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At least 703 records · Page 39

Plasma Waves Observed at Low Altitudes in the Tenuous Venus Nightside Ionosphere

The Pioneer Venus Orbiter Electric Field Detector (OEFD) measured many plasma wave bursts throughout the low altitude ionosphere during the final entry phase of the spacecraft. Apart from 100 Hz bursts observed at very low altitudes (approx. 130 km), the bursts fall into two classes. The first of these is a wideband signal that is observed in regions of low magnetic field, but average densities, in comparison to the prevailing ionospheric condition. This wideband signal is not observed in the 30 kHz channel of the OEFD, but is restricted to the 5.4 kHz channel and lower. Since these bursts are observed with roughly constant burst rate above 160 km altitude, we attribute them to ion acoustic mode waves generated by precipitating solar wind electrons. The second type of signal is restricted to 100 Hz only, and is observed in regions of low electron beta, consistent with whistler-mode waves. These waves could be generated by lightning in the Venus atmosphere if the vertical component of the magnetic field greater than 3.6 nT. Unfortunately, the spacecraft spin axis is mainly horizontal, and only that component of magnetic field can be measured. Alternatively, the 100 Hz bursts could be generated locally through gradient drift instabilities, provided the ambient magnetic field is horizontal. Because the ionosphere is very different during the entry phase, compared to the ionosphere as observed early in the Pioneer Venus mission, any conclusions regarding the source of the plasma waves detected during entry phase cannot be applied directly to the earlier observations.

Strangeway, R. J.↗

Ionic conductivity optimization of composite polymer electrolytes through filler particle chemical modification

The addition of filler particles to polymer electrolytes is known to increment their ionic conductivity (IC). A detailed understanding of how the interactions between the constituent materials are responsible for the enhancement remains to be developed. A significant contribution is ascribed to an increment of the polymer amorphous fraction, induced by the fillers, resulting in the formation of higher ionic conductivity channels in the polymer matrix. However, the dependence of IC on the particle weight load and its composition on the polymer morphology is not fully understood. This work investigates Li-ion transport in composite polymer electrolytes (CPE) comprising Bi-doped LLZO particles embedded in PEO:LiTFSI matrixes. We find that the IC optimizes for very low particle weight loads (5-10%) and that both its magnitude and the load are required, strongly dependent on the garnet particle composition. Based on structural characterization results and electrochemical impedance spectroscopy, a mechanism is proposed to explain these findings. It is suggested that the Li-molar content in the garnet particle controls its interactions with the polymer matrix, resulting at the optimum loads reported, in the formation of high ionic conductivity channels. We propose that filler particle chemical manipulation of the polymer morphology is a promising avenue for the further development of composite polymer electrolytes.

bismuth↗

Science Observations of Deep Space One

During the Deep Space One (DS1) primary mission, the spacecraft will fly by asteroid 1992 KD and possibly comet Borrelly. There are two technologies being validated on DS1 that will provide science observations of these targets, the Miniature Integrated Camera Spectrometer (MICAS) and the Plasma Experiment for Planetary Exploration (PEPE). MICAS encompasses a camera, an ultraviolet imaging spectrometer and an infrared imaging spectrometer. PEPE combines an ion and electron analyzer designed to determine the three-dimensional distribution of plasma over its field of view. MICAS includes two visible wavelength imaging channels, an ultraviolet imaging spectrometer, and an infrared imaging spectrometer all of which share a single 10-cm diameter telescope. Two types of visible wavelength detectors, both operating between about 500 and 1000 nm are used: a CCD with 13-microrad pixels and an 18-microrad-per-pixel, metal-on-silicon active pixel sensor (APS). Unlike the CCD the APS includes the timing and control electronics on the chip along with the detector. The UV spectrometer spans 80 to 185 nm with 0.64-nm spectral resolution and 316-microrad pixels. The IR spectrometer covers the range from 1200 to 2400 nm with 6.6-nm resolution and 54-microrad pixels PEPE includes a very low-power, low-mass micro-calorimeter to help understand plasma-surface interactions and a plasma analyzer to identify de individual molecules and atoms in the immediate vicinity of the spacecraft that have been eroded off the surface of asteroid 1992 KD. It employs common apertures with separate electrostatic energy analyzers. It measures electron and ion energies spanning a range of 3 eV to 30 keV, with a resolution of five percent. and measures ion mass from one to 135 atomic mass units with 5 percent resolution. It electrostatically sweeps its field of view both in elevation and azimuth. Both MICAS and PEPE represent a new direction for the evolution of science instruments for interplanetary spacecraft. These two instruments incorporate a large fraction of the capability of five instruments that had typically flown on NASA's deep space missions The Deep Space One science team acknowledges the support of Philip Varghese, David H. Lehman, Leslie Livesay, and Marc Rayman for providing invaluable assistance in making the science observations possible.

