas, 2) surface compositions exhibiting high catalytic activity, and 3) microstructural connectivity in the direction needed for fast mass and charge transport. In practice, however, MIECs.

08 HYDROGEN↗

Predictability of the tropical atmosphere

An examination of the deterministic predictability for tropics and middle-latitudes separately indicates that the theoretical upper limit of deterministic predictability for low latitudes is shorter than that for middle latitudes. Variability of time averages in low latitudes is mainly determined by the location and intensity of the large-scale Hadley and Walker circulations. Since these are largely influenced by the slowly varying boundary conditions of sea surface temperature and soil moisture, and since synoptic instabilities are not strong enough to change drastically the large scale flow, there is larger potential for predictability of monthly and seasonal means in low latitudes. It is conjectured that for short and medium range deterministic prediction, a prescribed diabatic heating field due to moist convection may be more useful than their explicit calculation from the evolving flow.

Shukla, J.↗

Scale disparity and spectral transfer in anisotropic numerical turbulence

To study the effect of cancellations within long-range interactions on local isotropy at the small scales, we calculate explicitly the degree of cancellation in distant interactions in the simulations of Yeung & Brasseur and Yeung, Brasseur & Wang using the single scale disparity parameter 's' developed by Zhou. In the simulations, initially isotropic simulated turbulence was subjected to coherent anisotropic forcing at the large scales and the smallest scales were found to become anisotropic as a consequence of direct large-small scale couplings. We find that the marginally distant interactions in the simulation do not cancel out under summation and that the development of small-scale anisotropy is indeed a direct consequence of the distant triadic group, as argued by Yeung, et. al. A reduction of anisotropy at later times occurs as a result of the isotropizing influences of more local energy-cascading triadic interactions. Nevertheless, the local-to-nonlocal triadic group persists as an isotropizing influence at later times. We find that, whereas long-range interactions, in general, contribute little to net energy transfer into or out of a high wavenumber shell k, the anisotropic transfer of component energy within the shell increases with increasing scale separations. These results are consistent with results by Zhou, and Brasseur & Wei, and suggest that the anisotropizing influences of long range interactions should persist to higher Reynolds numbers. The residual effect of the forced distant group in this low-Reynolds number simulation is found to be forward cascading, on average.

Zhou, YE↗

SPE-CZE-MS Quantifies Zeptomole Amounts of Phosphorylated Peptides

Capillary zone electrophoresis (CZE) is gaining attention in the field of single-cell proteomics for its ultralow-flow and high-resolution separation abilities. Even more sample-limited yet rich in biological information are phosphoproteomics experiments, as the phosphoproteome composes only a fraction of the whole cellular proteome. Rapid analysis, high sensitivity, and maximization of sample utilization are paramount for single-cell analysis. Some challenges of coupling CZE analysis with mass spectrometry analysis (MS) of complex mixtures include 1. sensitivity due to volume loading limitations of CZE and 2. incompatibility of MS duty cycles with electropherographic time scales. Here, we address these two challenges as applied to singlecell- equivalent phosphoproteomics experiments by interfacing a microchip-based CZE device integrated with a solid-phaseextraction (SPE) bed with the Orbitrap Astral mass spectrometer. Using 225 phosphorylated peptide standards and phosphorylated peptide-enriched mouse brain tissue, we investigate microchip-based SPE-CZE functionality, quantitative performance, and complementarity to nano-LC-MS (nLC-MS) analysis. We highlight unique SPE-CZE separation mechanisms that can empower fitfor- purpose applications in single-cell-equivalent phosphoproteomics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Mn dissolution mechanism in rock salt-type Li 4 Mn 2 O 5 cathodes

