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Thermal Model of the Promoted Combustion Test

Flammability of metals in high pressure, pure oxygen environments, such as rocket engine turbopumps, is commonly evaluated using the Promoted Combustion Test (PCT). The PCT emphasizes the ability of an ignited material to sustain combustion, as opposed to evaluating the sample's propensity to ignite in the first place. A common arrangement is a rod of the sample material hanging in a chamber in which a high pressure, pure oxygen environment is maintained. An igniter of some energetically combusting material is fixed to the bottom of the rod and fired. This initiates combustion, and the sample burns and melts at its bottom tip. A ball of molten material forms, and this ball detaches when it grows too large to be supported by surface tension with the rod. In materials which do not sustain combustion, the combustion then extinguishes. In materials which do sustain combustion, combustion re-initiates from molten residue left on the bottom of the rod, and the melt ball burns and grows until it detaches again. The purpose of this work is development of a PCT thermal simulation model, detailing phase change, melt detachment, and the several heat transfer modes. Combustion is modeled by a summary rate equation, whose parameters are identified by comparison to PCT results. The sensitivity of PCT results to various physical and geometrical parameters is evaluated. The identified combustion parameters may be used in design of new PCT arrangements, as might be used for flammability assessment in flow-dominated environments. The Haynes 214 nickel-based superalloy, whose PCT results are applied here, burns heterogeneously (fuel and oxidizer are of different phases; combustion takes place on the fuel surface). Heterogeneous combustion is not well understood. (In homogeneous combustion, the metal vaporizes, and combustion takes place in an analytically treatable cloud above the surface). Thermal modeling in heterogeneous combustion settings provides a means for linking test results more directly to detailed combustion mechanics, leading to improved data analysis, and improved understanding of heterogeneous combustion phenomena.

Jones, Peter D.↗

Roosevelt County 075: A petrologic chemical and isotopic study of the most unequilibrated known H chondrite

Roosevelt County (RC) 075 was recovered in 1990 as a single 258-gram stone. Classification of this meteorite is complicated by its highly unequilibrated nature and its severe terrestrial weathering, but we favor H classification. This is supported by O isotopes and estimates of the original Fe, Ni metal content. The O isotopic composition is similar to that of a number of reduced ordinary chondrites (e.g., Cerro los Calvos, Willaroy), although RC 075 exhibits no evidence of reduced mineral compositions. Chondrule diameters are consistent with classification as an L chondrite, but large uncertainties in chondrule diameters of RC 075 and poorly constrained means of H, L and LL chondrites prevent use of this parameter for reliable classification. Other parameters are compromised by severe weathering (e.g., siderophile element abundances) or unsuitable for discrimination between unequilibrated H, L and LL chondrites (e.g., Co in kamacite delta C-13). Petrologic subtype 3.2 +/- 0.1 is suggested by the degree of olivine heterogeneity, the compositions of chondrule olivines, the thermoluminescence sensitivity, the abundances and types of chondrules mapped on cathodoluminescence mosaics, and the amount of presolar SiC. The meteorite is very weakly shocked (S2), with some chondrules essentially unshocked and, thus, is classified as an H3.2(S2) chondrite. Weathering is evident by a LREE enrichment due to clay contamination, reduced levels of many siderophile elements, the almost total loss of Fe, Ni metal and troilite, and the reduced concentrations of noble gases. Some components of the meteorite (e.g., type IA chondrules, SiC) appear to preserve their nebular states, with little modification from thermal metamorphism. We conclude that RC 075 is the most equilibrated H chondrite yet recovered and may provide additional insights into the origin of primitive materials in the solar nebula.

Mccoy, T. J.↗

Influence of Specimen Preparation and Specimen Size on Composite Transverse Tensile Strength and Scatter

The influence of specimen polishing, configuration, and size on the transverse tension strength of two glass-epoxy materials, and one carbon-epoxy material, loaded in three and four point bending was evaluated. Polishing machined edges, arid/or tension side failure surfaces, was detrimental to specimen strength characterization instead of yielding a higher, more accurate, strength as a result of removing inherent manufacture and handling flaws. Transverse tension strength was typically lower for longer span lengths due to the classical weakest link effect. However, strength was less sensitive to volume changes achieved by increasing specimen width. The Weibull scaling law typically over-predicted changes in transverse tension strengths in three point bend tests and under-predicted changes in transverse tension strengths in four point bend tests. Furthermore, the Weibull slope varied with specimen configuration, volume, and sample size. Hence, this scaling law was not adequate for predicting transverse tension strength of heterogeneous, fiber-reinforced, polymer matrix composites.

