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593 records · Page 33

Some Recent Observations on the Burning of Isolated N-Heptane and Alcohol Droplets

In a joint program involving Prof. F.A. Williams of the University of California, San Diego and Dr. V. Nayagam of the National Center for Microgravity Research on Combustion and Fluid Dynamics, the combustion of liquid fuel droplets of n-heptane, n-decane, methanol, methanol-water, ethanol and ethanol-water having initial diameters between about 1 mm and 6 mm continues to be studied. The objectives of the work are to improve fundamental knowledge of droplet combustion dynamics for pure fuels and fuel-water mixtures through microgravity experiments and theoretical analyses. The Princeton contributions to the collaborative program supports the engineering design, data analysis, and data interpretation requirements for the study of initially single component, spherically symmetric, isolated droplet combustion studies through experiments and numerical modeling. The complementary UCSD contributions apply asymptotic theoretical analyses and are described in the published literature and in a companion communication in this conference. The combined program continues to focus on analyses of results obtained from Fiber Supported Droplet Combustion (FSDC) experiments (FSDC-2, STS- 94) conducted with the above fuels in shuttle cabin air and Droplet Combustion Experiment (DCE) data obtained for unsupported and fiber supported droplets of n-heptane in Helium-Oxygen mixtures and cabin air (STS-83, STS-94). The program is preparing for a second DCE experimental mission using methanol/methanol-water as fuels and helium-oxygen-nitrogen environments. DCE-2 is to be conducted aboard the International Space Station. Emphases of recent Princeton work are on the study of simple alcohols (methanol, ethanol) and alcohol/water mixtures as fuels, with time-dependent measurements of drop size, flame-standoff, liquid-phase composition, and finally, extinction. Ground based experiments have included bench-scale studies at Princeton and collaborative experimental studies in the 2.2 second drop tower at NASA-Glenn Research Center.

Dryer, F. L.↗

Survivability of Affordable High Temperature Polymer Matrix Composites for Propulsion Engine Components

PMR-type polyimides are regarded as state of the art high temperature polymers, due to their excellent thermo-mechanical properties and thermo-oxidative stability. One of their drawbacks, however is the inability to process them using cost-effective processing methods such as Resin Transfer Molding (RTM) and Resin Film Infusion (RFI). Development of low viscosity, high temperature polymers has been the subject of intense research. Recently, a new generation of low viscosity polyimides were synthesized by the introduction of twisted biphenyl or binapthyl groups into the backbone. This report details the progress for Year 1, which has involved acquiring samples and initiating Phases I and II of the proposed research. Specifically, studies of the process-property relationships of a series of polymers using oligomers based on 2,3,3' ,4'-biphenyltertracarboxylic dianhydride (PBDA) and a mixture of a diamine, BAX and a triamine, 1,3,5-Tris (4-aminophenoxybenzene), TAB, where the amount of TAB was varied have been initiated. The sample containing 10 percent TAB possesses a slightly higher degree of crystalline order versus that of the 20 percent TAB sample, based on x-ray diffraction studies of the b-staged oligomers. Both systems lose all of the crystalline order upon curing, however. The chemorheology has been studied as a function of the TAB content. While the magnitude of the viscosity is essentially the same for both systems, the cure kinetics of the 10 percent TAB system is faster than that for the 20 percent TAB system. The sample exhibits a melting-recrystallization-remelting behavior before the crosslinking commences. Correlation of other kinetic parameters, such as the activation energies for curing, the Tg and mechanical properties to the structure of these systems is underway. Future studies will involve characterization of mechanical and thermal properties of the pure resins and the fabrication of fiber reinforced composites using these materials.

Dean, Derrick↗

Stable carbon isotope fractionation by sulfate-reducing bacteria

Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.

Deltaproteobacteria/growth & development/metabolis↗

Continuation of tailored composite structures of ordered staple thermoplastic material

The search for the cost effective composite structure has motivated the investigation of several approaches to develop composite structure from innovative material forms. Among the promising approaches is the conversion of a planar sheet to components of complex curvature through sheet forming or stretch forming. In both cases, the potential for material stretch in the fiber direction appears to offer a clear advantage in formability over continuous fiber systems. A framework was established which allows the simulation of the anisotropic mechanisms of deformation of long discontinuous fiber laminates wherein the matrix phase is a viscous fluid. Predictions for the effective viscosities of a hyper-anisotropic medium consisting of collimated, discontinuous fibers suspended in viscous matrix were extended to capture the characteristics of typical polymers including non-Newtonian behavior and temperature dependence. In addition, the influence of fiber misorientation was also modeled by compliance averaging to determine ensemble properties for a given orientation distribution. A design tool is presented for predicting the effect of material heterogeneity on the performance of curved composite beams such as those used in aircraft fuselage structures. Material heterogeneity can be induced during manufacturing processes such as sheet forming and stretch forming of thermoplastic composites. This heterogeneity can be introduced in the form of fiber realignment and spreading during the manufacturing process causing radial and tangential gradients in material properties. Two analysis procedures are used to solve the beam problems. The first method uses separate two-dimensional elasticity solutions for the stresses in the flange and web sections of the beam. The separate solutions are coupled by requiring that forces and displacements match section boundaries. The second method uses an approximate Rayleigh-Ritz technique to find the solutions for more complex beams. Analyses are performed for curved beams of various cross-sections loaded in pure bending and with a uniform distributed load. Preliminary results show that the geometry of the beam dictates the effect of heterogeneity on performance. The role of heterogeneity is larger in beams with a small average radius-to-depth ration, R/t, where R is the average radius of the beam and t is the difference between the inside and outside radii. Results of the anlysis are in the form of stresses and displacements and are compared to both mechanics of materials and numerical solutions obtained using finite element analysis.

