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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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NASA NTRS2002

Tropospheric Trace Gas Interactions with Aerosols

Tropospheric aerosols are of considerable environmental importance. They modify the radiative budget of Earth by scattering and absorbing radiation, and by providing nuclei for cloud formation. Additionally, they provide surfaces for heterogeneous and multiphase reactions that affect tropospheric chemistry. For example, Dentener and Crutzen (1993) showed that reactions of N2O5 and NO3 with sulfate aerosols may significantly alter the tropospheric concentrations of NO(x), O3, and OH by converting NOx to HNO3 which is rapidly removed by precipitation. Zhang et al. (1994) assumed these same reactions would occur on dust aerosols and showed that dust outbreaks may reduce NO(x) levels by up to 50%. Dentener et al. (1996) studied the possible effect of reactions on dust on sulfate, nitrate, and O3 concentration. Heterogeneous and multiphase reactions on aerosols may also perturb the sulfur cycle the chlorine cycle and the bromine cycle. Because these reactions can release free chlorine and free bromine they might lead to the destruction of ozone in the marine boundary layer that may be important to include in models of tropospheric chemistry. The goal of our proposed work is to examine the role of heterogeneous and multiphase reactions in the tropospheric cycles of reactive nitrogen and sulfur.

Penner, Joyce E.↗
NASA NTRS2023

Arctic Tropospheric Ozone: Assessment of Current Knowledge and Model Performance

As the third most important greenhouse gas (GHG) after carbon dioxide (CO2) and methane (CH4), tropospheric ozone (O3) is also an air pollutant causing damage to human health and ecosystems. This study brings together recent research on observations and modeling of tropospheric O3 in the Arctic, a rapidly warming and sensitive environment. At different locations in the Arctic, the observed surface O3 seasonal cycles are quite different. Coastal Arctic locations, for example, have a minimum in the springtime due to O3 depletion events resulting from surface bromine chemistry. In contrast, other Arctic locations have a maximum in the spring. The 12 state-of-the-art models used in this study lack the surface halogen chemistry needed to simulate coastal Arctic surface O3 depletion in the springtime; however, the multi-model median (MMM) has accurate seasonal cycles at non-coastal Arctic locations. There is a large amount of variability among models, which has been previously reported, and we show that there continues to be no convergence among models or improved accuracy in simulating tropospheric O3 and its precursor species. The MMM underestimates Arctic surface O3 by 5 % to 15 % depending on the location. The vertical distribution of tropospheric O3 is studied from recent ozonesonde measurements and the models. The models are highly variable, simulating free-tropospheric O3 within a range of ±50 % depending on the model and the altitude. The MMM performs best, within ±8 % for most locations and seasons. However, nearly all models overestimate O3 near the tropopause (∼300 hPa or ∼8 km), likely due to ongoing issues with underestimating the altitude of the tropopause and excessive downward transport of stratospheric O3 at high latitudes. For example, the MMM is biased high by about 20 % at Eureka. Observed and simulated O3 precursors (CO, NOx, and reservoir PAN) are evaluated throughout the troposphere. Models underestimate wintertime CO everywhere, likely due to a combination of underestimating CO emissions and possibly overestimating OH. Throughout the vertical profile (compared to aircraft measurements), the MMM underestimates both CO and NOx but overestimates PAN. Perhaps as a result of competing deficiencies, the MMM O3 matches the observed O3 reasonably well. Our findings suggest that despite model updates over the last decade, model results are as highly variable as ever and have not increased in accuracy for representing Arctic tropospheric O3.

Arctic↗
NASA NTRS1994

Dimethylsulfide oxidation over the tropical South Atlantic: OH and other oxidants

The general course of events in the formation of a marine cloud begins with the emission of species which can eventually serve as nuclei around which water can condense to form a cloud droplet. In remote marine regions, cloud condensation nuclei (CCN) are primarily composed of sulfate, in either its acid or ammonium salt form. Most sulfate in these regions is the product of atmospheric oxidation of dimethyl sulfide (DMS), a reduced sulfur gas that is released by phytoplankton at the ocean surface. Therefore, in order to effectively quantify the links in the cloud-formation cycle, one must begin with a well-defined description of the atmospheric chemistry of DMS. The intent of this project has been to initiate development of a comprehensive model of the chemistry and dynamics responsible for the formation of clouds in the remote marine boundary layer. The primary tool in this work has been the Global/Regional Atmospheric Chemistry Event Simulator (GRACES), a global atmospheric chemistry model, which is under development within the Atmospheric Chemistry and Dynamics Branch of NASA-Ames Research Center. In this effort, GRACES was used to explore the first chemical link between DMS and sulfate by modeling the diurnal variation of DMS.

