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NASA NTRS2001

Impact of Gas Heating in Inductively Coupled Plasmas

Recently it has been recognized that the neutral gas in inductively coupled plasma reactors heats up significantly during processing. The resulting gas density variations across the reactor affect reaction rates, radical densities, plasma characteristics, and uniformity within the reactor. A self-consistent model that couples the plasma generation and transport to the gas flow and heating has been developed and used to study CF4 discharges. A Langmuir probe has been used to measure radial profiles of electron density and temperature. The model predictions agree well with the experimental results. As a result of these comparisons along with the poorer performance of the model without the gas-plasma coupling, the importance of gas heating in plasma processing has been verified.

Hash, D. B.↗

NASA NTRS2001

Biogenic Methane and the Rise of Oxygen

Oxygenic photosynthesis does not make the rise of oxygen inevitable. What is required is that reductant and oxygen be separated and permanently segregated. The usual picture for Earth is that oxygenic photosynthesis split CO2 into carbon and oxygen, with the carbon buried in sediments and the oxygen mostly taken up by oxides of iron and sulfur. The relatively small atmospheric reservoir of O2 is regulated by the carbon burial rate, reaction with volcanic and metamorphic gases, and oxidation of reduced carbon released as old sediments weather. Absent from this picture is a distinction between the Archean and modern times: on average, carbon burial fluxes would have been matched by oxygen losses then as now. Separation of reductant from oxidant is only provisional. No net oxidation of the continents occurs, and so no change of diagenetic, metamorphic, or volcanic gases is expected. Nor would any change in oxidative weathering be expected. Something more than carbon burial is required to make the Archean different. The escape of hydrogen to space permanently separates the reductant from the oxidant. Hydrogen escape is widely believed to have led to the present highly oxidized states of Mars and Venus. Hydrogen escape has usually been thought small for Archaean Earth, because water vapor is cold-trapped at the troposphere and thus held to levels of a few ppmv in the stratosphere. This cold trapping renders hydrogen escape negligible. However, methane is not cold trapped, and its expected abundance in the Archaean, given low oxygen levels and a biogenic source, would have been high, probably more than 100 times present. At such levels methane would have driven geologically significant levels of hydrogen escape. Additional information is contained in the original extended abstract.

Catling, David↗

NASA NTRS2001

An Overview of Modeling Middle Atmospheric Odd Nitrogen

Odd nitrogen (N, NO, NO2, NO3, N2O5, HNO3, HO2NO2, ClONO2, and BrONO2) constituents are important components in the control of middle atmospheric ozone. Several processes lead to the production of odd nitrogen (NO(sub y)) in the middle atmosphere (stratosphere and mesosphere) including the oxidation of nitrous oxide (N2O), lightning, downflux from the thermosphere, and energetic charged particles (e.g., galactic cosmic rays, solar proton events, and energetic electron precipitation). The dominant production mechanism of NO(sub y) in the stratosphere is N2O oxidation, although other processes contribute. Mesospheric NO(sub y) is influenced by N2O oxidation, downflux from the thermosphere, and energetic charged particles. NO(sub y) is destroyed in the middle atmosphere primarily via two processes: 1) dissociation of NO to form N and O followed by N + NO yielding N2 + O to reform even nitrogen; and 2) transport to the troposphere where HNO3 can be rapidly scavenged in water droplets and rained out of the atmosphere. There are fairly significant differences among global models that predict NO(sub y). NO(sub y) has a fairly long lifetime in the stratosphere (months to years), thus disparate transport in the models probably contributes to many of these differences. Satellite and aircraft measurement provide modeling tests of the various components of NO(sub y). Although some recent reaction rate measurements have led to improvements in model/measurement agreement, significant differences do remain. This presentation will provide an overview of several proposed sources and sinks of NO(sub y) and their regions of importance. Multi-dimensional modeling results for NO(sub y) and its components with comparisons to observations will also be presented.

