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At least 397 records · Page 22

Mechanism for the Efficient Homogeneous Nucleation of Ice in a Weakly Ionized, Ultracold Plasma

Abstract It is proposed that the rapid observed homogeneous nucleation of ice dust in a cold, weakly ionized plasma depends on the formation of hydroxide (OH − ) by fast electrons impacting water molecules. These OH − ions attract neutral water molecules because of the high dipole moment of the water molecules and so hydrates of the form (OH) − (H 2 O) n are formed. The hydrates continuously grow in the cold environment to become macroscopic ice grains. These ice grains are negatively charged as a result of electron impact and so continue to attract water molecules. Because hydroxide is a negative ion, unlike positive ions, it does not suffer recombination loss from collision with plasma electrons. Recombination with positive ions is minimal because positive ions are few in number (weak ionization) and slow-moving as result of being in thermal equilibrium with the cold background gas.

79 ASTRONOMY AND ASTROPHYSICS↗

Nuclear deformation as a source of the nonlinearity of the King plot in the Yb + ion

We perform atomic relativistic many-body calculations of the field isotope shifts and calculations of corresponding nuclear parameters for all stable even-even isotopes of the Yb + ion. We demonstrate that if we take nuclear parameters of the Yb isotopes from a range of the state of the art nuclear models, which all predict strong quadrupole nuclear deformation, and then calculate nonlinearity of the King plot caused by the difference in the deformation in different isotopes, the result is consistent with the nonlinearity observed in the experiment. In conclusion, the changes of nuclear rms radius between isotopes extracted from experiment are consistent with those obtained in the nuclear calculations.

74 ATOMIC AND MOLECULAR PHYSICS↗

Interstellar absorption lines toward gamma Arae

The available data on interstellar absorption lines in the spectrum of gamma Ara observed from the ground and with the Copernicus telescope have been analyzed to give column densities of various ion stages of H, C, N, O, Na, Mg, Si, P, S, Ar, Ca, Mn, and Fe. The element abundances with respect to H nuclei in H I regions are similar to the values for zeta Oph, with depletions relative to the sun tending to increase with increasing condensation temperature. For example, toward gamma Ara, Fe is depleted by a factor of 50; Mg, Si, and Mn by about 10; and S, P, and N little or none. Interstellar Si IV and probably S IV appear stronger than in most other stars, but still their low ratios to Si III and S III suggest that soft X-rays and low-energy cosmic rays are not important sources of ionization. The width of the O VI lines and the absence of N V have been interpreted as evidence for a collisionally ionized region with a temperature between 300,000 and 700,000 K containing at least 0.0004 of the total interstellar column density.

Morton, D. C.↗

Thermal ion heating in the vicinity of the plasmapause: A Dynamics Explorer guest investigation

The ion thermal structure of the plasmasphere was investigated in a series of experiments. It appears that energy may be generally available to ion and electrons in the vinicity of the plasmapause from Coulomb interactions between ambient thermal plasma and low energy ring current and suprathermal ions, particularly O+. The amount of energy transferred depends on the densities and energies of each of the components. The spatial distribution of heating in turn depends critically on the spatial distribution of the different populations, especially on the density gradients. The spatial distribution of the thermal plasma is found to vary significantly on a diurnal time scale and is complicated by the plasmasphere erosion and refilling processes associated with magnetic activity and its aftermath. Thermal ion composition also appears to be influenced by the heating taking place, often increasing the heavy ion population in the vicinity of the plasmapause. The observations of equatorial heating near the plasmapause in the presence of equatorial noise also raise the likelihood of a wave source of energy. It is not unreasonable to expect that both particle and wave heat sources are significant, although not necessarily at the same times and places.

Comfort, R. H.↗

The composition of heavy molecular ions inside the ionopause of Comet Halley

The RPA2-PICCA instrument aboard the Giotto spacecraft obtained 10-210 amu mass spectral of cold thermal molecular ions in the coma of Comet Halley. The dissociation products of the long chain formaldehyde polymer polyoxymethylene (POM) have recently been proposed as the dominant complex molecules in the coma of Comet Halley; however, POM alone cannot account for all of the features of the high resolution spectrum. An important component of the dust at Comet Halley is particles highly enriched in carbon, hydrogen, oxygen, and nitrogen relative to the composition of carbonaceous chondrites. Since this dust could be a source for the heavy molecules observed by PICCA, a search was conducted for other chemical species by determining all the molecules with mass between 20 and 120 amu which can be made from the relatively abundant C, H, O, and N, without regard to chemical structure.

