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At least 1,027 records · Page 57

Observations and analysis of O(1D) and NH2 line profiles for the coma of comet P/Halley

A set of high-resolution Fabry-Perot measurements of the coma of comet P/Halley was acquired in the (O I) 6300 A and NH2 6298.62 A emission lines. These high-resolution measurements provide the first optical observations capable of studying directly the photochemical kinetics and dynamic outflow of the coma. The observations were analyzed by a Monte Carlo Particle Trajectory Model. The agreement of the model and observed line profiles was excellent and verified the underlying dynamics, exothermic photodissociative chemistry, and collisional thermalization in the coma. The somewhat wider intrinsic line profile width for the O(1D) emission in 1986 January compared to 1986 May, is, for example, produced by the larger outflow speeds and gas temperatures nearer perihelion in January. The January O(1D) profile, which is wider than the January NH2 profile, is indicative of the photochemical kinetics in the dissociation of the parent molecules H2O and OH in the coma. The absolute calibration of the observations in 1986 January allowed the production rates for H2O and the NH2-parent molecules to be determined. The average daily water production rates derived from the O(1D) emission data for January 16 and 17 are presented. These very large water production rates are consistent with the extrapolated (and 7.6 day time variable) water production rates determined from the analysis of lower spectral resolution observations for O(1D) and H-alpha emissions that covered the time period up to January 13. The large production rates on January 16 and 17 establish that the maximum water production rate for comet Halley accurred pre-perihelion in January. Implications drawn from comparison with 18 cm radio emission data in January suggest that the peak water production rate was even larger. The average production rate for NH3 determined from the NH2 emission data for January 17 was (1.48 +/- 0.10) x 10(exp 28) molecules/s, yielding an NH3/H2O production rate ratio of 0.55%.

Smyth, William H.↗

Origin of the O(+) pick-up ions in the hehiosphere

The main sources for the ions in the interplanetary medium are the solar wind and the interstellar gas intruding into the heliosphere. Other sources, i.e. comets and planets can, however, contribute significantly locally. We present approximate expressions for deriving fluxes of pick-up ions originating from local neutral gas sources. Since the Io-torus is thought to be a relatively strong emitter of fast atoms, particular O and S, we used the O(+) data obtained by SWICS-Ulysses as a function of distance from Jupiter, both in and out-off the ecliptic plane in order to recognize a possible contribution of the Ionian source to the measured O(+). We find that - except for a very limited zone near the Jovian magnetosphere - the contribution of the Io-torus to the O(+) fluxes is minor, thus confirming our previous results on the pick-up H(+), He(+), N(+), O(+), and Ne(+) fluxes of interstellar origin.

Geiss, J.↗

Energy transfer between energetic ring current H(+) and O(+) by electromagnetic ion cyclotron waves

Electromagnetic ion cyclotron (EMIC) waves in the frequency range below the helium gyrofrequency can be excited in the equatorial region of the outer magnetosphere by cyclotron resonant instability with anisotropic ring current H(+) ions. As the unducted waves propagate to higher latitudes, the wave normal should become highly inclined to the ambient magnetic field. Under such conditions, wave energy can be absorbed by cyclotron resonant interactions with ambient O(+), leading to ion heating perpendicular to the ambient magnetic field. Resonant wave absorption peaks in the vicinity of the bi-ion frequency and the second harmonic of the O(+) gyrofrequrency. This absorption should mainly occur at latitudes between 10 deg and 30 deg along auroral field lines (L is greater than or equal to 7) in the postnoon sector. The concomitant ion heating perpendicular to the ambient magnetic field can contribute to the isotropization and geomagnetic trapping of collapsed O(+) ion conics (or beams) that originate from a low-altitude ionospheric source region. During geomagnetic storms when the O(+) content of the magnetosphere is significantly enhanced, the absorption of EMIC waves should become more efficient, and it may contribute to the observed acceleration of O(+) ions of ionospheric origin up to ring current energies.

