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At least 577 records · Page 32

Development of a cryogenic hydrogen maser at the NPL

A prototype Cold Hydrogen Maser (CHM) was being developed for the past year. The features of this CHM, which is designed to operate initially at 4.2 K, are the use of low loss alumina, and later sapphire, in the fabrication of the microwave cavity; possible use of superconductors for shielding; use of a cryogenic amplifier; possible coating material; and a reliable RF discharge circuit for the dissociation of hydrogen. A numerical simulation was performed to find the dimensions of the microwave cavity for the TE011 mode and the model was confirmed experimentally. The system will be used to test various wall coatings adsorbed on top of a PTFE buffer underlayer. The CHM is expected to be used as a flywheel frequency standard at the NPL with medium-term stability of one part in 10(exp 14) or better.

Mossavati, R.↗

Simulation studies for surfaces and materials strength

During this period investigations were carried out in three areas. Optimum energies and structures were estimated for single step ledges formed in the (111) surface of diamond. Binding energies of carbon atoms adsorbed on a (2x1) reconstructed Si(100) surface were calculated as a function of sub-monolayer coverages. Calculations were conducted to analyze the strain dependence of the binding energy of a carbon atom deposited on a (2x1) dimerized Si(100) surface. Results are discussed.

Halicioglu, Timur↗

Simulation studies for surfaces and materials strength

Optimum energies and structures were estimated for single step ledges formed on the diamond (111) surface. Binding energies of carbon atoms adsorbed on a (2x1) reconstructed Si(100) surface were calculated as a function of sub-monolayer coverages. Calculations were conducted to analyze the strain dependence of the binding energy of a carbon adatom deposited on a (2x1) dimerized Si(100) surface. Details and results of these studies are given as appendices.

Halicioglu, Timur↗

Fibers and materials of medical application

Efferent sorption methods of organism detoxication (by medical trend) are presented. Recently, specialists have shown their keen interest in the problem of treating exogenous and endogenous intoxications. This was stipulated by the growing production and accumulation of chemical products for industrial, agricultural, and domestic needs. To solve this problem the industrial production of carbon fibrous adsorbents was developed and implemented at NII Chimvolokno in St. Petersburg. A description of the carbon fibers is given. Also, application of modern composite materials for manufacturing compression-distraction apparatus used for setting fractured bones is described.

Fridman, L. I.↗

Mars atmosphere loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

The effects of loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the last 3.8 b.y. were examined. Sputtering is capable of efficiently removing all species from the upper atmosphere, including the light noble gases; N also is removed by photochemical processes. Due to the diffusive separation by mass above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter mass being preferentially lost. For C and O, this allows us to determine the size of nonatmospheric reservoirs that mix with the atmosphere; these reserviors can be accounted for by exchange with CO2 adsorbed in the regolith and with H2O in the polar ice deposits. Both simple analytical models and time-dependent models of the loss of volatiles from and supply to the Martian atmosphere were constructed. Both Ar and Ne require continued replenishment from outgassing over geologic time.

Jakosky, B. M.↗

Vertical transport of water in the Martian boundary layer

We are continuing our examination of the transport of H2O through the martian boundary layer, and we have written a one-dimensional numerical model of the exchange of H2O between the atmosphere and subsurface of Mars through the planetary boundary layer (PBL). Our goal is to explore the mechanisms of H2O exchange, and to elucidate the role played by the regolith in the local H2O budget. The atmospheric model includes effects of Coriolis, pressure gradient, and frictional forces for momentum, as well as radiation, sensible heat flux, and advection for heat. The model differs from Flasar and Goody by use of appropriate Viking-based physical constants and inclusion of the radiative effects of atmospheric dust. We specify the pressure gradient force or compute it from a simple slope model. The subsurface model accounts for conduction of heat and diffusion of H2O through a porous adsorbing medium in response to diurnal forcing. The model is initialized with depth-independent H2O concentrations (2 kg M(exp -3)) in the regolith, and a dry atmosphere. The model terminates when the atmospheric H2O column abundance stabilizes at 0.1 percent per sol.