Mitchell, David L.↗

Sodium-ion Battery

Room temperature rechargeable sodium-ion batteries (NIBs) are one of the most promising candidates for large-scale energy storage and load leveling of renewable energy sources due to the abundance, low cost of Na resources, and their relatively high energy density. NIBs are primarily based on intercalation chemistry and are similar to Lithium-ion batteries (LIB). The rich knowledge gained in LIBs for the past 4 decades have accelerated the discovery and development of high energy density NIBs cathode and anode materials. The use of sustainable Na, Al current collector, and Mn and Fe based cathode materials is expected to stabilize the cost and demand for Li, Co, Ni and Cu.

Omenya, Fredrick O.↗

Nitric oxide in star-forming regions - Further evidence for interstellar N-O bonds

Nitric oxide has been newly detected toward several star-forming clouds, including Orion-KL, Sgr B2(N), W33A, W51M, and DR21(OH) via its J = 3/2-1/2 transitions near 150 GHz, using the FCRAO 14 m telescope. Both lambda-doubling components of NO were observed toward all sources. Column densities derived for nitric oxide in these clouds are 10 to the 15th-10 to the 16th/sq cm, corresponding to fractional abundances of 0.5-1.0 x 10 to the -8th, relative to H2. Toward Orion-KL, the NO line profile suggests that the species arises primarily from hot, dense gas. Nitric oxide may arise from warm material toward the other clouds as well. Nitric oxide in star-forming regions could be synthesized by high-temperature reactions, although the observed abundances do not disagree with values predicted from low-temperature, ion-molecule chemistry by more than one order of magnitude.

Ziurys, L. M.↗

Intercalation-Induced Amorphization Boosts Aqueous Magnesium-Ion Storage

The design of aqueous battery cathode materials that can store divalent ions with high capacity and satisfactory reversibility is of great technical importance and challenge. Here, we report that divalent Mg 2+ storage is facilitated by an intercalation-induced amorphization of vanadate electrode materials. Electrokinetic analyses and in situ synchrotron X-ray diffraction and absorption spectroscopy collectively demonstrate that vanadate layered materials (Li–V 3 O 8 ) undergo a structural transformation to amorphization induced by Mg 2+ intercalation, and a reversible restoration of crystalline structure upon Mg 2+ deintercalation. Debye scattering simulations suggest that intercalation-induced turbostratic disorder, especially random rotations, translational shifts, oscillatory motions, or varied interlayer spacing of adjacent V–O molecular layers, could be responsible for the observed amorphization. The highly distorted local structure, in turn, facilitates Mg 2+ intercalation across the vanadate electrode materials, responsible for nearly 3/7 of the total Mg 2+ ions intercalated. The study presented reveals an intriguing relationship between ion transport and the reversible amorphization-to-crystallization dynamics it induces, opening a paradigm for designing advanced aqueous battery electrodes.

36 MATERIALS SCIENCE↗

Particle acceleration

Data is compiled from Solar Maximum Mission and Hinothori satellites, particle detectors in several satellites, ground based instruments, and balloon flights in order to answer fundamental questions relating to: (1) the requirements for the coronal magnetic field structure in the vicinity of the energization source; (2) the height (above the photosphere) of the energization source; (3) the time of energization; (4) transistion between coronal heating and flares; (5) evidence for purely thermal, purely nonthermal and hybrid type flares; (6) the time characteristics of the energization source; (7) whether every flare accelerates protons; (8) the location of the interaction site of the ions and relativistic electrons; (9) the energy spectra for ions and relativistic electrons; (10) the relationship between particles at the Sun and interplanetary space; (11) evidence for more than one acceleration mechanism; (12) whether there is single mechanism that will accelerate particles to all energies and also heat the plasma; and (13) how fast the existing mechanisms accelerate electrons up to several MeV and ions to 1 GeV.

Vlahos, L.↗

Location and source of ionospheric high latitude troughs

The global extent of the high-latitude troughs from altitudes between approximately 400 and 1100 km are explored using ion composition measurements from the satellite OGO 6. The trough locations are compared with prominent magnetosphere-ionosphere coupling signatures in order to understand the source and controlling mechanisms for these plasma depletions. It is found that, on the average, the troughs at all local times are in the vicinity of the auroral oval and move equatorward in response to increasing magnetic activity. The average trough location is compared with the average polar cap boundary as defined by the convection electric field reversal and the electron trapping boundary, as well as with the maximum horizontal magnetic disturbance associated with the large-scale field-aligned currents. It is concluded that the troughs are mainly the result of enhanced chemical O(+) losses in regions having high convection velocities.

