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At least 1,189 records · Page 66

Chemical bonding in americium oxides probed by X-ray spectroscopy

The electronic structure and the chemical state in Am binary oxides and Am-doped UO 2 were studied by means of X-ray absorption spectroscopy at shallow Am core (4d and 5d) edges. In particular, the Am 5f states were probed and the nature of their bonding to the oxygen states was analyzed. The interpretation of the experimental data was supported by the Anderson impurity model (AIM) calculations which took into account the full multiplet structure due to the interaction between 5f electrons as well as the interaction with the core hole. The sensitivity of the branching ratio of the Am 4d 3/2 and 4d 5/2 X-ray absorption lines to the chemical state of Am was shown using Am binary oxides as reference systems. The observed ratio for Am-doped UO 2 suggests that at least at low Am concentrations, americium is in the Am(III) state in the UO 2 lattice. To confirm the validity of the applied AIM approach, the analysis of the Am 4f X-ray photoelectron spectra of AmO 2 and Am 2 O 3 was also performed which revealed a good agreement between experiment and calculations. As a whole, AmO 2 can be classified as the charge-transfer compound with the 5f occupancy (n ƒ ) equal to 5.73 electrons, while Am 2 O 3 is rather a Mott–Hubbard system with n ƒ = 6.05.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Permanganate Oxidation of Glycolate on Corrosion of the Defense Waste Processing Facility (DWPF) Recycle Collection Tank (RCT), Transfer-line and Waste Tank Materials of Construction (MoC)

Savannah River Remediation (SRR) is evaluating the use of glycolic acid to replace formic acid as an alternate reductant for the Defense Waste Processing Facility (DWPF) at Savannah River Site (SRS). The replacement is aimed at reducing facility hazards, improving pH stability and rheological control, and lowering off gas production. Glycolate, which is the product that may remain, can also be carried downstream to High-Level Waste and Low-Level Waste facilities. Complete oxidation of glycolate and other organic species from the Sludge Receipt and Adjustment Tank (SRAT) may be necessary to minimize thermolytic hydrogen generation that can cause flammability issues. The glycolate oxidation may be performed in the Recycle Collection Tank (RCT). The RCT heel would be adjusted with sodium hydroxide to maintain the solution caustic and sodium nitrite as corrosion inhibitor prior to the addition of condensate that can be from the contents of the Slurry Mix Evaporator Condensate Tank (SMECT) or Offgas Condensate Tank (OGCT). The RCT tank collects the waste to be transferred via the Low Point Pump Pit – Recycle Pump Tank (LPPP-RPT) through a jacketed transfer-line to the Tank Farm facility. Scoping studies were performed to evaluate an oxidizing agent and sodium permanganate was selected as the best option for glycolate destruction. Testing was recommended to determine the impact on the Materials of Construction (MoC) due to the addition of sodium permanganate. The targeted concentration of sodium permanganate used equated to a 7:1 molar permanganate to glycolate ratio (nominally 0.002 M permanganate). However, to conservatively maximize the permanganate corrosivity, in some cases no glycolate was added.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

U, Th, Pb and REE abundances and Pb 207/Pb 206 ages of individual minerals in returned lunar material by ion microprobe mass analysis.

Results of ion microprobe analyses of Apollo 11, 12 and 14 material, showing that U, Th, Pb and REE are concentrated in accessory minerals such as apatite, whitlockite, zircon, baddeleyite, zirkelite, and tranquillityite. Th/U ratios are found to vary by over a factor of 40 in these minerals. K, Ba, Rb and Sr have been localized in a K rich, U and Th poor glass phase that is commonly associated with the U and Th bearing accessory minerals. Li is observed to be fairly evenly distributed between the various accessory phases. The phosphates have been found to have REE abundance patterns (normalized to the chondrite abundances) that are fairly flat, while the Zr bearing minerals have patterns that rise steeply, by factors of ten or more, from La to Gd. All the accessory minerals have large negative Eu anomalies. Radiometric age dates (Pb 207/Pb 206) of the individual U and Th bearing minerals compare favorably with the Pb 207/Pb 206 age of the bulk rocks.

