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Decoding IR Spectra of Cosmic Ices and Organics in the Laboratory

Tremendous strides have been made in our understanding of interstellar material over the past twenty-five years thanks to significant developments in observational IR astronomy and dedicated laboratory experiments. Twenty-five years ago the composition of interstellar dust was largely guessed at. Today the composition of interstellar dust is reasonably well understood. In the diffuse interstellar medium (ISM) the dust population is mainly comprised of small grains of silicates and amorphous carbon. In dark molecular clouds, the birthplace of stars and planets, these cold refractory dust particles are coated with mixed molecular ices whose composition is reasonably well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by early interstellar chemistry standards, is widespread throughout the Universe. This extraordinary progress has been made possible by the close collaboration of laboratory experimentalists and theoreticians with IR astronomers using groundbased, air-borne, and orbiting telescopes.

Allamandola, Louis J.

Compositional Variation in Apollo 16 Impact-Melt Breccias and Inferences for the Geology and Bombardment History of the Central Highlands of the Moon

High-precision data for the concentrations of a number of lithophile and siderophile elements were obtained on multiple subsamples from 109 impact-melt rocks and breccias (mostly crystalline) from the Apollo 16 site. Compositions of nearly all Apollo 16 melt rocks fall on one of two trends of increasing Sm concentration with increasing Sc concentration. The Eastern trend (lower Sm/Sc, Mg/Fe, and Sm/Yb ratios) consists of compositional groups 3 and 4 of previous classification schemes. These melt rocks are feldspathic, poor in incompatible and siderophile elements, and appear to have provenance in the Descartes formation to the east of the site. The Western trend (higher Sm/Sc. Mg/Fe, and Sm/ Yb ratios) consists of compositional groups 1 and 2. These relatively mafic, KREEP-bearing breccias are a major component (approx.35%) of the Cayley plains west of the site and are unusual, compared to otherwise similar melt breccias from other sites, in having high concentrations of Fe-Ni metal ( 1-2 %). The metal is the carrier of the low-Ir/Au (approx. 0.3 x chondritic) siderophile-element signature that is characteristic of the Apollo 16 site. Four compositionally distinct groups (1M, 1F, 2DB, and 2NR) of Western-trend melt breccias occur that are each represented by at least six samples. Compositional group 1 or previous classification schemes (the 'poikilitic' or 'LKFM' melt breccias) can be subdivided into two groups. Group 1M (represented by six samples, including 60315) is characterized by lower Al2O3 concentrations, higher MgO and alkali concentrations, and higher Mg/Fe and Cr/Sc ratios than group 1F (represented by fifteen samples, including 65015). Group 1M also has siderophile-element concentrations averaging about twice those of group lF and Ir/Au and Ir/Ni ratios that are even lower than those of other Western-trend melt rocks (Ir/Au = 0.24 +/- 0.03. CI-normalized). At the mafic extreme of group 2 ('VHA' melt breccias), the melt lithology occurring as clasts in feldspathic fragmental breccias from North Ray crater (group 2NR) is compositionally distinct from the melt lithology ofdimict breccias from the Cayley plains (group 2DB) in having higher concentrations of Sc, Cr, and heavy rare earth elements and lower concentrations of siderophile elements. The distinct siderophile-element signature (high absolute abundances, low Ir/Au ratio) suggest that the four groups ofmafic melt breccia are all somehow related. Ratios ofsome lithophile elements also suggest that they are more closely related to each other than then, are to melt breccias from other Apoll sites. However, none of the breccia compositions can be related to any of the others by any simple process of igneous fractionation or mixing involving common lunar materials. Thus, the origin of the four groups of mafic melt breccia is enigmatic. If they were produced in only one or two impacts, then a mechanism exists for generating regimes of impact-melt breccia in a single impact that are substantially different from each other in composition. For various reasons, including the problem of delivering large volumes of four different types of melt to the Apollo 16 site, it is unlikely that any of these breccias were produced in basin-forming impacts. If they were produced in as many as four crater-forming impacts, then the unusual siderophile-element signature is difficult to explain. Possible explanations are (1) the four groups of melt breccia all contain metal from a single, earlier impact, (2) they were each formed by related metal-rich meteoroids, or (3) some common postimpact process has resulted in metal of similar composition in each of four melt pools. Within a compositional group, most intrasample and intersample variation in lithophile element concentrations is caused by differences among samples in the proportion of a component of normative anorthosite or noritic anorthosite. In most cases, this compositional variation probably reflects variation in clast abundance. For group 2DB (and probably 2NR), differences in abundance of a component of ferroan anorthosite (estimated Al2O3 approx. 32%) accounts for the compositional variation. For groups 1M and 1F, the anorthositic component is more mafic (estimated Al203 approx. 26%). Some group-2 samples may be related by a troctolitic component of varying abundance.