Nelson, Robert M.↗

Electron–Ion Covariance Reveals Geometry-Resolved Inner-Shell Spectra in CS 2 Photodissociation

The chemical shifts of inner-shell atomic orbitals are highly sensitive to chemical bonding and molecular structure. In evolving systems, however, the spectra of distinct molecular species and geometries overlap, obscuring the underlying chemical dynamics. Here we demonstrate the use of electron–ion covariance analysis to combine the structural sensitivity of Coulomb explosion imaging with inner-shell spectroscopy, yielding geometry-specific spectra of transient and product species. We apply this approach to the excited state dynamics of CS 2 probed by ionization above the S 2p edge. Electron–ion covariance with time- and momentum-selected S + and S 2+ ions isolates distinct S 2p photoelectron spectra for ground-state CS 2 , bent photoexcited CS 2 , the CS photoproduct, and bare atomic sulfur ─ species whose spectra overlap strongly in the channel-averaged measurement. Clear chemical shifts are observed in the covariance photoelectron spectrum for each of these species, all of which are consistent with high-level calculations. Here, by extracting the atomic S contribution to the photoelectron spectrum in a finely time-resolved manner we can disentangle this contribution to the overall time-resolved photoelectron spectrum as the photodissociation proceeds. These results demonstrate the promise of electron–ion covariance as a general approach to geometry-resolved inner-shell spectroscopy, opening a route to tracking structural evolution through chemical shifts in complex photoexcited molecules.

Ionization↗

Metal-hydrogen-pi-bonded organic frameworks

We report the synthesis and characterization of a new series of permanently porous, three-dimensional metal–organic frameworks (MOFs), M-HAF-2 (M = Fe, Ga, or In), constructed from tetratopic, hydroxamate-based, chelating linkers. Here, the structure of M-HAF-2 was determined by three-dimensional electron diffraction (3D ED), revealing a unique interpenetrated hcb-a net topology. This unusual topology is enabled by the presence of free hydroxamic acid groups, which lead to the formation of a diverse network of cooperative interactions comprising metal–hydroxamate coordination interactions at single metal nodes, staggered π–π interactions between linkers, and H-bonding interactions between metal-coordinated and free hydroxamate groups. Such extensive, multimodal interconnectivity is reminiscent of the complex, noncovalent interaction networks of proteins and endows M-HAF-2 frameworks with high thermal and chemical stability and allows them to readily undergo postsynthetic metal ion exchange (PSE) between trivalent metal ions. We demonstrate that M-HAF-2 can serve as versatile porous materials for ionic separations, aided by one-dimensional channels lined by continuously π-stacked aromatic groups and H-bonding hydroxamate functionalities. As an addition to the small group of hydroxamic acid-based MOFs, M-HAF-2 represents a structural merger between MOFs and hydrogen-bonded organic frameworks (HOFs) and illustrates the utility of non-canonical metal-coordinating functionalities in the discovery of new bonding and topological patterns in reticular materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Research on high power, doped titanium-niobium oxide anodes

The main objective of this project is to synthesize titanium niobium oxide (TNO) that has a nanoporous structure with porous channels for rapid lithium diffusion, enabling extreme fast charging (XFC). The focus of this project is to improve the electronic conductivity and ion diffusion coefficient in TNO to achieve high capacities under extreme fast charge conditions. In addition, electrolytes with additives will be formulated to promote stable interphase formation on the NMC cathode surface to improve long cycling stability.