Andersen, C. A.↗

Adhesion and friction of iron-base binary alloys in contact with silicon carbide in vacuum

Single pass sliding friction experiments were conducted with various iron base binary alloys (alloying elements were Ti, Cr, Mn, Ni, Rh, and W) in contact with a single crystal silicon carbide /0001/ surface in vacuum. Results indicate that atomic size and concentration of alloying elements play an important role in controlling adhesion and friction properties of iron base binary alloys. The coefficient of friction generally increases with an increase in solute concentration. The coefficient of friction increases linearly as the solute to iron atomic radius ratio increases or decreases from unity. The chemical activity of the alloying elements was also an important parameter in controlling adhesion and friction of alloys, as these latter properties are highly dependent upon the d bond character of the elements.

Miyoshi, K.↗

Characterization of tropospheric desert aerosols at solar wavelengths by multispectral radiometry from Landsat

Characteristics of tropospheric desert aerosols are derived by comparing nadir spectral reflectivities computed from the radiative transfer models with reflectivities measured from Landsat. Over the ocean, reflectivities are compared, but over land the comparison is carried out by determining the ratios of the nadir reflectivity of the surface-atmosphere system over heavy aerosol concentration to the reflectivity of the underlying surface. This remote sensing technique is found to be a sensitive approach for measuring n sub 2, the imaginary part of the refractive index. The desert aerosols under study, in the Iran and Pakistan area, are essentially pure scatterers, inasmuch as an n sub 2 value of 0.001 + or - 0.001 was determined for each of the four Landsat spectral bands, that is, for a spectral interval from 0.5 to 1.1 microns.

Otterman, J.↗

Surface temperatures and glassy state investigations in tribology, part 5

Preliminary measurements of high shear rate viscosity at near atmospheric but variable pressure suggest the importance of low normal stress and cavitation or fluid fracture in the type of stress field existing in elastohydrodynam ic inlets and classical hydrodynamic configurations. An experimental basis is given for three regimes of traction in concentrated contacts: a thin film regime characterized by high traction and determined by lambda ratio, a thick film regime characterized by low traction and determined by the speed parameter, and the elastohydrodynamic regime for which traction is controlled by limiting shear stress. Traction measurements were performed with various liquids, two solid lubricants, and a grease. Film thickness and traction measurements of polymer blends and base oils are compared.

Bair, S.↗

Detailed design of a variable volume hydrogen maser

Identification of the hydrogen maser design parameters include the shape of the bulk, q (quality parameter), tuning factors, materials to be used, and operational temperature to offset the wall shift. Expressions for the statistic error on the measured frequency were derived. Localized variations in the concentration of excited atoms were studied and how the shape of the container (the ratio of surface to volume in particular) affects their behavior.

Cervenka, P. O.↗

A Model of the Influence of Neutral Air Dynamics on the Seasonal Variation in the Low Ionosphere

Recently it has become clear that the phenomena in the ionospheric D-region are determined to a great extent by dynamical processes in the strato-mesosphere D-region. In this respect much attention is paid to the study of the winter anomaly (WA) phenomenon on medium and short radiowaves, in which the meteorological character of the lower ionosphere is most prominent. Significant experimental data about the variations of the electron concentration, N, ion composition, temperature and dynamic regime during WA permit a better understanding of the character of the physical processes in the middle atmosphere. The influence of the neutral wind on the seasonal variation of the electron concentration N for the altitude interval 90 or = z or = 120 km, where the ratio upsilon sub in/omega sub i, of the ion-neutral collision frequency, upsilon sub in and the ion gyrofrequency, omega sub i decreases from 40 to 1 was evaluated. CIRA-72 is used as a model of the zonal wind.

Nestorov, G.↗

Comments on the BLAG model - The carbonate-silicate geochemical cycle and its effect on atmospheric carbon dioxide over the past 100 million years

A self-consistent method of determining initial conditions for the model presented by Berner, Lasaga, and Garrels (1983) (henceforth, the BLAG model) is derived, based on the assumption that the CO2 geochemical cycle was in steady state at t = -100 m.y. (million years). This initialization procedure leads to a dissolved magnesium concentration higher than that calculated by Berner, Lasaga, and Garrels and to a low ratio of dissolved calcium to bicarbonate prior to 60 m.y. ago. The latter prediction conflicts with the geologic record of evaporite deposits, which requires that this ratio remain greater than 0.5. The contradiction is probably caused by oversimplifications in the BLAG model, such as the neglect of the cycles of organic carbon and sulfur.