OBrien, T. Kevin↗

Combustion of Metals in Reduced-Gravity and Extra Terrestrial Environments

The combustion of metals is a field with important practical applications in rocket propellants, high-temperature flames, and material synthesis. Also, the safe operation of metal containers in high-pressure oxygen systems and with cryogenic fuels and oxidizers remains an important concern in industry. The increasing use of metallic components in spacecraft and space structures has also raised concerns about their flammability properties and fire suppression mechanisms. In addition, recent efforts to embark on unmanned and manned planetary exploration, such as on Mars, have also renewed the interest in metal/carbon-dioxide combustion as an effective in situ resource utilization technology. In spite of these practical applications, the understanding of the combustion properties of metals remains far behind that of the most commonly used fuels such as hydrocarbons. The lack of understanding is due to the many problems unique to metal- oxidizer reactions such as: low-temperature surface oxidation prior to ignition, heterogeneous reactions, very high combustion temperatures, product condensation, high emissivity of products, and multi-phase interactions. Very few analytical models (all neglecting the influence of gravity) have been developed to predict the burning characteristics and the flame structure details. Several experimental studies attempting to validate these models have used small metal particles to recreate gravity-free conditions. The high emissivity of the flames, rapid reaction, and intermittent explosions experienced by these particles have made the gathering of any useful information on burning rates and flame structure very difficult. The use of a reduced gravity environment is needed to clarify some of the complex interactions among the phenomena described above. First, the elimination of the intrusive buoyant flows that plague all combustion phenomena is of paramount importance in metal reactions due to the much higher temperatures reached during combustion. Second, a low-gravity environment is absolutely essential to remove the destructive effect of gravity on the shape of a molten metal droplet in order to study a spherically symmetric condition with large bulk samples. The larger size of the spherical metal droplet and the longer burning times available in reduced gravity extend the spatial and temporal dimensions to permit careful probing of the flame structure and dynamics. Third, the influence of the radiative heat transfer from the solid oxides can be studied more carefully by generating a stagnant spherical shell of condensed products undisturbed by buoyancy.

Branch, M.C.↗

Composition of Rheasilvia Basin on Asteroid Vesta

The focus of the present study is the compositional analysis of small-scale surface features within the Rheasil-Aa basin on asteroid Vesta. We are using data acquired by the Visible and InfraRed mapping Spectrometer (VIR) on the Dawn mission. Nominal spatial resolution of the data set considered in this study is 70m/px. The portion of Rheasil-Aa basin below 65degS has a howarditic composition, with the higher concentration of diogenitic versus eucritic material in the region between 45deg and 225degE-lon. However, there are several locations, such as craters Tarpeia and Severina and Parentatio Rupes, with lithologic characteristics different from the surroundings regions. Tarpeia crater has a eucritic patch in the west side of the crater, the bottom part ofthe wall and part of the floor. Severina, located in a region of Mg-rich pyroxene, has some diogenitic units on the walls of the crater. Also the Parentatio Rupes has an ob-AOUS diogenitic unit. These units extend for 10-20km, and their location, especially in the case of the two craters, suggests they formed before the cratering events and also before the Rheasil-Aa impact event. The origin of these units is still unclear; however, their characteristics and locations suggests heterogeneity in the composition of the ancient Vestan crust in this particular location of the surface.