For the first time, a detailed exploration of Mn dissolution in disordered rock salt (DRX) Li 4 Mn 2 O 5 is presented. Herein, we apply a suite of synchrotron and lab scale X-ray techniques to both the cathode and the separator harvested from pristine, charged, or cycled lithium half-cells containing the disordered rock salt (DRX) material Li 4 Mn 2 O 5 , in order to understand Mn dissolution processes throughout charging and discharging. Previous research has hypothesized two concurrent effects that may drive Mn dissolution in cells during cycling: acid-induced disproportionation of Jahn–Teller active Mn 3+ and structural rearrangement of the cathode lattice. Through depth probing of the Mn oxidation state in both the cathode and separator via soft X-ray absorption spectroscopy (XAS), hard XAS, and X-ray photoelectron spectroscopy (XPS) in progressive states-of-charge, as well as extended X-ray absorption fine structure (EXAFS) analysis of the local Mn environment, the primary driving force of Mn dissolution is determined to be high-voltage structural rearrangement above 4.2 V. Mn dissolution is, additionally, a main source of capacity fade in Li 4 Mn 2 O 5 DRX cells, which retain only 59% capacity after 20 cycles.

Theibault, Monica↗

Compressibility effects on dynamic stall of airfoils undergoing rapid transient pitching motion

The research was carried out in the Compressible Dynamic Stall Facility, CDSF, at the Fluid Mechanics Laboratory (FML) of NASA Ames Research Center. The facility can produce realistic nondimensional pitch rates experienced by fighter aircraft, which on model scale could be as high as 3600/sec. Nonintrusive optical techniques were used for the measurements. The highlight of the effort was the development of a new real time interferometry method known as Point Diffraction Interferometry - PDI, for use in unsteady separated flows. This can yield instantaneous flow density information (and hence pressure distributions in isentropic flows) over the airfoil. A key finding is that the dynamic stall vortex forms just as the airfoil leading edge separation bubble opens-up. A major result is the observation and quantification of multiple shocks over the airfoil near the leading edge. A quantitative analysis of the PDI images shows that pitching airfoils produce larger suction peaks than steady airfoils at the same Mach number prior to stall. The peak suction level reached just before stall develops is the same at all unsteady rates and decreases with increase in Mach number. The suction is lost once the dynamic stall vortex or vortical structure begins to convect. Based on the knowledge gained from this preliminary analysis of the data, efforts to control dynamic stall were initiated. The focus of this work was to arrive at a dynamically changing leading edge shape that produces only 'acceptable' airfoil pressure distributions over a large angle of attack range.

Chandrasekhara, M. S.↗

Response to Comment on "Does the Earth Have an Adaptive Infrared Iris?"

In his comment on Lindzen et al., Harrison found that the amount of high-level clouds, A, and the sea-surface temperature beneath clouds, T, averaged over a large oceanic domain in the western Pacific have secular linear trends of opposite signs over a period of 20 months. He found that when the linear trends are subtracted from the data, the correlation between the residual A and T is much reduced. His estimates of the confidence levels for the correlation indicate, moreover, that this correlation is not statistically significant. The domain-averaged A and, to a lesser degree, T, have distinct intra-seasonal and seasonal variations. These variations are influenced by the large-scale wind and temperature distributions and by the seasonal variation of insolation. To separate the local effect from the effect of slowly changing large-scale conditions, rather than subtracting 20-month linear trends from the series, which has the potential to spuriously extrapolate intra-seasonal and seasonal variations to even longer time scales, we subtracted 30-day running means of A and T from each time series; in effect, the data were high-pass filtered. The number of points (days), N, is reduced by this process from the original value of 510 to 480.