Grebowsky, J. M.↗

Oxygen Ion Heat Rate within Alfvenic Turbulence in the Cusp

The role that the cleft/cusp has in ionosphere-magnetosphere coupling makes it a dynamic and important region. It is directly exposed to the solar wind, making it possible for the entry of electromagnetic energy and precipitating electrons and ions from dayside reconnection and other dayside events. It is also a significant source of ionospheric plasma, contributing largely to the mass loading of the magnetosphere with large fluxes of outflowing ions. Crossing the cusp/cleft near 5100 km, the Polar instruments observe the common correlation of downward Poynting flux, ion energization, soft electron precipitation, broadband extremely low-frequency (BB-ELF) emissions, and density depletions. The dominant power in the BB-ELF emissions is now identified to be from spatially broad, low frequency Alfv nic structures. For a cusp crossing, we determine using the Electric Field Investigation (EFI), that the electric and magnetic field fluctuations are Alfv nic and the electric field gradients satisfy the inequality for stochastic acceleration. With all the Polar 1996 horizontal crossings of the cusp, we determine the O+ heating rate using the Thermal Ion Dynamics Experiment (TIDE) and Plasma Wave Investigation (PWI). We then compare this heating rate to other heating rates assuming the electric field gradient criteria exceeds the limit for stochastic acceleration for the remaining crossings. The comparison suggests that a stochastic acceleration mechanism is operational and the heating is controlled by the transverse spatial scale of the Alfvenic waves.

Coffey, Victoria N.↗

Flux Synthesis of a Metal Carbide Hydride Using Anthracene As a Reactant

In this study, La 15 (FeC 6 ) 4 H was synthesized from the reaction of iron and anthracene in La/Ni eutectic flux. Anthracene was the source of both the carbon and hydrogen in the product. The structure of this metal carbide hydride features hydride ions in tetrahedral interstitial sites surrounded by lanthanum ions, which was confirmed by single-crystal neutron diffraction studies. The trigonal planar FeC 6 units in which the central iron atom is coordinated by three ethylenide groups are similar to those found in La 3.67 FeC 6 , a previously reported compound that is formed in the absence of a hydride source. Magnetic susceptibility data confirm that the iron sites do not have magnetic moments. Density of states calculations indicate that La 15 (FeC 6 ) 4 H is metallic and is stabilized by the incorporation of hydride anions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resurgence of a Nation’s Radiation Science Driven by Its Nuclear Industry Needs

This article describes the radiation facilities and associated sample preparation, management, and analysis equipment currently in place at the Dalton Cumbrian Facility, a facility which opened in 2011 to support the UK’s nuclear industry. Examples of measurements performed using these facilities are presented to illustrate their versatility and the breadth of research they make possible. Results are presented from research which furthers our understanding of radiation damage to polymeric materials, radiolytic yield of gaseous products in situations relevant to nuclear materials, radiation chemistry in light water reactor cooling systems, material chemistry relevant to immobilization of nuclear waste, and radiation-induced corrosion of fuel cladding elements. Applications of radiation chemistry relevant to health care are also described. Research concerning the mechanisms of radioprotection by dietary carotenoids is reported. An ongoing open-labware project to develop a suite of modular sample handling components suited to radiation research is described, as is the development of a new neutron source able to provide directional beams of neutrons.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Laboratory IR Detection of H2O, CO2 in Ion-Irradiated Ices Relevant to Europa

Hydrogen peroxide has been identified on Europa (Carlson et al. 1999) based in part on the 3.50 micron absorption feature observed in Galileo NIMS spectra. The observed feature was fitted with laboratory reflectance spectra of H2O + H2O2. Since condensed phase molecules on Europa (H2O, CO2, SO2, and H2O2) are bombarded with a significant flux of energetic particles (H(+), O(n+), S(n+) and e-), we examined the proton irradiation of H2O at 80 K and the conditions for the IR detection of H2O2 near 3.5 microns. Contrary to expectations, H2O2 was not detected if pure H2O ice was irradiated at 80 K. This was an unexpected result since, H2O2 was detected if pure H2O was irradiated at 18 K. We find, however, that if H2O ice contains either O2 or CO2 then H2O2 is detected after irradiation at 80 K (Moore and Hudson, 1999). The source of O2 for the H2O ice on Europa could come from surface interactions with the tenuous oxygen atmosphere, or from the bombardment of the surface by O(n+).

Moore, Marla H.↗

Temporal Evolution of Solar Wind Ion Composition and Their Source Coronal Holes During the Declining Phase of Cycle 23. I. Low-Latitude Extension of Polar Coronal Holes

We analyzed 27 solar wind (SW) intervals during the declining phase of cycle 23, whose source coronal holes (CHs) can be unambiguously identified and are associated with one of the polar CHs. We found that the SW ions have a temporal trend of decreasing ionization state, and such a trend is different between the slow and fast SW. The photospheric magnetic field, both inside and at the outside boundary of the CH, also exhibits a trend of decrease with time. However, EUV line emissions from different layers of the atmosphere exhibit different temporal trends. The coronal emission inside the CH generally increases toward the CH boundary as the underlying field increases in strength and becomes less unipolar. In contrast, this relationship is not seen in the coronal emission averaged over the entire CH. For C and O SW ions that freeze-in at lower altitude, stronger correlation between their ionization states and field strength (both signed and unsigned) appears in the slow SW, while for Fe ions that freeze-in at higher altitude, stronger correlation appears in the fast SW. Such correlations are seen both inside the CH and at its boundary region. On the other hand, the coronal electron temperature correlates well with the SW ion composition only in the boundary region. Our analyses, although not able to determine the likely footpoint locations of the SW of different speeds, raise many outstanding questions for how the SW is heated and accelerated in response to the long-term evolution of the solar magnetic field.