Ammannito, Eleonora↗

Modeling the Prodromal Effects and Performance Reduction of Astronauts from Exposure to Large Solar Particle Events

In space exploration outside the Earth's geomagnetic field, radiation exposure from solar particle events (SPE) presents a health concern for astronauts, that could impair their performance and result in possibility of failure of the mission. Acute risks are especially of concern during spacewalks on the lunar surface because of the rapid onset of SPE's and science goals that involve long distances to crew habitats. Thus assessing the potential of early radiation effect under such adverse conditions is of prime importance. Here we present a biologic based mathematical model which describes the dose and time-dependent early human responses to ionizing radiation. We examine the possible early effects on crew behind various shielding materials from exposure to some historical large SPEs on the lunar and Mars surfaces. The doses and dose rates were calculated using the BRYNTRN code (Kim, M.Y, Hu, X, and Cucinotta, F.A, Effect of Shielding Materials from SPEs on the Lunar and Mars Surface, AIAA Space 2005, paper number AIAA-2005-6653, Long Beach, CA, August 30-September 1, 2005) and the hazard of the early radiation effects and performance reduction were calculated using the RIPD code (Anno, G.H, McClellan, G.E., Dore, M.A, Protracted Radiation-Induced Performance Decrement, Volume 1 Model Development,1996, Defense Nuclear Agency: Alexandria VA). Based on model assumptions we show that exposure to these historical SPEs do cause early effects to crew members and impair their performance if effective shielding and medical countermeasure tactics are not provided. The calculations show multiple occurrence of large SPEs in a short period of time significantly increase the severity of early illness, however early death from failure of the hematopoietic system is very unlikely because of the dose-rate and dose heterogeneity of SPEs. Results from these types of calculations will be a guide in design of protection systems and medical response strategy for astronauts in case of exposure to high dose irradiation during future space missions.

Hu, S.↗

Indigenous Carbon Embedded in Apollo 17 Black Volcanic Glass Surface Deposits

The assessment of indigenous organic matter in returned lunar samples was one of the primary scientific goals of the Apollo program. The levels of such organic material were expected to be and found to be small. Previous work on this topic includes Murphy et al. [1] who reported the presence of anthropogenic organics with sub-ppm concentrations in Apollo 11 fines. In Apollo 12 samples, Preti et al. [2] detected low levels, < 10 ppb or below, of more complex organic material that may have been synthesized by abrupt heating during analysis. Kvenvolden et al. [3] detected porphyrin-like pigments at the ng to pg level in an Apollo 11 bulk sample. Hodgson et al. [4] and Ponnamperuma et al. [5] suggested that most if not all porphyrins were synthesized from rocket fuel during module landing. Chang et al. [6] reported indigenous carbon ranging from 5-20 g/g in the form of metal carbides in Apollo 11 fines. Hare et al. [7] reported amino acids at he 50 ng/g level in Apollo 11 samples but suggested the results may be explained as contamination. More recently, Clemett et al. [8] reported simple polycyclic aromatic hydrocarbons at concentrations of < 1ppm in an Apollo 16 soil. Low concentrations of lunar organics may be a consequence not only of its paucity, but also its heterogeneous distribution. If the sample size required for a measurement is large relative to the localization of organics, detection is limited not by ultimate sensitivity but rather by the ability to distinguish an indigenous signature from background contamination [9].

Thomas-Keprta, Kathie L.↗

Forced Forward Smoldering Experiments Aboard The Space Shuttle

Smoldering is a basic combustion problem that presents a fire risk because it is initiated at low temperatures and because the reaction can propagate slowly in the material interior and go undetected for long periods of time. It yields a higher conversion of fuel to toxic compounds than does flaming, and may undergo a transition to flaming. To date there have been a few minor incidents of overheated and charred cables and electrical components reported on Space Shuttle flights. With the establishment of the International Space Station, and the planning of a potential manned mission to Mars, there has been an increased interest in the study of smoldering in microgravity. The Microgravity Smoldering Combustion (MSC) experiment is part of a study of the smolder characteristics of porous combustible materials in a spacecraft environment. The aim of the experiment is to provide a better fundamental understanding of the controlling mechanisms of smoldering combustion under normal- and microgravity conditions. This in turn will aid in the prevention and control of smolder originated fires, both on earth and in spacecrafts. The microgravity smoldering experiments have to be conducted in a space-based facility because smoldering is a very slow process and consequently its study in a microgravity environment requires extended periods of time. The microgravity experiments reported here were conducted aboard the Space Shuttle. The most recent tests were conducted during the STS-105 and STS-108 missions. The results of the forward smolder experiments from these flights are reported here. In forward smolder, the reaction front propagates in the same direction as the oxidizer flow. The heat released by the heterogeneous oxidation reaction is transferred ahead of the reaction heating the unreacted fuel. The resulting increase of the virgin fuel temperature leads to the onset of the smolder reaction, and propagates through the fuel. The MSC data are compared with normal gravity data to determine the effect of gravity on smolder.