Bell, Thomas L.↗

Profiles of Gamma-Ray Bursts and Their Component Pulses

One physically informative regularity of their otherwise heterogeneous ensemble, is that many Gamma-Ray Bursts consist of well defined pulses. To objectively quantify the temporal structure of BATSE bursts, we have developed an automatic modeling procedure that separates overlapping pulses and determines the energy-dependence of the pulse-shape parameters. No binning of photon arrival times is needed, so when applied to time-tagged events (TTE) the procedure captures variability information down to the shortest time scales present in the raw data. Maximizing the Bayesian likelihood function Pr(data/model) yields estimates of the model parameters, including the number of pulses present, and allows intercomparison of models of different forms. As with any nonlinear optimization, good initial guesses are crucial to avoid convergence to undesirable local minima. We find excellent initial pulse decompositions by wavelet-denoising a cumulative distribution of the raw photon arrival data; differentiation then gives a time profile mostly free of the systematic effects of degraded resolution (as in ordinary Fourier smoothing) and binning. We present statistical information on pulse rise-time, decay-time, peakedness, and amplitudes, plus their energy dependences - both within a single burst and for a large ensemble of bursts.

Scargle, Jeff D.↗

Characterization and Uncertainty Analysis of a Reference Pressure Measurement System for Wind Tunnels

This paper presents the calibration results and uncertainty analysis of a high-precision reference pressure measurement system currently used in wind tunnels at the NASA Langley Research Center (LaRC). Sensors, calibration standards, and measurement instruments are subject to errors due to aging, drift with time, environment effects, transportation, the mathematical model, the calibration experimental design, and other factors. Errors occur at every link in the chain of measurements and data reduction from the sensor to the final computed results. At each link of the chain, bias and precision uncertainties must be separately estimated for facility use, and are combined to produce overall calibration and prediction confidence intervals for the instrument, typically at a 95% confidence level. The uncertainty analysis and calibration experimental designs used herein, based on techniques developed at LaRC, employ replicated experimental designs for efficiency, separate estimation of bias and precision uncertainties, and detection of significant parameter drift with time. Final results, including calibration confidence intervals and prediction intervals given as functions of the applied inputs, not as a fixed percentage of the full-scale value are presented. System uncertainties are propagated beginning with the initial reference pressure standard, to the calibrated instrument as a working standard in the facility. Among the several parameters that can affect the overall results are operating temperature, atmospheric pressure, humidity, and facility vibration. Effects of factors such as initial zeroing and temperature are investigated. The effects of the identified parameters on system performance and accuracy are discussed.

Amer, Tahani↗

A high power, low temperature molten sodium battery

Low temperature molten sodium batteries promise low-cost, grid-scale energy storage using earth-abundant materials. To be economically viable, they must demonstrate high current (power) at relevant discharge times. Here a low temperature (135 °C) molten sodium battery with a NaI–AlCl 3 molten salt catholyte and NaSICON separator is explored, minimizing cell ohmic resistances and avoiding precipitation reactions in the molten salt catholyte. Operating currents were increased by as much as 100× compared to the energy-dense baseline design (197 Wh kg −1 and 248 mAh cm −2 ). Cells were cycled 100 times at 50 mA cm −2 (150 mW cm −2 ), averaging 99.8% coulombic efficiency and 79.7% energy efficiency for 30% of the theoretical capacity. Charging currents up to 250 mA cm −2 (1070 mW cm −2 ) are demonstrated for 10% of the theoretical capacity. Toward extending the accessible capacity in these high current systems, the volume ratio of catholyte molten salt to a graphite felt current collector was varied, altering (1) the local current density in the graphite felt and (2) the discharge time at a fixed current density. Optimizing the catholyte : felt ratio dramatically increased capacity utilization to 60% (102 mAh cm −2 ) at 50 mA cm −2 (150 mW cm −2 ) charge and 10 mA cm −2 discharge. This catholyte : felt ratio of 1.4 significantly decreased the cell impedance, minimizing electrode blocking effects seen previously in NaI–AlCl 3 catholytes. Together, these high areal loadings and impressive power outputs demonstrate how low temperature molten sodium batteries can compete with commercialized sodium systems operating at more than twice the temperature.

