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At least 91 records · Page 5

Molybdenum Valence in Basaltic Silicate Melts: Effects of Temperature and Pressure

The metal-silicate partitioning behavior of molybdenum has been used as a test for equilibrium core formation hypotheses [for example, 1-6]. However, current models that apply experimental data to equilibrium core-mantle differentiation infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Molybdenum, a multi-valent element with a valence transition near the fO2 of interest for core formation (approx.IW-2) will be sensitive to changes in fO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo(6+) can be either octahedrally or tetrahedrally coordinated. Here we present X-ray absorption near edge structure (XANES) measurements of Mo valence in basaltic run products at a range of P, T, and fO2 and further quantify the valence transition of Mo.

Danielson, L. R.↗

Kinetics and mechanism of the oxidation of S(IV) by ozone in aqueous solution with particular reference to SO2 conversion in nonurban tropospheric clouds

Results are presented from a laboratory study of the kinetics of the S(IV)-O3 reaction in aqueous solution, including measurements of the effects of UV radiation, dissolved transition metals, and an antioxidant (hydroquinone) on the rate. On the basis of the results, relative rates of S(IV) conversion by O3 in tropospheric cloud water are compared with those predicted for H2O2 and for O2. The reaction mechanism is discussed, with an outline given of the elements of a possible reaction scheme. Application of the rate constants obtained to SO2 conversion in cloud water predicts conversion rates by ozone to be competitive with those by H2O2 at pH above about 4.5 and to dominate at pH above about 5.5. It is pointed out that since these pH's are typical for nonurban tropospheric cloud water, ozone is a potentially important contributor to the overall oxidative conversion of SO2 to sulfate in the nonurban troposphere.

Maahs, H. G.↗

An Approach to Processable Polyimides

The use of polymer matrix composites (PMC's) in aircraft engines can lead to substantial weight savings over metals. This weight reduction correlates into better fuel economy, increased speed, and increased passenger load. Typically, high performance PMC's possess high thermal-oxidative stabilities (TOS) and high glass transition temperatures (Tg's) to withstand temperatures up to 316 C (600 F). One of the leading high temperature resins system available today is PMR-15 (Polymerization of Monomeric Reactants, MW=1500). This thermosetting polyimide utilizes addition curing through polymer endcaps which enables hand lay-up processing of carbon fiber composite parts with low void contents. However, the large amount of hand labor raises manufacturing costs and prohibits the use of PMR-15 in many aerospace applications. Resin Transfer Molding (RTM) provides an economical alternative, but it requires a melt Viscosity of less than 10(exp 3) centipoise (cP). This is much lower than the minimum melt viscosity of PMR-15 (about 10(exp 6) cP). To improve the processability of polyimides, the polymer backbone can be modified by incorporating flexible linkages, such as branching. bulky pendant groups, kinked structures, and twisted or non-coplanar moietes . The focus of this paper will be the introduction of non-coplanar biaryls into the PMR polyimide backbone to increase processability while maintaining high temperature performance.

Gariepy, Christopher A.↗

Experimental partitioning of Zr, Ti, and Nb between silicate liquid and a complex noble metal alloy and the partitioning of Ti between perovskite and platinum metal

El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.

Jurewicz, Stephen R.↗

Modeling of Carbon Nanotube Schottky Barrier Reduction for Holes in Air

A model is proposed for the previously reported lower Schottky barrier for holes Phi(sub Bh) in air than in vacuum at a metallic electrode - semiconducting carbon nanotube (CNT) junction. We consider that there is a transition region between the electrode and the CNT, and an appreciable potential can drop there. The role of the oxidation is to increase this potential drop with negatively charged oxygen molecules on the CNT, leading to lower Phi(sub Bh) after oxidation. The mechanism prevails in both p- and n-CNTs, and the model consistently explains the key experimental findings.

