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At least 415 records · Page 23

Effect of Surface-active Additives on Physical Properties of Slurries of Vapor-process Magnesium

The presence of 3 to 5 percent surface-active additive gave the lowest Brookfield apparent viscosity, plastic viscosity, and yield value that were obtained for slurry fuels containing approximately 50 percent vapor-process magnesium in JP-1 fuel. The slurries settled little and were easily remixed. A polyoxyethylene dodecyl alcohol was the most effective of 13 additives tested in reducing the Brookfield apparent viscosity and the yield value of the slurry. The seven most effective additives all had a hydroxyl group plus an ester or polyoxethylene group in the molecule. The densities of some of the slurries were measured.

Pinns, Murray L↗

Si-29 NMR spectroscopy of naturally-shocked quartz from Meteor Crater, Arizona: Correlation to Kieffer's classification scheme

We have applied solid state Si-29 nuclear magnetic resonance (NMR) spectroscopy to five naturally-shocked Coconino Sandstone samples from Meteor Crater, Arizona, with the goal of examining possible correlations between NMR spectral characteristics and shock level. This work follows our observation of a strong correlation between the width of a Si-29 resonance and peak shock pressure for experimentally shocked quartz powders. The peak width increase is due to the shock-induced formation of amorphous silica, which increases as a function of shock pressure over the range that we studied (7.5 to 22 GPa). The Coconino Sandstone spectra are in excellent agreement with the classification scheme of Kieffer in terms of presence and approximate abundances of quartz, coesite, stishovite, and glass. We also observe a new resonance in two moderately shocked samples that we have tentatively identified with silicon in tetrahedra with one hydroxyl group in a densified form of amorphous silica.

Boslough, M. B.↗

Bright soil units on Mars determined from ISM imaging spectrometer data

The lithology of bright Martian soil provides evidence for chemical and physical processes that have modified the planet's surface. Data from the ISM imaging spectrometer, which observed much of the equatorial region at a spatial resolution of approximately 22 km, cover the NIR wavelength range critical to ascertaining the presence and abundance of Fe-containing phases, hydroxylated silicates, and H2O in the bright soil. ISM data previously have revealed spatial variations in depth of the 3.0-microns H2O absorption suggesting differences in water content, a weak absorption at 2.2 microns indicative of metal-OH in phyllosilicate, and variations in the 1-micron Fe absorption indicative of differences in Fe mineralogy. This paper summarizes first results of a systematic investigation of spectral heterogeneity in bright soils observed by ISM. At least seven 'units' with distinctive properties were discriminated. Comparison of their spatial distributions with Viking data shows that they generally correspond with previously recognized morphologic, color, and thermal features. These correspondences and the units' spectral attributes provide evidence for lithologic differences between the soils in different geologic settings.

Murchie, Scott↗

Detection of tropospheric OH and HO2 by laser-induced fluorescence at low pressure using the 308nm excitation of OH

Laser-induced fluorescence (LIF) spectroscopy is a highly sensitive method for the direct in situ measurement of hydroxyl concentrations in the atmosphere. Its sensitivity and selectivity relies on the intense discrete UV-absorption lines of OH which are strongest around 282nm and 308nm. We have developed a LIF-instrument based on the low-pressure experiment (FAGE). However, we use 308nm instead of 282nm as excitation wavelength for OH, a concept that is also pursued by other groups. One advantage of the longer excitation wavelength is the higher detection sensitivity due to the about 6 times larger effective OH-fluorescence cross-section. Moreover, the O3/H2O-interference (OH self-generation by the laser) is about a factor of 200 smaller at 308nm than at 282nm. This keeps the interference level well below the projected detection limit of 10(exp 5) OH/cm(exp 3). Atmospheric HO2-radicals are detected by chemical conversion of HO2 into OH with NO.