Thorne, Richard M.↗

Atomic far-IR fine-structure line mapping of L1630, M17, and W3: Comparison of (O I) and (C II) distributions

We mapped the distribution of atomic far-IR line emission from (O I) and (C II) over parsec scales in the Galactic star-forming regions L1630, M17, and W3 using the MPE Far-Infrared Fabry-Perot Imaging spectrometer (FIFI) on board the NASA Kuiper Airborne Observatory. The lines mapped include (O I) 63 microns, (O I) 146 microns, and (C II) 158 microns. Comparison of the intensities and ratios of these lines with models of photodissociation regions (e.g., Tielens & Hollenbach 1985, ApJ, 344, 770) allows us to derive temperatures and densities of the primarily neutral atomic gas layers lying on the surfaces of UV-illuminated molecular gas. In general, the (C II) line arises ubiquitously throughout the molecular clouds while the (O I) lines are mainly confined to warm, dense gas (T is greater than 100 K, n is greater than 10(exp 4)/cu cm) near the sites of O and B stars. The distribution of (C II) in the star-forming clouds implies that the (C II) emission arises on the surfaces of molecular clumps throughout the clouds, rather than only at the boundary layer between molecular gas and H II regions.

Howe, J. E.↗

Temperature Dependence of the O + HO2 Rate Coefficient

A pulsed laser photolysis technique has been employed to investigate the kinetics of the radical-radical reaction O((sup 3)P) + HO2 OH + O2 over the temperature range 266-391 K in 80 Torr of N2 diluent gas. O((sup 3)P) was produced by 248.5-nm KrF laser photolysis of O3 followed by rapid quenching of O(1D) to O((sup 3)P) while HO2 was produced by simultaneous photolysis of H2O2 to create OH radicals which, in turn, reacted with H2O2 to yield HO2. The O((sup 3)P) temporal profile was monitored by using time-resolved resonance fluorescence spectroscopy. The HO2 concentration was calculated based on experimentally measured parameters. The following Arrhenius expression describes our experimental results: k(sub 1)(T) equals (2.91 +/- 0.70) x 10(exp -11) exp[(228 +/- 75)/T] where the errors are 2 sigma and represent precision only. The absolute uncertainty in k, at any temperature within the range 266-391 K is estimated to be +/- 22 percent. Our results are in excellent agreement with a discharge flow study of the temperature dependence of k(sub 1) in 1 Torr of He diluent reported by Keyser, and significantly reduce the uncertainty in the rate of this important stratospheric reaction at subambient temperatures.

Nicovich, J. M.↗

FUSE Observations of O VI Absorption in the Local Interstellar Medium

We report the results of an initial Far Ultraviolet Spectroscopic Explorer (FUSE) survey of O VI Lambda 1032 absorption along the lines of sight to eleven nearby white dwarfs, ten of which are within the Local Bubble (LB; d < or approximately equal 100 pc). A goal of this survey is to investigate the possible formation of O VI in the conductive interfaces between cool (about 10(exp 4) K) clouds immersed in the presumably hot (10(exp 6) K) gas within the LB. This mechanism is often invoked to explain the widespread presence of 0 VI throughout the Galactic disk. We find no 0 VI absorption toward two stars, and the column densities along three additional sight lines are quite low; N(O VI) about 5 x 10(exp 13)/sq cm. In several directions, we observe rather broad, shallow absorption with N(O VI) about 1 - 2 x 10(exp 13)/sq cm. Models of conductive interfaces predict narrow profiles with N(OVI) > or about equal to 10(exp 13)/sq cm per interface, in the absence of a significant transverse magnetic field. Hence, our observations of weak 0 VI absorption indicate that conduction is being quenched, possibly by non-radial magnetic fields. Alternatively, the gas within the LB may not be hot. Breitschwerdt & Schmutzler have proposed a model for the LB in which an explosive event within a dense cloud created rapid expansion and adiabatic cooling, resulting in a cavity containing gas with a kinetic temperature of T about 50,000 K, but with an ionization state characteristic of much hotter gas. This model has a number of attractive features, but appears to predict significantly more O VI than we observe.

Oegerle, W. R.↗

Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties.

Tyson, Daniel S.↗

Correlations of (Delta)O-17 with Chemical Characteristics Among Chondrite Groups

Demonstration of mass-independent O isotopic variations in solar system materials was a seminal discovery of meteoritics. These variations were thought to reflect incomplete mixing of O from different nucleosynthesis sources. Since then, two non-nucleosynthetic causes have been suggested: (1) differential photodissociation of distinct isotopomers of CO, enriching nebular gas in chemically reactive heavy O, and (2) gas-phase molecular reactions producing mass-independent O isotopic exchange. Nebular processes caused chemical fractionations that are observed in chondrite bulk compositions. If nebular processes also produced mass-independent O isotopic variations, then these may correlate with chondrite bulk chemistry.