Yamada, Toshishige↗

Earth's Early Biosphere and the Biogeochemical Carbon Cycle

Our biosphere has altered the global environment principally by influencing the chemistry of those elements most important for life, e g., C, N, S, O, P and transition metals (e.g., Fe and Mn). The coupling of oxygenic photosynthesis with the burial in sediments of photosynthetic organic matter, and with the escape of H2 to space, has increased the state of oxidation of the Oceans and atmosphere. It has also created highly reduced conditions within sedimentary rocks that have also extensively affected the geochemistry of several elements. The decline of volcanism during Earth's history reduced the flow of reduced chemical species that reacted with photosynthetically produced O2. The long-term net accumulation of photosynthetic O2 via biogeochemical processes has profoundly influenced our atmosphere and biosphere, as evidenced by the O2 levels required for algae, multicellular life and certain modem aerobic bacteria to exist. When our biosphere developed photosynthesis, it tapped into an energy resource that was much larger than the energy available from oxidation-reduction reactions associated with weathering and hydrothermal activity. Today, hydrothermal sources deliver globally (0.13-1.1)x10(exp l2) mol yr(sup -1) of reduced S, Fe(2+), Mn(2+), H2 and CH4; this is estimated to sustain at most about (0.2-2)xl0(exp 12)mol C yr(sup -1) of organic carbon production by chemautotrophic microorganisms. In contrast, global photosynthetic productivity is estimated to be 9000x10(exp 12) mol C yr(sup -1). Thus, even though global thermal fluxes were greater in the distant geologic past than today, the onset of oxygenic photosynthesis probably increased global organic productivity by some two or more orders of magnitude. This enormous productivity materialized principally because oxygenic photosynthesizers unleashed a virtually unlimited supply of reduced H that forever freed life from its sole dependence upon abiotic sources of reducing power such as hydrothermal emanations and weathering. Communities sustained by oxygenic photosynthesis apparently thrived wherever supplies of sunlight, moisture and nutrients were sufficient. Prior to the development of oxygenic photosynthesis, the net global effect of the ancient global biosphere was to facilitate chemical equilibrium between reduced species from thermal activity and weathering and more oxidized constituents in the surface environment. But even this ancient biosphere might have been globally pervasive. The global geothermal heat flow was substantially higher during Earth's first billion years, and thus reduced chemical species might have persisted in sunlit aquatic environments. Perhaps the substantial decline in thermal activity between 4000 and 3000 Ma created a driver for oxygenic photosynthesis to develop.

DesMarais, David↗

Fischer-Tropsch Catalyst for Aviation Fuel Production

As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

deLaRee, Ana B.↗

Fischer-Tropsch Catalyst for Aviation Fuel Production

As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to nonpetroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

DeLaRee, Ana B.↗

Electronic absorption spectra of lunar minerals

Techniques for obtaining information on the crystal chemistry of transition-metal ions from measurement of the electronic absorption spectra of lunar minerals are reviewed along with the theory of spectral interpretation. Typical polarized absorption spectra are examined for lunar pyroxenes, pyroxferroite, olivine, and plagioclase feldspars. Oxidation states of Fe, Ti, and Cr in lunar minerals are discussed, and conditions under which they crystallized are considered. It is shown how information on the gross mineralogy and petrology of different regions of the moon's surface may be extracted from remote reflectivity measurements of that surface.

Vaughan, D. J.↗

The Effect of Hydrogen Annealing and Sulfur Content on the Oxidation Resistance of PWA 1480

For many decades the dramatic effect of trace amounts of reactive elements on alumina and chromia scale adhesion has been recognized and widely studied. Although various theories have been used to account for such behavior, the connection between scale adhesion and sulfur segregation was initially reported by Smeggil et al. This study found strong surface segregation of sulfur from very low levels in the bulk which could then be curtailed by the addition of reactive elements. It was assumed that the reactive elements, which are strong sulfide formers, acted by getting sulfur in the bulk thus precluding sulfur segregation and weakening of the oxide-metal bond. Subsequent studies confirmed that adhesion could be produced by reducing the sulfur impurity level, without reactive elements. The understanding of this phenomenon has been applied to modern single crystal superalloys, where the addition of Y, although very effective, is problematic. Also problematic is definition of the level of sulfur that is acceptable and below which no further adhesion benefit is reached. Published works have indicated a broad transition defined by various materials and oxidation tests. The present study describes the oxidation behavior of one superalloy (PWA 1480) as a function of various sulfur contents produced by hydrogen annealing for various temperatures, times, and sample thicknesses. The purpose is to define more precisely a criterion for adhesion based on total sulfur reservoir and segregation potential.

Smialek, James L.↗

Compatibility Studies of Hydrogen Peroxide and a New Hypergolic Fuel Blend

Several preliminary materials compatibility studies have been conducted to determine the practicality of a new hypergolic fuel system. Hypergolic fuel ignites spontaneously as the oxidizer decomposes and releases energy in the presence of the fuel. The bipropellant system tested consists of high-test hydrogen peroxide (HTP) and a liquid fuel blend consisting of a hydrocarbon fuel, an ignition enhancer and a transition metal catalyst. In order for further testing of the new fuel blend to take place, some basic materials compatibility and HTP decomposition studies must be accomplished. The thermal decomposition rate of HTP was tested using gas evolution and isothermal microcalorimetry (IMC). Materials were analyzed for compatibility with hydrogen peroxide including a study of the affect welding has on stainless steel elemental composition and its relation to HTP decomposition. Compatibility studies of valve materials in the fuel blend were performed to determine the corrosion resistance of the materials.