Zent, Aaron P.↗

Theoretical determination of chemical rate constants using novel time-dependent methods

The work completed within the grant period 10/1/91 through 12/31/93 falls primarily in the area of reaction dynamics using both quantum and classical mechanical methodologies. Essentially four projects have been completed and have been or are in preparation of being published. The majority of time was spent in the determination of reaction rate coefficients in the area of hydrocarbon fuel combustion reactions which are relevant to NASA's High Speed Research Program (HSRP). These reaction coefficients are important in the design of novel jet engines with low NOx emissions, which through a series of catalytic reactions contribute to the deterioration of the earth's ozone layer. A second area of research studied concerned the control of chemical reactivity using ultrashort (femtosecond) laser pulses. Recent advances in pulsed-laser technologies have opened up a vast new field to be investigated both experimentally and theoretically. The photodissociation of molecules adsorbed on surfaces using novel time-independent quantum mechanical methods was a third project. And finally, using state-of-the-art, high level ab initio electronic structure methods in conjunction with accurate quantum dynamical methods, the rovibrational energy levels of a triatomic molecule with two nonhydrogen atoms (HCN) were calculated to unprecedented levels of agreement between theory and experiment.

Dateo, Christopher E.↗

The importance of environmental conditions in reflectance spectroscopy of laboratory analogs for Mars surface materials

Reflectance spectra are presented here for a variety of particulate, ferric-containing analogs to Martian soil (Fe(3+)-doped smectites and palagonites) to facilitate interpretation of remotely acquired spectra. The analog spectra were measured under differing environmental conditions to evaluate the influence of exposure history on water content and absorption features due to H2O in these samples. Each of these materials contains structural OH bonded to metal cations, adsorbed H2O, and bound H2O (either in a glass, structural site, or bound to a cation). Previous experiments involving a variety of Mars analogs have shown that the 3 micron H2O band in spectra of palagonites is more resistant to drying than the 3 micron H2O band in spectra of montmorillonites. Other experiments have shown that spectra of ferrihydrite and montmorillonites doped with ferric sulfate also contain sufficient bound H2O to retain a strong 3 micron band under dry conditions. Once the effects of the environment on bound water in clays, oxides, and salts are better understood, the hydration bands measured via reflectance spectroscopy can be used to gain information about the chemical composition and moisture content of real soil systems. Such information would be especially useful in interpreting observations of Mars where subtle spatial variations in the strengths of metal-OH and H2O absorptions have been observed in telescopic and ISM spectra. We measured bidirectional reflectance spectra of several Mars soil analogs under controlled environmental conditions to assess the effects of moisture content on the metal-OH and H2O absorptions. The samples analyzed include chemically altered montmorillonites, ferrihydrite. and palagonites from Hawaii and Iceland. Procedures for preparation of the cation-exchanged montmorillonites, ferric-salt doped montmorillonites, and ferric oxyhydroxides are described in detail elsewhere.

Bishop, J.↗

Mars atmospheric loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

We examine the effects of loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the last 3.8 b.y. Sputtering is capable of efficiently removing all species from the upper atmosphere including the light noble gases; N is removed by photochemical processes as well. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species with the lighter mass being preferentially lost. For C and O, this allows us to determine the size of nonatmospheric reservoirs that mix with the atmosphere; these reservoirs can be CO2 adsorbed in the regolith or H2O in the polar ice caps. We have constructed both simple analytical models and time-dependent models of the loss from and supply of volatiles to the Martian atmosphere.

Jakosky, B. M.↗

Simultaneous laboratory measurements of CO2 and H2O adsorption on palagonite: Implications for the Martian climate and volatile reservoir

We are measuring the simultaneous adsorption of H2O and CO2 on palagonite materials in order to improve the formulation of climate models for Mars. We report on the initial co-adsorption data. Models of the Martian climate and volatile inventory indicate that the regolith serves as one of the primary reservoirs of outgassed volatiles and that it exchanges H2O and CO2 with the atmosphere in response to changes in insolation associated with astronomical cycles. Physical adsorbate must exist on the surfaces of the cold particulates that constitute the regolith, and the size of that reservoir can be assessed through laboratory measurements of adsorption on terrestrial analogs. Many studies of the independent adsorption of H2O and CO2 on Mars analog were made and appear in the literature. Empirical expressions that relate the adsorptive coverage of each gas to the temperature of the soil and partial pressure have been derived based on the laboratory data. Numerical models incorporate these adsorption isotherms into climatic models, which predict how the adsorptive coverage of the regolith and hence, the pressure of each gas in the atmosphere will vary as the planet moves through its orbit. These models suggest that the regolith holds several tens to hundreds of millibars of CO2 and that during periods of high obliquity warming of the high-latitude regolith will result in desorption of the CO2, and a consequent increase in atmospheric pressure. At lower obliquities, the caps cool and the equator warms forcing the desorption of several tens of millibars of CO2, which is trapped into quasipermanent CO2 caps.