Hemming, Brooke L.↗
NASA NTRSDate not supplied

Modeling and Analysis of Stirling Power Convertors

Modeling and Analysis of Stirling Power Convertors Luis A. Rodriguez1 Steven M. Geng, Terry V. Reid, Scott D. Wilson NASA Glenn Research Center, Cleveland, OH, 44135, USA NASA Glenn’s Thermal Energy Conversion Branch is supporting the development of the next generation free-piston Stirling power convertors. American Superconductor (AMSC) and Sunpower Inc. are the two firms under contract to develop the Flexure Isotope Stirling Convertor (FISC) and the Sunpower Robust Stirling Convertor (SRSC), respectively. To comprehend and forecast convertor performance, Sage, ANSYS® Maxwell, and ANSYS® Fluent were used to model the Stirling thermodynamic cycle, alternator electromagnetics, and piston and displacer dynamics. I. Introduction Stirling convertors are being developed by NASA as a potential steady source of electrical power for NASA’s future scientific space missions. Currently, NASA Glenn Research Center has two corporations under contract, American Superconductor (AMSC) and Sunpower Inc., for the development of the next generation of free-piston Stirling convertors for dynamic radioisotope power systems. AMSC is developing the Flexure Isotope Stirling Convertor (FISC), which uses flexures to prevent side motion and rubbing of the piston. Similarly, Sunpower Inc, is developing the Sunpower Robust Stirling Convertor (SRSC). The SRSC uses gas bearings to prevent radial contact of the moving piston. As convertor development continues, it is increasingly important to understand and predict the interactions of components in the system, how they respond to one another, and how they perform as a response to changes in operating conditions. A suitable and enlightening way to demonstrate and foresee these interactions is with the use of accurate modeling software. Sage, ANSYS® Maxwell, and ANSYS® Fluent are the current modeling tools used by NASA to analytically determine convertor performance. Sage is a one-dimensional object-oriented commercial software package used for modeling and optimizing Stirling convertors for Dynamic Radioisotope Power Systems (DRPS) and it is one of the most accurate Stirling convertor codes in use by NASA. This code is the successor to GLIMPS (Globally-Implicit Stirling Cycle Simulation) and GLOP (GLIMPS Optimization) software created by Gedeon Associates [1]. Model input parameters are typically material/gas type, component physical dimensions, temperatures, frequency, charge pressure, and number of time/space nodes. Sage is used to model both the FISC’s and SRSC’s Stirling cycle thermodynamics and piston/displacer dynamics. Performance maps were created and analyzed for both power systems to better understand the relationship between the following conditions: cold-end temperature, hot-end temperature, piston/displacer amplitudes, pressure drop, and thermal input power. The synergy between these conditions will help determine parameter sensitivity. ANSYS® Maxwell was used to create a three-dimensional (3-D) axisymmetric model for both FISC and SRSC alternators. The significant physical components included in each model are the magnets, magnet carrier, outer/inner laminations, and the coil. Inputs to the model are piston amplitude, piston frequency, alternator load, coil resistance, tuning capacitance, and specific material properties. The alternator models calculate terminal voltage, current, piston/current phase, voltage/current phase, coil inductance, terminal power and efficiency. The RI2 losses, core (hysteresis and eddy) losses, and magnet/can eddy losses are also a part of the final results. ANSYS® Fluent is used to build 3-D computational fluid dynamic (CFD) models to examine the Stirling cycle thermodynamics for both the FISC and SRSC systems. Three-dimensional Computer Aided Design (CAD) models were used to create the physical components of each convertor. Steady-state simulations were conducted for hardware testing, prediction of environmental losses during testing, and generation of radiation look-up tables. The model inputs to the aforementioned analysis are the material properties and boundary thermal conditions. The steady-state model calculates temperature and heat flow distributions. Transient 3-D calculations were also part of the CFD analysis. In this study a physically reduced version of the FISC is used to obtain a prediction of available engine power. For the gas bearing SRSC, the transient effort is used to obtain a prediction of bearing pad performance and its sensitivity to micro-channel geometric variation. The model inputs to the transient simulations are the piston amplitude, displacer amplitude, frequency, displacer/piston phase angle, dynamic deforming CFD grid, temperature boundary conditions, and user defined files describing motion profile of piston/displacer. The results of the model are temperature distributions, heat distributions, and PV power produced at pre-determined conditions.