Jackman, Charles H.↗

NASA NTRS1995

Rotational And Rovibrational Energy Transfer In Electron Collisions With Molecules

Air flows around a hypervelocity reentry vehicle undergo dissociation, rovibrational excitation and ionization. More specifically the air, initially 80% N2 and 20% O2, in the shock layer consists of species such as N, O, N2, O2, NO, N+, O+, N+, O+, NO+ and 2 free electrons. It was pointed out in multi temperature models'' that the temperature of the rotational energy modes and the gas-kinetic translational temperature are quickly equilibrated by a few collisions and rise rapidly to high temperatures as 50000K before falling off to equilibrium value of 10000K. Contrary, the electronic and vibrational temperatures state energy distributions remain low (less than 15000K) because of the slow equilibration. Electron vibrational energy transfer is thought to play a crucial role in such a ionizing flow regime since chemical reaction rates and dissociation depend strongly on the vibrational temperatures. Modeling of these flowfields in principle require the rovibrational excitation and de-excitation cross section data for average electron energies from threshold up to several eV (leV=11605.4 K). In this lecture we focus on theoretical description of rotational effects i.e. energy transfer of electrons to molecules such that the molecular rotational (vojo goes to voj) or vibrational and rotational (v(sub 0)j(sub 0) goes to vj) states are changed. Excitation and de-excitation of electronic states was discussed in a previous talk at this conference.

Thuemmel, Helmar T.↗

NASA NTRS2001

Balanced Branching in Transcription Termination

The theory of stochastic transcription termination based on free-energy competition requires two or more reaction rates to be delicately balanced over a wide range of physical conditions. A large body of work on glasses and large molecules suggests that this should be impossible in such a large system in the absence of a new organizing principle of matter. We review the experimental literature of termination and find no evidence for such a principle but many troubling inconsistencies, most notably anomalous memory effects. These suggest that termination has a deterministic component and may conceivably be not stochastic at all. We find that a key experiment by Wilson and von Hippel allegedly refuting deterministic termination was an incorrectly analyzed regulatory effect of Mg(2+) binding.

Harrington, K. J.↗

NASA NTRS1996

Structure of Water Ice in the Solar System

Nearly all of the properties of solar system ices (chemical reaction rates, volatile retention and release, vaporization behavior, thermal conductivity, infrared spectral characteristics and the like) are a direct consequence of ice structure. However, the characterization of astrophysical ices and their laboratory analogs has typically utilized indirect measurements which yield phenomenological interpretations. When water ice is vapor-deposited at 14 K and warmed until it volatilizes in moderate vacuum, the ice undergoes a series of amorphous to amorphous and amorphous to crystalline structural transitions which we have characterized by diffraction methods. These structural transitions correlate with and underlie many phenomena observed in laboratory infrared and gas release experiments. The elucidation of the dynamic structural changes which occur in vapor-deposited water ice as a function of time, temperature and radiation history allows for the more complete interpretation of remote observations of astrophysical ices and their laboratory analogs.

Blake, David↗

NASA NTRS2002

Impacts of PSC Microphysics on Modelled Ozone Loss

Winter-long simulations of the 1999-2000 winter using a coupled microphysical/chemical model have been carried out to explore how PSC microphysics affects ozone loss. Although many models assures that water ice formation leads to denitrification, these simulations show that observed characteristics of the 1999-2000 winter can not be reproduced by such a denitrification mechanism. Instead, denitrification observations are best reproduced by a small number of particles freezing at temperatures near the nitric acid trihydration condensation point. Implications of such a mechanism for assessments of future ozone loss will be discussed. The simulations have also revealed that ozone loss during the 1999-2000 winter was sensitive to chlorine reactivation that occurred during February. Uncertainties in PSC microphysics and heterogeneous reaction rates both influence the modelled chlorine reactivation. For the 1999-2000 winter, these uncertainties have a larger effect on model ozone loss than denitrification. The role of denitrification would have increased if the Arctic vortex had persisted for a longer period.