Kasting, J. F.↗

Thermospheric hydrogen - The long-term solar influence

Atmospheric Explorer C and E satellite data are employed for a long-term analysis of the behavior of thermospheric hydrogen with respect to the 11 yr solar cycle. The data covered the period 1974-79 (increasing solar activity) and comprised in situ ionospheric (F region) and neutral atmospheric data. The data were analyzed statistically to characterize low latitude hydrogen behavior, e.g., the diurnal variation and mean concentration over the 5 yr data sampling period. Both the mean and daily maximum/minimum ratio (DMMR) varied with the solar F index. The escaping flux of H ions became a contant around 1000 K. Increasing thermospheric temperatures lowered the DMMR value. However, the DMMR values calculated were consistently large enough to require inclusion of neutral winds and/or diurnal variations in charge exchange fluxes moving in and out of the plasmasphere in any model for thermospheric hydrogen behavior.

Breig, E. L.↗

Development of computer models for correlating data of film cooling of nose cone under hypersonic flow

A 12.5 degree half cone with tangential slot injection at Mach 6.95 was studied to determine the heating rates to the surface of the body near and far downstream of the slot. The cone had a zero degree angle of attack. The heating rates were obtained using a computer program that was developed at NASA-Langley Research Center. The concentration of nitrogen from the slot into the boundary layer was also determined. The ratio of slot to freestream was varied to determine its effect on heating. The numerical heating rates were compared to other correlations obtained from experimental studies as well as theoretical laminar and turbulent results.

Sharpe, L., Jr.↗

Multiple-mode nonlinear free and forced vibrations of beams using finite element method

Multiple-mode nonlinear free and forced vibration of a beam is analyzed by the finite element method. The geometric nonlinearity is investigated. Inplane displacement and inertia (IDI) are also considered in the formulation. Harmonic force matrix is derived and explained. Nonlinear free vibration can be simply treated as a special case of the general forced vibration by setting the harmonic force matrix equal to zero. The effect of the higher modes is more pronouced for the clamped supported beam than the simply supported one. Beams without IDI yield more effect of the higher modes than the one with IDI. The effects of IDI are to reduce nonlinearity. For beams with end supports restrained from axial movement (immovable cases), only the hardening type nonlinearity is observed. However, beams of small slenderness ratio (L/R = 20) with movable end supports, the softening type nonlinearity is found. The concentrated force case yields a more severe response than the uniformly distributed force case. Finite element results are in good agreement with the solution of simple elliptic response, harmonic balance method, and Runge-Kutte method and experiment.

Mei, Chuh↗

In situ measurement of atomic hydrogen in the upper mesosphere

In situ measurements of H abundance between 73 and 93 km are reported for conditions of winter solstice, magnetic quiet, and a solar depression angle of 12 deg. The data were obtained by a rocket-borne instrument using the resonance fluorescence technique. A discharge source emitting photons at 1216 A was an integral part of the instrument. The instrument was radially deployed 80 cm by a boom from the front of the payload in order to avoid the shock created by the gas flow over the front of the payload. An attitude control system oriented the payload so that the gas flow was nearly perpendicular to the plane containing the incident and scattered photons, thus minimizing any correction for Doppler shift. The resonance radiation detector viewed a black backstop in order to minimize background radiation from the hydrogen geocorona; however, the background was not entirely eliminated. The signal-to-noise ratio was improved by summing the data in 1.8-s bins. The observed hydrogen concentration maximized at 85 km at 1.5 + or - 1.1 x 10 to the 8th atoms/cu cm.

Sharp, W. E.↗

Automated Water-Purification System

Reverse-osmosis system operates and maintains itself with minimal human attention, using programmable controller. In purifier, membranes surround hollow cores through which clean product water flows out of reverse-osmosis unit. No chemical reactions or phase changes involved. Reject water, in which dissolved solids concentrated, emerges from outer membrane material on same side water entered. Flow controls maintain ratio of 50 percent product water and 50 percent reject water. Membranes expected to last from 3 to 15 years.