Santare, Michael H.↗

The Importance of Contamination Knowledge - Insights into Mars Sample Return

The Astromaterials Acquisition and Curation Office at NASA Johnson Space Center (JSC), in Houston, TX (henceforth Curation Office) manages the curation of all past, present, and future extraterrestrial samples returned by NASA missions and shared collections from international partners, preserving their integrity for future scientific study while providing the samples to the international community in a fair and unbiased way. The Curation Office also curates all reference and witness materials for each mission (e.g., flight and non-flight hardware coupons; lubricants; non-flight, flight-like, and flown witness plates). These reference and witness materials provide the scientific community with the fundamental ability to reconstruct the contamination/alteration history of the sample collection through the course of the mission, with the overall goal of strengthening the scientific conclusions drawn from the study of returned materials. The information gained from characterizing the physical, biological, inorganic, and organic chemical properties of reference and witness materials is defined as the Contamination Knowledge (CK) of the sample collection. Unlike the data collected for Contamination Control (CC) and Planetary Protection (PP), CK is exclusively concerned with preserving reference and witness materials for study by future scientists upon sample return. Although CC and PP data collected for sample integrity and forward contamination purposes can be complementary to CK, they are two separate data sets with distinct objectives. A robust collection of samples for CK is necessary to allow the extraterrestrial material in a returned sample to be distinguished from terrestrial contamination. Traditionally CK is utilized by sample scientists in order to accomplish the mission’s scientific objectives, however this information can also be utilized by the Office of Planetary Protection to help evaluate the presence of any back contamination. Mars 2020, the first phase of a potential multipart Mars Sample Return (MSR) campaign, is expected to contribute to NASA’s Mars Exploration Program Science Goals by filling in knowledge gaps concerning: 1) the existence of past or present life on Mars, 2) the past and present climate of Mars, 3) the geology of Mars, and 4) hazards associated with human exploration of Mars. Although there is debate concerning which samples will best answer these questions, the necessity for proper sample blanks is well-understood. The CC and PP requirements, driven by the restricted Class V mission designation, are the most stringent of any sample return mission in recent history. The extremely low levels of allowable terrestrial contamination on the spacecraft and rover can complicate these analyses given the detection limits of current analytical instrumentation, especially in the case of biological contamination. By collecting and curating unanalyzed samples specifically for CK, future sample scientists will not be relegated to: 1) relying on data collected using possibly obsolete tools and techniques for return sample blanks, or 2) using remnants of extracted and/or cultured samples from ATLO (Assembly, Test, and Launch Operations), which could be incompatible with the desired experimental endpoints or state-of-the-art techniques available at the time of sample return.The addition of biological experimental endpoints to a sample return campaign’s objectives broadens the requisite range in preservation environments (e.g. inert ultra-pure nitrogen gaseous environment at 18 degrees Centigrade versus less than or equal to minus 80 degrees Centigrade) and types of CK samples. As a result, the Curation Office will also curate the following CK samples at less than or equal to minus 80 degrees Centigrade for the Mars 2020 mission: 1) unanalyzed swabs and wipes in sterile containers, 2) all recirculation filters from the clean rooms used for sample and caching subsystem assembly and all filters from the laminar flow benches used to assemble sample intimate hardware, and 3) witness plates collecting airborne contamination within the assembly clean rooms. It has been Curation Office policy since the Apollo missions to preserve as many pristine samples as possible for future scientific research. Although CK is required to be collected for all stages of the MSR campaign, the CK for the Mars 2020 mission is the most critical for understanding contamination in the returned samples given the intimacy between the Martian samples and the Mars 2020 flight hardware. This presentation highlights the importance of CK for sample return missions as well as the traditional and novel types of CK samples required for a successful MSR campaign.

Harrington, A. D.↗

Compositions of the Surfaces of Pluto and its Satellites

The information we have on the chemical compositions of the surfaces of Pluto and Charon has been obtained from Earth-based near-infrared spectroscopy. These bodies are seen in diffusely scattered sunlight upon which absorption bands diagnostic of specific ices are superimposed. Identified so far on Pluto are molecular nitrogen (N2), methane (CH4), carbon monoxide (CO), and ethane (C2H6), all in the frozen state. Charon has the clear spectral signature of H2O ice in the crystalline phase, plus an absorption band near 2.2 microns identified as a hydrated form of NH3. No diagnostic spectra of Pluto's other satellites are currently available. A fraction of Pluto's CH4 is dissolved in solid N2, which is in the hexagonal beta-phase. When a small concentration of CH4 exists in a N2 crystalline matrix, its absorption bands are shifted in wavelength by a small but detectable amount. Indeed the shifting of the CH4 bands is diagnostic of a host matrix. In the case of Pluto, the N2 band (2.148 microns) itself is detected, but for other trans-Neptunian objects where the N2 band cannot be seen, the shifted CH4 bands demonstrate the presence of N2 or (less likely) some other spectrally neutral and transparent matrix material (e.g., Ar). The absence of detectable CO2 and H2O ices on Pluto, while they are clearly present on the otherwise very similar Triton, is noteworthy. The ices of Pluto distributed non-uniformly across its surface, and the distribution shows long-term (decadal) changes. Both seasonal and secular changes may be occurring through transport across the surface as a result of changing temperature, and by seasonal changes in the vapor pressure equilibrium of the ice with the tenuous and variable atmosphere. Models of the photochemistry of the surface ices and the atmosphere of Pluto predict the presence of several materials not yet detected; the most abundant photoproducts are expected to be C2H2, C4H2, HCN, C2H6; HCN has been detected on Triton. Both Pluto and Charon have surface components in addition to the detected ices. These materials of presently unknown composition serve to reduce the albedos of both bodies below that expected for pure ices, and in the case of Pluto impart a yellow-brown coloration; the color of Charon is more nearly neutral. It is generally thought that the non-ice components are more refractory than the ices and that they may be complex carbonaceous materials derived from the ultraviolet and charged particle processing of the surface ices. Minerals are also plausible candidates for the non-ice fraction. The refractory colored components may constitute bedrock upon which variable amounts of the ices are alternately deposited and evaporated as the seasons change. Water ice is expected to be a component of the bedrock, although it has not yet been reliably identified.

