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At least 127 records · Page 7

Gravity Waves Near 300 km Over the Polar Caps

Distinctive wave forms in the distributions of vertical velocity and temperature of both neutral particles and ions are frequently observed from Dynamics Explorer 2 at altitudes above 250 km over the polar caps. These are interpreted as being due to internal gravity waves propagating in the neutral atmosphere. The disturbances characterized by vertical velocity perturbations of the order of 100 m/s and horizontal wave lengths along the satellite path of about 500 km. They often extend across the entire polar cap. The associated temperature perturbations indicate that the horizontal phase progression is from the nightside to the dayside. Vertical displacements are inferred to be of the order of 10 km and the periods to be of the order of 10(exp 3) s. The waves must propagate in the neutral atmosphere, but they usually are most clearly recognizable in the observations of ion vertical velocity and ion temperature. By combining the neutral pressure calculated from the observed neutral concentration and temperature with the vertical component of the neutral velocity, an upward energy flux of the order of 0.04 erg/sq cm-s at 250 km has been calculated, which is about equal to the maximum total solar ultraviolet heat input above that altitude. Upward energy fluxes calculated from observations on orbital passes at altitudes from 250 to 560 km indicate relatively little attenuation with altitude.

Johnson, F. S.↗

Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation

During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air−water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f (Isub x-)) and their correlation with ion properties. Although no correlation exists between f (sub x-) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(sub x-), dehydration free-energy ΔGdehyd, and polarizability alpha, follows the order: (R(sub x-)(exp −2)) > (R(sub x-)(exp −1)) >(R(sub x-) > delta G(sub dehyd) > alpha. The same pure physical process is observed in H2O and D2O. The factor f (sub x-) does not change with pH (6.8−8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol − and ethanol−water mixtures (0 <= xH2O <= 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I− on the air−water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I− < Br− < Cl− over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

iodine↗

Magnetospheric convection and the high-latitude F2 ionosphere

Behavior of the polar ionospheric F layer as it is convected through the cleft, over the polar cap, and through the nightside F layer trough zone is investigated. Passage through the cleft adds approximately 200,000 ions per cu cm in the vicinity of the F2 peak and redistributes the ionization above approximately 400-km altitude to conform with an increased electron temperature. The redistribution of ionization above 400-km altitude forms the 'averaged' plasma ring seen at 1000-km altitude. The F layer is also raised by approximately 20 km in altitude by the convection electric field. The time required for passage across the polar cap (25 deg) is about the same as that required for the F layer peak concentration to decay by e. The F layer response to passage through the nightside soft electron precipitation zone should be similar to but less than its response to passage through the cleft.

Knudsen, W. C.↗

Microstructure and corrosion of CrFeMnV multi-principal element alloy

In this study, a multi-principal element alloy consisting of equiatomic concentrations of Cr, Fe, Mn, and V was produced by arc melting. The combination of X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy indicated that the CrFeMnV MPEA was comprised of a BCC matrix with a dispersion of a secondary phase. Cyclic potentiodynamic polarization tests in 0.6M NaCl revealed high corrosion resistance – superior to that of stainless steel 304L, as evident from high breakdown and repassivation potentials. X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry provided insight into the formed multi-layer surface film after constant immersion and potentiostatic conditioning.

36 MATERIALS SCIENCE↗

An Estimate of the Dust Pickup Currents at Enceladus

The electrodynamic environment at Enceladus is often assumed to be driven exclusively by ions produced from the moon's south polar plume. In this presentation, we demonstrate that acceleration of moon-originating submicron dust by the reduced co-rotating E-field is capable of creating a substantial current perpendicular to the magnetic field. This pickup current may be comparable to the ion pickup current, and may be large enough to deflect the local magnetic field. We will analyze observations from the Langmuir Probe that is a component of Cassini's Radio and Plasma Wave Science (RPWS) package, along with associated plasma waves that reveal electron concentrations. We will especially examine the observations from the 12 March 2008 spacecraft passage by the body, where the spacecraft was moving primarily southward taking it along-side the jet/plume emitted from the south pole of the moon. The region of dust pickup is found to originate about 3-5 Enceladus radii northward of the moon, and extends to at least 10 radii southward of the moon. We attempt to quantify the dust pickup current and describe the effect the current might have on the overall magnetoplasma and E-field environment in the vicinity of the body.

