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At least 595 records · Page 33

Theoretical Study of the H2-ML(+) Binding Energies

The cooperative ligand effects are studied in MLH2(+) and the results are compared to the recent experiments of Kemper et al. The bonding in these compounds is principally electrostatic in origin; however, ligand to metal and metal to ligand donations are important, especially for H2. We show that differences arise among the vanadium, cobalt, and copper complexes which are due to 3d donation to H2. Electron correlation is required to describe the dative interaction, and we find that second order Moller-Plesset perturbation theory (MP2) yields a good description of these systems compared with higher levels of correlation (such as the modified coupled pair functional and coupled cluster approaches) and experiment. However, obtaining quantitative results requires higher levels of theory than MP2.

Maitre, Philippe↗

A Review of Single Source Precursors for the Deposition of Ternary Chalcopyrite Materials

The development of thin-film solar cells on flexible, lightweight, space-qualified durable substrates (i.e. Kapton) provides an attractive solution to fabricating solar arrays with high specific power, (W/kg). The syntheses and thermal modulation of ternary single source precursors, based on the [{LR}2Cu(SR')2In(SR')2] architecture in good yields are described. Thermogravimetric analyses (TGA) and Low temperature Differential Scanning Caloriometry, (DSC) demonstrate that controlled manipulation of the steric and electronic properties of either the group five-donor and/or chalcogenide moiety permits directed adjustment of the thermal stability and physical properties of the precursors. TGA-Evolved Gas Analysis, confirms that single precursors decompose by the initial extrusion of the sulphide moiety, followed by the loss of the neutral donor group, (L) to release the ternary chalcopyrite matrix. X-ray diffraction studies, EDS and SEM on the non-volatile pyrolized material demonstrate that these derivatives afford single-phase CuInS2/CuInSe2 materials at low temperature. Thin-film fabrication studies demonstrate that these single source precursors can be used in a spray chemical vapor deposition process, for depositing CuInS2 onto flexible polymer substrates at temperatures less than 400 C.

Banger, K. K.↗

High Current Hollow Cathode Plasma Plume Measurements

Plasma plume measurements are reported for a hollow cathode assembly (HCA) operated at discharge currents of 50, 70, and 100 A at xenon flow rates between 19 - 46 standard cubic centimeter per minute. The HCA was centrally mounted in the NASA-300MS Hall Thruster and was operated in the "spot" and "plume" modes with additional data taken with an applied magnetic field. Langmuir probes, retarding potential analyzers, and optical emission spectroscopy were employed to measure plasma properties near the orifice of the HCA and to assess the charge state of the near-field plasma. Electron temperatures (2-6 electron volt) and plasma potentials are consistent with probe-measured values in previous investigations. Operation with an applied-field yields higher discharge voltages, increased Xe III production, and increased signals from the 833.5 nm C I line. While operating in plume mode and with an applied field, ion energy distribution measurements yield ions with energies significantly exceeding the applied discharge voltage. These findings are correlated with high-frequency oscillations associated with each mode.

High frequency analysis↗

Materials Degradation in the Jovian Radiation Environment

The radiation environment of Jupiter represents a significant hazard for Europa Lander deorbit stage components, and presents a significant potential mission risk. The radiolytic degradation of ammonium perchlorate (AP) oxidizer in solid propellants may affect its properties and performance. The Monte Carlo code MONSOL was used for modeling of laboratory experiments on the electron irradiation of propellant samples. An approach for flattening dose profiles along the depth of irradiated samples is proposed. Depth-dose distributions produced by Jovian electrons in multi-layer slabs of materials are calculated. It is found that the absorbed dose in a particular slab is significantly affected by backscattered electrons and photons from neighboring slabs. The dose and radiolytic decomposition of AP crystals are investigated and radiation-induced chemical yields and weight percent of radical products are reported.

Miloshevsky, Gennady↗

In-Situ Alloying of GRCop-42 via Additive Manufacturing: Precipitate Analysis

GRCop-42, a Cu-4at% Cr-2at% Nb alloy, was designed as a high temperature, high strength, high heat flux material for rocket engine combustion chamber liners by NASA Glenn Research Center. In situ alloying of GRCop-42 (ISGRCop-42) using powder bed fusion (PBF) additive manufacturing (AM) takes elemental powders of Cu, Cr, and Nb to be introduced into the PBF environment and develop the GRCop alloy while simultaneously building an AM component. Elemental powders were milled together prior to printing in an effort to facilitate the alloying process. Success of the in situ alloying process may provide lower cost, faster lead times, alloying optimization, and more design freedom in the development of regeneratively-cooled rocket propulsion systems. Evaluation of the ISGRCop-42 was conducted using a phase extraction procedure to isolate the Cr2Nb precipitates from the pure Cu matrix. The isolated precipitates were then examined using x-ray powder diffraction (XRD), scanning electron microscopy (SEM), and energy dispersion spectroscopy (EDS). It was found that ISGRCop-42 successfully and repeatedly formed Cr2Nb at a yield as high as 89% of potential Cr2Nb. Further, it was identified that the preparation of the powder was the most influential factor in alloying success, and the second most influential factor was the laser power.