Pluto↗

Self-Regulating Water-Separator System for Fuel Cells

proposed system would perform multiple coordinated functions in regulating the pressure of the oxidant gas (usually, pure oxygen) flowing to a fuelcell stack and in removing excess product water that is generated in the normal fuel-cell operation. The system could function in the presence or absence of gravitation, and in any orientation in a gravitational field. Unlike some prior systems for removing product water, the proposed system would not depend on hydrophobicity or hydrophilicity of surfaces that are subject to fouling and, consequently, to gradual deterioration in performance. Also unlike some prior systems, the proposed system would not include actively controlled electric motors for pumping; instead, motive power for separation and pumping away of product water would be derived primarily from the oxidant flow and perhaps secondarily from the fuel flow. The net effect of these and other features would be to make the proposed system more reliable and safer, relative to the prior systems. The proposed system (see figure) would include a pressure regulator and sensor in the oxidant supply just upstream from an ejector reactant pump. The pressure of the oxidant supply would depend on the consumption flow. In one of two control subsystems, the pressure of oxidant flowing from the supply to the ejector would be sensed and used to control the speed of a set of a reciprocating constant-displacement pump so that the volumetric flow of nominally incompressible water away from the system would slightly exceed the rate at which water was produced by the fuel cell(s). The two-phase (gas/liquid water) outlet stream from the fuel cell(s) would enter the water separator, a turbinelike centrifugal separator machine driven primarily by the oxidant gas stream. A second control subsystem would utilize feedback derived from the compressibility of the outlet stream: As the separator was emptied of liquid water, the compressibility of the pumped stream would increase. The compressibility would be sensed, and an increase in compressibility beyond a preset point (signifying a decrease in water content below an optimum low level) would cause the outflow from the reciprocating pump to be diverted back to the separator to recycle some water.

Vasquez, Arturo↗

A finite-element-based perturbation model for the rotordynamic analysis of shrouded pump impellers: Part 1: Model development and applications

This study concerns the rotor dynamic characteristics of fluid-encompassed rotors, with special emphasis on shrouded pump impellers. The core of the study is a versatile and categorically new finite-element-based perturbation model, which is based on a rigorous flow analysis and what we have generically termed the 'virtually' deformable finite-element approach. The model is first applied to the case of a smooth annular seal for verification purposes. The rotor excitation components, in this sample problem, give rise to a purely cylindrical, purely conical, and a simultaneous cylindrical/conical rotor whirl around the housing centerline. In all cases, the computed results are compared to existing experimental and analytical data involving the same seal geometry and operating conditions. Next, two labyrinth-seal configurations, which share the same tooth-to-tooth chamber geometry but differ in the total number of chambers, were investigated. The results, in this case, are compared to experimental measurements for both seal configurations. The focus is finally shifted to the shrouded-impeller problem, where the stability effects of the leakage flow in the shroud-to-housing secondary passage are investigated. To this end, the computational model is applied to a typical shrouded-impeller pump stage, fabricated and rotor dynamically tested by Sulzer Bros., and the results compared to those of a simplified 'bulk-flow' analysis and Sulzer Bros.' test data. In addition to assessing the computed rotor dynamic coefficients, the shrouded-impeller study also covers a controversial topic, namely that of the leakage-passage inlet swirl, which was previously cited as the origin of highly unconventional (resonance-like) trends of the fluid-exerted forces. In order to validate this claim, a 'microscopic' study of the fluid/shroud interaction mechanism is conducted, with the focus being on the structure of the perturbed flow field associated with the impeller whirl. The conclusions of this study were solidified by the outcome of a numerical-certainty exercise, where the grid dependency of the numerical results is objectively examined. The final phase of the shrouded-impeller investigation involves the validation of a built-in assumption, in all other perturbation models, whereby single-harmonic tangential distributions of all the flow thermophysical properties are imposed. The last phase of the investigation course is aimed at verifying the fine details of the perturbed flow field in light of recent set of detailed LDA measurements in a smooth annular seal. Grid dependency of the fluid-induced forces is also investigated, and specific recommendations are made.

Baskharone, Erian A.↗

Effects of Structure and Hydrodynamics on the Sooting Behavior of Spherical Microgravity Diffusion Flames