Korotev, Randy L.

Experimental Assessment of the Emissions Control Potential of a Rich/Quench/Lean Combustor for High Speed Civil Transport Aircraft Engines

In support of Pratt & Whitney efforts to define the Rich burn/Quick mix/Lean burn (RQL) combustor for the High Speed Civil Transport (HSCT) aircraft engine, UTRC conducted a flametube-scale study of the RQL concept. Extensive combustor testing was performed at the Supersonic Cruise (SSC) condition of a HSCT engine cycle, Data obtained from probe traverses near the exit of the mixing section confirmed that the mixing section was the critical component in controlling combustor emissions. Circular-hole configurations, which produced rapidly-, highly-penetrating jets, were most effective in limiting NOx. The spatial profiles of NOx and CO at the mixer exit were not directly interpretable using a simple flow model based on jet penetration, and a greater understanding of the flow and chemical processes in this section are required to optimize it. Neither the rich-combustor equivalence ratio nor its residence time was a direct contributor to the exit NOx. Based on this study, it was also concluded that (1) While NOx formation in both the mixing section and the lean combustor contribute to the overall emission, the NOx formation in the mixing section dominates. The gas composition exiting the rich combustor can be reasonably represented by the equilibrium composition corresponding to the rich combustor operating condition. Negligible NOx exits the rich combustor. (2) At the SSC condition, the oxidation processes occurring in the mixing section consume 99 percent of the CO exiting the rich combustor. Soot formed in the rich combustor is also highly oxidized, with combustor exit SAE Smoke Number <3. (3) Mixing section configurations which demonstrated enhanced emissions control at SSC also performed better at part-power conditions. Data from mixer exit traverses reflected the expected mixing behavior for off-design jet to crossflow momentum-flux ratios. (4) Low power operating conditions require that the RQL combustor operate as a lean-lean combustor to achieve low CO and high efficiency. (5) A RQL combustor can achieve the emissions goal of EINOX = 5 at the Supersonic Cruise operating condition for a HSCT engine.

Rosfjord, T. J.

Experimental Assessment of the Emissions Control Potential of a Rich/Quench/ Lean Combustor for High Speed Civil Transport Aircraft Engines

In support of Pratt & Whitney efforts to define the Rich burn/Quick mix/Lean burn (RQL) combustor for the High Speed Civil Transport (HSCT) aircraft engine, UTRC conducted a flametube-scale study of the RQL concept. Extensive combustor testing was performed at the Supersonic Cruise (SSC) condition of an HSCT engine cycle. Data obtained from probe traverses near the exit of the mixing section confirmed that the mixing section was the critical component in controlling combustor emissions. Circular-hole configurations, which produced rapidly-, highly-penetrating jets, were most effective in limiting NO(x). The spatial profiles of NO(x) and CO at the mixer exit were not directly interpretable using a simple flow model based on jet penetration, and a greater understanding of the flow and chemical processes in this section are required to optimize it. Neither the rich-combustor equivalence ratio nor its residence time was a direct contributor to the exit NO(x). Based on this study, it was also concluded that: (1) While NO(x) formation in both the mixing section and the lean combustor contribute to the overall emission, the NOx formation in the mixing section dominates. The gas composition exiting the rich combustor can be reasonably represented by the equilibrium composition corresponding to the rich combustor operating condition. Negligible NO(x) exits the rich combustor. (2) At the SSC condition, the oxidation processes occurring in the mixing section consume 99 percent of the CO exiting the rich combustor. Soot formed in the rich combustor is also highly oxidized, with combustor exit SAE Smoke Number <3. (3) Mixing section configurations which demonstrated enhanced emissions control at SSC also performed better at part-power conditions. Data from mixer exit traverses reflected the expected mixing behavior for off-design jet to crossflow momentum-flux ratios. (4) Low power operating conditions require that the RQL combustor operate as a lean-lean combustor to achieve low CO and high efficiency. (5) An RQL combustor can achieve the emissions goal of EINO(x) = 5 at the Supersonic Cruise operating condition for an HSCT engine.

