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At least 1,099 records · Page 61

Isopotential Electron Titration of Ammonia Charge Transfer on Metal Catalysts

Electron transfer between adsorbates and surfaces determines the binding strength and reactivity of chemical moieties on materials designed for separations and catalysis. To quantify electron exchange, the extent of charge transfer resulting from ammonia adsorption on a Ru surface was measured by isopotential electron titration (IET) on a Ru catalytic condenser, where isopotential conditions were maintained between Ru and silicon separated by an insulating HfO 2 layer during gas phase ammonia adsorption. Charge transfer upon ammonia adsorption on a Ru catalytic condenser increased from 40 to 1200 nC/cm 2 at 75 and 225 °C, respectively. Charge transfer measurements provided a direct estimate of ammonia adsorption thermodynamics on Ru without knowing surface coverages a priori, revealing an adsorption enthalpy of −53 ± 10 kJ/mol and entropy of −61 ± 26 J/mol·K. Combining experimentally-measured charge transfer with kinetic Monte Carlo simulations informed adsorbate surface coverages determined that 0.058 electrons were transferred to the Ru surface for each molecular ammonia adsorption event (δ NH 3 = 0.058 ± 0.005 e – /NH 3 *), consistent with calculated Bader charges. The ability to measure the extent of charge transfer for adsorbed species provides a fundamental descriptor to understand existing and new chemically functional surfaces, providing a foundational method for the emerging field of thermochemical surface coulometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nuclear rotation at the fission limit in Rf 254

A ground-state rotational band in the fissile nucleus Rf254 was observed for the first time. Levels up to spin 14 and excitation energy of 1.56 MeV were observed. The Rf254 nuclei were produced using the Pb206(Ti50,2n) fusion-evaporation reaction. It is the weakest reaction channel ever studied using in-beam γ-ray spectroscopic methods. The reaction products were separated from the beam in the Argonne gas-filled analyzer (AGFA). The Rf254 nuclei were implanted into a double-sided Si strip detector at the AGFA focal plane and tagged with subsequent ground-state spontaneous fission decays using temporal and spatial correlations. Prompt γ rays in coincidence with the Rf254 recoils were detected in the Gammasphere array of Ge detectors. In order to identify the ground-state rotational band in Rf254, a method for identifying rotational bands in low statistics γ-ray spectra was developed. The deduced Rf254 kinematic moment of inertia is smaller compared to neighboring even-even nuclei. This is most likely associated with a slightly lower quadrupole deformation and stronger pairing correlations in Rf254. The behavior of the moment of inertia as a function of rotational frequency is similar to that of the lighter N=150 isotones Fm250 and No252.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

α decay of the neutron-deficient isotope At 190

The alpha decay of the neutron-deficient 190 At isotope was observed following the 103 Rh( 90 Zr, 3n) 190 At reaction at Argonne National Laboratory. The reaction products were separated from the beam using the Argonne Gas-Filled Analyzer and implanted into a double-sided Si strip detector. The spatial and temporal correlations between implanted nuclei and subsequent α decays towards the known daughter isotope 186 Bi were used to identify and characterize 190 At nuclei. In this paper, two possible decay scenarios are proposed for the 190 At → 186 Bi decay.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Fuel Property Effects of a Broad Range of Potential Biofuels on Mixing Control Compression Ignition Engine Performance and Emissions

Conventional diesel engines will continue to hold a vital role in the heavy- and medium-duty markets for the transportation of goods along with many other uses. The ability to offset traditional diesel fuels with low-net-carbon biofuels could have a significant impact on reducing the carbon footprint of these vehicles. A prior study screened several hundred candidate biofuel blendstocks based on required diesel blendstock properties and identified 12 as the most promising. Eight representative biofuel blendstocks were blended at a 30% volumetric concentration with EPA certification ultra-low-sulfur diesel (ULSD) and were investigated for emissions and fuel efficiency performance. This study used a single cylinder engine (based on the Ford 6.7L engine) using Conventional Diesel Combustion (CDC), also known as Mixing Control Compression Ignition (MCCI). The density, cetane number, distillation curve and sooting tendency (using the yield sooting index method) of the fuels were measured. Start of injection (SOI) timing and exhaust gas recirculation (EGR) sweeps were conducted at three separate speed-load operating points to examine fuel effects on the NOX/soot and NOX/efficiency trade-offs as well as to evaluate EGR tolerance. The results show that the biofuel blends all reduced NOX and soot emissions without penalty to engine efficiency, even improving efficiency for some of the blends at certain points, with one particular blend of polyoxymethylene ethers (POMEs) improving efficiency at all points while drastically reducing soot by 79%.

47 OTHER INSTRUMENTATION↗

Chemical fractionations in meteorites. V - Volatile and siderophile elements in achondrites and ocean ridge basalts.