Recent experimental, numerical and analytical work has shown that the stoichiometric mixture fraction (Z(sub st)) can have a profound effect on soot formation in diffusion flames. These findings were obtained at constant flame temperature (T(sub ad)), employing the approach described in Du and Axelbaum (1995, 1996). For example, a fuel mixture containing 1 mole of ethylene and 11.28 moles of nitrogen burning in pure oxygen ((Z(sub st)) = 0.78) has the same adiabatic flame temperature (2370 K) as that of pure ethylene burning in air ((Z(sub st)) = 0.064). An important finding of these works was that at sufficiently high (Z(sub st)), flames remain blue as strain rate approaches zero in counterflow flames, or as flame height and residence time approach infinity in coflowing flames. Lin and Faeth (1996a) coined the term permanently blue to describe such flames. Two theories have been proposed to explain the appearance of permanently-blue flames at high (Z(sub st)). They are based on (1) hydrodynamics and (2) flame structure. Previous experimental studies in normal gravity are not definitive as to which, if either, mechanism is dominant because both hydrodynamics and structure suppress soot formation at high (Z(sub st)) in coflowing and counterflowing diffusion flames. In counterflow flames with (Z(sub st)) < 0.5 streamlines at the flame sheet are directed toward the fuel. Newly formed soot is convected into richer regions, favoring soot growth over oxidation. For (Z(sub st)) > 0.5, convection at the flame is toward the oxidizer, thus enhancing soot oxidization. Thus, in counterflow flames, hydrodynamics causes soot to be convected towards the oxidizer at high (Z(sub st)) which suppresses soot formation. Axelbaum and co-workers maintain that while the direction of convection can impact soot growth and oxidation, these processes alone cannot cause permanently-blue flames. Soot growth and oxidation are dependent on the existence of soot particles and the presence of soot is invariably accompanied by yellow luminosity. Soot-particle inception, on the other hand, arises from gas-phase reactions and its dependence on flow direction is weak, similar to that of other gas-phase reactions in flames. For example, when the flame moves across the stagnation plane no significant changes in flame chemistry are observed. Furthermore, since the soot-inception zone has a finite thickness, soot has been produced in counterflow flames with (Z(sub st)) > 0.5. For large (Z(sub st)) the fuel concentration decreases and oxygen concentration increases in the soot forming regions of the flame. This yields a shift in the OH profile toward the fuel side of the flame, and this shift can dramatically influence soot inception because it essentially narrows the soot inception zone. Soot-free (permanently-blue) conditions can be realized when the structure of the flame is adjusted to the extent that significant oxidizing species exist on the fuel side of the flame at temperatures above the critical temperature for soot inception, ca. 1250 K. In previously considered flames it was impossible to independently vary flame structure and convection direction. In contrast, spherical diffusion flames (which generally require microgravity) allow both properties to be varied independently. We altered structure (Z(sub st)) by exchanging inert between the oxidizer and the fuel and we independently varied convection direction at the flame sheet by interchanging the injected and ambient gases. In this work we established four flames: (a) ethylene issuing into air, (b) diluted ethylene issuing into oxygen, (c) air issuing into ethylene, and (d) oxygen issuing into diluted ethylene. (Z(sub st)) is 0.064 in flames (a) and (c) and 0.78 in flames (b) and (d). The convection direction is from fuel to oxidizer in flames (a) and (b) and from oxidizer to fuel in flames (c) and (d). Under the assumption of equal diffusivities of all species and heat, the stoichiometric contours of these flames have identical temperatures and nitrogen concentrations.

Sunderland, P. B.↗

Structural Definition and Mass Estimation of Lunar Surface Habitats for the Lunar Architecture Team Phase 2 (LAT-2) Study

The Lunar Architecture Team Phase 2 study defined and assessed architecture options for a Lunar Outpost at the Moon's South Pole. The Habitation Focus Element Team was responsible for developing concepts for all of the Habitats and pressurized logistics modules particular to each of the architectures, and defined the shapes, volumes and internal layouts considering human factors, surface operations and safety requirements, as well as Lander mass and volume constraints. The Structures Subsystem Team developed structural concepts, sizing estimates and mass estimates for the primary Habitat structure. In these studies, the primary structure was decomposed into a more detailed list of components to be sized to gain greater insight into concept mass contributors. Structural mass estimates were developed that captured the effect of major design parameters such as internal pressure load. Analytical and empirical equations were developed for each structural component identified. Over 20 different hard-shell, hybrid expandable and inflatable soft-shell Habitat and pressurized logistics module concepts were sized and compared to assess structural performance and efficiency during the study. Habitats were developed in three categories; Mini Habs that are removed from the Lander and placed on the Lunar surface, Monolithic habitats that remain on the Lander, and Habitats that are part of the Mobile Lander system. Each category of Habitat resulted in structural concepts with advantages and disadvantages. The same modular shell components could be used for the Mini Hab concept, maximizing commonality and minimizing development costs. Larger Habitats had higher volumetric mass efficiency and floor area than smaller Habitats (whose mass was dominated by fixed items such as domes and frames). Hybrid and pure expandable Habitat structures were very mass-efficient, but the structures technology is less mature, and the ability to efficiently package and deploy internal subsystems remains an open issue.

Dorsey, John T.↗

Microwave Sterilization and Depyrogenation System

A fully functional, microgravity-compatible microwave sterilization and depyrogenation system (MSDS) prototype was developed that is capable of producing medical-grade water (MGW) without expendable supplies, using NASA potable water that currently is available aboard the International Space Station (ISS) and will be available for Lunar and planetary missions in the future. The microwave- based, continuous MSDS efficiently couples microwaves to a single-phase, pressurized, flowing water stream that is rapidly heated above 150 C. Under these conditions, water is rapidly sterilized. Endotoxins, significant biological toxins that originate from the cell walls of gram-negative bacteria and which represent another defining MGW requirement, are also deactivated (i.e., depyrogenated) albeit more slowly, with such deactivation representing a more difficult challenge than sterilization. Several innovations culminated in the successful MSDS prototype design. The most significant is the antenna-directed microwave heating of a water stream flowing through a microwave sterilization chamber (MSC). Novel antenna designs were developed to increase microwave transmission efficiency. These improvements resulted in greater than 95-percent absorption of incident microwaves. In addition, incorporation of recuperative heat exchangers (RHxs) in the design reduced the microwave power required to heat a water stream flowing at 15 mL/min to 170 C to only 50 W. Further improvements in energy efficiency involved the employment of a second antenna to redirect reflected microwaves back into the MSC, eliminating the need for a water load and simplifying MSDS design. A quick connect (QC) is another innovation that can be sterilized and depyrogenated at temperature, and then cooled using a unique flow design, allowing collection of MGW at atmospheric pressure and 80 C. The final innovation was the use of in-line mixers incorporated in the flow path to disrupt laminar flow and increase contact time at a given flow rate. These technologies can be employed in small-scale systems for efficient production of MGW in the laboratory or in a range of larger systems that meet various industrial requirements. The microwave antennas can also be adapted to selectively sterilize vulnerable connections to ultra-pure water production facilities or biologically vulnerable systems where microorganisms may intrude.