Baldridge, Jennifer↗

Potential Health Impacts, Treatments, and Countermeasures of Martian Dust on Future Human Space Exploration

The challenges of human space exploration produce some of humanity’s greatest technological and scientific advances, not excluding innovations in medicine. The microgravity environment causes a whole host of physiological changes, and exposure to dust on the Moon caused considerable pulmonary distress to astronauts during the Apollo missions. As the National Aeronautics and Space Administration (NASA)and other space organizations prepare for long duration exploration missions to Mars, the hazards and consequences of the Martian surface need to be accounted for. This review investigates how substances analogous to the hazardous components of Martian dust have caused disease in people on Earth. Because of the small grain size of Martian dust, dust on Mars is more likely to cause lung irritation, absorb into the bloodstream, and lead to diseases in astronauts. Toxic components of Martian dust to astronaut health include perchlorates, silica, nanophase iron oxides, and gypsum in addition to trace amounts of toxic metals whose abundances are debated: chromium, beryllium, arsenic, and cadmium. Predicted effects of dust exposure ranges from asymptomatic to life threatening, with many substances being carcinogenic and most damage impacting the pulmonary system. The longer transit time for astronauts to return home makes the operations of performing emergency medical treatment more difficult and increases both the likelihood and consequences of developing chronic disease. Exposure mitigation needs to be prioritized; however, supplements may be taken to prevent disease from breakthrough exposures and treatment regimens could lessen morbidity and mortality. Treatments and equipment need to be carefully thought out and transported with the astronauts to be prepared for all possible scenarios.

Justin L Wang↗

Understanding Microbial Contributions to Planetary Atmosphere

Should our search of distant, extrasolar planetary atmospheres encounter evidence of life, that evidence will most likely be the gaseous products of microorganisms. Our biosphere was exclusively microbial for over 80 percent of its history and, even today, microbes strongly influence atmospheric composition. Life's greatest environmental impact arises from its capacity for harvesting energy and creating organic matter. Microorganisms catalyze the equilibration of C, S and transition metal species at temperatures where such reactions can be very slow in the absence of life. Sunlight has been harvested through photosynthesis to create enormous energy reservoirs that exist in the form of coexisting reservoirs of reduced, organic C and S stored in Earth's crust, and highly oxidized species (oxygen, sulfate and ferric iron) stored in the crust, oceans and atmosphere. Our civilization taps that storehouse of energy by burning fossil fuels. As astrobiologists, we identify the chemical consequences of distant biospheres as expressed in the atmospheres of their planets. Our approach must recognize that planets, biospheres and atmospheres evolve and change. For example, a tectonically more active early Earth hosted a thermophilic, non-photosynthetic biosphere and a mildly reducing, carbon dioxide-rich and oxygen-poor atmosphere. Microorganisms acquired energy by consuming hydrogen and sulfide and producing a broad array of reduced C and S gases, most notably, methane. Later, diverse types of bacterial photosynthesis developed that enhanced productivity but were incapable of splitting water to produce oxygen. Later, but still prior to 2.6 billion years ago, oxygenic photosynthesis developed. We can expect to encounter distant biospheres that represent various stages of evolution and that coexist with atmospheres ranging from mildly reducing to oxidizing compositions. Accordinaly, we must be prepared to interpret a broad range of atmospheric compositions, all containing signatures of life. Remarkably little is known about the composition of our own earlier atmosphere, particularly prior to the rise of oxygen levels some 2.0 to 2.2 billion years ago. Thus, field and laboratory observations and theoretical simulations should be conducted to examine the relationships between the structure and function of microbial ecosystems and their gaseous products. Ecosystems that are analogs of our ancient biosphere (e.g., based upon chemosynthesis or non-oxygenic photosynthesis, thermophilic and subsurface communities, etc.) should be included. Because key environmental parameters such as temperature and levels of hydrogen, carbon dioxide and oxygen varied during planetary evolution, their consequences for microbial ecosystems should be explored.