Mittlefehldt, D. W.↗

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al foil Impacts

In January 2006, the STARDUST mission successfully returned dust samples from the tail of comet 81P/Wild 2 in two principal collection media, low density silica aerogel and Al foil. While hypervelocity impacts at 6.1 km/s, the encounter velocity of STARDUST, into Al foils are generally highly disruptive for natural, silicate-dominated impactors, previous studies have shown that many craters retain sufficient residue to allow a determination of the elemental and isotopic compositions of the original projectile. We have used the NanoSIMS to perform C, N, and O isotope imaging measurements on four large (59-370 microns diameter) and on 47 small (0.32-1.9 microns diameter) Al foil impact craters as part of the STARDUST Preliminary Examination. Most analyzed residues in and around these craters are isotopically normal (solar) in their C, N, and O isotopic compositions. However, the debris in one large crater shows an average 15N enrichment of approx. 450 %, which is similar to the bulk composition of some isotopically primitive interplanetary dust particles. A 250 nm grain in another large crater has an O-17 enrichment with approx. 2.65 times the solar O-17/O-16 ratio. Such an O isotopic composition is typical for circumstellar oxide or silicate grains from red giant or asymptotic giant branch stars. The discovery of this circumstellar grain clearly establishes that there is authentic stardust in the cometary samples returned by the STARDUST mission. However, the low apparent abundance of circumstellar grains in Wild 2 samples and the preponderance of isotopically normal material indicates that the cometary matter is a diverse assemblage of presolar and solar system materials.

Stadermann, Frank J.↗

Discovery of X-Ray-Emitting O-Ne-Mg-Rich Ejecta in the Galactic Supernova Remnant Puppis A

We report on the discovery of X-ray-emitting O-Ne-Mg-rich ejecta in the middle-aged Galactic O-rich supernova remnant Puppis A with Chandra and XMM-Newton. We use line ratios to identify a low-ionization filament running parallel to the northeastern edge of the remnant that requires super-solar abundances, particularly for O, Ne, and Mg, which we interpret to be from O-Ne-Mg-rich ejecta. Abundance ratios of Ne/O, Mg/O, and Fe/O are measured to be [approx]2, [approx]2, and <0.3 times the solar values. Our spatially resolved spectral analysis from the northeastern rim to the western rim otherwise reveals sub-solar abundances consistent with those in the interstellar medium. The filament is coincident with several optically emitting O-rich knots with high velocities. If these are physically related, the filament would be a peculiar fragment of ejecta. On the other hand, the morphology of the filament suggests that it may trace ejecta heated by a shock reflected strongly off the dense ambient clouds near the northeastern rim.

Katsuda, Satoru↗

Grease-Resistant O Rings for Joints in Solid Rocket Motors

There is a continuing effort to develop improved O rings for sealing joints in solid-fuel rocket motors. Following an approach based on the lessons learned in the explosion of the space shuttle Challenger, investigators have been seeking O-ring materials that exhibit adequate resilience for effective sealing over a broad temperature range: What are desired are O rings that expand far and fast enough to maintain seals, even when metal sealing surfaces at a joint move slightly away from each other shortly after ignition and the motor was exposed to cold weather before ignition. Other qualities desired of the improved O rings include adequate resistance to ablation by hot rocket gases and resistance to swelling when exposed to hydrocarbon-based greases used to protect some motor components against corrosion. Five rubber formulations two based on a fluorosilicone polymer and three based on copolymers of epichlorohydrin with ethylene oxide were tested as candidate O-ring materials. Of these, one of the epichlorohydrin/ethylene oxide formulations was found to offer the closest to the desired combination of properties and was selected for further evaluation.

Harvey, Albert R.↗

Mineral-Catalysed Formation of Marine NO and N 2 O on the Anoxic Early Earth

Microbial denitrification converts fixed nitrogen species into gases in extant oceans. However, it is unclear how such transformations occurred within the early nitrogen cycle of the Archean. Here 5we present experimental anoxic surface-catalyzed reduction of nitrite and nitrate via green rust and magnetite combined with diffusion and photochemical modeling. We find that in a Fe 2+ -rich marine environment, Fe minerals could have catalyzed abiotic denitrification reactions leading to the formation of nitric oxide (NO) and nitrous oxide (N 2 O). Nitrate did not exhibit reactivity in the presence of either mineral or aqueous Fe2+, however, both minerals induced rapid nitrite reduction 10to NO and N 2 O. While N 2 O escaped into the atmosphere (63% of nitrite-nitrogen, with green rust as catalyst), NO remained associated with precipitates (7%) serving as a potential shuttle to the benthic ocean.The modeling suggests that marine N 2 O emissions would have sustained 0.8-6 ppb of atmospheric N 2 O without a protective ozone layer. Our findings add detail to the as yet incompletely documented Archean nitrogen cycle, implying a globally distributed process driven 15by chemical kinetics similar to those of modern enzymatically mediated conversions.