Tacina, Robert R.

Recent developments in polyimide and bismaleimide adhesives

Research on high temperature resin systems has intensified. In the Aerospace Industry, the motivation for this increased activity has been to replace heat resistant alloys of aluminum, stainless steel and titanium by lighter weight glass and carbon fiber reinforced composites. Applications for these structures include: (1) engine nacelles involving long time exposure (thousands of hours) to temperatures in the 150 to 300 C range, (2) supersonic military aircraft involving moderately long exposure (hundreds of hours) to temperatures of 150 to 200 C, and (3) missile applications involving only brief exposure (seconds or minutes) to temperatures up to 500 C and above. Because of fatigue considerations, whenever possible, it is preferable to bond rather than mechanically fasten composite structures. For this reason, the increased usage of high temperature resin matrix systems for composites has necessitated the devlopment of compatible and equally heat stable adhesive systems. The performance of high temperature epoxy, epoxy phenolic and condensation polyimide adhesives is reviewed. This is followed by a discussion of three recently developed types of adhesives: (1) condensation reaction polyimides having improved processing characteristics; (2) addition reaction polyimides; and (3) bismaleimides.

Politi, R. E.

Theoretical models for Mars and their seismic properties

Theoretical seismic properties of the planet Mars are investigated on the basis of the various models which have been proposed for the internal composition of the planet. The latest interpretation of gravity-field data, assuming a lower value of the moment of inertia, would require a less dense mantle and a larger core than previous models. If Mars is chondritic in composition, the most reasonable models are an incompletely differentiated H-chondrite or a mixture of H-chondrites and carbonaceous chondrites. Seismic profiles, travel times, and free oscillation periods are computed for various models, with the aim of establishing which seismic data is crucial for deciding among the alternatives. A detailed discussion is given of the seismic properties which could - in principle - help answer the questions of whether Mars' core is liquid or solid and whether Mars has a partially molten asthenosphere in its upper mantle.

Okal, E. A.

The composition of ultra-heavy cosmic rays

Preliminary results on the composition of ultraheavy nuclei in the cosmic rays are now available from experiments on HEAO-3 and Ariel-VI satellites. These results are compared with the composition predicted for reasonable propagation models using source abundances similar to those of solar system material. The effects of varying model parameters and of preferential acceleration are discussed. Discrepancies between predicted and observed abundances are larger than can be accounted for solely by first ionization potential effects and are interpreted in terms of a nucleosynthesis process.

Protheroe, R. J.

Pulse propagation in a laminated composite plate and nondestructive evaluation

The surface response of a laminated composite plate with delamination cracks has been studied in this paper. The objective of this study is to analyze the surface response both in the time and frequency domains due to delamination cracks at different depths in a cross-ply composite plate. For reasons of simplicity, attention has been focused here on two-dimensional (plane-strain) motions. The source of excitation is taken to be a line vertical force acting perpendicular to the fibers in a lamina. Numerical results are presented, showing peak responses at certain resonance frequencies. A comparison of these results with those for a uniaxial graphite epoxy plate shows characteristic differences.

Ju, T. H.