Farrell, William M.↗

Revealing the Electrochemical Kinetics of Electrolytes in Nanosized LiFePO 4 Electrodes

Lithium-ion battery rate performance is ultimately limited by the electrolyte, yet the behaviors of electrolytes during high-rate (dis)charge remain elusive to electrochemical measurement. Herein, we develop and study a nanosized LiFePO 4 model system in which the electrolyte completely controls the electrochemical kinetics of the porous electrode. Impedance spectroscopy, cyclic voltammetry, and rate performance testing prove that ion transport in the electrolyte is the sole rate-limiting process, even in thin electrodes. A novel pseudo-steady-state extrapolation (S3E) method for Tafel analysis shows that LiFePO 4 obeys Butler-Volmer kinetics with a transfer coefficient of 3. The combination of these unexpectedly rapid interfacial kinetics and an activation barrier for phase transformation causes extreme reaction heterogeneity, which manifests as a moving reaction zone. Resistance versus capacity analysis enables direct measurement of electrolyte resistance growth during high-rate (dis)charge, revealing how the interaction between concentration polarization and a moving reaction zone controls electrolyte rate performance in LiFePO 4 electrodes. This work elucidates the profound impacts of the electrolyte on electrochemical measurements in porous battery electrodes: when the active material is not rate limiting, it is impossible to directly measure the intrinsic kinetics of the active material, but conversely, it becomes possible to directly measure the kinetics of the electrolyte.

Electrochemistry↗

The ionosphere of Uranus - A myriad of possibilities

A one-dimensional model has been used to study the effects of exospheric temperature, methane and water influx, ionospheric outflow, and electron precipitation on the composition and structure of the ionosphere of Uranus. Peak ion concentrations range from 1000 to 1 million per cu cm with a wide variation in peak altitude, which depends strongly on the exospheric temperature. In all the cases considered, H(+) is the major ion in the topside ionosphere. At altitudes near or below the peak, H3(+) and CH5(+) can dominate, depending on the magnitude of CH4 and H2O influx. Atomic hydrogen column depths above the methane absorbing layer exceed 10 to the 17th per sq cm and can produce large (400 R) emissions of resonantly scattered Lyman-alpha. In the sunlit polar cap, electron precipitation with energy fluxes of 0.6 to 1.0 erg/sq cm s results in direct production of Lyman-alpha emissions that exceed 1 kR.

Chandler, M. O.↗

A cosmic and solar X-ray and gamma-ray instrument for a scout launch

An overview is presented for a set of simple and robust X-ray and gamma ray instruments which have both cosmic and solar objectives. The primary solar scientific objective is the study of the beaming of energetic electrons and ions in solar flares. The instrument will measure spectra and polarization of flare emissions up to 10 MeV. At X-ray energies both the directly emitted flux and the reflected albedo flux will be measured with a complement of six X-ray sensors. Each of these detectors will have a different high Z filter selected to optimize both the energy resolution and high rate capabilities in the energy band 10 to 300 keV. At energies greater than 100 keV seven 7.6 x 7.6 cm NaI and a set of 30 concentric plastic scattering detectors will record the spectra and polarization of electron bremsstrahlung and nuclear gamma rays. All of the components of the instrument are in existence and have passed flight tests for earlier space missions. The instrument will use a spinning solar oriented Scout spacecraft. The NaI detectors will act as a self-modulating gamma ray detector for cosmic sources in a broad angular band which lies at 90 degrees to the Sun-Earth vector and hence will scan the entire sky in 6 months.