DesMarais, David J.↗

Electronic spectroscopy of diatomic molecules

This article provides an overview of the principal computational approaches and their accuracy for the study of electronic spectroscopy of diatomic molecules. We include a number of examples from our work that illustrate the range of application. We show how full configuration interaction benchmark calculations were instrumental in improving the understanding of the computational requirements for obtaining accurate results for diatomic spectroscopy. With this understanding it is now possible to compute radiative lifetimes accurate to within 10% for systems involving first- and second-row atoms. We consider the determination of the infrared vibrational transition probabilities for the ground states of SiO and NO, based on a globally accurate dipole moment function. We show how we were able to assign the a(sup "5)II state of CO as the upper state in the recently observed emission bands of CO in an Ar matrix. We next discuss the assignment of the photoelectron detachment spectra of NO and the alkali oxide negative ions. We then present several examples illustrating the state-of-the-art in determining radiative lifetimes for valence-valence and valence-Rydberg transitions. We next compare the molecular spectroscopy of the valence isoelectronic B2, Al2, and AlB molecules. The final examples consider systems involving transition metal atoms, which illustrate the difficulty in describing states with different numbers of d electrons.

Partridge, Harry↗

Behavior of the Si/SiO2 interface observed by Fowler-Nordheim tunneling

Thin-oxide (40-50 A) metal oxide semiconductor (MOS) structures are shown to exhibit, before large levels of electron tunnel injection, the near-ideal behavior predicted for a uniform trapezoidal barrier with thick-oxide properties. The oscillatory field dependence caused by electron-wave interference at the Si/SiO2 interface suggests an abrupt, one-monolayer barrier transition (approximately 2.5 A) consistent with earlier work. After tunnel injection of 10 to the 17th - 5 x 10 to the 18th electrons/sq cm, the barrier undergoes appreciable degradation, leading to enhanced tunneling conductance. Reproducible behavior is observed among different samples. This effect is found to be consistent with the generation of positive states in the region of the oxide near the Si/SiO2 interface (less than 20 A), where the tunneling electrons emerge into the oxide conduction band.

Maserjian, J.↗

NASA Tech Briefs, August 2005

Topics include: Hidden Identification on Parts: Magnetic Machine-Readable Matrix Symbols; System for Processing Coded OFDM Under Doppler and Fading; Multipurpose Hyperspectral Imaging System; Magnetic-Flux-Compensated Voltage Divider; High-Performance Satellite/Terrestrial-Network Gateway; Internet-Based System for Voice Communication With the ISS; Stripline/Microstrip Transition in Multilayer Circuit Board; Dual-Band Feed for a Microwave Reflector Antenna; Quadratic Programming for Allocating Control Effort; Range Process Simulation Tool; Simulator of Space Communication Networks; Computing Q-D Relationships for Storage of Rocket Fuels; Contour Error Map Algorithm; Portfolio Analysis Tool; Glass Frit Filters for Collecting Metal Oxide Nanoparticles; Anhydrous Proton-Conducting Membranes for Fuel Cells; Portable Electron-Beam Free-Form Fabrication System; Miniature Laboratory for Detecting Sparse Biomolecules; Multicompartment Liquid-Cooling/Warming Protective Garments; Laser Metrology for an Optical-Path-Length Modulator; PCM Passive Cooling System Containing Active Subsystems; Automated Electrostatics Environmental Chamber; Estimating Aeroheating of a 3D Body Using a 2D Flow Solver; Artificial Immune System for Recognizing Patterns; Computing the Thermodynamic State of a Cryogenic Fluid; Safety and Mission Assurance Performance Metric; Magnetic Control of Concentration Gradient in Microgravity; Avionics for a Small Robotic Inspection Spacecraft; and Simulation of Dynamics of a Flexible Miniature Airplane.

Source record↗

Surface plasmon dispersion analysis in the metal-oxide-metal tunnel diode

A detailed model of surface plasmon dispersion in the metal-oxide-metal tunnel diode is presented in order to clarify the spectral emission from this diode. The model predicts the location of the spectral peaks and the emission between the peaks by considering the effects of retardation on the surface plasmon. A nonradiative mode is found to play a major role in the transition from the visible to UV peaks in the diode spectra.

Donohue, J. F.↗

Correlation of normal and superconducting properties and unified approach to the description of high Tc oxides

We present a unified approach based on the Fermi liquid picture which allows us to describe the normal as well as the superconducting properties of the doped cuprates. The theory that is presented is for the doped compounds which are metallic. One can distinguish two interrelated, but nevertheless, different directions in the physics of high T(sub c): one involving the problem of carrier doping and the transition to the metallic state, and the second being the description of the metallic state. It is important that this metallic phase undergoes the transition into the superconducting state; as a result, our analysis is directly related to the origin of high T(sub c). We are using a quasi-2D Fermi liquid model to estimate the fundamental parameters of these very interesting materials. We find that this description is able to describe these materials and also that phonons and plasmons play a major role in the mechanism of high T(sub c).

Kresin, V. Z.↗