Fernandez-Pello, A. C.↗

NASA Microgravity Combustion Science Program

Combustion is a key element of many critical technologies used by contemporary society. For example, electric power production, home heating, surface and air transportation, space propulsion, and materials synthesis all utilize combustion as a source of energy. Yet, although combustion technology is vital to our standard of living, it poses great challenges to maintaining a habitable environment. For example, pollutants, atmospheric change and global warming, unwanted fires and explosions, and the incineration of hazardous wastes are major problem areas which would benefit from improved understanding of combustion. Effects of gravitational forces impede combustion studies more than most other areas of science since combustion involves production of high-temperature gases whose low density results in buoyant motion, vastly complicating the execution and interpretation of experiments. Effects of buoyancy are so ubiquitous that their enormous negative impact on the rational development of combustion science is generally not recognized. Buoyant motion also triggers the onset of turbulence, yielding complicating unsteady effects. Finally, gravity forces cause particles and drops to settle, inhibiting deconvoluted studies of heterogeneous flames important to furnace, incineration and power generation technologies. Thus, effects of buoyancy have seriously limited our capabilities to carry out 'clean' experiments needed for fundamental understanding of flame phenomena. Combustion scientists can use microgravity to simplify the study of many combustion processes, allowing fresh insights into important problems via a deeper understanding of elemental phenomena also found in Earth-based combustion processes and to additionally provide valuable information concerning how fires behave in microgravity and how fire safety on spacecraft can be enhanced.

King, Merrill K.↗

The Metastable Persistence of Vapor-Deposited Amorphous Ice at Anomalously High Temperatures

Studies of the gas release, vaporization behavior and infrared (IR) spectral properties of amorphous and crystalline water ice have direct application to cometary and planetary outgassing phenomena and contribute to an understanding of the physical properties of astrophysical ices. Several investigators report anomalous phenomena related to the warming of vapor-deposited astrophysical ice analogs. However gas release, ice volatilization and IR spectral features are secondary or tertiary manifestations of ice structure or morphology. These observations are useful in mimicking the bulk physical and chemical phenomena taking place in cometary and other extraterrestrial ices but do not directly reveal the structural changes which are their root cause. The phenomenological interpretation of spectral and gas release data is probably the cause of somewhat contradictory explanations invoked to account for differences in water ice behavior in similar temperature regimes. It is the microstructure, micromorphology and microchemical heterogeneity of astrophysical ices which must be characterized if the mechanisms underlying the observed phenomena are to be understood. We have been using a modified Transmission Electron Microscope to characterize the structure of vapor-deposited astrophysical ice analogs as a function of their deposition, temperature history and composition. For the present experiments, pure water vapor is deposited at high vacuum onto a 15 K amorphous carbon film inside an Hitachi H-500H TEM. The resulting ice film (approx. 0.05 micrometers thick) is warmed at the rate of 1 K per minute and diffraction patterns are collected at 1 K intervals. These patterns are converted into radial intensity distributions which are calibrated using patterns of crystalline gold deposited on a small part of the carbon substrate. The small intensity contributed by the amorphous substrate is removed by background subtraction. The proportions of amorphous and crystalline material in each pattern are determined by subtracting a percentage of crystalline component relative to amorphous and pure crystalline endmembers. Vapor-deposited water ice undergoes two amorphous to amorphous structural transformations in the temperature range 15-130 K with important astrophysical implications. The onset of cubic crystallization occurs at 142-160 K (at 1K per minute heating rates) during which the 220 and 311 diffraction maxima appear and 0.1 micrometer crystallites can be seen in bright field images. This transition is time dependent.