Forrest, D. J.↗

Highly swollen ROMP-based gels

In this study, the leakage of organic solvent during the transportation and storage is one of the major threats to the environment. Networks/gels acting as the absorbing materials for organic solvents are the most promising solution for the organic solvent pollution. Here, we report the synthesis of highly swollen networks/gels in high yield (≥95%) via ring opening metathesis polymerization (ROMP) using Grubbs’ first generation catalyst/initiator (G1), a crosslinker (1,1'-(methylenedi-4,1-phenylene)bis-exo-7-oxanorbornenecarboximide) and monofunctional monomer/diluent (exo-N-phenyl-7-oxanorbornenecarboximide). The mesh size of the network was varied by keeping the concentration of monomer constant while changing the concentrations of crosslinker and G1 (initiator). The swelling capacity of the network in N,N-dimethylformamide (DMF) solvent increased from 41 to 53 and to 61 with the increase of theoretical mesh size (molar ratio of monomer to crosslinker) from 20 to 40 and to 60, respectively. By further increasing the mesh size from 60 to 80 there was no significant change in swelling capacities (63). Thus, the gel with the mesh size of 60 was selected for swelling capacity analysis in other polar organic solvents such as dimethyl sulfoxide (DMSO), dichloromethane (DCM), chloroform and lithium-ion battery electrolyte solution (1.0 M LiPF 6 in ethylene carbonate (EC)/diethyl carbonate (DEC) = 50/50 (v/v)). They showed the decreased swelling capacity value from 61 to 57, 40, 31 and 5, respectively. For a controlled mesh size ROMP-based gel, we observed the highest swelling capacity values to date.

36 MATERIALS SCIENCE↗

Driving force and pathway in polyelectrolyte complex coacervation

There is notable discrepancy between experiments and coarse-grained model studies regarding the thermodynamic driving force in polyelectrolyte complex coacervation: experiments find the free energy change to be dominated by entropy, while simulations using coarse-grained models with implicit solvent usually report a large, even dominant energetic contribution in systems with weak to intermediate electrostatic strength. Here, using coarse-grained, implicit-solvent molecular dynamics simulation combined with thermodynamic analysis, we study the potential of mean force (PMF) in the two key stages on the coacervation pathway for symmetric polyelectrolyte mixtures: polycation–polyanion complexation and polyion pair–pair condensation. We show that the temperature dependence in the dielectric constant of water gives rise to a substantial entropic contribution in the electrostatic interaction. By accounting for this electrostatic entropy, which is due to solvent reorganization, we find that under common conditions (monovalent ions, room temperature) for aqueous systems, both stages are strongly entropy-driven with negligible or even unfavorable energetic contributions, consistent with experimental results. Furthermore, for weak to intermediate electrostatic strengths, this electrostatic entropy, rather than the counterion-release entropy, is the primary entropy contribution. From the calculated PMF, we find that the supernatant phase consists predominantly of polyion pairs with vanishingly small concentration of bare polyelectrolytes, and we provide an estimate of the spinodal of the supernatant phase. Finally, we show that prior to contact, two neutral polyion pairs weakly attract each other by mutually induced polarization, providing the initial driving force for the fusion of the pairs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

This manuscript describes a synthetic strategy and structure–property investigation of unprecedented phosphonium-based zwitterionic homopolymers (polyzwitterions) and random copolymers (zwitterionomers). Free radical polymerization of 4-(diphenylphosphino)styrene (DPPS) provided neutral polymers containing reactive triarylphosphines. Quantitative postpolymerization alkylation of these pendant functionalities generated a library of polymers containing various concentrations of neutral phosphines, phosphonium ions, and phosphonium sulfobetaine zwitterions. The zwitterionic homo- and copolymers exhibited significantly higher glass transition temperatures (T g ) and enhanced mechanical reinforcement in comparison to neutral and phosphonium analogues. These changes in T g and mechanical properties were attributed to nanoscale morphological domains, which formed due to electrostatic interactions between zwitterionic groups, as revealed by X-ray scattering and broadband dielectric spectroscopy (BDS). BDS revealed increased static dielectric constants (>25) for the phosphonium zwitterionomers compared to ionomeric or neutral analogues. These high static dielectric constants for the solvent-free polyzwitterions supported their stronger polarization response in comparison with polymers containing neutral phosphines and phosphonium ions, and these interactions accounted for morphological differences and enhanced mechanical behavior. This work describes a versatile strategy for modulating electrostatic interactions with tunable mechanical properties for an unprecedented family of zwitterionic polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion Transport in 2D Nanostructured $\pi$-Conjugated Thieno[3,2- b ]thiophene-Based Liquid Crystal