25 ENERGY STORAGE↗

HCNH(+) - A new interstellar molecular ion

The first interstellar detection of HCNH(+) is reported. The J = 1-0, 2-1, and 3-2 rotational transitions of this molecule at 74, 148, and 222 GHz have been observed toward Sgr B2. Using a large velocity gradient model calculation, the column density of HCNH(+) is found to be about 4 x 10 to the 14th/sq cm, about one order of magnitude less than that estimated for HCO(+) and HCN in this source. Such a column density implies a fractional abundance of at least one to several orders of magnitude larger than predicted by numerous ion-molecule models. Coupled with a relatively low abundance of HCN and a small HNC/HCN ratio, this suggests that HCNH(+) is not channeled into HCN or HNC as rapidly as thought.

Ziurys, L. M.↗

Properties of a Novel Ion-Exchange Film

A new ion-exchange material (based on polyacrylic acid) and some of its analytical applications have been reported. This paper contains data on the ion-exchange properties of the film form of the material and its potential application to the decontamination of waste water and drinking water. The film has a high exchange capacity of 5 to 6 meq/g and a pK(sub a) of 5.7. The calcium form is the most effective for removing metal ions from solution, and the optimum pH range is between 5 and 7. The exchange rates are slower for the film than for bead and powder forms of the ion-exchange material; otherwise, the properties are similar. The film is effective when hard water solutions are employed and also when metal ions are in the complex matrix of waste water from electroplating. The film can be used in flow systems having a flow channel large enough to allow passage of turbid solutions.

Street, Kenneth W.↗

Mode Transitions in Hall Effect Thrusters

Mode transitions have been commonly observed in Hall Effect Thruster (HET) operation where a small change in a thruster operating parameter such as discharge voltage, magnetic field or mass flow rate causes the thruster discharge current mean value and oscillation amplitude to increase significantly. Mode transitions in a 6-kW-class HET called the H6 are induced by varying the magnetic field intensity while holding all other operating parameters constant and measurements are acquired with ion saturation probes and ultra-fast imaging. Global and local oscillation modes are identified. In the global mode, the entire discharge channel oscillates in unison and azimuthal perturbations (spokes) are either absent or negligible. Downstream azimuthally spaced probes show no signal delay between each other and are very well correlated to the discharge current signal. In the local mode, signals from the azimuthally spaced probes exhibit a clear delay indicating the passage of "spokes" and are not well correlated to the discharge current. These spokes are localized oscillations propagating in the ExB direction that are typically 10-20% of the mean value. In contrast, the oscillations in the global mode can be 100% of the mean value. The transition between global and local modes occurs at higher relative magnetic field strengths for higher mass flow rates or higher discharge voltages. The thrust is constant through mode transition but the thrust-to-power decreased by 25% due to increasing discharge current. The plume shows significant differences between modes with the global mode significantly brighter in the channel and the near-field plasma plume as well as exhibiting a luminous spike on thruster centerline. Mode transitions provide valuable insight to thruster operation and suggest improved methods for thruster performance characterization.

interplanetary exploration↗

Properties of a Novel Ion-Exchange Film

A new ion-exchange material (based on polyacrylic acid) and some of its analytical applications have been reported. This paper contains data on the ion-exchange properties of the film form of the material and its potential application to the decontamination of waste water and drinking water. The film has a high exchange capacity of 5 to 6 meq/g and a pK(sub a) of 5.7. The calcium form is the most effective for removing metal ions from solution, and the optimum pH range is between 5 and 7. The exchange rates are slower for the film than for bead and powder forms of the ion-exchange material; otherwise, the properties are similar. The film is effective when hard water solutions are employed and also when metal ions are in the complex matrix of waste water from electroplating. The film can be used in flow systems having a flow channel large enough to allow passage of turbid solutions.