Blake, David F.↗

The Decomposition of Carbonates and Organics on Mars

The return and analysis of pristine material that is relict of a putative period of chemical evolution is a fumdamental goal of the exobiological exploration of Mars. In order to accomplish this objective, it is desirable to find oxidant-free regions where pristine material can be accessed at the shallowest possible depth (ideally directly from the surface). The objective of our ongoing research is to understand the spatial and temporal distribution of oxidants in the martian regolith and the redox chemistry of the soil; in effect to understand the chemical mechanisms and kinetics relating to the in-situ destruction of organics and the formation of the reactive species responsible for the Viking biology results. In this work, we report on experimental studies of oxidizing processes that may contribute to carbonate and organic degradation on Mars. Organic molecules directly exposed to solar UV may decomposed either directly into CO2, or into more volatile organic fragments. Organic macromolecules not directly exposed to high UV flux are most likely to be affected by atmospheric oxidants which can diffuse to their surfaces. The oxidizing processes examined include: gas-phase oxidants, UV photolysis, and UV-assisted heterogeneous catalysis. For example, assuming a meteroritic infall rate of 4 x 10(exp -4) g/m^2yr (Flynn and McKay 1990) and a flux of organic carbon of 2 x 10(exp -5) g/m^2yr, laboratory measurements of the UV-assisted decomposition of benzenehexacarboxylic acid (mellitic acid, a likely intermediate of kerogen oxidation), indicate its decomposition rate on Mars would exceed the total flux of organic carbon to the planet by over four orders of magnitude. Our measurements indicate that although the decomposition temperature of kerogens in some cases exceeds the temperature limit of the Viking GCMS, it is unlikely kerogens or their decomposition intermediates were present at the Viking landings sites at levels above the GCMS detection limits.

Quinn, Richard C.↗

Stability of Pseudobrookite-Type Titanium Oxides

Orthorhombic, (Bbmm), (Al, Fe, Cr, Ti)(sub 2) TiO5-(Mg, Fe)Ti2O5 solid solutions (pseudobrookites, s.l.) are found either as an oxidation product of ilmenite and/or spinel or a primary crystallizing phase in igneous and metamorphic rocks on Earth (e.g., basalt flows, crustal and mantle xenoliths, hornfels), and basaltic rocks on the Moon. Moreover, orthorhombic oxides are often part of the crystalline matrix in glass/ceramics with useful applications, and play a major role in the industrial production of TiO2. To fully exploit the potential of these compounds as petrogenetic indicators and/or useful materials we need to quantitatively understand the factors controlling their properties and stability, and thus, to extrapolate beyond the calibrating experiments. For that purpose, we need to combine thermochemistry, phase equilibrium, and in situ P-V-T-cation disorder experimental data that presently either are incomplete or lacking. Perhaps, the most complete data set is that for MgTi2O5 (karrooite) which allows the calibration of models for the Gibbs free energy of the MgTi2O5 as a function of pressure, temperature, and the Mg2+-Ti4+ distribution between the two nonequivalent octahedral sites. Consequently, the effect of cation disorder on MgTi2O5 stability, and the phase relations among MgTi2O5, other titanium oxides, and silicate minerals can be examined. Calculated phase relations in the Mg-Ti-Si-O system and phase equilibrium experiments in Fe-bearing compositions suggest that pseudobrookite-type oxides may be a more common in rocks than previously realized. However, homogeneous and heterogeneous equilibria, and crystallization paths likely affect their stability. For example, isobaric increases in temperature favor disordering and thus entropy-stabilization, in contrast, isothermal increases in pressure have the opposite effect. Although, currently, the potential effect of composition to cation disorder cannot be fully explored, it appears that enrichment in trivalent cations probably enhances entropy-stabilization and thus may increase the stability of (Al, Fe, Cr, Ti)-rich pseudobrookites relative to that of (Mg, Fe)-rich ones. In addition, high-temperature, nearly isothermal, decompression paths of olivine+orthopyroxene+oxide assemblages may favor pseudobrookites (s.l.) over rutile and/or ilmenite, in contrast, cooling at low pressures seems to favor ilmenite and/or rutile. In the case of crustal and mantle xenoliths, the presence or absence of orthorhombic oxides is probably controlled by reactions with olivine, orthopyroxene, ilmenite, and rutile. In oceanic mantle xenoliths such reactions may also involve a TiO2-enriched but not SiO2-enriched melt/fluid, because pseudobrookites (s.l.) would react with the SiO2-enriched melt/fluid to form orthopyroxene and rutile. Parenthetically, experiments and model calculations in the Mg-Ti-Si-O system suggest that low degree partial melting of low-TiO2 bulk compositions may produce Ti-enriched liquids in equilibrium with olivine, orthopyroxen ad=nd MgTi2O5, rutile or ilmenite.