Drdla, K.↗

NASA NTRS2002

Laboratory Astrophysics Needs of the Herschel Space Observatory

The science teams of the Herschel Space Observatory have identified a number of areas where laboratory study is required for proper interpretation of Herschel observational data. The most critical is the collection and compilation of laboratory data on spectral line frequencies, transition probabilities and energy levels for the known astrophysical atomic and molecular species in 670 to 57 micron wavelength range of Herschel. The second most critical need is the compilation of collisional excitation cross sections for the species known to dominate the energy balance in the ISM and the temperature dependent chemical reaction rates. On the theoretical front, chemical and radiative transfer models need to be prepared in advance to assess calibration and identify instrument anomalies. In the next few years there will be a need to incorporate spectroscopists and theoretical chemists into teams of astronomers so that the spectroscopic surveys planned can he properly calibrated and rapidly interpreted once the data becomes available. The science teams have also noted that the enormous prospects for molecular discovery will be greatly handicapped by the nearly complete lack of spectroscopic data for anything not already well known in the ISM. As a minimum, molecular species predicted to exist by chemical models should be subjected to detailed laboratory study to ensure conclusive detections. This has the greatest impact on any astrobiology program that might be proposed for Herschel. Without a significant amount of laboratory work in the very near future Herschel will not be prepared for many planned observations, much less addressing the open questions in molecular astrophysics.

Pearson, J. C.↗

NASA NTRS2002

Chemical Amplification with Encapsulated Reagents

Autocatalysis and chemical amplification are characteristic properties of living systems, and they give rise to behaviors such as increased sensitivity, responsiveness, and self-replication. Here we report a synthetic system in which a unique form of compartmentalization leads to nonlinear, autocatalytic behavior. The compartment is a reversibly formed capsule in which a reagent is sequestered. Reaction products displace the reagent from the capsule into solution and the reaction rate is accelerated. The resulting self-regulation is sensitive to the highly selective molecular recognition properties of the capsule.

Chen, Jian↗

NASA NTRS2003

Status of Middle Atmosphere-Climate Models: Results SPARC-GRIPS

The middle atmosphere is an important component of the climate system, primarily because of the radiative forcing of ozone. Middle atmospheric ozone can change, over long times, because of changes in the abundance of anthropogenic pollutants which catalytically destroy it, and because of the temperature sensitivity of kinetic reaction rates. There is thus a complex interaction between ozone, involving chemical and climatic mechanisms. One question of interest is how ozone will change over the next decades , as the "greenhouse-gas cooling" of the middle atmosphere increases but the concentrations of chlorine species decreases (because of policy changes). concerns the climate biases in current middle atmosphere-climate models, especially their ability to simulate the correct seasonal cycle at high latitudes, and the existence of temperature biases in the global mean. A major obstacle when addressing this question This paper will present a summary of recent results from the "GCM-Reality Intercomparison Project for SPARC" (GRIPS) initiative. A set of middle atmosphere-climate models has been compared, identifying common biases. Mechanisms for these biases are being studied in some detail, including off-line assessments of the radiation transfer codes and coordinated studies of the impacts of gravity wave drag due to sub-grid-scale processes. ensemble of models will be presented, along with numerical experiments undertaken with one or more models, designed to investigate the mechanisms at work in the atmosphere. The discussion will focus on dynamical and radiative mechanisms in the current climate, but implications for coupled ozone chemistry and the future climate will be assessed.

Pawson, Steven↗

NASA NTRS2003

Ultraviolet Radiation and Stratospheric Ozone

Ultraviolet radiation from the sun produces ozone in the stratosphere and it participates in the destruction of ozone. Absorption of solar ultraviolet radiation by ozone is the primary heating mechanism leading to the maximum in temperature at the stratopause. Variations of solar ultraviolet radiation on both the 27-day solar rotation period and the 11-year solar cycle affect ozone by several mechanisms. The temperature and ozone in the upper stratosphere respond to solar uv variations as a coupled system. An increase in uv leads to an increase in the production of ozone through the photolysis of molecular oxygen. An increase in uv leads to an increase in temperature through the heating by ozone photolysis. The increase in temperature leads to a partially-offsetting decrease in ozone through temperature-dependent reaction rate coefficients. The ozone variation modulates the heating by ozone photolysis. The increase in ozone at solar maximum enhances the uv heating. The processes are understood and supported by long-term data sets. Variation in the upper stratospheric temperatures will lead to a change in the behavior of waves propagating upward from the troposphere. Changes in the pattern of wave dissipation will lead to acceleration or deceleration of the mean flow and changes in the residual or transport circulation. This mechanism could lead to the propagation of the solar cycle uv variation from the upper stratosphere downward to the lower stratosphere. This process is not well-understood and has been the subject of an increasing number of model studies. I will review the data analyses for solar cycle and their comparison to model results.