Steffen Buessecker↗

Build-To-Replace Strategy to Reduce O&M Costs of Advanced Reactors

This paper targets the goal of reducing fixed operations and maintenance (O&M) costs to $2/MWh for advanced reactor (AR) designs, an order of magnitude reduction from current nuclear fleets. Such goal will be severely constrained if the underlying assumptions of O&M approaches and practices are not questioned and reexamined, especially today when changes can be implemented effectively and efficiently. Achieving a 90% reduction in AR O&M costs requires a completely new way of thinking – a paradigm shift – not through incremental, technology-focused approaches alone. Here, we address this challenge by evaluating the impact of moving to shorter design life for major structures, systems and components (SSCs) and shorter, more predictable refurbishment cycles as modeled by the commercial airline industry. This paper provides a brief overview of this different mindset to O&M applied to ARs: the build-to-replace approach. We provide a direct example of analysis of a build-to-replace scenario by identifying and evaluating scenarios for reduced system and component lifetimes and associated replacement and refurbishment schedules to evaluate impacts on O&M costs and other lifecycle elements such as SSC reliability.

97 - MATHEMATICS AND COMPUTING↗

Mouse osteoblastic cell line (MC3T3-E1) expresses extracellular calcium (Ca2+o)-sensing receptor and its agonists stimulate chemotaxis and proliferation of MC3T3-E1 cells

The calcium-sensing receptor (CaR) is a G protein-coupled receptor that plays key roles in extracellular calcium ion (Ca2+o) homeostasis in parathyroid gland and kidney. Osteoblasts appear at sites of osteoclastic bone resorption during bone remodeling in the "reversal" phase following osteoclastic resorption and preceding bone formation. Bone resorption produces substantial local increases in Ca2+o that could provide a signal for osteoblasts in the vicinity, leading us to determine whether such osteoblasts express the CaR. In this study, we used the mouse osteoblastic, clonal cell line MC3T3-E1. Both immunocytochemistry and Western blot analysis, using an antiserum specific for the CaR, detected CaR protein in MC3T3-E1 cells. We also identified CaR transcripts in MC3T3-E1 cells by Northern analysis using a CaR-specific riboprobe and by reverse transcription-polymerase chain reaction with CaR-specific primers, followed by nucleotide sequencing of the amplified products. Exposure of MC3T3-E1 cells to high Ca2+o (up to 4.8 mM) or the polycationic CaR agonists, neomycin and gadolinium (Gd3+), stimulated both chemotaxis and DNA synthesis in MC3T3-E1 cells. Therefore, taken together, our data strongly suggest that the osteoblastic cell line MC3T3-E1 possesses both CaR protein and mRNA very similar, if not identical, to those in parathyroid and kidney. Furthermore, the CaR in these osteoblasts could play a key role in regulating bone turnover by stimulating the proliferation and migration of such cells to sites of bone resorption as a result of local release of Ca2+o.

Non-NASA Center↗

Research advances on cobalt-free cathodes for Li-ion batteries - The high voltage LiMn 1.5 Ni 0.5 O 4 as an example

LiMn 1.5 Ni 0.5 O 4 is one of the most promising cathode materials for use in either next generation lithium-ion batteries or all solid-state batteries. However, despite the significant Research and Development (R&D) carried out throughout the last two decades the material has not made serious inroads into market. One of the major reasons is the lack of consistency in the reported intrinsic properties and electrochemical performance owing to major controversies in synthesis, crystal structure and bulk and interfacial properties of LiMn 1.5 Ni 0.5 O 4 , notably in contact with electrolytes. This paper is a compelling review providing an assessment on the mainstream R&D dealing with the various crystal structures of LiMn 1.5 Ni 0.5 O 4 and their evolutions observed during synthesis and cycling in correlation with their electrochemical performance. Influence of electrolytes and additives along with modifications through doping and surface treatments are interrelated, and the electronic and ionic transport properties of the ordered and disordered LiMn 1.5 Ni 0.5 O 4 phases are discussed. Overall, this review provides a detailed assessment on LiMn1.5Ni0.5O4 and the underlying mechanisms governing its electrochemical performance broadly providing a focused framework for further advancement towards commercialization.