Leveraging the self-assembling behavior of liquid crystals designed for controlling ion transport is of both fundamental and technological significance. Here, we have designed and prepared a liquid crystal that contains (2,5-bis(5-(2,5,8,11-tetraoxatridecan-13-yl)thiophen-2yl)thieno[3,2-b]thiophene (BTTT) as mesogenic core and conjugated segment and symmetric tetra(ethylene oxide) (EO4) as polar side chains for ionic conducting regions. Driven by the crystallization of the BTTT cores, BTTT/dEO4 exhibits well-ordered smectic phases below 71.5 °C as confirmed by differential scanning calorimetry, polarized optical microscope, temperature dependent wide-angle X-ray scattering and grazing incidence wide-angle X-ray scattering (GIWAXS). We adopted a combination of experimental GIWAXS and molecular dynamics (MD) simulations to better understand the molecular packing of BTTT/dEO4 films, particularly when loaded with the ion conducting salt, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Ionic conduction of BTTT/dEO4 is realized by the addition of LiTFSI, with the material able to maintain smectic phases up to r = [Li + ]/[EO] = 0.1. In this work, The highest ionic conductivity of 8 × 10 -3 S/cm was attained at an intermedium salt concentration of r = 0.05. It was also found that ion conduction in BTTT/dEO4 is enhanced by forming a smectic layered structure with irregular interfaces between the BTTT and EO4 layers and by the lateral film expansion upon salt addition. This can be explained by the enhancement of the misalignment and configurational entropy of the side chains, which increase their local mobility and that of the solvated ions. Our molecular design thus illustrates how, beyond the favorable energetic interactions that drive the assembly and ion solvating domains, modulation of entropic effects can also be favorably harnessed to improve ion conduction.

thin film electrochemical impedance spectroscopy↗

Electronic and magnetic properties of the topological semimetal SmMg 2 Bi 2

Dirac semimetals show nontrivial physical properties and can host exotic quantum states like Weyl semimetals and topological insulators under suitable external conditions. Here, by combining angle-resolved photoemission spectroscopy measurements (ARPES) and first-principle calculations, we demonstrate that the Zintl-phase compound SmMg 2 Bi 2 is in close proximity to a topological Dirac semimetallic state. ARPES results show a Dirac-like band crossing at the zone center near the Fermi level (E F ), which is further confirmed by first-principle calculations. Theoretical studies also reveal that SmMg 2 Bi 2 belongs to a Z 2 topological class and hosts spin-polarized states around the E F . Zintl's theory predicts that the valence state of Sm in this material should be Sm 2+ , however, we detect many Sm-4f multiplet states (flat-bands) whose energy positions and relative intensities suggest the presence of both dominant Sm 2+ and minor Sm 3+ . The small concentration (2.5%) of Sm 3+ in the bulk of a crystal is inferred to arise from Sm vacancies in the crystal. It is also evident that these flat bands and other dispersive states are strongly hybridized when they cross each other. Due to the presence of Sm 3+ ions, the temperature dependence of the magnetic susceptibility χ (T) shows a Curie-Weiss-like contribution in the low-temperature region, in addition to the Van Vleck-like behavior expected for the Sm 2+ ions. The present study will help to better understand the electronic structure, magnetism, and transport properties of related materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The influence of ionization events on atmospheric ozone

Atmospheric ionization events can modify the concentration of neutral species in the stratosphere and mesosphere. In particular, ozone is destroyed because of the production of significant quantities of odd nitrogen and hydrogen compounds which react photochemically to destroy ozone. Direct evidence of ozone depletion comes from data taken during and following two solar flares generating large fluxes of 10-100 Mev protons, which bombarded the polar stratosphere and mesosphere. Observations of ozone taken during X-ray emission by solar flares and energetic electron precipitation during aurorae indicates ozone destruction above 50 km by ionization produced odd hydrogen. Lightning is apparently a large contributor to the tropospheric odd nitrogen budget. Ion propulsion induced dumping of the inner proton radiation belt represents a human activity which may influence stratospheric NOx.

Aikin, A. C.↗

Non-stoichiometry Governs the Pathway from Amorphous to Crystalline Calcium Carbonate

