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At least 487 records · Page 27

Characteristic of Nitron for Use as a Chemical Sensor in Studies of the Upper Atmosphere

We are investigating the use of nitron as a potential chemical sensor for nitric acid and other electron deficient nitrogen oxides. Solutions of nitron in 1-propanol, toluene, and chloroform have been tested for use on a piezoelectric quartz crystal microbalance. We are testing various solvents and metal cations which can maximize the lifetime and reaction specificity of nitron so that they may be used as chemical coatings for stratospheric measurement of trace gases. Results of the work to date will be shown, and future direction discussed.

Meadows, Kapres↗

Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

Schlosser, Herbert↗

Theoretical Study of the Electronic Spectra of a Polycyclic Aromatic Hydrocarbon, Naphthalene, and its Derivatives

In order to preselect possible candidates for the origin of diffuse interstellar bands observed, semiempirical quantum mechanical method INDO/S was applied to the optical spectra of neutral, cationic, and anionic states of naphthalene and its hydrogen abstraction and addition derivatives. Comparison with experiment shows that the spectra of naphthalene and its ions were reliably predicted. The configuration interaction calculations with single-electron excitations provided reasonable excited state wavefunctions compared to ab initio calculations that included higher excitations. The degree of similarity of the predicted spectra of the hydrogen abstraction and derivatives to those of naphthalene and ions depends largely on the similarity of the it electron configurations. For the hydrogen addition derivatives, very little resemblance of the predicted spectra to naphthalene was found because of the disruption of the aromatic conjugation system. The relevance of these calculations to astrophysical issues is discussed within the context of these polycyclic aromatic hydrocarbon models. Comparing the calculated electronic energies to the Diffuse Interstellar Bands (DIBs), a list of possible candidates of naphthalene derivatives is established which provides selected candidates for a definitive test through laboratory studies.

Du, Ping↗

Carbon in The Universe: PAHs and Clusters

Following the initial demonstration of this new technique (Science 265 1686 (1994)) and its application to a series of neutral PAHs which have been proposed as condidates for the UIRs (Nature 380, 227 (1996)), we have concentrated on two major aspects of this project. 1. Developing a detailed model for infrared emission spectra of a collection of highly excited PAH molecules, in which experimental bandshapes and temperature-dependent redshifts are used in conjunction with ab initio vibrational frequencies and intensities to simulate the UIR bands. This shows that a collection of nine different cations (as large as ovalene) reproduce the UIR features better than do a collection of the corresponding neutrals, but a detailed match with the UIRs is not obtained. 2. Construction of SPIRES apparatus for the study of PAH ion emission spectra. The design of this experiment is shown and described. Unfortunately a disasterous accident occurred just as we were preparing to start the testing of the ion apparatus. A vacuum implosion occurred, destroying the liquid He cooled monochromator. It has taken us nearly one full year to reconstruct this, and we arc only now in the final testing of the new system. We expect to try the ion experiments by the end of summer.

Saykally, Richard J.↗

Sintering and Creep Behavior of Plasma-Sprayed Zirconia and Hafnia Based Thermal Barrier Coatings

The sintering and creep of plasma-sprayed ceramic thermal barrier coatings under high temperature conditions are complex phenomena. Changes in thermomechanical and thermophysical properties and in the stress response of these coating systems as a result of the sintering and creep processes are detrimental to coating thermal fatigue resistance and performance. In this paper, the sintering characteristics of ZrO2-8wt%y2O3, ZrO2-25wt%CeO2-2.5wt%Y2O3, ZrO2-6w%NiO- 9wt%Y2O3, ZrO2-6wt%Sc2O3-2wt%y2O3 and HfO2-27wt%y2O3 coating materials were investigated using dilatometry. It was found that the HfO2-Y2O3 and baseline ZrO2-Y2O3 exhibited the best sintering resistance, while the NiO-doped ZrO2-Y2O3 showed the highest shrinkage strain rates during the tests. Higher shrinkage strain rates of the coating materials were also observed when the specimens were tested in Ar+5%H2 as compared to in air. This phenomenon was attributed to an enhanced metal cation interstitial diffusion mechanism under the reducing conditions. It is proposed that increased chemical stability of coating materials will improve the material sintering resistance.