Zent, A. P.↗

The anaerobic degradation of organic matter in Danish coastal sediments - Iron reduction, manganese reduction, and sulfate reduction

A combination of porewater and solid phase analysis as well as a series of sediment incubations are used to quantify organic carbon oxidation by dissimilatory Fe reduction, Mn reduction, and sulfate reduction, in sediments from the Skagerrak (located off the northeast coast of Jutland, Denmark). Solid phase data are integrated with incubation results to define the zones of the various oxidation processes. At S(9), surface Mn enrichments of up to 3.5 wt pct were found, and with such a ready source of Mn, dissimilatory Mn reduction was the only significant anaerobic process of carbon oxidation in the surface 10 cm of the sediment. At S(4) and S(6), active Mn reduction occurred; however, most of the Mn reduction may have resulted from the oxidation of acid volatile sulfides and Fe(2+) rather than by a dissimilatory sulfate. Dissolved Mn(2+) was found to completely adsorb onto sediment containing fully oxidized Mn oxides.

Canfield, Donald E.↗

XPS analysis of the effect of fillers on PTFE transfer film development in sliding contacts

The development of transfer films atop steel counterfaces in contact with unfilled and bronze-filled PTFE has been studied using X-ray photoelectron spectroscopy. The sliding apparatus was contained within the vacuum of the analytical system, so the effects of the native oxide, hydrocarbon, and adsorbed gaseous surface layers of the steel upon the PTFE transfer behavior could be studied in situ. For both the filled and the unfilled PTFE, cleaner surfaces promoted greater amounts of transfer. Metal fluorides, which formed at the transfer film/counterface interface, were found solely in cases where the native oxide had been removed to expose the metallic surface prior to sliding. These fluorides also were found at clean metal/PTFE interfaces formed in the absence of frictional contact. A fraction of these fluorides resulted from irradiation damage inherent in XPS analysis. PTFE transfer films were found to build up with repeated sliding passes, by a process in which strands of transfer filled in the remaining counterface area. Under these reported test conditions, the transfer process is not expected to continue atop previously deposited transfer films. The bronze-filled composite generated greater amounts of transfer than the unfilled PTFE. The results are discussed relative to the observed increase in wear resistance imparted to PTFE by a broad range of inorganic fillers.

Blanchet, T. A.↗

Application of Ion Mobility Spectrometry (IMS) in forensic chemistry and toxicology with focus on biological matrices

The IMS (Ion Mobility Spectroscopy) instrument 'Ionscan' takes advantage of the fact that trace quantities of illicit drugs are adsorbed on dust particles on clothes, in cars and on other items of evidence. The dust particles are collected on a membrane filter by a special attachment on a vacuum cleaner. The sample is then directly inserted into the spectrometer and can be analyzed immediately. We show casework applications of a forensic chemistry and toxicology laboratory. One new application of IMS in forensic chemistry is the detection of psilocybin in dried mushrooms without any further sample preparation.

Bernhard, Werner↗

Computer simulation of astrophysical ices

Understanding the physical chemical processes which affect the structure and composition of astrophysical ices is of central importance to our understanding of the early solar system and early earth. Laboratory experiments on amorphous ice analogues of cometary ices have shown that amorphous ices exhibit a rich and complex morphology. Computer simulation results for ice deposition with the solutes Ne, CH4, and CO are presented. The relative fraction of adsorbed solutes which are subsequently ejected from the growing ice has implications on the composition of comets relative to the composition of the primitive environment in which they formed.

Wilson, M. A.↗

Collisional desorption of NO by fast O atoms

Surface-adsorbed NO figures largely in the mechanism that produces visible glow around spacecraft in low Earth orbit (LEO). In view of the potential interference to optical observations such a glow represents, we have investigated the collision-induced desorption of NO from Al, Ni, and Z306 Chemglaze-coated surfaces at 96 K by hyperthermal (8 km/s) oxygen atoms. The removal of surface NO was followed by the monitoring of the visible fluorescence of electronically excited NO2 produced through the surface-mediated reaction O + NO. A variability in collisional desorption rate with material was observed. The limited data suggest a removal efficiency of 4 to 8% of the impinging O atom flux. Implications for the atmospheric scouring of contaminants from external surfaces of LEO spacecraft are discussed.

