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At least 937 records · Page 52

Structure and dynamics of short-chain polymerized ionic liquids

Combining experimental results obtained with X-ray scattering and field-gradient nuclear magnetic resonance (NMR) and an assessment of new and previous dielectric and rheology data, our study focuses on the molecular weight (M w ) evolution of local structure and dynamics in a homologous series of covalently bonded ionic liquids. Performed on a family of electrolytes with a tailored degree of ionic decoupling, this study reveals the differences between monomeric and oligomeric melts with respect to their structural organization, mass and charge transport, and molecular diffusion. Our work demonstrates that for the monomeric compound, the broadband conductivity and mechanical spectra reflect the same underlying distribution of activation barriers and that the Random Barrier Model describes fairly well both the ionic and structural relaxation processes in these materials. Moreover, the oligomers with chains comprising ten segments only exhibit both structural and dynamical fingerprints of a genuine polymer. A comparison of conductivity levels estimated using the self-diffusion coefficients probed via NMR and those probed directly with dielectric spectroscopy reflects the emerging of ion correlations which are affecting the macroscopic charge transport in these materials in a chain-length dependent manner.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phonon Thermal Conductivity and Phase Equilibria of Fractal Bi–Sb Nanoparticles

The thermal conductivity component associated with lattice vibrations is one of the quantities determining the thermoelectric activity of a material. We have simulated the dependences of phase composition and the phonon component of the thermal conductivity associated with it on the shape of nanoparticles of a Bi–Sb alloy with an equiatomic composition and with core–shell configuration. The shape of a particle is simulated by a coefficient corresponding to the extent of deviation of the particle shape from spherical or by its fractal dimension. It is shown that mutual solubilities of components depend on the nanoparticle shape and on the mutual arrangement of coexisting phases, and the thermodynamic equilibrium position for particles with complex morphology corresponds to the homogeneous state. Homogenization of a nanoparticle reduces the phonon component of its thermal conductivity by 70–80%.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Modeling and Analysis of Polarization Losses in Solid Oxide Fuel Cells with Siloxane Contamination

In this study, the degradation of the solid-oxide fuel cell (SOFC) nickel-yttria stabilized zirconia anode under decamethyltetrasiloxane (L4) contamination is examined with experiments and modeling. A model is developed for the polarization losses based on the charge transfer coefficient,α, and diffusion layer thickness,δ, and fitted to the experimental data to understand how the siloxane degrades the SOFC performance with time. The results of the model indicate that the total polarization losses increase approximately 44% over the course of the 180 min experiment at 350 mA cm −2 . Activation losses dominate the polarization losses initially but decrease in their total contribution while concentration losses increase. Scanning electron microscopy (SEM) with wavelength dispersive X-ray spectroscopy (WDS) elemental mapping indicates that silicon deposition is highest at the outer edge of the anode and forms a barrier layer to fuel diffusion, increasing concentration losses. When the model is applied to other previous D4 and L4 siloxane experiments conducted over a period of 40 h, similar trends in polarization losses are observed. Polarization losses increase more rapidly with D4 compared to L4 siloxane contamination, with concentration losses increasing the fastest with both types of siloxane.

Electrochemistry↗

Simultaneous active and passive microwave response of the earth - The Skylab radscat experiment

The Skylab microwave radiometer-scatterometer experiment S-193 was designed to collect simultaneous information on the radiometric emission and the backscatter from the earth from orbital altitude for the first time. A primary driving force was ascertaining the response from the oceans of both active and passive systems to variations in wind, and the ability of the passive system to aid in calibrating the active system. Numerous overland applications were also explored. Preliminary results of backscatter and emission from sea and atmosphere are shown for hurricane Ava and for two flights across the Gulf of Mexico. The results tend to confirm the most recent theoretical prediction of an approximately square-law relation between scattering coefficient for horizontal polarization and windspeed, with a somewhat smaller dependence for vertical polarization. Overland measurements show that scatterometer signals at 30 deg increase and radiometer signals decrease for terrain that has recently experienced rainfall.