Zhu, Dongming↗

The Preparation and Structural Characterization of Three Structural Types of Gallium Compounds Derived from Gallium (II) Chloride

The three compounds Ga2Cl4(4-mepy)2 (1),[GaCl2(4-mepy)4]GaCl4x1/2(4-mepy); (2) and GaCl2(4-mepy)2(S2CNEt2); (3) (4-mepy= 4-methylpyridine) have been prepared from reactions of gallium (II) chloride in 4-methylpyridine and characterized by single-crystal X-ray analysis. Small variations in the reaction conditions for gallium(II) chloride can produce crystals with substantially different structural properties. The three compounds described here encompass a neutral gallium(II) dimer in which each gallium is four-coordinate, an ionic compound containing both anionic and cationic gallium complex ions with different coordination numbers and a neutral six-coordinate heteroleptic

Gordon, Edward M.↗

Optical Experiments With Manganese Doped Yttrium Orthoaluminate, a Potential Material for Holographic Recording and Data Storage

The YAlO3 host crystal has a distorted perovskite structure that belongs to the orthorhombic centrosymmetric Pbnm space group. The cationic sites in the structure available for Mn substitution are the relatively large strongly distorted YO12 polyhedral (Y3+ ionic radius R(sub Y) = 1.02 A) and the smaller nearly ideal AlO6 octahedra R(sub Al) = 0.53 A). Manganese may enter YAlO3 in the form of Mn2+ ions (R(sub Mn)= 0.96 A), substituting most likely Y3+ ions, and Mn3+ ions (R(sub Mn) = 0.65 A) or Mn4+ ions (R(sub Mn) = 0.53 A) substituting Al3+ ions. The latter substitution is most probable because of dimensional parameters. Point defects, which are common in YAl03, may provide the charge compensation required for substitution.

Warren, Matthew E.↗

Preparation and Dielectric Measurements of the Rare Earth Green Phases R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb)

It has been demonstrated that R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb) does not undergo significant densification unless the sintering temperatures are near the incongruent melting point or the sintering times are long. Good quality powders of Y2BaCuO(5-x) have been synthesized by using oxide raw materials or precursors such as acetates and nitrates. The acetates- and the nitrates-derived yttrium green phase resulted in finer particle sizes, acceptable dielectric properties and lower melting temperatures than those processed via oxide raw materials. The hot pressing technique has been employed to produce a dense R2BaCuO(5-x) (R=Y,Gd) substrate with satisfactory dielectric properties. Reactivity to reducing conditions, i.e. graphite die, limited the optimization of the properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO,.,,. Oxygen treatment at 950 OC has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO(5-x). Oxygen treatment at 950 C has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. The dielectric constants of the rare earth green phases R2BaCuO(5-x) were found to be low. Relaxation peaks were detected at low temperatures (T less than 150 K) and at high temperatures (150 less than T greater than 420 K). The dielectric losses and conductivities at 77 K were measured to be in the range of 10(exp -4) and 10(exp -12) (Omega-cm)(exp -1), respectively. Many parameters were found to exhibit dependencies on the rare earth cation sizes.

Gonzalez-Titman, Carlos↗

Determination of Creep Behavior of Thermal Barrier Coatings Under Laser Imposed High Thermal and Stress Gradient Conditions

A laser sintering/creep technique has been established to determine the creep behavior of thermal barrier coatings under steady-state high heat flux conditions. For a plasma sprayed zirconia-8 wt. % yttria coating, a significant primary creep strain and a low apparent creep activation energy were observed. Possible creep mechanisms involved include stress induced mechanical sliding and temperature and stress enhanced cation diffusion through the splat and grain boundaries. The elastic modulus evolution, stress response, and total accumulated creep strain variation across the ceramic coating are simulated using a finite difference approach. The modeled creep response is consistent with experimental observations.

Zhu, Dongming↗

The Kinetics of the Trimethoxyboroxine-Induced Thermal Polymerization of Phenyl Glycidyl Ether

The kinetics of the bulk thermal polymerization of phenyl glycidyl ether induced by trimethoxyboroxine were investigated. Infrared absorption spectroscopy and gel permeation chromatography were used to follow the course of polymerization, while proton and boron-2 NMR spectroscopy were used to support the kinetic model developed. The postulated mechanism involves a fast-initiated, non-stationary cationic polymerization with five elementary steps, including spontaneous and monomer transfer as well as a termination reaction. The trimethoxyboroxine was found to be incorporated into the structure of the cured polymer. Tile polymerization was followed at several temperatures and with several ratios of initial concentrations of trimethoxyboroxine to phenyl glycidyl ether.