Ahlstrom, Harlow G.↗

mm-wave observations of stratospheric HCN at tropical latitudes

Middle and upper stratospheric HCN has been measured using ground-based mm-wave emission spectroscopy during a series of observations made in Mauna Kea, HI, in June 1986. A volume mixing ratio of 190 + or - 40 pptv at about 40 km, and a decrease of concentration with altitude that is considerably slower than that predicted by current models are found. This could be an indication of an atmospheric source of HCN as yet unidentified.

Jaramillo, M.↗

Aerosol characterization in smoke plumes from a wetlands fire

Results are presented from airborne measurements of aerosol mass loading, size distribution, and elemental composition obtained in a smoke plume from a fire at a Florida wildlife refuge. It is found that there was a high concentration of carbon-containing aerosols and salt crystals in the 0.1-0.2 micron size range; the composition and morphology of the aerosols differed with size. Aerosol mass concentrations are used in conjunction with those obtained for CO2 in order to calculate ratios of aerosol and CO2. The ratios are noted to be higher for the smoldering phase of the fire than for its flaming phase.

Woods, David C.↗

Geochemical evidences for two chondritic-like cometary or asteroidal impacts before and at the K/T boundary

A number of geological and palaeontological evidences support multiple impacts of cometary showers within a short time (approximately 1-3 Ma) and their connection with mass extinctions. Observations include clustered crater ages, stratigraphic horizons of impact ejecta closely spaced in time, and evidence for stepwise mass extinctions spanning intervals of 1-3 Ma. For the K/T boundary, three candidates, Popigai, Manson, and Yucatan, have been proposed as impact craters. Two distinct strata at the K/T boundary in western North America have been interpreted as evidence for two sequential impacts. If multiple impacts occurred within a time span of about 1 Ma then multiple Ir enrichments should be observed. DSDP Hole 577B on the Shatsky Plateau in the northern Pacific at K/T time is the first site. Samples contain approximately greater than 97 percent CaCO3, which exhibit clear chemical signals associated with asteroidal/cometary impact. Ir, Fe, and Cr data are presented. From the Th-normalized data, two satellite peaks below the major peak at 78 cm and 81 cm of 577B-1-4 are clearly shown. The major Ir peak (K/T boundary) is at 72 cm. Fe and Cr, from C1-like impactor ejecta fallout, also show two peaks at the same positions. For hole 738C on the southern Kerguelen Plateau, Ir values reach a peak concentration of 18 ppb in the clay layer at 96.0-96.2 cm in section 20R-5, and gradually tail off. In the sample 115 cm above the boundary, Ir concentrations have still not reached background levels. From the Ir peak downward to the lowermost sample analyzed at 102 cm, the Ir concentration is still as high as 1.7 ppb. From the Th-normalized data, we observe a small Ir/Th peak at 100-101 cm. Though this peak is within the error margin, the trend is clear. Fe and Cr exhibit the same pattern. The third case is Hole 690C on the Queen Maud Ridge. Again, the Ir/Th plot indicates the strong possibility of satellite peaks at approximately 52 cm. The main peak is at 39-40 cm. For the Stevns Klint K/T boundary layers, the stratification of trace elements appears threefold with peak concentrations in sublayers A1, A3, and B2 for different element groups, including Ir. C1 ratios for many siderophile elements found in combined layers III and IV, corresponding to layers A, B, C, and D, strongly support the impact hypothesis. Also, multiple Ir anomalies in the K/T section at Lattengebirge, Bavarian Alps are reported. Recent works on Ni-rich spinels and Ir at the K/T boundaries clearly establish cometary/asteroidal impacts at the K/T boundary. Lastly, cometary showers can explain the enhanced Ir contents over approximately a 1 Ma interval in Gubbio shales.

Liu, Y.-G.↗

The Wavelength-Dispersive Spectrometer and Its Proposed Use in the Analytical Electron Microscope

The Analytical Electron Microscope (AEM) equipped with a wavelength-dispersive spectrometer (WDS) should have the ability to resolve peaks which normally overlap in the spectra from an energy-dispersive spectrometer (EDS). With a WDS it should also be possible to measure lower concentrations of elements in thin foils due to the increased peak-to-background ratio compared with EDS. The WDS will measure X-ray from the light elements (4 less than Z less than 1O) more effectively. This paper addresses the possibility of interfacing a compact WDS with a focussing circle of approximately 4 cm to a modem AEM with a high-brightness (field emission) source of electrons.

Goldstein, Joseph I.↗