The spectrum of the planetary nebula IC 418

A detailed high-spectral-resolution study of the spectrum of IC 418 is made for the region 3650 to 10050 A, using the Hamilton echelle spectrograph of Lick Observatory, and of the UV spectral region with archival International Ultraviolet Explorer (IUE) data. From high-resolution images in both the near- and mid-infrared, Hora et al. (1993) showed that IC 418 probably has a compact shell interior to the detached, well-known, main shell emission. If one assumes a black body or Hubeny (or standard LTE) model atmosphere energy distribution, it does not appear possible to construct a fully satisfactory nebula model that will simultaneously represent the H-beta flux, the (O III) 5007/H-beta ratio, and the scale of this planetary nebula (PN). Fortunately, IUE and IR data supply information on ions in addition to those optically observed so that the chemical composition can be reasonably well established by summing over concentrations of observed ions. In spite of the fact that IC 418 is carbon rich in sense of having a C/O ratio exceeding the solar value, it is a 'metal-poor' object. Possibly it resembles IC 4997 but in a more advanced evolutionary phase. The central star is variable and has a strong wind.

Hyung, Siek

REE Partition Coefficients from Synthetic Diogenite-Like Enstatite and the Implications of Petrogenetic Modeling

Determining the petrogenesis of eucrites (basaltic achondrites) and diogenites (orthopyroxenites) and the possible links between the meteorite types was initiated 30 years ago by Mason. Since then, most investigators have worked on this question. A few contrasting theories have emerged, with the important distinction being whether or not there is a direct genetic link between eucrites and diogenites. One theory suggests that diogenites are cumulates resulting from the fractional crystallization of a parent magma with the eucrites crystallizing, from the residual magma after separation from the diogenite cumulates. Another model proposes that diogenites are cumulates formed from partial melts derived from a source region depleted by the prior generation of eucrite melts. It has also been proposed that the diogenites may not be directly linked to the eucrites and that they are cumulates derived from melts that are more orthopyroxene normative than the eucrites. This last theory has recently received more analytical and experimental support. One of the difficulties with petrogenetic modeling is that it requires appropriate partition coefficients for modeling because they are dependent on temperature, pressure, and composition. For this reason, we set out to determine minor- and trace-element partition coefficients for diogenite-like orthopyroxene. We have accomplished this task and now have enstatite/melt partition coefficients for Al, Cr, Ti, La, Ce, Nd, Sm, Eu, Dy, Er, Yb, and La.

Schwandt, C. S.

Europa: Processes and Habitability

This viewgraph presentation reviews the known and possible geologic processes of Europa. It shows slides of Europa, with different terrains (ridged plains and molten plains), and a possible view of the interior. Europa's eccentric orbit is reviewed. The presentation also reviews Europa's composition. The possible reasons for Europa's geology are reviewed. Also the possiblity that life exists on Europa is raised. The planned Europa Geophysical Explorer mission is also reviewed.

Europa

Comparison of Several Global Mixing Performance Metrics for High-Speed Fuel Injectors

To experimentally assess and compare the mixing performance of high-speed fuel injectors for scramjet engines, quantitative global metrics are needed. The one-dimensional metric most commonly used to assess the degree of mixing completeness at a given downstream station is the mixing efficiency parameter. The experimental determination of the mixing efficiency parameter requires measurement of the spatial distributions of both the fuel mass fraction and the mass flux. Standard in-stream gas sampling techniques can be used to measure the fuel mass fraction distribution, however the mass flux distribution is not easily determined experimentally because it requires the measurement of three independent aerothermodynamic variables in addition to the mixture composition. For this reason, several metrics that can be calculated from the fuel distribution alone are commonly used to assess mixing performance. Because these other metrics do not provide a mass flux-weighted measure of the local degree of mixing completeness, they may not correlate well with the mixing efficiency parameter. Therefore, if the substitute metrics are to be used to compare the mixing performance of candidate fuel injector concepts, it is important to understand their relationships to the mixing efficiency parameter in a representative scramjet combustor flowfield. This work investigates the relationships between the mixing efficiency parameter and several substitute metrics that are able to be measured with the current experimental setup of the Enhanced Injection and Mixing Project at the NASA Langley Research Center for baseline strut and ramp injectors. The results of these comparisons have revealed that it is possible to glean different (i.e., incorrect) conclusions about which injector is the better mixer when the substitute mixing performance metrics are used instead of the mixing efficiency parameter, thereby highlighting the importance of mass flux-weighted mixing performance metrics.

Ground, Cody R.