Moore, R. K.↗

Transitions in shallow convection - An explanation for lateral cell expansion

The generalized, seven-coefficient model presented for two-dimensional Rayleigh-Benard convection successfully simulates one way in which lateral cell expansion can occur as the value of the imposed vertical temperature difference is changed. The triad of interacting wavenumbers is varied as the vertical heating rate is varied and only the energetically active components are retained, so that transitional behavior within two-dimensional convective flow can be both simulated and physically interpreted as the representation of the cell expansion process via successive secondary branching. It is found that while a two-dimensional cell broadening mechanism is likely to operate for small Prandtl number values, a three-dimensional mechanism is expected at values greater than about 0.7.

Chang, H.-R.↗

Chemistry and transport in a three-dimensional stratospheric model - Chlorine species during a simulated stratospheric warming

The distributions in the stratosphere of a variety of chemical species were calculated for a 6-day period during the February 1979 stratospheric major warming, using winds derived from a spectral forecast model which included O(x), NO(x), HO(x), and ClO(x) chemistries as well as longitudinally varying reaction rate coefficients and photolysis rates for these molecules. The results obtained indicate a particular importance of chemistry and transport for the Cl-containing species ClO, ClONO2, HCl, and HOCl. Dynamical effects dominate the variability of HCl, while diurnal effects dominate that of ClONO2 and ClO. The effects of strong planetary wave activity may be seen in terms of large longitudinal variability of the total HCl and ClONO columns in the stratosphere; in the middle and high northern latitudes, it is sufficiently large to exceed the diurnal variability of the column.

Kaye, Jack A.↗

Aerosol backscatter studies supporting LAWS

Optimized Royal Signals and Radar Establishment (RSRE), Laser True Airspeed System (LATAS) algorithm for low backscatter conditions was developed. The algorithm converts backscatter intensity measurements from focused continuous-wave (CW) airborne Doppler lidar into backscatter coefficients. The performance of optimized algorithm under marginal backscatter signal conditions was evaluated. The 10.6 micron CO2 aerosol backscatter climatologies were statistically analyzed. Climatologies reveal clean background aerosol mode near 10(exp -10)/kg/sq m/sr (mixing ratio units) through middle and upper troposhere, convective mode associated with planetary boundary layer convective activity, and stratospheric mode associated with volcanically-generated aerosols. Properties of clean background mode are critical to design and simulation studies of Laser Atmospheric Wind Sounder (LAWS), a MSFC facility Instrument on the Earth Observing System (Eos). Previous intercomparisons suggested correlation between aerosol backscatter at CO2 wavelength and water vapor. Field measurements of backscatter profiles with MSFC ground-based Doppler lidar system (GBDLS) were initiated in late FY-88 to coincide with independent program of local rawinsonde releases and overflights by Multi-spectral Atmospheric Mapping Sensor (MAMS), a multi-channel infrared radiometer capable of measuring horizontal and vertical moisture distributions. Design and performance simulation studies for LAWS would benefit from the existence of a relationship between backscatter and water vapor.

Rothermel, Jeffry↗

Properties of the gravity fields of terrestrial planets

The properties of the gravity fields of the earth, Mars, and Venus, as expressed by spherical harmonic coefficients, are examined, using the harmonic expansions of the respective planetary topographies reported by Balmino et al. (1973), Bills and Ferrari (1978), and Bills and Kobrick (1985). The items examined include the spectral magnitudes and slopes of the gravity coefficients; the correlations between gravity and topography; and the correlations among different gravity harmonics, expressed by axiality and angularity. It was found that Venus differs from the other two planets in its great apparent depths of compensation, indicating a tectonics dominated by a stiff upper mantle. In addition, Venus has less activity deep in the mantle than do earth or Mars. Mars is marked by large gravity irregularities, as well as by their axial symmetry on a global scale. Although earth is probably the most peculiar planet, spherical harmonics do not bring out its varied characteristics. It is clearly a more active planet than Venus, with activity deep in the mantle. The lower magnitude of its higher harmonics is considered to be due to water recycled to the upper mantle.