Stolarski, R.↗

NASA NTRS2004

Solar Oscillations

Oscillations were first detected in the solar photosphere in 1962 by Leighton and students. In 1970 it was calculated that these oscillations, with a period near five minutes, were the manifestations of acoustic waves trapped in the interior. The subsequent measurements of the frequencies of global oscillation modes from the spatio-temporal power spectrum of the waves made possible the refinement of solar interior models. Over the years, increased understanding of the nuclear reaction rates, the opacity, the equation of state, convection, and gravitational settling have resulted. Mass flows shift the frequencies of modes leading to very accurate measurements of the interior rotation as a function of radius and latitude. In recent years, analogues of terrestrial seismology have led to a tomography of the interior, including measurements of global north-south flows and flow and wave speed measurements below features such as sunspots. The future of helioseismology seems bright with the approval of NASA's Solar Dynamics Observatory mission, to be launched in 2008.

Duvall, Thomas↗

NASA NTRS1993

Mass balance approaches for estimating the intestinal absorption and metabolism of peptides and analogues: theoretical development and applications

A theoretical analysis for estimating the extent of intestinal peptide and peptide analogue absorption was developed on the basis of a mass balance approach that incorporates convection, permeability, and reaction. The macroscopic mass balance analysis (MMBA) was extended to include chemical and enzymatic degradation. A microscopic mass balance analysis, a numerical approach, was also developed and the results compared to the MMBA. The mass balance equations for the fraction of a drug absorbed and reacted in the tube were derived from the general steady state mass balance in a tube: [formula: see text] where M is mass, z is the length of the tube, R is the tube radius, Pw is the intestinal wall permeability, kr is the reaction rate constant, C is the concentration of drug in the volume element over which the mass balance is taken, VL is the volume of the tube, and vz is the axial velocity of drug. The theory was first applied to the oral absorption of two tripeptide analogues, cefaclor (CCL) and cefatrizine (CZN), which degrade and dimerize in the intestine. Simulations using the mass balance equations, the experimental absorption parameters, and the literature stability rate constants yielded a mean estimated extent of CCL (250-mg dose) and CZN (1000-mg dose) absorption of 89 and 51%, respectively, which was similar to the mean extent of absorption reported in humans (90 and 50%). It was proposed previously that 15% of the CCL dose spontaneously degraded systematically; however, our simulations suggest that significant CCL degradation occurs (8 to 17%) presystemically in the intestinal lumen.(ABSTRACT TRUNCATED AT 250 WORDS).

Non-NASA Center↗

NASA NTRS2005

Lunar and Planetary Science XXXVI, Part 15

Contents include the following: Impact Metamorphism of Subsurface Organic Matter on Mars: A Potential Source for Methane and Surface Alteration. Preliminary Study of Polygonal Impact Craters in Argyre Region, Mars. Geochemistry of the Dark Veinlets in the Granitoids from the Souderfjarden Impact Structure, Finland: Preliminary Results. An Experimental Method to Estimate the Chemical Reaction Rate in Vapor Clouds: An Application to the K/T Impact. Study of the Apollo 16 Landing Site: Re-Visit as a Standard Site for the SELENE Multiband Imager. First X-Ray Observation of Lunar Farside from Hayabusa X-Ray Spectrometer. Lunar X-Ray Fluorescence Spectrometry from SELENE Lunar Polar Orbiter. Origin and Thermal History of Lithic Materials in the Begaa LL3 Chondrite. Evidence of Normal Faulting and Dike Intrusion at Valles Marineris from Pit Crater Topography. Evidence of Tharsis-Radial Dike Intrusion in Southeast Alba Patera from MOLA-based Topography of Pit Crater Chains. Are They Really Intact? Evaluation of Captured Micrometeoroid Analogs by Aerogel at the Flyby Speed of Stardust. Numerical Simulations of Impactor Penetration into Ice-Over-Water Targets. A Probable Fluid Lava Flow in the Hebes Mensa (Mars) Studied by HRSC Images. New Drill-Core Data from the Lockne Crater, Sweden: The Marine Excavation and Ejection Processes, and Post-Impact Environment. Cross-Sectional Profile of Baltis Vallis Channel on Venus: Reconstruction from Magellan SAR Brightness Data.