Street, Kenneth W.↗

Single Event Effects Test Report IXYS IXTA96P085T P-Channel -85V MOSFET

This study was undertaken to determine the destructive single event effect and degradation susceptibility of the IXTA96P085T P-Channel -85V MOSFET from IXYS. The device was monitored for destructive single event effects and degradation during exposure to a heavy ion beam at the Berkeley Accelerator Space Effects (BASE) Facility at the Lawrence Berkeley National Laboratory (LBNL). Gate and drain currents were measured during irradiation and a basic set of electrical characterizations was performed following each fluence exposure to assess heavy ion induced damage. The test date was April 10, 2024. This characterization is application specific.

MOSFET↗

Single Event Effects Test Report Vishay Siliconix Si7113DN P-Channel 100V MOSFET

This study was undertaken to determine the destructive single event effect and degradation susceptibility of the Si7113DN P-Channel 100V MOSFET from Vishay Siliconix. The device was monitored for destructive single event effects and degradation during exposure to a heavy ion beam at the Berkely Accelerator Space Effects (BASE) Facility at the Lawrence Berkely National Laboratory (LBNL).

MOSFET↗

High resolution masks for ion milling pores through substrates of biological interest

The feasibility was investigated of electrochemically oxidizing vapor deposited aluminum coatings to produce porous aluminum oxide coatings with submicron pore diameters and with straight channels normal to the substrate surface. Porous aluminum oxide coatings were produced from vapor deposited aluminum coatings on thin stainless steel (304), copper, Teflon (FEP) and Kapton substrates and also on pure aluminum substrates. Scanning electron microscope examination indicated that porous oxide coatings can be produced with straight channels, appropriate pore diameters and none or minimal intervening residual aluminum. The oxide coatings on the copper and Kapton substrates had the straightest channels and in general were superior to those fabricated on the other substrate materials. For oxide coatings fabricated at 600 V and 300 V, pore diameters were 0.4-0.6, and 0.3 micron with center-to-center spacing of 0.7-0.8, and 0.4 micron, respectively. Estimated direct labor and materials costs to prepare an oxide mask is anticipated to be about $4-$6 per square foot.

Donovan, S. S.↗

Alpha-helical hydrophobic polypeptides form proton-selective channels in lipid bilayers

Proton translocation is important in membrane-mediated processes such as ATP-dependent proton pumps, ATP synthesis, bacteriorhodopsin, and cytochrome oxidase function. The fundamental mechanism, however, is poorly understood. To test the theoretical possibility that bundles of hydrophobic alpha-helices could provide a low energy pathway for ion translocation through the lipid bilayer, polyamino acids were incorporated into extruded liposomes and planar lipid membranes, and proton translocation was measured. Liposomes with incorporated long-chain poly-L-alanine or poly-L-leucine were found to have proton permeability coefficients 5 to 7 times greater than control liposomes, whereas short-chain polyamino acids had relatively little effect. Potassium permeability was not increased markedly by any of the polyamino acids tested. Analytical thin layer chromatography measurements of lipid content and a fluorescamine assay for amino acids showed that there were approximately 135 polyleucine or 65 polyalanine molecules associated with each liposome. Fourier transform infrared spectroscopy indicated that a major fraction of the long-chain hydrophobic peptides existed in an alpha-helical conformation. Single-channel recording in both 0.1 N HCl and 0.1 M KCl was also used to determine whether proton-conducting channels formed in planar lipid membranes (phosphatidylcholine/phosphatidylethanolamine, 1:1). Poly-L-leucine and poly-L-alanine in HCl caused a 10- to 30-fold increase in frequency of conductive events compared to that seen in KCl or by the other polyamino acids in either solution. This finding correlates well with the liposome observations in which these two polyamino acids caused the largest increase in membrane proton permeability but had little effect on potassium permeability. Poly-L-leucine was considerably more conductive than poly-L-alanine due primarily to larger event amplitudes and, to a lesser extent, a higher event frequency. Poly-L-leucine caused two populations of conductive events, one in the 0.1-0.5 pA range, and one in the 1.0-5.0 pA range, whereas nearly all events caused by poly-L-alanine were in the 0.1-0.5 pA range at an applied voltage of +60 mV. The channel-like activity appeared to switch between conductive and nonconductive states, with most open-times in the range of 50-200 ms. We conclude that hydrophobic polyamino acids produce proton-conducting defects in lipid bilayers that may be used to model functional proton channels in biological membranes.