Kaula, William M.↗

A Statistical Simulation Approach to Safe Life Fatigue Analysis of Redundant Metallic Components

This paper introduces a dual active load path fail-safe fatigue design concept analyzed by Monte Carlo simulation. The concept utilizes the inherent fatigue life differences between selected pairs of components for an active dual path system, enhanced by a stress level bias in one component. The design is applied to a baseline design; a safe life fatigue problem studied in an American Helicopter Society (AHS) round robin. The dual active path design is compared with a two-element standby fail-safe system and the baseline design for life at specified reliability levels and weight. The sensitivity of life estimates for both the baseline and fail-safe designs was examined by considering normal and Weibull distribution laws and coefficient of variation levels. Results showed that the biased dual path system lifetimes, for both the first element failure and residual life, were much greater than for standby systems. The sensitivity of the residual life-weight relationship was not excessive at reliability levels up to R = 0.9999 and the weight penalty was small. The sensitivity of life estimates increases dramatically at higher reliability levels.

Matthews, William T.↗

Evaluating Soil Moisture Retrievals from ESA's SMOS and NASA's SMAP Brightness Temperature Datasets

Two satellites are currently monitoring surface soil moisture (SM) using L-band observations: SMOS (Soil Moisture and Ocean Salinity), a joint ESA (European Space Agency), CNES (Centre national d'tudes spatiales), and CDTI (the Spanish government agency with responsibility for space) satellite launched on November 2, 2009 and SMAP (Soil Moisture Active Passive), a National Aeronautics and Space Administration (NASA) satellite successfully launched in January 2015. In this study, we used a multilinear regression approach to retrieve SM from SMAP data to create a global dataset of SM, which is consistent with SM data retrieved from SMOS. This was achieved by calibrating coefficients of the regression model using the CATDS (Centre Aval de Traitement des Donnes) SMOS Level 3 SM and the horizontally and vertically polarized brightness temperatures (TB) at 40 deg incidence angle, over the 2013 - 2014 period. Next, this model was applied to SMAP L3 TB data from Apr 2015 to Jul 2016. The retrieved SM from SMAP (referred to here as SMAP_Reg) was compared to: (i) the operational SMAP L3 SM (SMAP_SCA), retrieved using the baseline Single Channel retrieval Algorithm (SCA); and (ii) the operational SMOSL3 SM, derived from the multiangular inversion of the L-MEB model (L-MEB algorithm) (SMOSL3). This inter-comparison was made against in situ soil moisture measurements from more than 400 sites spread over the globe, which are used here as a reference soil moisture dataset. The in situ observations were obtained from the International Soil Moisture Network (ISMN; https:ismn.geo.tuwien.ac.at) in North of America (PBO_H2O, SCAN, SNOTEL, iRON, and USCRN), in Australia (Oznet), Africa (DAHRA), and in Europe (REMEDHUS, SMOSMANIA, FMI, and RSMN). The agreement was analyzed in terms of four classical statistical criteria: Root Mean Squared Error (RMSE),Bias, Unbiased RMSE (UnbRMSE), and correlation coefficient (R). Results of the comparison of these various products with in situ observations show that the performance of both SMAP products i.e. SMAP_SCA and SMAP_Reg is 48 similar and marginally better to that of the SMOSL3 product particularly over the PBO_H2O, SCAN, and USCRN sites. However, SMOSL3 SM was closer to the in situ observations over the DAHRA and Oznet sites. We found that the correlation between all three datasets and in situ measurements is best (R 0.80) over the Oznet sites and worst (R 0.58) over the SNOTEL sites for SMAP_SCA and over the DAHRA and SMOSMANIA sites (R 0.51 and R 0.45 for SMAP_Reg and SMOSL3, respectively). The Bias values showed that all products are generally dry, except over RSMN, DAHRA, and Oznet (and FMI for SMAP_SCA). Finally, our analysis provided interesting insights that can be useful to improve the consistency between SMAP and SMOS datasets.