NaSICON↗

The shedding of an anticyclonic eddy from the Alaskan Stream as observed by the Geosat altimeter

The evolution of a meander into an anticyclonic eddy which separates from the Alaskan Stream in the vicinity of the central Aleutian Islands is observed in two years of sea surface height anomalies computed from Geosat Exact Repeat Mission altimeter data. The observed region of meander growth and eddy separation agrees with that predicted by theory. Spin down times based on vorticity are much longer than those based on energies. This is consistent with an eddy's ability to maintain its integrity as it decays. Representative height, diameter, and velocity scales of the eddy are characteristic of rings spawned by other current systems. Assuming a ring structure for this eddy, the estimated ring volume represents a 21 percent transport anomaly referred to the mean annual transport into the Bering Sea.

Okkonen, Stephen R.↗

Impactor control of central peak and peak-ring formation

The relation between the depth and diameter of excavation for impacts typically is assumed to be proportional. Such an assumption is consistent with the constant aspect ratio (diameter:depth) observed for simple craters found in a wide range of planetary settings and crater-scaling laws derived from laboratory experiments. Although complex craters exhibit evidence for floor uplift and rim collapse of a transient profile, they are typically thought to resemble initially smaller, simple craters. At large scales, however, early-time processes consume a greater fraction of crater growth and the assumption of late-time equivalence of energy release as a point source becomes inappropriate. The authors propose instead that crater diameter, depth, and impactor penetration represent separable dependent variables that underscore the fundamental difference between impact and point-source explosion excavation processes. An important consequence of this perspective is that central pits, peaks, and rings may represent contrasting target responses to impactor penetration and could provide an important indicator of impactor dimensions.

Schultz, Peter H.↗

Auroral E-fields from DE-1 and -2 at magnetically conjugate points

The results of studies of the electric field measurements from the two Dynamics Explorer satellites are reviewed. There are times at which DE-2 measured electric fields at the auroral ionosphere while DE-1 obtained nearly simultaneous measurement at a higher altitude on the same magnetic field lines. When these electric fields are mapped to a common altitude it is found that the large-scale electric fields are similar, but the small-scale electric fields have a larger amplitude at the higher altitude. Through the use of Fourier analysis it is shown that these results are evidence for a magnetic field-aligned potential drop between the two satellites. While these results were made possible by the satellites' altitude separation, it is also possible to take advantage of the fact that the satellites may pass through the same geomagnetic location with a time separation. This was useful for confirming that sinusoidal electric field oscillations which were detected near one conjunction were due to spatial rather than temporal variations, since similar oscillations were found at the same location at different times. The observed spatial oscillations can be explained by a simple model of magnetosphere-ionosphere coupling.

Weimer, D. R.↗

Electromagnetic deep-probing (100-1000 KMS) of the Earth's interior from artificial satellites: Constraints on the regional emplacement of crustal resources

The two stages of analysis of MAGSAT magnetic data which are designed to evaluate electromagnetic induction effects are described. The first stage consists of comparison of data from contiguous orbit passes over large scale geologic boundaries, such as ocean-land interfaces, at several levels of magnetic disturbance. The purpose of these comparisons is to separate induction effects from effects of lithospheric magnetization. The procdure for reducing the data includes: (1) identifying and subtracting quiet time effects; (2) modelling and subtracting first order ring current effects; and (3) projecting an orbit track onto a map as a nearly straight line so it can serve as an axis on which to plot the corresponding orbit pass data in the context of geography. The second stage consists of comparison of MAGSAT data with standard hourly observatory data. The purpose is to constrain the time evolution of ionospheric and magnetospheric current systems. Qualitative features of the ground based dataset are discussed. Methods for reducing the ground based data are described.