In Situ alloying↗

Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K

The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < |CH3|(sub 0)/|C2H3|(sub 0) < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.

Thorn, R. Peyton, Jr.↗

Biosynthetic Porphyrins and the Origin of Photosynthesis

Since the prebiotic atmosphere was anaerobic, if not reducing, a useful function of primordial photosynthesis would have been to photooxidize reduced substrates such as Fe(+2), S(-2) or reduced organic molecules and to emit hydrogen. Experiments have shown that the early biogenic pigments uroporphyrin and coproporphyrin do photooxidize organic compounds and emit hydrogen in the presence of a platinum catalyst. These experiments were carried out in dilute aqueous solution near neutral pH under anaerobic atmosphere, and quantum yields near 10-2 were obtained. Thus relevant prebiotic conditions were maintained. Rather then to further optimize conditions, attempts were made to replace the platinum catalyst by a more prebiotically suitable catalyst. Trials with an Fe4S4(SR)4 cluster, in analogy to the present hydrogenase and nitrogenase, were not successful. However, experiments using cobalt complexes to catalyze the formation of hydrogen are promising. In analogy with biological photosynthetic systems which group pigments, electron transfer molecules and enzymes in clusters for efficiency, it was found that binding the biogenic porphyrins to the polyvinyl alcohol used to support the platinum catalyst did increase the quantum yield of the reaction. It was also found that ultraviolet light can serve to photo-oxidize porphyrinogens to porphyrins under anaerobic conditions. Thus the formation of the colorless porphyriogens by the extraordinarily simple biosynthetic pathway would not be a problem because of the prevalence of UV light in the prebiotic, anoxic atmosphere.

David Mauzerall↗

Sub-Daily Northern Hemisphere Ionospheric Maps Using the IGS GPS Network

Ionospheric total electron content (TEC) data derived from dual-frequency GPS signals from 30 globally distributed IGS network sites are fit to a simple ionospheric shell model, yielding, simultaneously, values for the satellite and receiver biases, and a map of the ionosphere in the northern hemisphere every 12 hours during the period of Jan. 1-15, 1993. RMS residuals of 2-3 TEC units are observed over the 20-80 degree latitude band. Various systematic errors affecting the TEC estimates are discussed. The capability of using these global maps to produce ionosphere calibrations for sites at which no GPS data are available is investigated.

ionospheric total electron content GPS global iono↗

Experiments on the origin of molecular chirality by parity non-conservation during beta-decay

Experiments are described to test a theory for the origin of optical activity wherein the longitudinally polarized electrons resulting from parity violation during radioactive beta decay, and their resulting circularly polarized Bremsstrahlung, might interact asymmetrically with organic matter to yield optically active products. Experiments involve subjecting a number of racemic and optically active amino acid samples to irradiation in a 61700 Ci90SR-90Y beta radiation source for a period of 1.34 years, then examining them for any asymmetric effects by means of optical rotatory dispersion and analytical gas chromatography. In the cases of D,L-leucine, norleucine, norvaline and proline as solids, of D,L-leucine in solution and of D,L-tyrosine in alkaline solution no optical rotation was observed during CRD measurements in the 250-630 nm spectral region. While slight differences were noted in the percent radiolysis of solid D- (12.7%) and L-leucine (16.2%) as determined by GC, no enrichment of either enantiomer was found.

Bonner, W. A.↗

Evolution of ion emission yield of alloys with the nature of the solute. 2: Interpretation

Solid solutions of transition elements in copper, nickel, cobalt, iron, and aluminum matrices were analyzed by observing secondary ion emissions under bombardment with 6.2-keV argon ions. Enchancement of the production of solute-element ions was observed. An ion emission model is proposed according to which the ion yield is governed by the probability of an atom leaving the metal in a preionized state. The energy distribution of the valence electrons of the solute atoms is the bases of the probability calculation.

Blaise, G.↗

Charge equilibrium and radiation of low-energy cosmic rays passing through interstellar medium

The charge equilibrium and radiation of an oxygen and an iron beam in the MeV per nucleon energy range, representing a typical beam of low-energy cosmic rays passing through the interstellar medium, are considered. Electron loss of the beam has been taken into account by means of the first Born approximation, allowing for the target atom to remain unexcited or to be excited to all possible states. Electron-capture cross sections have been calculated by means of the scaled Oppenheimer-Brinkman-Kramers approximation, taking into account all atomic shells of the target atoms and capture into all excited states of the projectile. The capture and loss cross sections are found to be within 20%-30% of the existing experimental values for most of the cases considered. Radiation of the beam due to electron capture into the excited states of the ion, collisional excitation, and collisional inner-shell ionization, taking into account the fluorescence yield of the ions, has been considered. Effective X-ray production cross sections and multiplicities for the most energetic X-ray lines emitted by the Fe and O beams have been calculated, and error estimates made for the results.