Akse, James R.↗

Stability of the Martian atmosphere: Is heterogeneous catalysis essential?

A comprehensive homogeneous gas phase photochemical model is developed to study the problem of stability of the Martian atmosphere. The one-dimensional model extends from the ground up to 220 km, passing through the homopause at 125 km. The model thus couples the lower (neutral) atmosphere to the ionosphere above which provides significant downward flux of carbon monoxide and oxygen atoms. It is concluded on the basic of currently accepted values for globally and seasonally averaged water vapor abundance, dust opacity and the middle atmospheric eddy mixing coefficient, as well as the relevant laboratory data (particularly the temperature dependence of CO2 absorption cross section and the rate constant for CO+OH reaction), that the rate of re-formation of carbon dioxide exceeds its photolytic destruction rate by about 40%. Furthermore, it is found that this result is virtually independent of the choice of eddy mixing coefficient, unless its value in the middle atmosphere exceeds 10(exp 8) sq cm/sec or is far smaller than 10(exp 5)sq cm/sec, or the dust opacity, unless it exceeds unity, or the water vapor mixing ratio at the surface, unless it is far smaller (less than or = 1 ppm) or far greater (greater than or = 500 ppm) than the average value (approximately 150 ppm). Since none of these extremes represent globally and seasonally averaged conditions on Mars, we propose that the present model requires existence of a mechanism to throttle down the recycling rate of carbon dioxide on Mars. Therefore, it is suggested that a heterogeneous process which provides a sink to the species that participate in the recycling of CO2, i.e., H2O, H2O2, OH, CO or O, in particular, may be necessary to bring about the balance between the CO2 recycling rate and its photolytic destruction rate. Aerosols of dust or ice (pure or doped water or carbon dioxide ice present in the atmosphere of Mars) can provide the appropriate adsorption sites for the above heterogeneous process. Despite our conclusion that some heterogeneous process may be needed, it is important to recognize that one-dimensional models can only provide first-order results which, most likely, represent globally and seasonally averaged conditions. However, it is only after actual temporal, latitudinal and longitudinal variations of relevant atmospheric parameters are included in the model that one can determine fuly whether the problem of atmospheric stabiltiy still continues to persist and whether some heterogeneous process is required to correct it.

Atreya, Sushil K.↗

Laboratory studies of the newly discovered infrared band at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io: the tentative identification of CO2

We discuss over 120 laboratory experiments pertaining to the identification of the new absorption band discovered by Trafton et al. (1991) at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io. It is shown that this band is not due to overtones or combinations of the fundamental bands associated with the molecules (or their chemical complexes) already identified on Io, namely, SO2, H2S, and H2O. Thus, this band is due to a new, previously unidentified, component of Io. Experiments also demonstrate that the band is not due to molecular H2 frozen in SO2 frosts. Since the frequency of this band is very close to the first overtone of the nu 3 asymmetric stretching mode of CO2, we have investigated the spectral behavior of CO2 under a variety of conditions appropriate for Io. The profile of the Io band is not consistent with the rotational envelope expected for single, freely rotating, gaseous CO2 under Io-like conditions. It was found that pure, solid CO2 and CO2 intimately mixed in a matrix of solid SO2 and H2S produce bands with similar widths (5-10 cm-1), but that these bands consistently fall at frequencies about 10-20 cm-1 (approximately 0.007 micrometer) lower than the Io band. CO2 in SO2 : H2S ices also produces several additional bands that are not in the Io spectra. The spectral fit improves, however, as the CO2 concentration in SO2 increases, suggesting that CO2-CO2 interactions might be involved. A series of Ar : CO2 and Kr : CO2 matrix isolation experiments, as well as laboratory work done elsewhere, show that CO2 clustering shifts the band position to higher frequencies and provides a better fit to the Io band. Various laboratory experiments have shown that gaseous CO2 molecules have a propensity to cluster between 80 and 100 K, temperatures similar to those found on the colder regions of Io. We thus tentatively identify the newly discovered Io band at 4705.2 cm-1 (2.1253 micrometers) with CO2 multimers or "clusters" on Io. Whether these clusters are buried within an SO2 frost, reside on the surface, or are in a residual, steady-state "atmospheric aerosol" population over local coldtraps is not entirely clear, although we presently favor the latter possibility. The size of these clusters is not well defined, but evidence suggests groups of more than four molecules are required. The absorption strength of the 2 nu 3 CO2 cluster overtone determined in the laboratory, in conjunction with the observed strength of the Io band, suggests that the disk-integrated abundance of CO2 is less than 1% that of the SO2. Studies of the sublimation behavior of CO2 indicate that it probably resides predominantly in the cooler areas (< 100 K) of Io. The relative constancy of the Io feature over a variety of orbital phases suggests that the polar regions may contain much of the material. Some consequences of the physical properties of CO2 under conditions pertinent to Io are discussed. The presence of CO2 clusters on Io could be verified by the detection of any one of several other infrared bands associated with the CO2 molecule, of which the strongest are the nu 3 12CO2 asymmetric stretch fundamental near 2350 cm-1 (4.25 micrometers) and the nu 2 bending mode fundamental near 660 cm-1 (15.1 micrometers). Weaker bands that may also be detectable include the nu 3 13CO2 asymmetric stretch fundamental near 2280 cm-1 (4.39 micrometers), the 2 nu 2 + nu 3 combination/overtone band near 3600 cm-1 (2.78 micrometers), and the nu 1 + nu 3 combination band near 3705 cm-1 (2.70 micrometers).