Xirouchakis, Dimistrios↗

Containerless processing of glass forming melts: D-1, MEA/A-2 experiment 81F01 conducted on STS-61A flight, October 1985

Results of experiment 81F01, which was conducted in the Material Experiment Assembly MEA/A-2 on the D-1 Spacelab Mission (STS-61A), are presented. The general plan of the experiment was to heat, melt, and quench six spherical samples of different glass forming compositions while they were levitated in a single axis acoustic levitator furnace (SAAL). In addition, two non-melting sintered alumina samples were used to check the operational characteristics of the SAAL under reduced gravity conditions. Three of the eight samples were levitated between 1250 and 1500 C before the lack of coolant created an over-temperature condition that caused the SAAL to shut down prematurely. Two of the three samples processed were calcia-gallia-silica and soda-lime-silica glass forming compositions. Evidence of a two to three times increase in the tendency for glass formation was obtained for the calcia-gallia-silica. The final glass appeared reasonably homogeneous even though it was made from hot pressed powders containing deliberate heterogeneities. A photographic record was obtained of the microgravity sample processing sequences.

Day, D. E.↗

The Mineralogy of Circumstellar Silicates Preserved in Cometary Dust

Interplanetary dust particles (IDPs) contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula. Cometary IDPs have remained relatively unaltered since their accretion because of the lack of parent body thermal and aqueous alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these particles because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars. Five circumstellar grains have been identified including three amorphous silicate grains and two polycrystalline aggregates. All of these grains are between 0.2 and 0.5 micrometers in size. The isotopic compositions of all five presolar silicate grains fall within the range of presolar oxides and silicates, having large (17)O-enrichments and normal (18)O/(16)O ratios (Group 1 grains from AGB and RG stars). The amorphous silicates are chemically heterogeneous and contain nanophase FeNi metal and FeS grains in a Mg-silicate matrix. Two of the amorphous silicate grains are aggregates with subgrains showing variable Mg/Si ratios in chemical maps. The polycrystalline grains show annealed textures (equilibrium grains boundaries, uniform Mg/Fe ratios), and consist of 50-100 nm enstatite and pyrrhotite grains with lesser forsterite. One of the polycrystalline aggregates contains a subgrain of diopside. The polycrystalline aggregates form by subsolidus annealing of amorphous precursors. The bulk compositions of the five grains span a wide range in Mg/Si ratios from 0.4 to 1.2 (avg. 0.86). The average Fe/Si (0.40) and S/Si (0.21) ratios show a much narrower range of values and are approximately 50% of their solar abundances. The latter observation may indicate a decoupling of the silicate and sulfide components in grains that condense in stellar outflows. The amorphous silicate grains described here were not extensively affected by irradiation, sputtering, or thermal processing and may represent relatively pristine circumstellar grains. They are strong candidates for the "dirty silicates" in astronomical observations of circumstellar dust shells. The polycrystalline grains were originally amorphous silicate grains that were likely annealed in the early solar nebula but the processing was not sufficient to erase their anomalous oxygen isotopic compositions.

Keller, L. P.↗

An investigation of voids formation mechanisms and their effects on freeze and thaw processes of lithium and lithium fluoride

The mechanisms of void formation during the cooldown and freezing of lithium coolant within the primary loop of SP-100 type systems are investigated. These mechanisms are: (1) homogeneous nucleation; (2) heterogeneous nucleation; (3) normal segregation of helium gas dissolved in liquid lithium; and (4) shrinkage of lithium during freezing. To evaluate the void formation potential due to segregation, a numerical scheme that couples the freezing and mass diffusion processes in both the solid and liquid regions is developed. The results indicated that the formation of He bubbles is unlikely by either homogeneous or heterogeneous nucleation during the cooldown process. However, homogeneous nucleation of He bubbles following the segregation of dissolved He in liquid lithium ahead of the solid-liquid interface is likely to occur. Results also show that total volume of He void is insignificant when compared to that of shrinkage voids. In viewing this, the subsequent research focuses on the effects of shrinkage void forming during freezing of lithium on subsequent thaw processes are investigated using a numerical scheme that is based on a single (solid/liquid) cell approach. The cases of lithium-fluoride are also investigated to show the effect of larger volume shrinkage upon freezing on the freeze and thaw processes. Results show that a void forming at the wall appreciably reduces the solid-liquid interface velocity, during both freeze and thaw, and causes a substantial rise in the wall temperature during thaw. However, in the case of Li, the maximum wall temperature was much lower than the melting temperature of PWC-11, which is used as the structure material in the SP-100 system. Hence, it is included that a formation of hot spots is unlikely during the startup or restart of the SP-100 system.