SMOS↗

Characteristics of the Hot Workability of an AZ91D Magnesium Alloy Using 3D Processing Maps

Hot compression tests were carried out on an a homogenized as-cast AZ91D magnesium alloy at temperatures ranging from 220 °C to 380 °C and strain rates ranging from 0.001 to 10 s{sup −1} by means of a Gleeble-3500 thermo mechanical simulator. True stress-–true strain curves were given. A constitutive modeling of the homogenized alloy was proposed to describe the flow characteristic. The deformation activation energy was estimated to be 142.27 kJ mol{sup −1}. Continuous three-dimensional (3D) processing maps were developed based on the true stress–true strain data as a function of strain, temperature, and strain rate. A detailed interpretation of the established 3D processing maps was conducted. The results showed that the variation of the 3D processing maps was significantly strain dependent. Dynamic recrystallization domains with high-power dissipation efficiencies and instability domains with negative instability coefficient were identified from the 3D power dissipation maps and the 3D instability maps, respectively. It was also revealed that the instability domains distinctly became enlarged with the increasing strain. Optimized temperature and strain rate ranges at various strains were determined. Furthermore, hot workability characteristics were clarified through examining the microstructures obtained under conditions falling within stability and instability domains with various strains. The results proved that the developed 3D processing maps can provide an accurate prediction of the hot deformation behavior for the homogenized AZ91D alloy.

36 MATERIALS SCIENCE↗

Bio-Inspired adaptive damping in hydrokinetic energy harnessing using flow-induced oscillations

A hydrokinetic energy converter using Flow Induced Oscillations (FIOs) of a one-degree-of-freedom cylinder-oscillator, with nonlinear adaptive damping and linear spring stiffness, is introduced and studied experimentally. Comparison to a linear-oscillator in FIO shows that this new converter, with velocity-proportional damping coefficient, is more effective in galloping, where both flow and cylinder speeds are higher. It also impacts VIV, since the converter is no longer restricted by fixed damping, which results either in ceasing motion due to excessive damping, or in low harnessed energy due to insufficient damping. The impact is most profound in the VIV to galloping transition where adaptive damping prevents shutting down of hydrokinetic energy conversion. Damping-to-velocity rate, linear spring-stiffness, and flow-velocity are the experimental parameters with Reynolds number 30,000 ≤ Re ≤ 120,000. Here, experimental results for amplitude response, frequency response, energy harvesting, efficiency and instantaneous energy of the converter are presented and discussed. The main conclusions are: (1) The nonlinear, adaptive, velocity-proportional damping coefficient increases the harnessed power. (2) The operational range of flow velocities increases. (3) At lower flow speeds, the adaptive damping stabilizes the unstable oscillations typically occurring in this region. (4) At higher flow speeds, adaptive damping results in higher harnessed power than constant damping, thus, better emulating passively a corresponding, natural, active motion by fish. (5) Increase of 51%–95% in converted power by the nonlinear oscillator compared to linear oscillator has been measured. (6) The adaptive damping converter reaches a plateau in harnessed efficiency at high flow velocity (fully developed galloping).

13 HYDRO ENERGY↗

Electronically driven collapse of the bulk modulus in δ -plutonium

Plutonium metal exhibits an anomalously large softening of its bulk modulus at elevated temperatures that is made all the more extraordinary by the finding that it occurs irrespective of whether the thermal expansion coefficient is positive, negative, or zero—representing an extreme departure from conventional Grüneisen scaling. We show here that the cause of this softening is the compressibility of plutonium’s thermally excited electronic configurations, which has thus far not been considered in thermodynamic models. We show that when compressible electronic configurations are thermally activated, they invariably give rise to a softening of the bulk modulus regardless of the sign of their contribution to the thermal expansion. The electronically driven softening of the bulk modulus is shown to be in good agreement with elastic moduli measurements performed on the gallium-stabilized δ phase of plutonium over a range of temperatures and compositions and is shown to grow rapidly at small concentrations of gallium and at high temperatures, where it becomes extremely sensitive to hydrostatic pressure.