MAGNETIC FIELDS↗

Compositional analysis of organosolv poplar lignin by using high-performance liquid chromatography/high-resolution multi-stage tandem mass spectrometry

Organosolv treatment is an efficient and environmentally friendly process to degrade lignin into small compounds. The capability of characterizing the individual compounds in the complex mixtures formed upon organosolv treatment is essential for the optimization of the further lignin conversion processes and for the rational genetic engineering of plants used to produce lignin in order to improve lignin properties. In this study, an organosolv poplar lignin sample was initially analyzed by high-resolution mass spectrometry coupled with negative-ion mode electrospray ionization ((-)ESI HRMS). Lignin monomers and dimers were found to constitute the majority of the compounds in the organosolv lignin sample. Larger lignin oligomers, such as trimers and tetramers, and some not lignin-related compounds, were also detected. A high-performance liquid chromatograph/linear quadrupole ion trap/orbitrap mass spectrometer capable of multi-stage high-resolution tandem mass spectrometry experiments (HRMS n ), equipped with an (-)ESI source (HPLC/(-)ESI HRMS n ), was employed to separate the unknown compounds in the organosolv mixture and to obtain structural information for the deprotonated compounds via collision-activated dissociation (CAD) HRMS n experiments. To improve the understanding of the CAD behavior of deprotonated lignin-related compounds, 16 deprotonated model compounds with different functionalities and linkage types were examined. This approach enabled the assignment of likely structures for several lignin monomers, dimers, trimers, and tetramers, and some not lignin-related compounds, most likely fatty acids. Based on the proposed structures, compounds in the organosolv lignin sample contain β-O-4, 5–5, β-5, and possibly also 4-O-5 linkages. Most compounds contain G- and S-monomeric units although a small amount of H-units were also detected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

O-16 excesses in Murchison and Murray hibonites - A case against a late supernova injection origin of isotopic anomalies in O, Mg, Ca, and Ti

Ion probe measurements of the oxygen isotopic composition of seven hibonite samples from the CM chondrites Murchison and Murray are reported. All samples show large O-16 excesses relative to terrestrial oxygen. The data for all samples plot along the carbonaceous chondrite O-16-rich mixing line and show no evidence for isotopic mass fractionation effects characteristic of FUN inclusions. These hibonites have the largest Ca-48 and Ti-50 isotopic anomalies found to date; thus there is no intrinsic relationship between anomalies of a nucleosynthetic origin and isotopic mass fractionation effects. The large O-16 excess seen in the sample with the largest measured Ca-48 and Ti-50 depletions argues against a late injection of exotic material from a nearby supernova as a source for the isotopic anomalies.

Fahey, A. J.↗

Selective cobalt and nickel electrodeposition for lithium-ion battery recycling through integrated electrolyte and interface control

Abstract Molecularly-selective metal separations are key to sustainable recycling of Li-ion battery electrodes. However, metals with close reduction potentials present a fundamental challenge for selective electrodeposition, especially for critical elements such as cobalt and nickel. Here, we demonstrate the synergistic combination of electrolyte control and interfacial design to achieve molecular selectivity for cobalt and nickel during potential-dependent electrodeposition. Concentrated chloride allows for the speciation control via distinct formation of anionic cobalt chloride complex (CoCl 4 2- ), while maintaining nickel in the cationic form ([Ni(H 2 O) 5 Cl] + ). Furthermore, functionalizing electrodes with a positively charged polyelectrolyte (i.e., poly(diallyldimethylammonium) chloride) changes the mobility of CoCl 4 2- by electrostatic stabilization, which tunes cobalt selectivity depending on the polyelectrolyte loading. This strategy is applied for the multicomponent metal recovery from commercially-sourced lithium nickel manganese cobalt oxide electrodes. We report a final purity of 96.4 ± 3.1% and 94.1 ± 2.3% for cobalt and nickel, respectively. Based on a technoeconomic analysis, we identify the limiting costs arising from the background electrolyte, and provide a promising outlook of selective electrodeposition as an efficient separation approach for battery recycling.

36 MATERIALS SCIENCE↗