The controlled crystallization of calcium carbonate underlies the elaborate architectures of marine corals, the design of biomimetic materials, and the global carbon cycle. Despite its ubiquity, the chemical mechanisms that govern the crystallization of calcium carbonate from its amorphous precursor, amorphous calcium carbonate (ACC), remain elusive, largely due to the difficulty in resolving the structure and chemistry of this transient amorphous state. Here, we use time-lapse photography, image analysis, spatially resolved pH determination, in situ synchrotron pair distribution function (PDF) analysis, and dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (NMR) spectroscopy to reveal pervasive compositional variability in ACC that underpins its metastability and crystallization. By evaluating the kinetics of the amorphous-to-crystalline transition across different solution chemistries, we demonstrate that ACC is non-stoichiometric and CO 3 -deficient. Counterions from the precursor (e.g., NO 3 - from Ca(NO 3 ) 2 ) substitute into the ACC network, displacing CO 3 ions and mediating both ACC stability and transformation. Crystallization proceeds through refinement of the stoichiometry toward CaCO 3 and uptake of free CO 3 2- anions. Furthermore, these findings are consistent across a wide range of concentrations and different carbonate sources, explaining the diverse behaviors observed for ACC and providing a chemical framework for controlling calcium carbonate crystallization.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Permeability of lipid bilayers to amino acids and phosphate

Permeability coefficients for amino acid classes, including neutral, polar, hydrophobic, and charged species, were measured and compared with values for other ionic solutes such as phosphate. The rates of efflux of glycine, lysine, phenylalanine, serine and tryptophan were determined after they were passively entrapped in large unilamellar vesicles (LUVs) composed of egg phosphatidylcholine (EPC) or dimyristoylphosphatidylcholine (DMPC). The following permeability coefficients were obtained for: glycine, 5.7 x 10(-12) cm s-1 (EPC), 2.0 x 10(-11) cm s-1 (DMPC); serine, 5.5 x 10(-12) cm s-1 (EPC), 1.6 x 10(-11) cm s-1 (DMPC); lysine, 5.1 x 10(-12) cm s-1 (EPC), 1.9 x 10(-11) cm s-1 (DMPC); tryptophan, 4.1 x 10(-10) cm s-1 (EPC); and phenylalanine, 2.5 x 10(-10) cm s-1 (EPC). Decreasing lipid chain length increased permeability slightly, while variations in pH had only minor effects on the permeability coefficients of the amino acids tested. Phosphate permeability was in the range of 10(-12)-10(-13) cm s-1 depending on the pH of the medium. The values for the polar and charged amino acids were surprisingly similar to those previously measured for monovalent cations such as sodium and potassium, which are in the range of 10(-12)-10(-13) cm s-1, depending on conditions and the lipid species used. This observation suggests that the permeation rates for the neutral, polar and charged amino acids are controlled by bilayer fluctuations and transient defects, rather than partition coefficients and Born energy barriers. The results are relevant to the permeation of certain peptides into lipid bilayers during protein translocation and membrane biogenesis.

NASA Discipline Exobiology↗

A catalog of ionospheric F region irregularity behavior based on Ogo 6 retarding potential analyzer data

Review of in situ data obtained with the aid of the retarding potential analyzer on board Ogo 6 which reveal the nature of ionospheric irregularities in the total ion concentration above 400 km. Except for the high-latitude regions, the ionosphere is usually observed to be very smooth in the daytime, but considerable structure is observed at night, particularly near the equator and at Atlantic longitudes. Although most of the irregularities observed appear to be stochastic in nature, many nearly monochromatic waveforms are observed near the equator. The topics discussed include the midlatitude scintillation boundary, large-amplitude equatorial irregularities, the fluctuation spectrum of typical F-region irregularities, the lower edge of the equatorial F region, sinusoidal waveforms, ground glass irregularities, breaking wave irregularities, and regions of smooth and irregular ionization inside the polar cap.

Mcclure, J. P.↗

Investigation of possible lower hybrid emission from the NASA Lewis Bumpy Torus plasma

Radio frequency emission detected near the lower hybrid frequency of the NASA Lewis Bumpy Torus plasma is studied, using a simple detection system that consists of a spectrum analyzer and a 50-ohm miniature co-axial antenna concentrically located in a re-entrant quartz tube. The frequency shift of a broad emission peak is monitored as a function of the background pressure, electrode voltage, and the strength of the dc magnetic field. Simultaneous measurements of the average plasma density are made with a polarization diplexing microwave interferometer. Information from the experiment is discussed with particular reference to the role of atomic or molecular species of deuterium in the emissions, the strength of the dc magnetic field in the emitting region, the geometric location of the emitting region of the plasma, the lower hybrid plasma density as compared with the average plasma density, and the relation of the ion spoke geometry to the lower hybrid emission.

Mallavarpu, R.↗