36 MATERIALS SCIENCE↗

Observations of hydromagnetic turbulence in the solar wind

MHD turbulence is studied by analyzing magnetic field and plasma observations from Helios-1 and -2 at minimum solar activity. The steady conditions in the plasma flows and the magnetic field sector structure in 1975/1976 facilitate an investigation of the radial evolution of the turbulence from 0.29 to 1AU. In high speed streams the fluctuations in the solar wind velocity v and the magnetic field b are highly correlated (the correction coefficient almost being one), which indicates that the turbulence is mainly Alfvenic in high speed plasma. While some general fluctuation properties remain essentially unchanged from 0.29 to 1AU, power spectral analysis reveals a different frequency composition of the Alfvenic turbulence at different heliocentric distances. At 0.3AU much more 'high' frequency fluctuations contribute to the total power in the magnetic field and velocity fluctuations than at 1AU. The contributions of field magnitude fluctuations are found to be distance and frequency dependent. Magnetic field spectra with an extended frequency range up to 470Hz show certain frequency bands, where the steepness of the spectra is independent of the helicocentric distance.

Denskat, K. U.↗

Effective Field Theory Analysis and Active Neutron Veto Design for the Cryogenic Dark Matter Search

Astrophysical measurements and cosmological predictions suggest the exists of a large amount of matter in the universe that does not interact via electromagnetic forces. This non-luminescent matter, known dark matter, exists in halos that encompass and are within galaxies, including the Milky Way. Therefore, dark matter particles should should be directly detectable by experiments on Earth, such as the Super Cryogenic Dark Matter Search (SuperCDMS). Dark matter is assumed to be low mass (< 100 GeV/c2) and interact via the weak force using either a spin-independent or spin-dependent coupling. However, making incorrect assumptions about dark matter interactions can lead to misleading results. Because interactions with dark matter particles are rare, direct detection experiments must be able to shield for or reject backgrounds to very low levels. Low energy neutron backgrounds that make it to the detectors are especially dangerous, because they cannot be easily distinguished from the expected dark matter signal. Scintillator doped with a high neutron-capture cross-section material can be used to detect neutrons via their resulting gamma rays. Examples of such detectors using liquid scintillator have been successfully used in past high-energy physics (HEP) experiments. However, a liquid scintillator can leak and is not as amenable to modular or complex shapes as a solid scintillator. The light outputs and efficiencies of gadolinium-loaded polystyrene-based scintillators have been explored using a wide variety of gadolinium compounds with varying concentrations. Collection strategies using a wavelength shift- ing (WLS) fiber and silicon photomultipliers (SiPMs) were also evaluated as a possible neutron veto for an upgrade to SuperCDMS SNOLAB. The scattering of dark matter particles off nuclei in direct detection experiments can be described in terms of a multidimensional effective field theory (EFT). A new systematic analysis technique is developed using the EFT approach and Bayesian inference methods to exploit, when possible, the energy-dependent information of the detected events, experimental efficiencies, and backgrounds. Highly dimensional likelihoods are calculated over the mass of the weakly interacting massive particle (WIMP) and multiple EFT coupling coefficients, which can then be used to set limits on these parameters and choose models (EFT operators) that best fit the direct detection data. Expanding the parameter space beyond the standard spin-independent isoscalar cross section and WIMP mass reduces tensions between previously published experiments. Combining these experiments to form a single joint likelihood leads to stronger limits than when each experiment is considered on its own. Simulations using two nonstandard operators (O3 and O8) are used to test the proposed analysis technique in up to five dimensions and demonstrate the importance of using multiple likelihood projections when determining constraints on WIMP mass and EFT coupling coefficients. In particular, this shows that an explicit momentum dependence in dark matter scattering can be identified. CDMSlite Run 2 was a search for Weakly Interacting Massive Particles (WIMPs) with a cryogenic 600 g Germanium detector operated deep underground. It was operated in a mode optimizing sensitivity to WIMPs of relatively low mass, 2 - 20 GeV, while sacrificing background rejection. An EFT analysis of CDMSlite Run 2 data from SuperCDMS Soudan is presented here. A binned likelihood Bayesian analysis was performed on the data, optimizing over the parameters of EFT interactions and the recoil energy spectra due to the dominant Compton scattering and tritium backgrounds. Recoil energy regions within 5σ of known activation peaks were removed from the analysis. The Bayesian evidences of the resulting likelihoods show that CDMSlite Run 2 data is entirely consistent with the background models with no EFT interaction necessary. Upper limits on the WIMP mass and coupling coefficients amplitudes and phases are presented for each EFT operator.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Database of Nonaqueous Proton-Conducting Materials