Luis A Rodriguez↗
NASA NTRS2004

Fabrication of MEMS-Based Microshutter Arrays for Optical Transmission Selection

A MEMS-based programmable aperture mask is under development at the NASA Goddard Space Flight Center. Termed the Microshutter (u-shutter) Array, the device will be used to control the transmission of light, with both high efficiency and contrast, to a multi-object spectrometer on the James Webb Space Telescope. Fabrication of the p-shutter array employs several novel designs and processing techniques. The current generation of micro-shutters consists of 128x64 pixel arrays with unit cell dimensions of 100x200 microns. Shutters are patterned in silicon nitride and sit on a 100 micron silicon frame that is DRIE etched below each shutter. The front and back sides of the device are shown. A magnetic cobalt-iron alloy patterned on top of the shutter allows it to be actuated 90 degrees out-of-plane, into the frame, by an external magnetic field. An electrode on the shutter and a vertical electrode on the sidewall of the frame, approximately 90pm deep, allow them to be electrostatically latched in their rotated position. The vertical electrode is deposited and patterned on the backside of the frame in a single step using a directionally controlled evaporation. Individual addressing of shutters for electrostatic latching is accomplished via a crosspoint addressing scheme, with no on-chip active components. A portion of an array with shutters in the open, latched, and closed positions is shown. Light loss at shutter edges is minimized by an overhanging aluminum light-shield that is anchored to the frame. A photoresist sacrificial layer is used to raise the light-shield up and over the 2 micron gap that surrounds each pixel. After completion, arrays are subjected to life cycle, environmental and optical testing. Fabricated devices have survived 10(exp 6) actuation cycles at both room and cryogenic temperatures and a 14g rms launch-simulation test. Optical testing has shown contrast measurements between open and closed shutters up to 10000:1.

Lynch, Bernard A.↗
NASA NTRS2022

Improved Global Wetland Carbon Isotopic Signatures Support Post-2006 Microbial Methane Emission Increase

Atmospheric concentrations of methane, a powerful greenhouse gas, have strongly increased since 2007. Measurements of stable carbon isotopes of methane can constrain emissions if the isotopic compositions are known; however, isotopic compositions of methane emissions from wetlands are poorly constrained despite their importance. Here, we use a process-based biogeochemistry model to calculate the stable carbon isotopic composition of global wetland methane emissions. We estimate a mean global signature of −61.3 ± 0.7‰ and find that tropical wetland emissions are enriched by ~11‰ relative to boreal wetlands. Our model shows improved resolution of regional, latitudinal and global variations in isotopic composition of wetland emissions. Atmospheric simulation scenarios with the improved wetland isotopic composition suggest that increases in atmospheric methane since 2007 are attributable to rising microbial emissions. Our findings substantially reduce uncertainty in the stable carbon isotopic composition of methane emissions from wetlands and improve understanding of the global methane budget.

Methane↗
NASA NTRS1998

The Influences of Airmass Histories on Radical Species During POLARIS

The POLARIS mission focused on understanding the processes associated with the decrease of polar stratospheric ozone from spring to fall at high latitudes. This decrease is linked primarily to in situ photochemical destruction by reactive nitrogen species, NO and NO2, which also control other catalytic loss cycles. Steady state models have been used to test photochemistry and radical behavior but are not always adequate in simulating radical species observations. In some cases, air mass history can be important and trajectory models give an improved simulation of the radical species. Trajectory chemistry models, however, still consistently underestimate NO and NO2 abundances compared to measurements along the ER-2 flight track. The Goddard chemistry on trajectory model has been used to test updated rate constants for NO2 + OH, NO2 + O and OH + HNO3, key reactions that affect NO and NO2 abundances. We present comparisons between the modified Goddard chemistry on trajectory model, the JPL steady state model and observations from selected flights.