Source record↗

NASA NTRS2005

Using In-Situ Deposition of Metallic Thin Films on Mars to Monitor Atmospheric H20

We describe the use of a novel sensor, designed to characterize the reactive nature of the Martian atmosphere, to also characterize the instantaneous abundance of atmospheric H,O. The sensor deposits, in situ, a thin silver film onto a sapphire substrate and monitors oxidation by measuring resistance of the Ag film during both deposition and subsequent oxidation [1,2]. . The evaporation source is placed in the center of a hollow, open-ended tube. On flash heating the source, evaporated metallic silver rapidly reacts with oxidizing gases in the tube, depositing on the tube walls as a resisitive Ag oxide film. Unoxidized silver deposits over the Ag oxides, once the oxidizing gases in the vicinity of the source have been consumed. Since the ends of the tube are open, atmospheric gases in the tube cause a time delay as the evaporated silver initially reacts with the available O2, and H2O; once oxidizing gases in the tube are significantly depleted, a silver film closes the chemiresistor circuit. In principle this operation mode provides a repeatable measure of the variable H2O abundance, since O2, levels are constant in the atmosphere. To explore the utility of the instrument as an H2O sensor, predict its behavior, and identify possible failure modes, we developed a numerical model of the instrument, and exercised it for Mars conditions. The model predicts the behavior of the electrical circuit, the temperature dependence of resistivity for each component, and the resultant Joule heating. The model balances Joule heating against radiation, sensible heat loss to ambient CO2, and, latent heat loss from sublimating Ag. The flux of Ag atoms from the source is tracked continuously. In the gas phase, the number density of Ag, O2, and H2O is calculated, along with their reaction rates on collision. The model suggests that Ag substantially depletes H2O only near the center of the tube. The model supports the hypothesis that the onset of high conductivity between the A u electrodes is a function of the H2O abundance in the ambient gas, but only to a limit; when H2O abundances are buffered at or above 240K (an H2O abundance that would not have occurred on Mars), metallic Ag never deposits in excess of Ago, and the circuit does not close. A significant difference in the Mars simulation is that the Ag source sublimates more quickly, primarily because of differences in sensible heat fluxes from the source. This allows subsequent heating of the W filament used to support the Ag source. Had the originally-designed experimental sequence been carried out on Mars, the filament might have melted, making subsequent investigations impossible.

Zent, A. P.↗

NASA NTRS2004

Reformer Fuel Injector

Today's form of jet engine power comes from what is called a gas turbine engine. This engine is on average 14% efficient and emits great quantities of green house gas carbon dioxide and air pollutants, Le. nitrogen oxides and sulfur oxides. The alternate method being researched involves a reformer and a solid oxide fuel cell (SOFC). Reformers are becoming a popular area of research within the industry scale. NASA Glenn Research Center's approach is based on modifying the large aspects of industry reforming processes into a smaller jet fuel reformer. This process must not only be scaled down in size, but also decrease in weight and increase in efficiency. In comparison to today's method, the Jet A fuel reformer will be more efficient as well as reduce the amount of air pollutants discharged. The intent is to develop a 10kW process that can be used to satisfy the needs of commercial jet engines. Presently, commercial jets use Jet-A fuel, which is a kerosene based hydrocarbon fuel. Hydrocarbon fuels cannot be directly fed into a SOFC for the reason that the high temperature causes it to decompose into solid carbon and Hz. A reforming process converts fuel into hydrogen and supplies it to a fuel cell for power, as well as eliminating sulfur compounds. The SOFC produces electricity by converting H2 and CO2. The reformer contains a catalyst which is used to speed up the reaction rate and overall conversion. An outside company will perform a catalyst screening with our baseline Jet-A fuel to determine the most durable catalyst for this application. Our project team is focusing on the overall research of the reforming process. Eventually we will do a component evaluation on the different reformer designs and catalysts. The current status of the project is the completion of buildup in the test rig and check outs on all equipment and electronic signals to our data system. The objective is to test various reformer designs and catalysts in our test rig to determine the most efficient configuration to incorporate into the specific compact jet he1 reformer test rig. Additional information is included in the original extended abstract.