Hofzumahaus, Andreas↗

Tropospheric HO2 determination by FAGE

In the present work, HO2 is determined by FAGE, a method which employs low-pressure laser-excited fluorescence to observe the hydroxyl radical HO, using chemical modulation to distinguish the desired signal from the background. In the HO2 determination mode, NO is added to the low-pressure flowing sample, converting HO2 to HO.

Hard, Thomas M.↗

Solventless, curable fluid oligomeric systems for high performance microwave, acoustical and mechanical applications

While establishing the basis for a 'Technology 2000' product plan several years ago we plugged in the usual factors contributing toward product success: price/performance justifiable; profitable, warranting high quality maintenance, enhancement, and specific property improvement; narrow inventory requirements; and raw material integrable backwards with easily variable properties (molecular weight, functionality, and isomer control). We resolved this by selecting radical functional, low molecular weight polybutadiene liquid polymers. Encouraged by the need for solid rocket binders, several companies embarked on various perceptions of binder performance requirements over four decades ago. Initially dominated by progress of liquid polysulfides, soon a few settled primarily upon polybutadiene based binders. Such an approach in a few instances was exploited quite viably with a series of functional group terminated liquid polybutadienes: hydroxyl, mercaptan, carboxyl, vinyl, and amine. Good results are obtained for oligomers, liquid polymers, and their hybrids. The only significant limits on compounded products has been solvent resistance and oxidative sensitivity, unless sufficient proportion of sulfide or nitrile moiety is incorporated. For convenience, they have been grouped under the trademarks Nylane, Seamax, Oligomax, and Castomax.

Lefave, G. M.↗

Martian spectral units derived from ISM imaging spectrometer data

Based on results of the Viking mission, the soil layer of Mars has been thought to be fairly homogeneous and to consist of a mixture of as few as two components, a 'dark gray' basaltic material and a 'bright red' altered material. However, near-infrared reflectance spectra measured recently both telescopically and from spacecraft indicate compositional heterogeneity beyond what can be explained by just two components. In particular, data from the ISM imaging spectrometer, which observed much of the equatorial region at a spatial resolution of approximately 22 km, indicate spatial differences in the presence and abundance of Fe-containing phases, hydroxylated silicates, and H2O. The ISM data was used to define, characterize, and map soil 'units' based on their spectral properties. The spatial distribution of these 'units' were compared to morphologic, visible color, and thermal inertia features recognized in Viking data.

Murchie, S.↗

A quick look method of detecting water of hydration in small solar system bodies

The action of aqueous alteration of the near-subsurface material on asteroids and probably some satellites in the Solar System constitutes part of the formation history of the Solar System. The C-class asteroids (and subclasses B, G, and F) were initially believed to have undergone aqueous alteration based on their low albedos and neutral broadband visible and near-infrared colors. These spectra exhibit a sharp drop at wavelengths shorter than 0.55 microns due to a strong ferric oxide intervalence change transfer transition. This IVCT comprises multiple absorptions that are not uniquely indicative of phyllosilicates, but rather are present in the spectrum of any object containing Fe(2+) and Fe(3+) in its surface material. A definitive indication of aqueous alteration came when the broad IR absorption feature having a minimum near 3.0 microns indicative of structural hydroxyl (OH) and interlayer and and absorbed water in phyllosilicates was identified in the IR photometry of many C-class asteroids. Additional mineralogical compositional evidence of aqueously-altered asteroids has come as the result of high SNR narrowband spectrophotometry in the visible and near-infrared spectral regions taken using a CCD/spectrograph combination. An absorption feature centered at 0.7 microns indicative of an Fe(2+) - Fe(3+) charge transfer transition in oxidized iron in phyllosilicates in spectra of some low-albedo asteroids, especially C and G class, and CM2 carbonaceous chondrite meteorites was identified in the CCD spectra. The correlation and covariance of the 0.7-micron and 3.0-micron features were examined by comparing observations of asteroids common to both the CCD reflectance spectra and the 3.0-micron multicolor photometry data sets. Thirty-one pairs of observations were included in this training group. The results of the statistical study indicate that with a 95% confidence level, 84% of the objects observed either having or not having the 0.7-micron feature will correspondingly have the 3.0-micron water of hydration feature.