This work presents the assembly of 48 papers, representing 74 different compounds and blends, into a machine-readable database of nonaqueous proton-conducting materials. SMILES was used to encode the chemical structures of the molecules, and we tabulated the reported proton conductivity, proton diffusion coefficient, and material composition for a total of 3152 data points. The data spans a broad range of temperatures ranging from -70 to 260 °C. To explore this landscape of nonaqueous proton conductors, DFT was used to calculate the proton affinity of 18 unique proton carriers. The results were then compared to the activation energy derived from fitting experimental data to the Arrhenius equation. It was found that while the widely recognized positive correlation between the activation energy and proton affinity may hold among closely related molecules, this correlation does not necessarily apply across a broader range of molecules. This work serves as an example of the potential analyses that can be conducted using literature data combined with emerging research tools in computation and data science to address specific materials design problems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling Henry's law and phase separations of water–NaCl–organic mixtures with solvation and ion-pairing

Empirical measurements of solution vapor pressure of ternary acetonitrile (MeCN) H 2 O–NaCl–MeCN mixtures were recorded, with NaCl concentrations ranging from zero to the saturation limit, and MeCN concentrations ranging from zero to an absolute mole fraction of 0.64. After accounting for speciation, the variability of the Henry's law coefficient at vapor–liquid equilibrium (VLE) of MeCN ternary mixtures decreased from 107% to 5.1%. Solute speciation was modeled using a mass action solution model that incorporates solute solvation and ion-pairing phenomena. Two empirically determined equilibrium constants corresponding to solute dissociation and ion pairing were utilized for each solute. When speciation effects were considered, the solid–liquid equilibrium of H 2 O–NaCl–MeCN mixtures appear to be governed by a simple saturation equilibrium constant that is consistent with the binary H 2 O–NaCl saturation coefficient. Further, our results indicate that the precipitation of NaCl in the MeCN ternary mixtures was not governed by changes in the dielectric constant. Our model indicates that the compositions of the salt-induced liquid–liquid equilibrium (LLE) boundary of the H 2 O–NaCl–MeCN mixture correspond to the binary plateau activity of MeCN, a range of concentrations over which the activity remains largely invariant in the binary water–MeCN system. Broader comparisons with other ternary miscible organic solvent (MOS) mixtures suggest that salt-induced liquid–liquid equilibrium exists if: (1) the solution displays a positive deviation from the ideal limits governed by Raoult's law; and (2) the minimum of the mixing free energy profile for the binary water-MOS system is organic-rich. Finally, this work is one of the first applications of speciation-based solution models to a ternary system, and the first that includes an organic solute.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polar convection patterns under quiet conditions

Convection electric field patterns at high latitudes appropriate to periods of low geomagnetic activity are presented. The postulate that the global Joule dissipation rate is a minimum is employed to derive characteristic field distributions for the situation when ring current ohmic losses are negligible and the auroral oval enhancement of height-integrated Hall conductivity is small. The fast Fourier transform is introduced to compute Fourier coefficients of discrete field-aligned current data, and the method is shown to be quite useful in this context as a least squares fitting routine. The model calculations demonstrate the approach of the high-latitude ionosphere toward the perfect shielding configuration predicted by the theory for quiet times.

Barbosa, D. D.↗