Pierson, James M.↗
NASA NTRS2020

Durability of YSZ Coated Ti2AlC in 1300 °C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300 °C for 500 h. A 160 µm thick yttria stabilized zirconia (YSZ) coating was applied to a Ti2AlC MAX phase bar sample by plasma spray physical vapor deposition (PS-PVD) and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No thermal barrier coating (TBC) spallation or recession was observed, only a 2.4 mg/cm2 mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111)flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to equilibrium teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21 to 23 μm under the heated YSZ face and ~13 to 15 μm on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and partial etching of the underlying Al2O3 scale by volatile hydroxides formed in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample via creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions, with thermal expansion matching playing a key role. The purpose of this study was to demonstrate long term durability of YSZ/MAX phase system in aggressive high temperature burner rig testing. MAX phases have been keenly studied because of their unique crystal structure and intriguing properties (Refs. 1 and 2). Having Mn+1(Al,Si)(C,N)n general composition, they are defined as ceramics, but possess unusual desirable attributes such as high conductivity, thermal shock resistance, easy machinability, and deformation tolerance. The mechanical properties derive from weak M-(Al,Si) bonding in the basal plane that leads to sliding and kinking in preference to catastrophic crack growth. Like most ceramics they are phase stable at high temperatures, generally up to 1500 °C. High temperature oxidation resistance is excellent for alumina-forming Ti3AlC2, Ti2AlC, and Cr2AlC, as reviewed by Tallman, et al. (Ref. 3). Compatibility with α-Al2O3 scales is further enhanced in cyclic exposures by a close matching of thermal expansion coefficients, (Ref. 4) i.e., (~9.3, 10.2, 11.3×10–6/K for Al2O3, Ti2AlC, and YSZ, to be discussed). Turbine environments generally contain 10 percent water vapor in the combustion gases, therefore moisture effects can be a concern for some materials (Ref. 5). Furnace tests of MAX phases in high temperature steam generally showed little effect on Al2O3 scale growth (Ref. 6). However, high velocity and high pressure gas can influence scale losses by the formation of volatile reaction products, such as TiO(OH)2 and Al(OH)3 (Refs. 7 to 10). This phenomenon had been discussed for 1100 to 1300 °C high pressure burner rig tests of Ti2AlC (Ref. 11). A single cubic growth rate parameter kcubic was measurably lower than comparable furnace TGA data, but it could be matched reasonably well if corrected for a slight volatility term. In general, a two-parameter cubic-linear growth-volatility law was believed to apply. Corresponding scale volatility loss rates, directly measured at 1300 °C on a pre-oxidized sample, were moderate (0.012 mg/cm2/h) and largely attributed to removal of the initial TiO2 transient scale. A related CH4 burner study of high purity Cr2AlC MAX phase demonstrated 1200 °C durability after 500 rapid (5 min. heat and 2 min. cool) thermal shock cycling (29 h hot time) (Ref. 12). Heating and cooling rates were ~1000 and 500 °C per minute, with a gas velocity of 5 m/s, producing a 75 °C/mm gradient. A 7 μm Al2O3 surface scale and a 13 μm Cr7C3 depletion zone formed with no signs of failure. No evidence of scale volatility was evident, although weight change was not provided, the velocity was moderate, and the total hot time was not extensive. The same high gradient BRT was used to produce 1400 °C surface temperatures for a YSZ/Cr2AlC/IN738 system in the first study of MAX phases used as bond coats for thermal barrier coatings (TBC) (Ref. 25). Here TBC failure was reported after 745 cycles, with only a 1.5 μm Al2O3 scale entrained within a porous, Cr7C3 bondcoat depletion phase. YSZ thermal barrier coatings have been considered to be a compatible complement to Al-MAX phases because of thermal expansion matching and extremely low volatility in water vapor. Initial studies showed superior oxidative stability up to 1300 °C, for long times (at least 500 h) for Ti2AlC substrates and less (268 h) for Cr2AlC, while withstanding large alumina TGO scale thickness (~35 to 40 μm) (Refs. 13 and 14). By comparison, typical superalloy systems can only survive 1150 °C maximum interface temperatures for extended periods, with a maximum sustained TGO below 10 μm (Ref. 15). High temperature SiC based systems are known to form slow-growing SiO2 scales. But these are subject to rate enhancement and volatile Si(OH)4 products in the presence of water vapor, as described comprehensively by Opila, et al. (Refs. 5, 16 to 19). Net weight losses are generally observed in high velocity, high pressure burner rig studies (e.g., 0.084 mg/cm2/h at 1300 °C) (Ref. 20). Furthermore, the loss rates have been shown from chemical physics to scale with v1/2 and pH2O 2 (Ref. 16). Low activity, moisture-resistant environmental barrier coatings (EBC), such as rare earth silicates, are needed to prevent substrate recession under turbine conditions (Refs. 21 to 23).