Mixed-Domain Charge Transport in S-Se Alloys as a Li-S Battery Cathode Material

Lithium-sulfur batteries are emerging candidate systems for the next-generation long-range electric aircraft application owing to their potential to deliver high energy density per weight. Their cathodes are to be made primarily with sulfur, but sulfur by itself has much too low electron conductivity to serve as a useful cathode. An idea that has been suggested to overcome this bottleneck is to alloy sulfur with selenium in the hope that electron mobility, which is thought to improve charge transport at some expense of increased weight and reduced energy density. However, understanding of these alloy structures and their transport mechanism is insufficient, and electron mobility at varying degrees of selenium content is not well charted, which are critical for determining the optimum selenium content and testing whether this strategy is generally feasible. The difficulty of computationally characterizing these alloy systems is rooted in the structure. The structures of both sulfur and selenium exhibit eight-atom rings that pack together in various orientations to form their respective crystals. For one, because these crystals (and presumably their alloys as well) feature multiple polymorphs such that their structural coherence is rather unclear. Secondly, these are also relatively large systems (32 atoms per cell) with low-symmetry, which complicate computation both in terms of accuracy and efficiency. Thirdly, such semi-molecular, semi-crystalline structures lead to a combination of band-transport characteristics and hopping-transport characteristics, each of which is a domain with its own physics and set of computational, theoretical challenges. In addition, there is a general dearth of experimental transport data for sulfur-selenium alloys. In this study, we make a comprehensive attempt to tackle this problem using a wide array of first-principles methods. We generate special quasirandom structures to simulate alloy structures, and compute their first-principles Raman spectra for comparison with experimental data to ensure their structural soundness. We then proceed to use recently developed, state-of-the-art tool (AMSET) in order to efficiently compute electronic mobilities under band transport of pure sulfur, pure selenium, as well as their alloys of various compositions at a reasonable accuracy. We then sample numerous dimer configurations of nearest-neighbor eight-atom-ring-pairs and compute electronic hopping rates between them, which yields hopping mobility. A combination of these efforts lead to a general mapping of electron transport behaviors throughout the alloy range. Preliminary results show that introduction of selenium into sulfur initially damages electron mobility due to disorder but eventually improves it beyond that of pure sulfur with additional selenium content, ultimately peaking at the pure-selenium limit. Band transport dominates for holes in sulfur and electrons in selenium, but in all other cases, hopping transport is dominant. Ongoing efforts include determination of charge concentration and conductivity, as well as performing multiphysics modeling to determine the optimum selenium content for best tradeoff between conductivity and energy density for aircraft range.

Junsoo Park

Idunn Mons as the landing site of the Venera-D mission: scientific relevance and possible operational tests on Mount Etna.

Along with the recently selected NASA DAVINCI [1] and VERITAS [2] missions, and with the ESA EnVision mission [3], the Roscosmos Venera-D mission [4,5] opens the new decade of Venus exploration. Among these missions, the Venera-D is the only one to be equipped with a lander which could drill the surface of Venus and analyze its chemical composition. For this reason, it is crucial to select a future landing site based on its scientific relevance, as well as on safety constraints. We propose here Idunn Mons (Figure 1a), a major large volcano of Imdr Regio, as the landing site for the Venera-D mission. We also indicate Mount Etna in Italy (Figure 1b) as a suitable test site on Earth for drilling tests and in-situ elemental and mineralogical analyses [6,7].

venus

Abstraction and Assume-Guarantee Reasoning for Automated Software Verification

Compositional verification and abstraction are the key techniques to address the state explosion problem associated with model checking of concurrent software. A promising compositional approach is to prove properties of a system by checking properties of its components in an assume-guarantee style. This article proposes a framework for performing abstraction and assume-guarantee reasoning of concurrent C code in an incremental and fully automated fashion. The framework uses predicate abstraction to extract and refine finite state models of software and it uses an automata learning algorithm to incrementally construct assumptions for the compositional verification of the abstract models. The framework can be instantiated with different assume-guarantee rules. We have implemented our approach in the COMFORT reasoning framework and we show how COMFORT out-performs several previous software model checking approaches when checking safety properties of non-trivial concurrent programs.