Lopata, Eugene S.↗

Heterogeneity Determination and Purification of Commercial Hen Egg-White Lysozyme

Hen egg-white lysozyme (HEWL) is widely used as a model protein, although its purity has not been adequately characterized by modern biochemical techniques. We have identified and quantified the protein heterogeneities in three commercial HEWL preparations by sodium dodecyl sulfate polyacrylamide gel electrophoresis with enhanced silver staining, reversed-phase fast protein liquid chromatography (FPLC) and immunoblotting with comparison to authentic protein standards. Depending on the source, the contaminating proteins totalled 1-6%(w/w) and consisted of ovotransferrin, ovalbumin, HEWL dimers, and polypeptides with approximate M(sub r) of 39 and 18 kDa. Furthermore, we have obtained gram quantities of electrophoretically homogeneous [> 99.9%(w/w)] HEWL by single-step semi-preparative scale cation-exchange FPLC with a yield of about 50%. Parallel studies of crystal growth kinetics, salt repartitioning and crystal perfection with this highly purified material showed fourfold increases in the growth-step velocities and significant enhancement in the structural homogeneity of HEWL crystals.

Thomas, B. R.↗

A Preliminary Study on the Vapor/Mist Phase Lubrication of a Spur Gearbox

Organophosphates have been the primary compounds used in vapor/mist phase lubrication studies involving ferrous bearing material. Experimental results have indicated that the initial formation of an iron phosphate film on a rubbing ferrous surface, followed by the growth (by cationic diffusion) of a lubricious pyrophosphate-type coating over the iron phosphate, is the reason organophosphates work well as vapor/mist phase lubricants. Recent work, however, has shown that this mechanism leads to the depletion of surface iron atoms and to eventual lubrication failure. A new organophosphate formulation was developed which circumvents surface iron depletion. This formulation was tested by generating an iron phosphate coating on an aluminum surface. The new formulation was then used to vapor/mist phase lubricate a spur gearbox in a preliminary study.

Morales, Wilfredo↗

Microgravity Transport Phenomena Experiment (MTPE) Overview

The Microgravity Transport Phenomena Experiment (MTPE) is a fluids experiment supported by the Fundamentals in Biotechnology program in association with the Human Exploration and Development of Space (BEDS) initiative. The MTP Experiment will investigate fluid transport phenomena both in ground based experiments and in the microgravity environment. Many fluid transport processes are affected by gravity. Osmotic flux kinetics in planar membrane systems have been shown to be influenced by gravimetric orientation, either through convective mixing caused by unstably stratified fluid layers, or through a stable fluid boundary layer structure that forms in association with the membrane. Coupled transport phenomena also show gravity related effects. Coefficients associated with coupled transport processes are defined in terms of a steady state condition. Buoyancy (gravity) driven convection interferes with the attainment of steady state, and the measurement of coupled processes. The MTP Experiment measures the kinetics of molecular migration that occurs in fluids, in response to the application of various driving potentials. Three separate driving potentials may be applied to the MTP Experiment fluids, either singly or in combination. The driving potentials include chemical potential, thermal potential, and electrical potential. Two separate fluid arrangements are used to study membrane mediated and bulk fluid transport phenomena. Transport processes of interest in membrane mediated systems include diffusion, osmosis, and streaming potential. Bulk fluid processes of interest include coupled phenomena such as the Soret Effect, Dufour Effect, Donnan Effect, and thermal diffusion potential. MTP Experiments are performed in the Microgravity Transport Apparatus (MTA), an instrument that has been developed specifically for precision measurement of transport processes. Experiment fluids are contained within the MTA fluid cells, designed to create a one dimensional flow geometry of constant cross sectional area, and to facilitate fluid filling and draining operations in microgravity. The fluid cells may be used singly for bulk solutions, or in a Stokes diaphragm configuration to investigate membrane mediated phenomena. Thermal and electrical driving potentials are applied to the experiment fluids through boundary plates located at the ends of the fluid cells. In the ground based instrument, two constant temperature baths circulate through reservoirs adjacent to the boundary plates, and establish the thermal environment within the fluid cells. The boundary plates also serve as electrodes for measurement and application of electrical potentials. The Fluid Manipulation System associated with the MTA is a computer controlled system that enables storage and transfer of experiment fluids during on orbit operations. The system is used to automatically initiate experiments and manipulate fluids by orchestrating pump and valve operations through scripted sequences. Unique technologies are incorporated in the MTA for measurement of fluid properties. Volumetric Flow Sensors have been developed for precision measurement of total fluid volume contained within the fluid cells over time. This data is most useful for measuring the kinetics of osmosis, where fluid is transported from one fluid cell to another through a semipermeable membrane. The MicroSensor Array has been designed to perform in situ measurement of several important fluid parameters, providing simultaneous measurement of solution composition at multiple locations within the experiment fluids. Micromachined sensors and interface electronics have been developed to measure temperature, electrical conductivity, pH, cation activity, and anion activity. The Profile Refractometer uses a laser optical system to directly image the fluid Index of Refraction profile that exists along the MTA fluid cell axis. A video system acquires images of the RI profile over time, and records the transport kinetics that occur upon application of chemical, thermal, or electrical driving potentials. Image processing algorithms have been developed to analyze the refractometer images on a pixel by pixel basis, calibrating and scaling the measured Index of Refraction profile to correlated solution properties of interest such as density, concentration, and temperature. Additional software has been developed to compile the processed images into a three dimensional matrix that contains fluid composition data as a function of experiment time and position in the fluid cell. These data are combined with data from the other sensor systems, and analyzed in the context of transport coefficients associated with the various transport phenomena. Analysis protocols have been developed to measure the transient kinetics, and steady state distribution of fluid components that occur in response to the applied driving potentials. The results are expressed in terms of effective transport coefficients. Experiments have been performed using a variety of solutes, and results generated are that are in agreement with published transport coefficient values.