Smialek, James L.↗
NASA NTRS2000

The Distribution of Carbon Monoxide in the GOCART Model

Carbon monoxide (CO) is an important trace gas because it is a significant source of tropospheric Ozone (O3) as well as a major sink for atmospheric hydroxyl radical (OH). The distribution of CO is set by a balance between the emissions, transport, and chemical processes in the atmosphere. The Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model is used to simulate the atmospheric distribution of CO. The GOCART model is driven by the assimilated meteorological data from the Goddard Earth Observing System Data Assimilation System (GEOS DAS) in an off-line mode. We study the distribution of CO on three time scales: (1) day to day fluctuation produced by the synoptic waves; (2) seasonal changes due to the annual cycle of CO sources and sinks; and (3) interannual variability induced by dynamics. Comparison of model results with ground based and remote sensing measurements will also be presented.

Fan, Xiaobiao↗
NASA NTRS1981

Enhancement of peptide bond formation by polyribonucleotides on clay surfaces in fluctuating environments

The selective effects of polyribonucleotides on the formation of glycine peptide bonds in glycine on clay surfaces are investigated as a model for a template mechanism for the effects of polynucleotides on peptide bond formation. Free oligoglycine yields were determined for the cycling reaction of glycine in the presence and absence of clay and polyribonucleotides or polydeoxyribonucleotides. The polyribonucleotides are observed to lead to increases of up to fourfold increases in oligoglycine formed, with greater enhancements for poly-G nucleotides than for poly-A, poly-U and poly-C, indicating a codonic bias. Polydeoxyribonucleotides are found to provide no enhancement in peptide formation rates, and yields were also greatly reduced in the absence of clay. A mechanism for peptide synthesis is proposed which involves the activation of glycine on the clay surface, followed by the formation of esters between glycine and the 2-prime OH groups of the polyribonucleotide and peptide bonds between adjacent amino acyl esters. It is pointed out that if this mechanism is correct, it may provide a basis for a direct template translation process, which would produce a singlet genetic code.

White, D. H.↗
NASA NTRS1989

The effects of pretreatment conditions on a Pt/SnO2 catalyst for the oxidation of CO in CO2 lasers

CO oxidation catalysts with high activity at 25 to 100 C are important for long life, closed cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 was shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment of no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady state yield is attained. This dip was found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.

Schryer, David R.↗
NASA NTRS1990

The effect of H2O and pretreatment on the activity of a Pt/SnO2 catalyst

CO oxidation catalysts with high activity at 25 C to 100 C are important for long-life, closed-cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 has been shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment or no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady-state yield is attained. This dip has been found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.

Vannorman, John D.↗
NASA NTRS1998

Analysis of IUE Observations of Hydrogen in Comets

The 15-years worth of hydrogen Lyman-alpha observations of cometary comae obtained with the International Ultraviolet Explorer (IUE) satellite had gone generally unanalyzed because of two main modeling complications. First, the inner comae of many bright (gas productive) comets are often optically thick to solar Lyman-alpha radiation. Second, even in the case of a small comet (low gas production) the large IUE aperture is quite small as compared with the immense size of the hydrogen coma, so an accurate model which properly accounts for the spatial distribution of the coma is required to invert the infrared brightnesses to column densities and finally to H atom production rates. Our Monte Carlo particle trajectory model (MCPTM), which for the first time provides the realistic full phase space distribution of H atoms throughout the coma has been used as the basis for the analysis of IUE observations of the inner coma. The MCPTM includes the effects of the vectorial ejection of the H atoms upon dissociation of their parent species (H2O and OH) and of their partial collisional thermalization. Both of these effects are crucial to characterize the velocity distribution of the H atoms. This combination of the MCPTM and spherical radiative transfer code had already been shown to be successful in understanding the moderately optically thick coma of comet P/Giacobini-Zinner and the coma of comet Halley that varied from being slightly to very optically thick. Both of these comets were observed during solar minimum conditions. Solar activity affects both the photochemistry of water and the solar Lyman-alpha radiation flux. The overall plan of this program here was to concentrate on comets observed by IUE at other time during the solar cycle, most importantly during the two solar maxima of 1980 and 1990. Described herein are the work performed and the results obtained.