Suder, Jennifer L.↗

NASA NTRS2001

Hydrogen/Air Fuel Nozzle Emissions Experiments

The use of hydrogen combustion for aircraft gas turbine engines provides significant opportunities to reduce harmful exhaust emissions. Hydrogen has many advantages (no CO2 production, high reaction rates, high heating value, and future availability), along with some disadvantages (high current cost of production and storage, high volume per BTU, and an unknown safety profile when in wide use). One of the primary reasons for switching to hydrogen is the elimination of CO2 emissions. Also, with hydrogen, design challenges such as fuel coking in the fuel nozzle and particulate emissions are no longer an issue. However, because it takes place at high temperatures, hydrogen-air combustion can still produce significant levels of NOx emissions. Much of the current research into conventional hydrocarbon-fueled aircraft gas turbine combustors is focused on NOx reduction methods. The Zero CO2 Emission Technology (ZCET) hydrogen combustion project will focus on meeting the Office of Aerospace Technology goal 2 within pillar one for Global Civil Aviation reducing the emissions of future aircraft by a factor of 3 within 10 years and by a factor of 5 within 25 years. Recent advances in hydrocarbon-based gas turbine combustion components have expanded the horizons for fuel nozzle development. Both new fluid designs and manufacturing technologies have led to the development of fuel nozzles that significantly reduce aircraft emissions. The goal of the ZCET program is to mesh the current technology of Lean Direct Injection and rocket injectors to provide quick mixing, low emissions, and high-performance fuel nozzle designs. An experimental program is planned to investigate the fuel nozzle concepts in a flametube test rig. Currently, a hydrogen system is being installed in cell 23 at NASA Glenn Research Center's Research Combustion Laboratory. Testing will be conducted on a variety of fuel nozzle concepts up to combustion pressures of 350 psia and inlet air temperatures of 1200 F. Computational fluid dynamics calculations, with the Glenn developed National Combustor Code, are being performed to optimize the fuel nozzle designs.

Smith, Timothy D.↗

NASA NTRS2002

Thermal Cyclic Behavior of Thermal and Environmental Barrier Coatings Investigated Under High-Heat-Flux Conditions

Environmental barrier coatings (EBC's) have been developed to protect silicon-carbide- (SiC) based ceramic components in gas turbine engines from high-temperature environmental attack. With continuously increasing demands for significantly higher engine operating temperature, future EBC systems must be designed for both thermal and environmental protection of the engine components in combustion gases. In particular, the thermal barrier functions of EBC's become a necessity for reducing the engine-component thermal loads and chemical reaction rates, thus maintaining the required mechanical properties and durability of these components. Advances in the development of thermal and environmental barrier coatings (TBC's and EBC's, respectively) will directly impact the successful use of ceramic components in advanced engines. To develop high-performance coating systems, researchers must establish advanced test approaches. In this study, a laser high-heat-flux technique was employed to investigate the thermal cyclic behavior of TBC's and EBC's on SiC-reinforced SiC ceramic matrix composite substrates (SiC/SiC) under high thermal gradient and thermal cycling conditions. Because the laser heat flux test approach can monitor the coating's real-time thermal conductivity variations at high temperature, the coating thermal insulation performance, sintering, and delamination can all be obtained during thermal cycling tests. Plasma-sprayed yttria-stabilized zirconia (ZrO2-8 wt% Y2O3) thermal barrier and barium strontium aluminosilicate-based environmental barrier coatings (BSAS/BSAS+mullite/Si) on SiC/SiC ceramic matrix composites were investigated in this study. These coatings were laser tested in air under thermal gradients (the surface and interface temperatures were approximately 1482 and 1300 C, respectively). Some coating specimens were also subject to alternating furnace cycling (in a 90-percent water vapor environment at 1300 C) and laser thermal gradient cycling tests (in air), to investigate the water vapor effect. All cyclic tests were conducted using a 60-min hot-time temperature.

Zhu, Dongming↗