25 ENERGY STORAGE↗

Al 2 O 3 /TiO 2 coated separators: Roll-to-roll processing and implications for improved battery safety and performance

Heat generation is one of the major concerns with lithium-ion batteries (LIB) while charging them at higher currents, which could inadvertently impact the rate performance and reduce the safety of the cell. Polymer separator is one of the least thermal conductive components of a LIB. In addition, commercial separators for LIB are made from polyolefin membranes that tend to shrink and curl at higher temperatures due to their lower melting temperature (~130 °C). Developing separators with improved thermal stability and higher electrolyte uptake is essential for enhancing the safety as well as the performance of the LIB. In this work, a thin layer of ceramic coatings (Al 2 O 3 and TiO 2 ) is applied on propylene (PP) membrane to improve the thermal stability and electrolyte affinity without compromising the rate performance. A slurry with 100% Al 2 O 3 coated on the polypropylene separator exhibited the best improvement in thermal stability ( shrinkage of 0.6% vs 6.0% for uncoated membrane) and excellent rate performance with 92% capacity retention at 2C. The Al 2 O 3 coated separator demonstrated excellent electrolyte wettability compared to the uncoated membrane. The cross-plane thermal conductivity of the ceramic coated separators is analyzed to understand their heat transfer behavior. The thermal conductivity of the separator is improved by ~3.2 times with the Al 2 O 3 coating.

25 ENERGY STORAGE↗

Structural Distortions and Uniaxial Negative Thermal Expansion in the Polar Dion–Jacobson Oxide RbNdTa 2 O 7

We provide deeper insight into the crystal structures, sequential structural phase transitions (I2cm → Cmce → I4/mcm → P4/mmm), thermal expansion, and electronic properties of the n = 2 Dion–Jacobson polar oxide RbNdTa 2 O 7 , through X-ray powder diffraction, neutron powder diffraction, Raman studies, and density functional theory calculations. We observed a uniaxial negative thermal expansion (NTE) across the first-order transition, I2cm → Cmce, where the unit cell contracts along the c-axis, which is driven by a contraction of the NdTa 2 O 6 layer. Here, this NTE occurs within the temperature range of the first-order phase transition and contrasts with the corkscrew mechanism typically observed in Ruddlesden–Popper phases. In RbNdTa 2 O 7 , the I2cm (hybrid improper ferroelectric) → Cmce (antipolar) transition involves crucial changes in the bond lengths of Nd and Ta polyhedra, coupled with polar to antipolar displacement of the Nd ions, leading to a net contraction in the NdTa 2 O 6 layer along the c-axis, while preserving the overall octahedral tilting magnitude. This transition highlights the intricate interplay between the Nd and Ta coordination and the associated TaO 6 distortions. Temperature-dependent Raman spectra analysis further confirms the first-order structural transition and associated NTE, providing evidence for increased bond stiffness across this transition. Additionally, using neutron powder diffraction, we have determined that the transition I4/mcm → P4/mmm occurs at approximately 1150 K. Finally, we have calculated from DFT + U, the partial density of states, the energy bandgaps, and effective masses of the charge carriers of the polar ground structure.

Chemical structure↗

Theoretical Kinetics Predictions for Reactions on the NH 2 O Potential Energy Surface

Recent modeling studies of ammonia oxidation, which are motivated by the prospective role of ammonia as a zero-carbon fuel, have indicated significant discrepancies among the existing literature mechanisms. In this study, high-level theoretical kinetics predictions have been obtained for reactions on the NH 2 O potential energy surface, including the NH 2 + O, HNO + H, and NH + OH reactions. These reactions have previously been highlighted as important reactions in NH 3 oxidation with high sensitivity and high uncertainty. The potential energy surface is explored with coupled cluster calculations, including large basis sets and high-level corrections to yield high-accuracy (~0.2 kcal/mol 2σ uncertainty) estimates of the stationary point energies. Variational transition state theory is used to predict the microcanonical rate constants, which are then incorporated in master equation treatments of the temperature- and pressure-dependent kinetics. For radical–radical channels, the microcanonical rates are obtained from variable reaction coordinate transition state theory implementing directly evaluated multireference electronic energies. The analysis yields predictions for the total rate constants as well as the branching ratios. We find that the NO + H 2 channel contributes 10% of the total NH 2 + O flux at combustion temperatures, although this channel is not included in modern NH 3 oxidation mechanisms. Modeling is used to illustrate the ramifications of these rate predictions on the kinetics of NH 3 oxidation and NO x formation. Finally, the present results for NH 2 + O are important for predicting the chain branching and formation of NO in the oxidation of NH 3 and thermal DeNO x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