Rule, D. W.↗

Bremsstrahlung in the scattering of low-energy electrons by neutral atomic systems

By elementary methods, the cross section for electron-atom and electron-molecule bremsstrahlung is computed in the limit when the incident electron energy is much less than Ry. The procedure employs the classical soft-photon emission probability formula for general (h/2pi)(omega), yielding a simple expression for the bremsstrahlung cross section in terms of the total elastic scattering cross section. The validity of the method is discussed, and results are compared with more elaborate and accurate calculations. Comparison is made with ('free-free') opacity calculations for the associated process at the temperature (6300 K) of the solar atmosphere. For chi sub omega = (h/2pi)(omega)/kT = 1, the computed absorption coefficient is within 2, 7, and 12 percent of accurate calculations for scatterings by H, He, and H2, respectively. The general dependence of the opacity on chi sub omega is described well by the simple formula, although the error is larger for higher chi sub omega; it is suggested that the inaccuracy at high frequencies is due to the failure of the soft-photon approximation.

Gould, R. J.↗

Mapping the Structure of Heterogeneous Materials

Image-processing microdensitometer/Fourier analyzer yields statistics of subcomponent distribution. Nondestructive method for studying structure heterogeneous materials uses energy-dispersive X-ray analysis in scanning electron microscope. Scanning microdensitometer/Fourier analyzer (SMFA) is applied to SEM images to obtain statistics about sample structure. Method originally developed for studying effect on combustion of fine structure of composite solid propellants.

Strand, L. D.↗

Time optimal robotic manipulator motions and work places for point to point tasks

High productivity requires that manipulators perform complex tasks quickly. Recently, optimal control algorithms have been developed which enable manipulators to move quickly, but only for simple motions. A method is presented here which combines simple time optimal motions in an optimal manner to yield the minimum time motions for an important class of complex manipulator tasks composed of point to point moves, such as assembly, electronic component insertion and spot welding. This method can also be used to design manipulator actions and work places so that tasks can be completd in minimum time. The method has been implemented in a CAD software package. Examples are presented which show the methods effectiveness.

Dubowsky, S.↗

Development of high-lift wing modifications for an advanced capability EA-6B aircraft

NASA-Langley has been in a development program aimed at improvements of the EA-6B electronic countermeasures aircraft's maneuvering capabilities; one objective of this effort is the investigation of relatively simple wing design modifications which could yield improved low speed high lift performance with minimum degradation of higher-speed performance. Various two- and three-dimensional low speed and transonic CFD techniques have accordingly been used during the design effort, which involved leading-edge slat and trailing-edge flap contour evaluations by both computation and wind tunnel experiment. Significant low-speed maximum-lift enhancements were obtained without cruise-speed deterioration.

Waggoner, Edgar G.↗

Langmuir turbulence in the auroral ionosphere 2: Nonlinear theory and simulations

A theoretical interpretation of sounding rocket measurements of intense Langmuir wave fields (less than or equal to 500 mV/m) driven by a stream of 20 eV to 4 keV electrons in the lower auroral zone is developed. This interpretation is based on the ability of the 10 microseconds sampling rate of the wave detector to temporally resolve the structure of the Langmuir wave field envelope. A modified form of the Zakharov equations is used to numerically study beam-driven Langmuir turbulence in the presence of a moderate magnetic field (OMEGA (sub e) approximately equals Omega (sub pe). Strong Landau damping on observed nonthermal scattered electrons, which is treated in a companion paper (Newman et al., this issue), plays an important role by inhibiting backscatter cascade and the development of strong turbulence. A parameterized model of the linear electron stream-driven wave instability is introduced, which incorporates limited quasilinear plateau formation. A reasonable set of parameters is found that yields semiquantitative agreement between observed properties of the Langmuir fields and the results of Zakharov equation simulations, including the amplitude and characteristic frequency of the electric field envelope modulations.

Newman, D. L.↗

Multi-Spacecraft Observations of Interplanetary Shocks

Using multi-spacecraft observations primarily from ACE and WIND, and from IMP 8 and Geotail when available, the 3-dimensional structure of interplanetary shocks on the hundred Earth radii scale will be discussed. The complete magnetic field, and solar wind ion and electron data sets were used to fit the shocks with a full non-linear least squares fit "Rankine-Hugoniot" technique yielding the local shock surface normals and speeds with associated uncertainties. Multi-spacecraft results reveal that on the distance scale of ACE's L1 halo orbit the shocks deviate significantly from a simple planar geometry. This result has important consequences for the prediction of the exact arrival times of interplanetary shocks at the Earth's magnetosphere, and hence, on the reliability of space weather predictions. It also has implications on the coherence scale of solar wind structures and their evolution from the Sun to Earth.

Szabo, A.↗