Mason, Larry W.↗

Permeation Resistance of Chlorinated Polyethylene Against Hydrazine Fuels

The permeation resistance of chlorinated polyethylene (CPE) used in chemical protective clothing against the aerospace fuels hydrazine, monomethylhydrazine (MMH), and uns-dimethylhydrazine (UDMH) was determined by measuring breakthrough times and time-averaged vapor transmission rates using an ASTM F 739 permeation cell. Two exposure scenarios were simulated: a 2 hour (h) fuel vapor exposure, and a liquid fuel "splash" followed by a 2 h vapor exposure. To simulate internal suit pressure during operation, a positive differential pressure of 0.3 in. water (75 Pa) on the collection side of the permeation apparatus was used. Breakthrough was observed after exposure to liquid MMH, and to vapor and liquid UDMH. No breakthrough was observed after exposure to vapor and liquid hydrazine, or vapor MMH. A model was then used to calculate propellant concentrations inside a totally encapsulating chemical protective suit based on the ASTM permeation data obtained in the present study. Concentrations were calculated under conditions of fixed vapor transmission rate, variable breathing air flow rate, and variable splash exposure area. Calculations showed that the maximum allowable permeation rates of hydrazine fuels through CPE were of the order of 0.05 to 0.08 ng sq cm/min for encapsulating suits with low breathing air flow rates (of the order of 5 scfm or 140 L/min). Above these permeation rates, the 10 parts per billion (ppb) threshold limit value time - weighted average could be exceeded for chemical protective suits having a CPE torso. To evaluate suit performance at ppb level concentrations, use of a sensitive analytical method such as cation exchange high performance liquid chromatography with amperometric detection was found to be essential.

Waller, J. M.↗

The Thermal Emission Imaging System (THEMIS) Instrument for the Mars 2001 Orbiter

The primary objective of the Thermal Emission Imaging System (THEMIS) on the Mars Surveyor '01 Orbiter is to study the composition of the Martian surface at high spatial resolution. THEMIS will map the surface mineralogy using multi-spectral thermal infrared images in 8 spectral bands from 6.5 to 14.5 microns. In addition, a band centered at 15 microns will be used to map atmospheric temperatures and provide an important aid in separating the surface and atmospheric components. The entire planet will be mapped at 100 m resolution within the available data volume using a multi-spectral, rather than hyperspectral, imaging approach. THEMIS will also acquire 20 m resolution visible images in up to 5 spectral bands using a replica of the Mars 98 Orbiter (MARCI) and Lander (MARDI) cameras. Over 15,000 panchromatic (3,000 5-color), 20 x 20 km images will be acquired for morphology studies and landing site selection. The thermal-infrared spectral region contains the fundamental vibrational absorption bands of most minerals which provide diagnostic information on mineral composition. All geologic materials, including carbonates, hydrothermal silica, sulfates, phosphates, hydroxides, silicates, and oxides have strong absorptions in the 6.5-14.5 micron region. Silica and carbonates, which are key diagnostic minerals in thermal spring deposits, are readily identified using thermal-IR spectra. In addition, the ability to identify all minerals allows the presence of aqueous minerals to be interpreted in the proper geologic context. An extensive suite of studies over the past 35 years has demonstrated the utility of vibrational spectroscopy for the quantitative determination of mineralogy and petrology. The fundamental vibrations within different anion groups, such as C03, S04, P04, and SiO4, produce unique, well separated spectral bands that allow carbonates, sulfates, phosphates, silicates, oxides, and hydroxides to be readily identified. Additional stretching and bending modes involving major cations, such as Mg, Fe, Ca, and Na, allow Further mineral identification, such as the excellent discriminability of minerals within the silicate and carbonate groups.