Combi, Michael R.↗
NASA NTRS2007

NASA 9-Point LDI Code Validation Experiment

This presentation highlights the experimental work to date to obtain validation data using a 9-point lean direct injector (LDI) in support of the National Combustion Code. The LDI is designed to supply fuel lean, Jet-A and air directly into the combustor such that the liquid fuel atomizes and mixes rapidly to produce short flame zones and produce low levels of oxides of nitrogen and CO. We present NOx and CO emission results from gas sample data that support that aspect of the design concept. We describe this injector and show high speed movies of selected operating points. We present image-based species maps of OH, fuel, CH and NO obtained using planar laser induced fluorescence and chemiluminescence. We also present preliminary 2-component, axial and vertical, velocity vectors of the air flow obtained using particle image velocimetry and of the fuel drops in a combusting case. For the same combusting case, we show preliminary 3-component velocity vectors obtained using a phase Doppler anemometer. For the fueled, combusting cases especially, we found optical density is a technical concern that must be addressed, but that in general, these preliminary results are promising. All optical-based results confirm that this injector produces short flames, typically on the order of 5- to-7-mm long at typical cruise and high power engine cycle conditions.

Hicks, Yolanda R.↗
NASA NTRS1989

The nitrogen cycle on Mars

Nirtogen is an essential element for the evolution of life, because it is found in a variety of biologically important molecules. Therefore, N is an important element to study from a exobiological perspective. In particular, fixed nitrogen is the biologically useful form of nitrogen. Fixed nitrogen is generally defines as NH3, NH4(+), NO(x), or N that is chemically bound to either inorganic or organic molecules, and releasable by hydrolysis to NH3 or NH4(+). On Earth, the vast majority of nitrogen exists as N2 in the atmosphere, and not in the fixes form. On early Mars the same situations probably existed. The partial pressure of N2 on early Mars was thought to be 18 mb, significantly less than that of Earth. Dinitrogen can be fixed abiotically by several mechanisms. These mechanisms include thernal shock from meteoritic infall and lightning, as well as the interaction of light and sand containing TiO2 which produces NH3 that would be rapidly destroyed by photolysis and reaction with OH radicals. These mechanisms could have been operative on primitive Mars.The chemical processes effecting these compounds and possible ways of fixing or burying N in the Martian environment are described. Data gathered in this laboratory suggest that the low abundance of nitrogen along (compared to primitive Earth) may not significantly deter the origin and early evolution of a nitrogen utilizing organisms. However, the conditions on current Mars with respect to nitrogen are quite different, and organisms may not be able to utilize all of the available nitrogen.

Mancinelli, Rocco L.↗
NASA NTRS1991

Three-Dimensional Model Synthesis of the Global Methane Cycle

A synthesis of the global methane cycle is presented to attempt to generate an accurate global methane budget. Methane-flux measurements, energy data, and agricultural statistics are merged with databases of land-surface characteristics and anthropogenic activities. The sources and sinks of methane are estimated based on atmospheric methane composition and variations, and a global 3D transport model simulates the corresponding atmospheric responses. The geographic and seasonal variations of candidate budgets are compared with observational data, and the available observations are used to constrain the plausible methane budgets. The preferred budget includes annual destruction rates and annual emissions for various sources. The lack of direct flux measurements in the regions of many of these fluxes makes the unique determination of each term impossible. OH oxidation is found to be the largest single term, although more measurements of this and other terms are recommended.