NASA Center ARC↗

Prototype development and test results of a continuous ambient air monitoring system for hydrazine at the 10 ppb level

A Hydrazine Vapor Area Monitor (HVAM) system is currently being field tested as a detector for the presence of hydrazine in ambient air. The MDA/Polymetron Hydrazine Analyzer has been incorporated within the HVAM system as the core detector. This analyzer is a three-electrode liquid analyzer typically used in boiler feed water applications. The HVAM system incorporates a dual-phase sample collection/transport method which simultaneously pulls ambient air samples containing hydrazine and a very dilute sulfuric acid solution (0.0001 M) down a length of 1/4 inch outside diameter (OD) tubing from a remote site to the analyzer. The hydrazine-laden dilute acid stream is separated from the air and the pH is adjusted by addition of a dilute caustic solution to a pH greater than 10.2 prior to analysis. Both the dilute acid and caustic used by the HVAM are continuously generated during system operation on an "as needed" basis by mixing a metered amount of concentrated acid/base with dilution water. All of the waste water generated by the analyzer is purified for reuse by Barnstead ion-exchange cartridges so that the entire system minimizes the generation of waste materials. The pumping of all liquid streams and mixing of the caustic solution and dilution water with the incoming sample are done by a single pump motor fitted with the appropriate mix of peristaltic pump heads. The signal to noise (S/N) ratio of the analyzer has been enhanced by adding a stirrer in the MDA liquid cell to provide mixing normally generated by the high liquid flow rate designed by the manufacturer. An onboard microprocessor continuously monitors liquid levels, sample vacuum, and liquid leak sensors, as well as handles communications and other system functions (such as shut down should system malfunctions or errors occur). The overall system response of the HVAM can be automatically checked at regular intervals by measuring the analyzer response to a metered amount of calibration standard injected into the dilute acid stream. The HVAM system provides two measurement ranges (threshold limit value (TLV): 10 to 1000 parts per billion (ppb)/LEAK: 100 ppb to 10 parts per million (ppm)). The LEAK range is created by dilution of the sulfuric acid/hydrazine liquid sample with pure water. This dual range capability permits the analyzer to quantify ambient air samples whose hydrazine concentrations range from 10 ppb to as high as 10 ppm. The laboratory and field prototypes have demonstrated total system response times on the order of 10 to 12 minutes for samples ranging from 10 to 900 ppb in the lLV mode and is greater than 2 minutes for samples ranging from 100 to 1300 ppb in the LEAK mode. Service intervals of over 3 months have been demonstrated for continuous 24 hour/day, 7 day/week usage. The HVAM is made up of a purged cabinet that contains power supplies, RS422 signal transmission capabilities, a UPS, an on-site warning system, and a Line Replaceable Unit (LRU). The LRU includes all of the liquid flow system, the analyzer, the control/data system microprocessor and assorted flow and liquid-level sensors. The LRU is mounted on a track slide system so it can be serviced inplace or totally removed and quickly exchanged with another calibrated unit, thus minimizing analyzer downtime. Once an LRU is removed from an analyzer enclosure, it can be brought to a laboratory facility for complete calibration and periodic maintenance.

Meneghelli, Barry↗

The Cool Flames Experiment

A space-based experiment is currently under development to study diffusion-controlled, gas-phase, low temperature oxidation reactions, cool flames and auto-ignition in an unstirred, static reactor. At Earth's gravity (1g), natural convection due to self-heating during the course of slow reaction dominates diffusive transport and produces spatio-temporal variations in the thermal and thus species concentration profiles via the Arrhenius temperature dependence of the reaction rates. Natural convection is important in all terrestrial cool flame and auto-ignition studies, except for select low pressure, highly dilute (small temperature excess) studies in small vessels (i.e., small Rayleigh number). On Earth, natural convection occurs when the Rayleigh number (Ra) exceeds a critical value of approximately 600. Typical values of the Ra, associated with cool flames and auto-ignitions, range from 104-105 (or larger), a regime where both natural convection and conduction heat transport are important. When natural convection occurs, it alters the temperature, hydrodynamic, and species concentration fields, thus generating a multi-dimensional field that is extremely difficult, if not impossible, to be modeled analytically. This point has been emphasized recently by Kagan and co-workers who have shown that explosion limits can shift depending on the characteristic length scale associated with the natural convection. Moreover, natural convection in unstirred reactors is never "sufficiently strong to generate a spatially uniform temperature distribution throughout the reacting gas." Thus, an unstirred, nonisothermal reaction on Earth does not reduce to that generated in a mechanically, well-stirred system. Interestingly, however, thermal ignition theories and thermokinetic models neglect natural convection and assume a heat transfer correlation of the form: q=h(S/V)(T(bar) - Tw) where q is the heat loss per unit volume, h is the heat transfer coefficient, S/V is the surface to volume ratio, and (T(bar) - Tw ) is the spatially averaged temperature excess. This Newtonian form has been validated in spatially-uniform, well-stirred reactors, provided the effective heat transfer coefficient associated with the unsteady process is properly evaluated. Unfortunately, it is not a valid assumption for spatially-nonuniform temperature distributions induced by natural convection in unstirred reactors. "This is why the analysis of such a system is so difficult." Historically, the complexities associated with natural convection were perhaps recognized as early as 1938 when thermal ignition theory was first developed. In the 1955 text "Diffusion and Heat Exchange in Chemical Kinetics", Frank-Kamenetskii recognized that "the purely conductive theory can be applied at sufficiently low pressure and small dimensions of the vessel when the influence of natural convection can be disregarded." This was reiterated by Tyler in 1966 and further emphasized by Barnard and Harwood in 1974. Specifically, they state: "It is generally assumed that heat losses are purely conductive. While this may be valid for certain low pressure slow combustion regimes, it is unlikely to be true for the cool flame and ignition regimes." While this statement is true for terrestrial experiments, the purely conductive heat transport assumption is valid at microgravity (mu-g). Specifically, buoyant complexities are suppressed at mu-g and the reaction-diffusion structure associated with low temperature oxidation reactions, cool flames and auto-ignitions can be studied. Without natural convection, the system is simpler, does not require determination of the effective heat transfer coefficient, and is a testbed for analytic and numerical models that assume pure diffusive transport. In addition, mu-g experiments will provide baseline data that will improve our understanding of the effects of natural convection on Earth.