Eighteen achondrites and 4 terrestrial basalts (3 ocean ridge, 1 continental) were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Co, Cs, Cu, Ga, In, Ir, Rb, Se, Tl and Zn. Samples included 7 eucrites, 5 howardites, 2 nakhlites, 2 shergottites, an angrite, and an aubrite. Light and dark portions of the gas-rich meteorites Kapoeta and Pesyanoe were analyzed separately. Nakhlites and shergottites have volatile element abundances similar to those in ocean ridge basalts; eucrites, howardites, and angrites show greater depletions by an order of magnitude and less similar abundance patterns. In terms of a two-component model of planetary accretion, the parent planets contained the following percentages of low-temperature material: eucrites 0.8, nakhlites 38, shergottites 28. Shergottites may be genetically related to L-chondrites. The siderophile element pattern of achondrites resembles that of the moon, but with less extreme depletions.

Laul, J. C.↗

Control of turbofan lift engines for VTOL aircraft

The use of turbofan engines as lift units for VTOL aircraft poses new engine control problems. At low flight speeds, the lift units must provide the fast thrust response needed for aircraft attitude and height control. The results are presented of an analytical study of the dynamics and control of turbofan lift engines, and methods are proposed for meeting the response requirements imposed by the VTOL aircraft application. Two types of lift fan engines are discussed: the integral and remote. The integral engine is a conventional two-spool, high bypass ratio turbofan designed for low noise and short length. The remote engine employs a gas generator and a lift fan which are separated by a duct, and which need not be coaxial. For the integral engine, a control system design is presented which satisfies the VTOL response requirements. For the remote engine, two unconventional methods of control involving flow transfer between lift units are discussed. Both methods are shown to have thrust response near the required levels.

Sellers, J. F.↗

Analysis of organogenic compounds in Apollo 11, 12, and 14 lunar samples.

DCl was used to distinguish hydrocarbons produced by acid treatment from hydrocarbons originally present in the samples when volatiles released by acid and thermal treatments from Apollo 11, 12, and 14 lunar samples were studied by quadrupole mass spectrometry and gas chromatography mass spectrometry. Multiple ion plotting permitted separation of deuterated from nondeuterated hydrocarbons in the DCl products. Stepwise thermal treatment was used to distinguish the source of the volatile compounds. The presence of LM rocket exhaust products was traced in two samples, and the presence of high-temperature stable nitrides in some samples is indicated.

Flory, D. A.↗

Control of turbofan lift engines for VTOL aircraft.

This paper presents the results of an analytical study of the dynamics and control of turbofan lift engines, and proposes methods of meeting the response requirements imposed by the VTOL aircraft application. Two types of lift fan engines are discussed: the integral and remote. The integral engine is a conventional two-spool, high bypass ratio turbofan designed for low noise and short length. The remote engine employs a gas generator and a lift fan which are separated by a duct, and which need not be coaxial. For the integral engine, a control system design is presented which satisfies the VTOL response requirements. For the remote engine, two unconventional methods of control involving flow transfer between lift units are discussed.

Sellers, J. F.↗

An environmental chamber system for prolonged metabolic studies on small animals

Measurement of metabolic adaptation to marginally stressful environments requires both precise regulation of a variety of atmospheric factors for extended periods of time and the capacity to employ sensitive parameters in an undisturbed subject. This paper describes a metabolic chamber system which can simultaneously maintain groups of small animals in two completely separate closed environments having different pressures, temperatures and gas compositions for an indefinite period. Oxygen consumption, carbon dioxide production, food and water consumption and animal activity cycles can be continuously monitored and quantified 24 h per day while the animals are in an unrestrained state. Each chamber can be serviced and the animals handled, injected and sacrificed without subjecting them to barometric stress. Several unique electrical and mechanical components allow semi-automated data collection on a continuous basis for indefinite periods of time.

Jordan, J. P.↗

Counter pumping debris excluder and separator

A dirt separator and excluder for removing entrained debris from gas turbine shaft seals is described. A helical groove pattern is constructed on the rotating shaft with the pumping pattern such that it tends to pump seal pressurizing gas toward the gas turbine seal. A second helical groove pattern is provided on the stationary housing or counter rotating member coaxial with the shaft, and this pattern is designed to provide pumping in the direction opposite from that of the groove pattern on the shaft. Gas with entrained debris entering this grooved area will be subjected to high centrifugal forces due to the swirl motion induced by the groove pattern and the rotation of the shaft. This debris is centrifuged outwardly into the outer groove pattern on the housing or counter rotating member. Because the outer groove pattern has a pumping direction opposite from that of the seal, dirt is pumped away from the seal and can be collected in a suitable debris trap remote from the seal location.

Ludwig, L. P.↗

Novel duplex vapor-electrochemical method for silicon solar cells

A process was developed for the economic production of high purity Si from inexpensive reactants, based on the Na reduction of SiF4 gas. The products of reaction (NaF, Si) are separated by either aqueous leaching or by direct melting of the NaF-Si product mixture. Impurities known to degrade solar cell performance are all present at sufficiently low concentrations so that melt solidification (e.g., Czochralski) will provide a silicon material suitable for solar cells.