Fung, I.↗
NASA NTRS1999

Seasonal and Interannual Variabilities in Tropical Tropospheric Ozone

This paper presents a detailed characterization of seasonal and interannual variability in tropical tropospheric column ozone (TCO). TCO time series are derived from 20 years (1979-1998) of total ozone mapping spectrometer (TOMS) data using the convective cloud differential (CCD) method. Our study identifies three regions in the tropics with distinctly different zonal characteristics related to seasonal and interannual variability. These three regions are the eastern Pacific, Atlantic, and western Pacific. Results show that in both the eastern and western Pacific seasonal-cycle variability of northern hemisphere (NH) TCO exhibits maximum amount during NH spring whereas largest amount in southern hemisphere (SH) TCO occurs during SH spring. In the Atlantic, maximum TCO in both hemispheres occurs in SH spring. These seasonal cycles are shown to be comparable to seasonal cycles present in ground-based ozonesonde measurements. Interannual variability in the Atlantic region indicates a quasi-biennial oscillation (QBO) signal that is out of phase with the QBO present in stratospheric column ozone (SCO). This is consistent with high pollution and high concentrations of mid-to-upper tropospheric O3-producing precursors in this region. The out of phase relation suggests a UV modulation of tropospheric photochemistry caused by the QBO in stratospheric O3. During El Nino events there is anomalously low TCO in the eastern Pacific and high values in the western Pacific, indicating the effects of convectively-driven transport of low-value boundary layer O3 (reducing TCO) and O3 precursors including H2O and OH. A simplified technique is proposed to derive high-resolution maps of TCO in the tropics even in the absence of tropopause-level clouds. This promising approach requires only total ozone gridded measurements and utilizes the small variability observed in TCO near the dateline. This technique has an advantage compared to the CCD method because the latter requires high-resolution footprint measurements of both reflectivity and total ozone in the presence of tropopause-level cloud tops.

Ziemke, J. R.↗
NASA NTRS2009

Use of Raman Spectroscopy and Delta Volume Growth from Void Collapse to Assess Overwrap Stress Gradients Compromising the Reliability of Large Kevlar/Epoxy COPVs

Composite Overwrapped Pressure Vessels (COPVs) are frequently used for storing pressurized gases aboard spacecraft and aircraft when weight saving is desirable compared to all-metal versions. Failure mechanisms in fibrous COPVs and variability in lifetime can be very different from their metallic counterparts; in the former, catastrophic stress-rupture can occur with virtually no warning, whereas in latter, a leak before burst design philosophy can be implemented. Qualification and certification typically requires only one burst test on a production sample (possibly after several pressure cycles) and the vessel need only meet a design burst strength (the maximum operating pressure divided by a knockdown factor). Typically there is no requirement to assess variability in burst strength or lifetime, much less determine production and materials processing parameters important to control of such variability. Characterizing such variability and its source is crucial to models for calculating required reliability over a given lifetime (e.g. R = 0.9999 for 15 years). In this paper we present a case study of how lack of control of certain process parameters in COPV manufacturing can result in variations among vessels and between production runs that can greatly increase uncertainty and reduce reliability. The vessels considered are 40-inch ( NASA Glenn Research center, Cleveland, OH, 44135 29,500 in3 ) spherical COPVs with a 0.74 in. thick Kevlar49/epoxy overwrap and with a titanium liner of which 34 were originally produced. Two burst tests were eventually performed that unexpectedly differed by almost 5%, and were 10% lower than anticipated from burst tests on 26-inch sister vessels similar in every detail. A major observation from measurements made during proof testing (autofrettage) of the 40-inch vessels was that permanent volume growth from liner yielding varied by a factor of more than two (150 in3 to 360 in3 ), which suggests large differences in the residual stress gradient through their overwraps. This resulted in large uncertainty in true fiber stress ratio (fiber stress at operating pressure divided by fiber stress at burst) which governs lifetime. The vessels were originally designed with tight safety margins, so it became crucial to develop a non-destructive evaluation (NDE) technique to directly measure the overwrap residual stress state of each vessel, and to identify those vessels at highest risk of having poor reliability. This paper describes a Raman Spectroscopy technique for measuring certain patterns of fluctuation in fiber elastic strains over the outside vessel surface (where all but one wrap is exposed at certain locations) that are shown to directly correlate to increased fiber stress ratios and reduced reliability.

Kezirian, Michael T.↗