NASA Discipline Exobiology↗

Post-Hydration Crosslinking of Ion Exchange Membranes to Control Water Content

The utilization of crosslinking as a technique to limit excess water uptake in ion exchange membranes is a well-established approach. However, traditional methods involve performing the crosslinking reaction before the membrane self-segregates into hydrophilic and hydrophobic domains upon exposure to water. In this study, we employ numerical and molecular simulations to explore the potential of post-hydration crosslinking of the polymer at subsaturated conditions. This process allows for the development of a nanosegregated morphology, which establishes well-connected but narrow water channels, while limiting additional sorption of water. The significant reduction in membrane swelling observed in our study indicates that post-hydration crosslinking could be a promising approach to regulate water uptake in ion exchange membranes. Here based on our analyses, we propose chemical crosslinking strategies that may yield high membrane gel fractions.

36 MATERIALS SCIENCE↗

Directional ballistic transport in the two-dimensional metal PdCoO2

Abstract In an idealized infinite crystal, the material properties are constrained by the symmetries of the unit cell. The point-group symmetry is broken by the sample shape of any finite crystal, but this is commonly unobservable in macroscopic metals. To sense the shape-induced symmetry lowering in such metals, long-lived bulk states originating from an anisotropic Fermi surface are needed. Here we show how a strongly facetted Fermi surface and the long quasiparticle mean free path present in microstructures of PdCoO 2 yield an in-plane resistivity anisotropy that is forbidden by symmetry on an infinite hexagonal lattice. We fabricate bar-shaped transport devices narrower than the mean free path from single crystals using focused ion beam milling, such that the ballistic charge carriers at low temperatures frequently collide with both of the side walls that define the channel. Two symmetry-forbidden transport signatures appear: the in-plane resistivity anisotropy exceeds a factor of 2, and a transverse voltage appears in zero magnetic field. Using ballistic Monte Carlo simulations and a numerical solution of the Boltzmann equation, we identify the orientation of the narrow channel as the source of symmetry breaking.

36 MATERIALS SCIENCE↗

Binding of the substrate analog methanol in the oxygen-evolving complex of photosystem II in the D1-N87A genetic variant of cyanobacteria

The solar water-splitting protein complex, photosystem II (PSII), catalyzes one of the most energetically demanding reactions in nature by using light energy to drive a catalyst capable of oxidizing water. The water oxidation reaction is catalyzed at the Mn 4 Ca-oxo cluster in the oxygen-evolving complex (OEC), which cycles through five light-driven S-state intermediates (S 0 –S 4 ). A detailed mechanism of the reaction remains elusive as it requires knowledge of the delivery and binding of substrate water in the higher S-state intermediates. In this paper, we use two-dimensional (2D) hyperfine sublevel correlation spectroscopy, in conjunction with quantum mechanics/molecular mechanics (QM/MM) and density functional theory (DFT), to probe the binding of the substrate analog, methanol, in the S 2 state of the D1-N87A variant of PSII from Synechocystis sp. PCC 6803. The results indicate that the size and specificity of the “narrow” channel is altered in D1-N87A PSII, allowing for the binding of deprotonated 13 C-labeled methanol at the Mn4(IV) ion of the catalytic cluster in the S 2 state. This has important implications on the mechanistic models for water oxidation in PSII.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