Vilas, F.↗

Estimates of the changes in tropospheric chemistry which result from human activity and their dependence on NO(x) emissions and model resolution

As a consequence of the non-linear behavior of the chemistry of the atmosphere and because of the short lifetime of nitrogen oxides (NO(x)), two-dimensional models do not give an adequate description of the production and destruction rates of NO(x) and their effects on the distributions of the concentration of ozone and hydroxyl radical. In this study, we use a three-dimensional model to evaluate the contribution of increasing NO(x) emissions from industrial activity and biomass burning to changes in the chemical composition of the troposphere. By comparing results obtained from longitudinally-uniform and longitudinally-varying emissions of NO(x), we demonstrate that the geographical representation of the NO(x) emissions is crucial in simulating tropospheric chemistry.

Kanakidou, Maria↗

Quantitative remote sensing of ammonium minerals, Cedar Mountains, Esmeralda County, Nevada

Mineral-bound ammonium (NH4+) was discovered by the U.S. Geological Survey in the southern Cedar Mountains of Esmeralda County, Nevada in 1989. At 10 km in length, this site is 100 times larger than any previously known occurrence in volcanic rocks. The ammonium occurs in two hydrothermally altered, crystal-rich rhyolitic tuff units of Oligocene age, and is both structurally and stratigraphically controlled. This research uses Advanced Visible/Infrared Imaging Spectrometer (AVIRIS) data to quantitatively map the mineral-bound ammonium (buddingtonite) concentration in the altered volcanic rocks. Naturally occurring mineral-bound ammonium is fairly rare; however, it has been found to occur in gold-bearing hydrothermal deposits. Because of this association, it is thought that ammonium may be a useful too in exploration for gold and other metal deposits. Mineral-bound ammonium is produced when an ammonium ion (NH4+) replaces the alkali cation site (usually K+) in the crystal structure of silicate minerals such as feldspars, micas and clays. Buddingtonite is an ammonium feldspar. The ammonium originates in buried organic plant matter and is transported to the host rock by hydrothermal fluids. Ammonium alteration does not produce visible changes in the rock, and it is barely detectable with standard x-ray diffraction methods. It is clearly identified, however, by absorption features in short wave-infrared (SWIR) wavelengths (2.0 - 2.5 micrometers). The ammonium absorption features are believed to be caused by N-H vibrational modes and are analogous to hydroxyl (O-H) vibrational modes, only shifted slightly in wavelength. Buddingtonite absorption features in the near- and SWIR lie at 1.56, 2.02 and 2.12 micrometers. The feature at 2.12 micrometer is the strongest of the three and is the only one used in this study. The southern Cedar Mountains are sparsely vegetated and are an ideal site for a remote sensing study.

Baugh, William M.↗

Effects of biomass burning on summertime nonmethane hydrocarbon concentrations in the Canadian wetlands