Pearlman, Howard↗

Micrometer to Atomic Scale Characterisation of Primitive Astromaterials Using A Novel Method, Metis-Fa: A Coordinated Atom Probe Tomography, Transmission Electron Microscopy and NanoSIMS Approach

Introduction: Presolar grains preserve isotopic, chemical and microstructural records of physical and chemical processing, and formation mechanisms within a vast range of evolved stellar systems, the interstellar medium, solar nebula and their parent bodies. These evolutionary records are preserved at the micrometric to atomic scale, requiring coordinated studies to expand our understanding of evolutionary processes occurringthroughout ours and external stellar systems [1]. NanoSIMS enabled rapid in situ identification and isotopic characterisation of presolar grains and their stellar origins using 17O/16O and 18O/16O, and 13C/12C isotopic ratios [1]. Coordination with transmission electron microscopy (TEM) revealed crystallographic and localised contextual relationships and quantitively constrained their major and minor compositions [1]. However, trace elements cannot be quantified, the most sensitive geochemical tracers of environmental conditions, essential to unravelling the chemical record of their evolutionary pathway and parent stellar systems [2-3] . Furthermore, owing to the combination of technical limitations (only 5 – 7 isotopes can be measured per NanoSIMS run) and their small grain sizes of 100 nm < 3 μm (with rare exceptions in nanodiamonds (2 nm ≤) and SiC (< 40 μm)), the number of measurable isotopes per grain volume is limited [1,3] . Through more comprehensive isotopic studies of presolar grains, NanoSIMS studies have shown the importance of the latter, identifying Fe and Mg as important indicators of nuclear synthetic processing and their stellar origins, respectively [4- 5]. Coordination of NanoSIMS and Atom Probe Tomography (APT) revealed morphological signatures, and isotopic and chemical signatures at major to trace levels without requirements for preselection of elements [6]. However, crystallographic signatures in localized contextual relationships cannot be measured. Consequently, coordination of NanoSIMS, TEM and APT is essential to gain access to almost all contextual, structural and geochemical signatures within each presolar grain.Transmission electron microscopy requires a 100 nm thin lamella which is unstable in APT and would not produce any viable data. Atom probe tomography requires a needle-shaped specimen which when measured in TEM removes the local context, impacts the quality of the TEM diffraction images due to the shank angle of the needle, and can alter the chemistry of beam sensitive materials from the higher degree of surface exposure at the tip. To address these issues, we developed METIS-Fa (Multi-technical measurements of Electron Transparent materials using an Indium Sandwich - a FIB approach). A novel method which enables coordination of NanoSIMS, TEM and APT for generalized and targeted studies of individual grains, including beam sensitive materials, without compromising sample preparation requirements for TEM and APT. This method requires only indium and a Focus Ion Beam (FIB), minimizing the movement of fragile materials while still enabling preparation of TEM lamella into APT needles. Samples: Initial experimental development and testing of the method occurred at Astromaterials Research and Exploration Science (ARES), Johnson Space Centre (JSC), NASA and APT measurements and needle preparation occurred at JdLC, Curtin University. Synthetic silicate samples were used as analogs for presolar silicates when performing a trial run of the method. Samples were extracted from a polished thin section created at JSC, NASA, comprised of 38 wt.% Si, 17 wt.% FeO, 13 wt.% MgO, 12 wt.% Al, 11 wt.% Ca based on electron microprobe analysis (EMPA) [8] . Experimental details, pressure and temperature conditions were presented in [8] and references therein. Testing of the capability to target individual grains in mineral matrices using this method for acquisition in APT, measured matrix regions in meteoritic thin sections of primitive meteorites. These meteorites and their identified presolar grains for future targeted studies are detailed in [9]. Techniques: The TEM-FIB lamella were prepared using a FIB. An e-beam assisted pt deposition was used as a protective coating for the synthetic and meteoritic samples. When targeting individual grains, a secondary e-beam assisted pt deposition button is placed over the desired grain before the protective coating to denote its location. A JEOL 2500SE field-emission TEM was used for high-resolution imaging, energy-dispersive X-ray (EDX) and electron diffraction data.TheMETIS-Fa method was experimentally designed, tested and executed using a FIB at ARES, JSCNASA. Needles for APT were prepared using the Tescan Lyra3 GM Dual Beam Focus Ion Beam (FIB) Field Emission SEM (FE-SEM) at the JdLC, Curtin University. Atom probe tomography measurements were conducted using a CAMECA Local Electrode Atom Probe, LEAP 4000X HR. Two pure indium needles were analyzed initially to constraining acquisition parameters and stability under the beam. Manual acquisition was required to maintain evaporation of specimen’s at the apex and monitor interactions with measurement parameters. Experimental Design: Indium foil is pressed onto an Al stub with a pneumatic press and mounted into the FIB adjacent to the TEM-FIB lamella of interest. Using a FIB, two indium slices (5 μm x ~300 nm x 3 μm) are extracted from indium foil and aligned with the TEM-FIB lamella before touching the TEM-FIB lamella. Each slice is then attached through cold welding to the FIB-TEM lamella. This approach eliminates the need for chemical treatments and proved effective for aligning the Indium within the region of interest for APT, holding it in place for up to 4 days during testing.Once both indium slices are attached within their pre-determined region per grain targeting requirements, they are gradually melted onto the FIB-TEM lamella.When targeting a specific grain, measurements should be taken of the pt button and its distance from edge to edge of the lamella before and after sandwiching. A secondary button should be placed over the same region after the Indium slices have been attached to improve precision when preparing APT needles. Results: Figure 1 shows two indium slices melted onto a FIB-TEM lamella, adding additional bulk for preparation into APT needles as shown in Figure 2 [7] . The latter was essential so samples could be measured in TEM and APT without compromising sample preparation requirements and consequently data quality and acquisition stability. METIS-Fa proved effective forimproving geometry. Figure 3 shows a successful APTrun of the synthetic silicate. EMPA, TEM and APTshowed no chemical alterations. During targetingtesting, a solar silicate grain was successfully identifiedand measured in TEM, and prepared into an APTneedle. However, the indium was melted too long during sample preparation, causing expansion andformation of internal porosity leading to sample loss.Conclusion: METIS-Fa greatly expands the number of isotopic and chemical signatures measured per grain volume, and enables measurements of contextual, structural, crystallographic, isotopic and geochemical signatures within individual grains. Gaining access to such a vast range of evolutionary signatures required for expanding our understanding of external stellar and planetary systems and the evolution of our solar system. This method was designed for application to a vast range of phases including being sensitive materials and thus provides a way for coordination of NanoSIMS, TEM and APT not just for the study of presolar grains and by extension primitive astromaterials, but studies in a vast range of other fields including the geosciences and material sciences.Acknowledgments: Thankyou to ARES, JSC, NASA; JdLC Curtin University and Space Science Technology Centre for the use of laboratory facilities and funding [confirm].