Nanis, L.↗

Soft X-ray spectral observations of low-luminosity active galaxies

The X-ray spectra of a sample of 12 low-luminosity AGNs observed using the solid state spectrometer on the HEAO 2 satellite are investigated. The AGNs discussed here have X-ray luminosities below about 10 to the 44th erg/s, and thus form a sample complementary to the higher luminosity sample discussed by Petre et al. (1984). The spectra are well described by a simple model consisting of a power law, with photon spectral index about 1.7, plus absorption by cold gas. The objects in the sample can be separated into three groups: (1) those whose spectra show no significant absorption; (2) those for which the X-ray source is totally covered by a spatially uniform absorbing medium; and (3) those for which partial covering by 'patchy' absorbers is indicated. Column densities and covered fractions do not correlate systematically with X-ray luminosity. Implications regarding physical conditions in AGNs are discussed.

Reichert, G. A.↗

Coronal X-ray activity preceding solar flares

The characteristics of coronal emplacements preceding solar flares were investigated based on a comprehensive survey of Skylab soft X-ray images. A search interval of 30 min before flare was used in the X-ray observations. X-ray images with preflare enhancements were compared with high resolution H-alpha images and photospheric magnetograms and preflare enhancements were found in a statistically significant number of the observed preflare intervals. The enhancement events consisted of loops, kernels, and sinuous features with one to three separate preflare structures appearing in each interval. Typical gas pressures in the preflare X-ray features were estimated on the order of a few dyne per sq cm and densities were 4-10 x 10 to the -9th per cu cm for assumed average temperatures. H-alpha brightenings in the form of knots and patches were found in conjunction with the X-ray preflare features in nearly all of the intervals. It is concluded that H-alpha emission is characteristic of preflare emission processes. The observational data are interpreted within the framework of existing loop preheating models, and the results are discussed in detail.

Webb, D. F.↗

Cometary MHD and chemistry

An MHD and chemical comet-coma model was developed, applying the computer program of Huebner (1985) for the detailed chemical evolution of a spherically expanding coma and the program of Schmidt and Wegman (1982) and Wegman (1987) for the MHD flow of plasma and magnetic field in a comet to the Giotto-mission data on the ion abundances measured by the HIS ion mass spectrometer. The physics and chemistry of the coma are modeled in great detail, including photoprocesses, gas-phase chemical kinetics, energy balance with a separate electron temperature, multifluid hydrodynamics with a transition to free molecular flow, fast-streaming atomic and molecular hydrogen, counter and cross streaming of the ionized species relative to the neutral species in the coma-solar wind interaction region with momentum exchange by elastic collisions, mass-loading through ion pick-up, and Lorentz forces of the advected magnetic field. The results, both inside and outside of the contact surface, are discussed and compared with the relevant HIS ion mass spectra.

Wegmann, R.↗

Numerical simulations of magnetized jets

The present axisymmetric numerical simulations of light hypersonic jets allow unmagnetized jets and jets carrying a dynamically important magnetic field to be contrasted. After decelerating a weakly magnetized jet through a series of weak, oblique shocks, a Mach disk and a strong annular shock are encountered near the outer edges of the contact discontinuity separating the shocked fluid from the shocked ambient gas. Upon passing the annular shock, the gas quickly expands and enters a backflowing cocoon surrounding the jet. The overall speed of advance of the jet is reduced; matter near the jet axis which passes through the terminal Mach disk accumulates in a plug, and gas is discharged into the cocoon by the intermittent shedding of vortices. When magnetic stresses dominate, however, the jet is rapidly decelerated via a Mach disk and strong annular shock.

Lind, Kevin R.↗

Interactive calculation procedures for mixed compression inlets

The proper design of engine nacelle installations for supersonic aircraft depends on a sophisticated understanding of the interactions between the boundary layers and the bounding external flows. The successful operation of mixed external-internal compression inlets depends significantly on the ability to closely control the operation of the internal compression portion of the inlet. This portion of the inlet is one where compression is achieved by multiple reflection of oblique shock waves and weak compression waves in a converging internal flow passage. However weak these shocks and waves may seem gas-dynamically, they are of sufficient strength to separate a laminar boundary layer and generally even strong enough for separation or incipient separation of the turbulent boundary layers. An understanding was developed of the viscous-inviscid interactions and of the shock wave boundary layer interactions and reflections.

Reshotko, Eli↗

Ionized carbon in the Large Magellanic Cloud

The 158 micron 2P3/2-2P1/2 fine-structure transition of C(+) at selected locations in the LMC. The C II emission is most intense toward far-infrared continuum peaks and generally is not seen in positions exhibiting strong CO J = 2-1 radiation. Where both C II and CO emission are detected, the V(LSR) centroids are similar but the C II line is wider. The differences in spatial distribution and spectral shape suggest a more pronounced physical separation between the predominantly neutral atomic and molecular gas regions than is the case in the Galaxy. In the LMC, the intense and extended C II emission near 30 Dor implies a total amount of C(+) several times greater than that of Galactic molecular cloud complexes. An attempt was made to detect the 289 micron J = 9-8 transition of (C-12)O in a few locations. The observed upper intensity limit for N159 implies that moderate density molecular gas fills less than 5 percent of the beam and that most of the low J CO emission comes from lower density gas.

Boreiko, R. T.↗