Approximately 900 whole air samples were collected and assayed for selected C2-C10 hydrocarbons and seven halocarbons during the 5-week Arctic Boundary Layer Expedition (ABLE) 3B conducted in eastern Canadian wetland areas. In more than half of the 46 vertical profiles flown, enhanced nonmethane hydrocarbon (NMHC) concentrations attributable to plumes from Canadian forest fires were observed. Urban plumes, also enhanced in many NMHCs, were separately identified by their high correlation with elevated levels of perchloroethene. Emission factors relative to ethane were determined for 21 hydrocarbons released from Canadian biomass burning. Using these data for ethane, ethyne, propane, n-butane, and carbon monoxide enhancements from the literature, global emissions of these four NMHCs were estimated. Because of its very short atmospheric lifetime and its below detection limit background mixing ratio, 1,3-butadiene is an excellent indicator of recent combustion. No statistically significant emissions of nitrous oxide, isoprene, or CFC 12 were observed in the biomass-burning plumes encountered during ABLE 3B. The presence of the short-lived biogenically emitted isoprene at altitudes as high as 3000 m implies that mixing within the planetary boundary layer (PBL) was rapid. Although background levels of the longer-lived NMHCs in this Canadian region increase during the fire season, isoprene still dominated local hydroxyl radical photochemistry within the PBL except in the immediate vicinity of active fires. The average biomass-burning emission ratios for hydrocarbons from an active fire sampled within minutes of combustion were, relative to ethane, ethene, 2.45; ethyne 0.57; propane, 0.25; propene, 0.73; propyne, 0.06; n-butane, 0.09; i-butane, 0.01; 1-butene, 0.14; cis-2-butene, 0.02; trans-2-butene, 0.03; i-butylene, 0.07; 1,3-butadiene, 0.12; n-pentane, 0.05; i-pentane, 0.03; 1-pentene, 0.06; n-hexane, 0.05; 1-hexene, 0.07; benzene, 0.37; toluene, 0.16.

Blake, D. R.↗

High-resolution Fourier transform spectroscopy of the Meinel system of OH

The infrared spectrum of the hydroxyl radical OH, between 1850 and 9000/cm has been measured with a Fourier transform spectrometer. The source, a hydrogen-ozone diffusion flame, was designed to study the excitation of rotation-vibration levels of the OH Meinel bands under conditions similar to those in the upper atmosphere which produce the nighttime OH airglow emission. Twenty-three bands were observed: nine bands in the Delta upsilon = 1 sequence, nine bands in the Delta upsilon = 2 sequence, and five bands in the Delta upsilon = 3 sequence. A global nonlinear least-squares fit of 1696 lines yielded molecular parameters with a standard deviation of 0.003/cm. Term values are computed, and transition frequencies in the Delta upsilon = 3, 4, 5, 6 sequences in the near-infrared are predicted.

Abrams, Mark C.↗

Stratospheric OH measurements with a far-infrared limb observing spectrometer

The Far-Infrared Limb Observing Spectrometer (FILOS) is an instrument designed to measure the hydroxyl radical (OH) and other chemical species in the upper atmosphere using limb emission in the far-infrared region of the spectrum. FILOS uses three Fabry-Perot etalons in series to obtain high spectral resolution near 101/cm and 118/cm. The instrument concept, calibration, and atmospheric measurements are discussed.

Pickett, H. M.↗

Chemically anomalous, pre-accretionally irradiated grains in interplanetary dust -- interstellar grains?

Ultrafine-grained matrix is a unique and fundamental building block of chondritic porous (CP) interplanetary dust particles. Most IDPs so far determined to be of cometary origin belong to the CP class. The matrix in CP IDPs is not homogeneous but rather a loose mixture of discrete single crystals (e.g., olivine, pyroxene, Fe sulfides) and polyphase grains. The petrographic diversity observed among the polyphase grains suggest that they were formed under variable physiochemical conditions. One particular class of polyphase grains are a dominant component in cometary IDPs. Although their occurrence is well documented, the terminology used to describe them is confused. They have been called many names. Here they are simply called GEMS (Glass with Embedded Metal and Sulfides). The bulk compositions of GEMS are within a factor of 3 chondritic (solar) for all major elements except C. Quantitative thin-film X-ray (EDS) analyses have shown that GEMS are systematically depleted in Mg and Si, enriched in S, Fe, and Ni, and stoichiometrically enriched in O. Electron energy-loss spectroscopy (EELS) suggests that the excess O is present as hydroxyl (-OH) groups. These same chemical 'anomalies' were observed in solar-wind-irradiated amorphous rims on the surfaces of IDPs, suggesting that the compositions of GEMS reflect prior exposure to ionizing radiation. In order to test this hypothesis, a sample of Allende (CV3) matrix was exposed to proton flux. Radiation-damaged amorphous rims on olivine and pyroxene crystals in the Allende sample were found to be depleted in Mg and Ca, enriched in S, Fe, and Ni, and stoichiometrically enriched in O. Thus, the compositions of GEMS are indeed consistent with exposure to ionizing radiation. This study suggests that chemical as well as isotopic anomalies may be used to identify presolar interstellar grains in primitive meteoritic materials.