Sonnenfroh, David M.↗

Low-temperature and low atmospheric pressure infrared reflectance spectroscopy of Mars soil analog materials

Infrared reflectance spectra of carefully selected Mars soil analog materials have been measured under low atmospheric pressures and temperatures. Chemically altered montmorillonites containing ferrihydrite and hydrated ferric sulfate complexes are examined, as well as synthetic ferrihydrate and a palagonitic soil from Haleakala, Maui. Reflectance spectra of these analog materials exhibit subtle visible to near-infrared features, which are indicative of nanophase ferric oxides or oxyhydroxides and are similar to features observed in the spectra of the bright regions of Mars. Infrared reflectance spectra of these analogs include hydration features due to structural OH, bound H2O and adsorbed H2O. The spectal character of these hydration features is highly dependent on the sample environment and on the nature of the H2O/OH in the analogs. The behavior of the hydration features near 1.9 micrometers, 2.2 micrometers, 2.7 micrometers, 3 micrometers, and 6 micrometers are reported here in spetra measured under Marslike atmospheric environment. In spectra of these analogs measured under dry Earth atmospheric conditions the 1.9-micrometer band depth is 8-17%; this band is much stonger under moist conditions. Under Marslike atmospheric conditions the 1.9-micrometer feature is broad and barely discernible (1-3% band depth) in spectra of the ferrihydrite and palagonitic soil samples. In comparable spectra of the ferric sulfate-bearing montmorillonite the 1.9-micrometer feature is also broad, but stronger (6% band depth). In the low atmospheric pressure and temperature spectra of the ferrihydrite-bearing montmorillonite this feature is sharper than the other analogs and relatively stronger (6% band depth). Although the intensity of the 3- micrometer band is weaker in spectra of each of the analogs when measured under Marslike conditions, the 3-micromter band remains a dominant feature and is especially broad in spectra of the ferrihydrite and palagonitic soil. The structural OH features observed in these materials at 2.2-2.3 micrometers and 2.27 micrometers remain largely unaffected by the environmental conditions. A shift in the Christiansen feature towards shorter wavelengths has also been observed with decreasing atmospheric pressure and temperature in the midinfrared spectra of these samples.

Bishop, Janice L.↗

Mars atmospheric loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

We examine the effects of the loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the past 3.8 billion years. Sputtering is capable of efficiently removing species from the upper atmosphere, including the light noble gases; nitrogen and oxygen are removed by photochemical processes as well. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter mass being preferentially lost. For carbon and oxygen, this allows us to determine the size of nonatmospheric reservoirs which mix with the atmosphere; these reservoirs can be CO2 adsorbed in the regolith and H2O in the polar ice caps. We have constructed both simple analytical models and time-dependent models of the loss of volatiles from and supply to the martian atmosphere. Both argon and neon require continued replenishment from outgassing over geologic time. For argon, sputtering loss explains the fractionation of (Ar-36)/(Ar-38) without requiring a distinct epoch of hydrodynamic escape (although fractionation of Xe isotopes still requires very early hydrodynamic loss). For neon, the current (Ne-22)/(Ne-20) ratio represents a balance between loss to space and continued resupply from the interior; the similarity of the ratio to the terrestrial value is coincidental. For nitrogen, the loss by both sputtering and photochemical escape would produce a fractionation of (N-15)/(N-14) larger than observed; an early, thicker carbon dioxide atmosphere could mitigate the nitrogen loss and produce the observed fractionation, as could continued outgassing of juvenile nitorgen. Based on the isotopic constraints, the total amount of carbon dioxide lost over geologic time is probably on the order of tens of millibars rather than a substantial fraction of a bar. The total loss from solar-wind-induced sputtering and photochemical escape, therefore, does not seem able to explain the loss of a putative thick, early atmosphere withput requiring formation of extensive surface carbonate deposits or other nonatmospheric reservoirs for CO2.

Jakosky, Bruce M.↗

A Real-Time Nonvolatile Residue (NVR) Monitor

New development and application of device described in "Surface-Acoustic-Wave Piezoelectric Microbalance," (LAR-14476). Active sensing element of Real-Time NVR Monitor comprises pair of piezoelectric surface-acoustic-wave resonators resonating at frequency of 200 MHz. Bare, uncoated resonator exposed to atmosphere and directly in contact with airborne volatile and nonvolatile materials leaving residues on surface. Resonant frequency of exposed resonator decreases with increasing mass of adsorbed residue; resulting beat frequency between two resonators increases with mass and serves as sensitive real-time indication of airborne contaminants or non-volatile residue.

Bowers, William D.↗