Chaki, S.

Surface compositional and structural aspects of Martian samples

There are many excellent reasons to examine the surface composition of a wide range of Martian samples. The existing spectral data indicate that many dust and soil particles have a thin Fe(+3) layer with a typical particle size in the 10 micrometer to 400 micrometer range. In view of the high CO2 content of the atmosphere, one might expect that surface carbonates should be present. In addition to chemisorbed material there will probably exist physisorbed atmospheric components of the atmosphere including oxygen, nitrogen and water vapor. The latter could possibly give rise to some hydrated minerals. Using ultra-high-vacuum/mass spectrographic techniques it should be possible to detect physisorbed and moderately strong chemisorbed species on the particle surfaces with a temperature programmed degassing procedure. In some instances such an approach is capable of helping distinguish between volcanic and impact generated materials by detecting the presence of fumerolic gases. Such gases typically condense on the exterior of the ejected particles. Additionally surface atomic and chemical compositions should be examined by a combination of modern surface analytical techniques. The combination we currently have in Buffalo at SUNY would appear to be one of the best available including ESCA (150 micrometer spot capability) Auger (SAM) with 300 A focussing for surface compositional surveys, SIMS for high sensitivity trace element detection and ISS for immediate surface layer analysis.

Cadenhead, D. A.

Electrically Conducting, Ca-Rich Brines, Rather Than Water, Expected in the Martian Subsurface

If Mars ever possessed a salty liquid hydrosphere, which later partly evaporated and froze down, then any aqueous fluids left near the surface could have evolved to become dense eutectic brines. Eutectic brines, by definition, are the last to freeze and the first to melt. If CaC12-rich, such brines can remain liquid until temperatures below 220 K, close to the average surface temperature of Mars. In the Martian subsurface, in intimate contact with the Ca-rich basaltic regolith, NaC1-rich early brines should have reacted to become Ca-rich. Fractional crystallization (freezing) and partial melting would also drive brines toward CaC12-rich compositions. In other words, eutectic brine compositions could be present in the shallow subsurface of Mars, for the same reasons that eutectic magma compositions are common on Earth. Don Juan Pond, Antarctica, a CaC12-rich eutectic brine, provides a possible terrestrial analog, particularly because it is fed from a basaltic aquifer. Owing to their relative density and fluid nature, brines in the Martian regolith should eventually become sandwiched between ice above and salts beneath. A thawing brine sandwich provides one explanation (among many) for the young gullies recently attributed to seepage of liquid water on Mars. Whether or not brine seepage explains the gullies phenomenon, dense, CaC12-rich brines are to be expected in the deep subsurface of Mars, although they might be somewhat diluted (temperatures permitting) and of variable salt composition. In any case, they should be good conductors of electricity.

Burt, D. M.

Progressive Damage and Failure Analysis of Bonded Composite Joints at High Energy Dynamic Impacts

Both wing and fuselage structures utilize bonded composite joints for structural efficiency in modern commercial and military aircraft. To ensure compliance with certification requirements mechanical fasteners are typically used as a failsafe mechanism for appropriate strength in the event of complete stiffener disbond. However, the use of fasteners decreases the structural efficiency of the structure by adding weight. This establishes the requirement to better exploit the efficiency of bonded structures and fully understand the failure behavior of adhesively bonded composite structures, particularly when subjected to elevated loading rates due to high energy dynamic impacts (HEDI). For this reason, the NASA Advanced Composite Consortium (ACC) HEDI team developed an experimentation and numerical modeling program for high rate loading of composite joints. In the present work, the response of adhesively bonded composite joints subjected to elevated loading rates is studied numerically and validated against experimental results. Due to dynamic considerations of experiments, the idea of wedge insert was extended to use with Split Hopkinson Pressure Bar (SHPB) testing techniques. Mode-I and Mode-II test configurations were simulated to evaluate the capability of two continuum damage material (CDM) models in LS-DYNA, namely MAT162 and MAT261. Three different levels of fidelity were considered to investigate the level of detail required to numerically predict the failure behavior and the results from high fidelity analysis are presented.

MAT261