Hermance, J. F.↗

Machine Learning Interatomic Potentials for Modeling Framework Flexibility and Water Uptake in NbOFFIVE-1-Ni Metal–Organic Framework

Metal–organic frameworks (MOFs), with their distinctive porous structures and tunable chemical properties, have shown immense promise in the separation and storage of gases. Currently, the accurate simulation of their adsorptive properties remains challenging, especially for systems where the molecules fit very tightly into the pores. Traditional simulation methods often approximate the frameworks as rigid and do not account for the framework flexibility seen in materials such as NbOFFIVE-1-Ni. First-principles molecular dynamics (FPMD) simulations offer the desired accuracy in modeling this flexibility but are limited by their extensive computational demands, rendering them impractical for long simulations. Conversely, classical force field-based simulations offer computational efficiency but lack the necessary accuracy. Here, to break this accuracy-efficiency trade-off, we have developed machine learning interatomic potentials trained on energies and forces from FPMD to model the framework flexibility of NbOFFIVE-1-Ni in the presence of water over nanosecond time scales. Furthermore, by integrating MLIP-driven molecular dynamics (MLIP-MD) with grand canonical Monte Carlo (GCMC) simulations, we further incorporated framework flexibility into adsorption predictions, yielding water adsorption isotherms that better align with experimental data compared to those of conventional GCMC simulations. These advances offer new opportunities for the design and optimization of MOFs in gas storage and separation applications.

adsorption↗

Determination of inverted-V stability from Dynamics Explorer satellite data

The longevity of a number of inverted-V electron precipitation events was measured by comparing electron distributions acquired from the two Dynamics Explorer spacecraft during close proximity passes through the southern auroral zone. Common events were identified in the two data sets for time separations up to 18 min. The maximum energy attained within an inverted-V sometimes varied between observations indicating growth or decay of the event. The number of events increasing in energy was roughly equal to those exhibiting decreasing energy, suggesting similar time scales for growth and decay. Observations closely spaced in time (minutes) had some events not in common, implying either a sudden cessation of the event or a limited spatial extent precluding observation by one of the two spacecraft due to its orbital displacement. A statistical study of 28 close proximity passes showed that the number of matched inverted-V events exceeded those which were unmatched. This was not true for comparisons of random pairs of electron distribution plots for the two spacecraft. This implies that the close proximity events observed by both spacecraft were not just random coincidences.

Thieman, J. R.↗

The abundances of elements and isotopes in the solar wind

Solar wind abundances have now been measured for eleven elements and the isotopes of the noble gases. Aside from solar wind protons and alpha particles, which have been studied extensively since the 1960's, information for heavier elements is limited. Nevertheless, two effects stand out. First is the enrichment of abundances of elements with low first ionization potential (FIP), most likely the combined result of an atom-ion separation process in the upper chromosphere, and a marginal coupling of low-charge-state heavy ions to protons and alphas during the acceleration of the solar wind. Second, there is variability in the solar wind composition over a whole range of time scales. Recent measurements carried out in the earth's magnetosheath during times that included high-speed coronal-hole-associated flows indicate a significantly lower overabundance of low FIP elements. Given the fact that the He/H ratio is remarkably constant in the coronal hole solar wind, this result suggests that both enrichment and variability are reduced in such flows.

Gloeckler, George↗

Corvid meteoroids are not ejecta from the Giordano Bruno impact

The study points out three difficulties with the hypothesis of Hartung (1993) that the Corvid meteor system, observed only once in 1937, may be the return of the clump of ejecta from the formation of a lunar crater, specifically, an event recorded in the chronicles of Gervase of Canterbury on June 25, 1178, which Hartung (1976) previously suggested may be an eyewitness account of the formation of the lunar crater Giordano Bruno. On the basis of this, he predicts that another Corvid shower may be observed in 2003 or 2006. This hypothesis is rejected on the contention that it is implausible that a clump of ejecta could be launched into heliocentric orbit with a low enough dispersion in velocity among separate pieces that it would produce a meteor shower in just one year and not others. Subsequent perturbations by the earth on parts of the clump passing near the earth but not impacting would destroy the coherence of the clump on a time scale much shorter than the 759-yr interval proposed. There are so many orbits that could yield a shower after 759 yr that it is unlikely that a prediction of a return in a specific year would be correct.

Harris, A. W.↗