Christensen, P. R.↗

The Role of Calcium in the Response of Osteoblasts to Mechanical Stimulation

A major biomedical concern in the exploration and development of space is the rapid loss of bone associated with extended periods of spaceflight. Mineral content, bone formation, matrix protein production and total body calcium are all reduced during long-term periods of weightlessness. These effects of weightlessness appears to be due to decreases in the anabolic function of osteoblasts and osteocytes rather than changes in the resorptive activity of osteoclasts. Conversely, subjecting the skeleton to exogenous mechanical loading increases matrix protein synthesis and bone formation rate, a process which also appears mediated through osteogenic cells. Osteoblasts have been shown to respond to a number of types of mechanical stimulation. However recently we have demonstrated that osteoblasts respond to fluid shear, but not physiologic levels of mechanical strain, with increases in expression of the matrix protein, osteopontin. We have also shown similar responses in other markers for the anabolic response in bone. The expression of the early response gene, c-fos, and the inducible-isoform of the prostaglandin synthetic enzyme, cyclooygenase-2 (COX-2), both increase rapidly in response to fluid shear, but not strain. How osteoblasts and osteocytes perceive mechanical stimuli and convert this stimulus into a biochemical event within the cell is still unknown. However, examination of the cellular events following mechanical stimulation indicate that two of the earliest responses are a rapid increase in intracellular calcium ([Ca(2+)](sub i)) and a reorganization of the actin cytoskeleton. The increase in [Ca(2+)](sub i) is dependent on the presence of extracellular Ca(2+), suggesting the activation of membrane Ca(2+) channel. We have previously characterized a mechanosensitive, cation-selective channel (MSCC) in osteoblast-like clonal cells, which we postulate is important in this early response to mechanical loading. Using an antisense oligodeoxynucleotide strategy, we have tentatively identified this channel as an isoform of the alc subunit of the dihydropyridine-sensitive, voltage sensitive Ca(2+) channel (VSCC). However, a major component in this mechanically induced rise in [Ca(2+)](sub i) is the release of Ca(2+) from intracellular stores. The actin cytoskeleton also rapidly responds to fluid shear with an increase in stress fiber formation and a realignment of the cell parallel to the direction of flow. To ascertain whether these two observations are related and how they effect shear-induced gene expression, we examined the role of Ca(2+) channels and intracellular Ca(2+) release on cytoskeletal reorganization and the resultant increases in the expression and production of c-fos and COX-2 in response to fluid shear.

Duncan, R. L.↗

Solid Phase Luminescence of Several Rare Earth Ions on Ion-Exchange Films

The development and characterization of a novel ion-exchange film for solid-phase fluorometry and phosphorimetry is reported. This new cation-exchange material is suitable for spectroscopic applications in the ultraviolet and visible regions. It is advantageous because it, as a single entity, is easily recovered from solution and mounted in the spectrofluorometers. After preconcentration on the film, the luminescence intensity of lanthanide ions is several orders of magnitude greater than that of the corresponding solution, depending on the volume of solution and the amount of film. This procedure allows emission spectral measurements and determination of lanthanide ions at solution concentrations of < 5 (micro)g/L. The film may be stored for subsequent reuse or as a permanent record of the analysis. The major drawback to the use of the film is slow uptake of analyte due to diffusion limitations.

Tanner, Stephen P.↗

Light-Activated Amino Acid Transport Systems in Halobacterium halobium Envelope Vesicles: Role of Chemical and Electrical Gradients

The accumulation of 20 commonly occurring L-amino acids by cell envelope vesicles of Halobacterium halobium, in response to light-induced membrane potential and an artificially created sodium gradient, has been studied. Nineteen of these amino acids are actively accumulated under either or both of these conditions. Glutamate is unique in that its uptake is driven only by a chemical gradient for sodium. Amino acid concentrations at half-maximal uptake rates (Km) and maximal transport rates (V(sub max) have been determined for the uptake of all 19 amino acids. The transport systems have been partially characterized with respect to groups of amino acids transported by common carriers, cation effects, and relative response to the electrical and chemical components of the sodium gradient, the driving forces for uptake. The data presented clearly show that the carrier systems, which are responsible for uptake of individual amino acids, are as variable in their properties as those found in other organisms, i. e., some are highly specific for individual amino acids, some transport several amino acids competitively, some are activated by a chemical gradient of sodium only, and some function also in the complete absence of such a gradient. For all amino acids, Na(+) and K(+) are both required for maximal rate of uptake. The carriers for L-leucine and L-histidine are symmetrical in that these amino acids are transported in both directions across the vesicle membrane. It is suggested that coupling of substrate transport to metabolic energy via transient ionic gradients may be a general phenomenon in procaryotes.

MacDonald, Russell E.↗