Bradley, J. P.↗

The nanosphere iron mineral(s) in Mars soil

A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.

Banin, A.↗

Measurement of tropospheric OH and HO2 by laser-induced fluorescence at low pressure

The hydroxyl radical (OH) is the primary oxidant in the atmosphere, responsible for many photochemical reactions that affect both regional air quality and global climate change. Because of its high reactivity, abundances of OH in the troposphere are less than 1 part per trillion by volume (pptv) and thus difficult to measure accurately. This paper describes an instrument for the sensitive detection of OH in the troposphere using low-pressure laser-induced fluorescence. Ambient air is expanded into a low pressure detection chamber, and OH is both excited and detected using the A(sup 2) Epsilon(+)(v prime = 0) yields X(sup 2)Pi(v double prime = 0) transition near 308 nm. An injector upstream of the detection axis allows for the addition of reagent NO to convert ambient HO2 to OH using the fast reaction HO2 + NO yields OH + NO2. Using recent advances in laser and detector technologies, this prototype instrument is able to detect less than 1 x 10(exp 5) molecules/cu cm (0.004 pptv) of OH with an integration time of 30 s with negligible interferences.

Stevens, P. S.↗

Design and development of an all-solid-state laser unit for microgravity combustion applications

The laser-induced fluorescence (LIF) technique is a sensitive and noninvasive method for imaging of flames and for monitoring of temperature and the presence of transient molecular species in flames. Our research effort has two major objectives: (1) to use LIF to study the fundamentals of microgravity combustion via spectroscopic characterization of free radicals, and (2) to design and develop an all-solid-state portable laser unit for combustion studies in a microgravity environment. Well-characterized free radicals, namely hydroxyl (OH) and methoxy (CH3O), have analytically convenient bands that can be laser-excited in the 280-298 nm spectral region with the newly discovered solid-state tunable laser, which is based on the LiCaAIF6:Ce3+(LiCAF:Ce) single crystal pumped by the quadrupled (266 nm) output of a Q-switched YAG:Nd laser. The 266 nm YAG radiation (of about 10 mJ pulse energy) was split into two beams of about equal intensity, one used for photolysis of the free radical precursor and the other used for pumping the laser crystal. Tunability of the LiCAF:Ce laser was provided by a step-motor-driven Littrow-mounted diffraction grating. Laser excitation spectra of the CH3O radical was recorded in the 291.5-296.5 nm region with 0.15 cm(exp -1) resolution. Laboratory experiments have thus successfully shown that the idea of using the LiCAF:Ce laser as a dual-purpose photolysis and excitation source can pay rich dividends and that such a laser can be the center piece of an all-solid-state portable device that can be used for routine analytical investigations of microgravity combustion phenomena.

Kamal, Mohammed M.↗

The Imaging Spectrometric Observatory for the ATLAS 1 mission

The Imaging Spectrometric Observatory (ISO) was flown on the ATLAS 1 mission and was enormously successful, providing a baseline database on the coupled stratospheric, mesospheric, thermospheric, and ionospheric regions. Specific ISO accomplishments include measurements of the hydroxyl radical, studies of the global ionosphere, retrieval of the concentrations of neutral species from the ISO data, studies of mesospheric oxygen emissions, retrieval of mesospheric O from oxygen emissions, studies of the OH Meinel bands and the search for the Herzberg III bands, search for metallic species, studies of thermospheric nitric oxide, auroral study of molecular nitrogen emissions, and studies of thermospheric species. Apart from participation in the data analysis, the primary post-flight responsibility of Marshall Space Flight Center was the delivery of the final post mission dataset. Support provided by the University of Alabama in Huntsville is described.

Torr, Douglas G.↗