Nicole D Nevill↗

Extraterrestrial Helium (He@C60) Trapped in Fullerenes in the Sudbury Impact Structure

Fullerenes (C60 and C70) have recently been identified in a shock-produced breccia (Onaping Formation) associated with the 1.85-Ga Sudbury Impact Crater. The presence of parts-per-million levels of fullerenes in this impact structure raises interesting questions about the processes that led to the formation of fullerenes and the potential for delivery of intact organic material to the Earth by a large bolide (e.g., asteroid or comet). Two possible scenarios for the presence of fullerenes in the Sudbury impact deposits are that (1) fullerenes are synthesized within the impact plume from the C contained in the bolide; or (2) fullerenes are already present in the bolide and survived the impact event. The correlation of C and trapped noble gas atoms in meteorites is well established. Primitive meteorites contain several trapped noble gas components that have anomalous isotopic compositions, some of which may have a presolar origin. Several C-bearing phases, including SiC, graphite, and diamond, have been recognized as carriers of trapped noble gases. It has also been suggested that fullerenes (C60 and C70) might be a carrier of noble gas components in carbonaceous chondrites. Recently, fullerenes have been detected in separate samples in the Allende meteorite. Carbon-60 is large enough to enclose the noble gases He, Ne, Ar, Kr, and Xe, but it is too small to contain diatomic gases such as N2 or triatomic gases such as CO2. Recent experimental work has demonstrated that noble gases of a specific isotopic composition can be introduced into synthetic fullerenes at high temperatures and pressures; these encapsulated gases can then be released by the breaking of one or more C bonds during step-heating under vacuum. These thermal-release patterns for He encapsulated within the C60 molecule (He@C60) are similar to the patterns for acid residues of carbonaceous chondrites, suggesting that fullerenes could be an additional carrier of trapped noble gases in acid residues of meteorites. Analysis and Results: In order to characterize the noble gas compositions of the Sudbury fullerenes, we undertook a systematic study of acid-resistant residues throughout the C-rich layer (Black member) of the Onaping Formation. Samples were demineralized and extracted using standard techniques. The Onaping extracts were analyzed using several techniques, including UV-Vis adsorption, electro spray mass spectrometry, and laser desorption (linear and reflectron) time-of-flight (TOF) mass spectrometry (LDMS). The Sudbury fullerenes were then separated and purified using HPLC coupled with a photo diode array detector. The HPLC extracts containing the purified fullerenes were loaded into a metal tube furnace within a glove box under a N atmosphere in preparation for noble gas analyses. The 3-He and 4-He content of the fullerene extracts was measured using previously reported standard techniques . Discussion: Fullerenes (C60 and C70) in the Sudbury Impact Structure have been found to contain trapped He with a 3-He/4-He ratio greater than 5 x 10(exp -4). The 3-He/4-He ratio exceeds the accepted solar value by more than 30% and is more than 10x higher than the maximum reported mantle value. Terrestrial nuclear reactions or cosmic-my bombardment are not sufficient to generate such a high ratio. The 3-He/4-He ratios in the Sudbury fullerenes are similar to those determined for interplanetary dust particles. The greater-than-solar ratios of 3-He/4-He in the Sudbury fullerenes may indicate a presolar origin, although alternative mechanisms occurring in the ISM to explain these high ratios (e.g., spallation reactions, selective He implantation, etc.) cannot be entirely ruled out. We are currently attempting to isolate enough fullerene material to measure anomalous Ne (or Kr or Xe) contained within the C60 (e.g., the "pure" 22-Ne component) and thus determine whether the Sudbury fullerenes are indeed presolar in origin.

Becker, L.↗