El-Genk, Mohamed S.↗

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Sutton, S. R.↗

Physics-Based Methods of Failure Analysis and Diagnostics in Human Space Flight

The Integrated Health Management (IHM) for the future aerospace systems requires to interface models of multiple subsystems in an efficient and accurate information environment at the earlier stages of system design. The complexity of modern aeronautic and aircraft systems (including e.g. the power distribution, flight control, solid and liquid motors) dictates employment of hybrid models and high-level reasoners for analysing mixed continuous and discrete information flow involving multiple modes of operation in uncertain environments, unknown state variables, heterogeneous software and hardware components. To provide the information link between key design/performance parameters and high-level reasoners we rely on development of multi-physics performance models, distributed sensors networks, and fault diagnostic and prognostic (FD&P) technologies in close collaboration with system designers. The main challenges of our research are related to the in-flight assessment of the structural stability, engine performance, and trajectory control. The main goal is to develop an intelligent IHM that not only enhances components and system reliability, but also provides a post-flight feedback helping to optimize design of the next generation of aerospace systems. Our efforts are concentrated on several directions of the research. One of the key components of our strategy is an innovative approach to the diagnostics/prognostics based on the real time dynamical inference (DI) technologies extended to encompass hybrid systems with hidden state trajectories. The major investments are into the multiphysics performance modelling that provides an access of the FD&P technologies to the main performance parameters of e.g. solid and liquid rocket motors and composite materials of the nozzle and case. Some of the recent results of our research are discussed in this chapter. We begin by introducing the problem of dynamical inference of stochastic nonlinear models and reviewing earlier results. Next, we present our analytical approach to the solution of this problem based on the path integral formulation. The resulting algorithm does not require an extensive global search for the model parameters, provides optimal compensation for the effects of dynamical noise, and is robust for a broad range of dynamical models. In the following Section the strengths of the algorithm are illustrated illustrated by inferring the parameters of the stochastic Lorenz system and comparing the results with those of earlier research. Next, we discuss a number of recent results in application to the development of the IHM for aerospace system. Firstly, we apply dynamical inference approach to a solution of classical three tank problems with mixed unknown continuous and binary parameters. The problem is considered in the context of ground support system for filling fuel tanks of liquid rocket motors. It is shown that the DI algorithm is well suited for successful solution of a hybrid version of this benchmark problem even in the presence of additional periodic and stochastic perturbation of unknown strength. Secondly, we illustrate our approach by its application to an analysis of the nozzle fault in a solid rocket motor (SRM). The internal ballistics of the SRM is modelled as a set of one-dimensional partial differential equations coupled to the dynamics of the propellant regression. In this example we are specifically focussed on the inference of discrete and continuous parameters of the nozzle blocking fault and on the possibility of an application of the DI algorithm to reducing the probability of "misses" of an on-board FD&P for SRM. In the next section re-contact problem caused by first stage/upper stage separation failure is discussed. The reaction forces imposed on the nozzle of the upper stage during the re-contact and their connection to the nozzle damage and to the thrust vector control (TVC) signal are obtained. It is shown that transient impact induced torquean be modelled as a response of an effective damped oscillator. A possible application of the DI algorithm to the inference of damage parameters and predicting fault dynamics ahead of time using the actuator signal is discussed. Finally, we formulate Bayesian inferential framework for development of the IHM system for in-flight structural health monitoring (SHM) of composite materials. We consider the signal generated by piezoelectric actuator mounted on composite structure generating elastic waves in it. The signal received by the sensor is than compared with the baseline signal. The possibility of damage inference is discussed in the context of development of the SHM.

Smelyanskiy, Vadim N.↗

Assimilation by lunar mare basalts: Melting of crustal material and dissolution of anorthite

We discuss techniques for calculating the amount of crustal assimilation possible in lunar magma chambers and dikes based on thermal energy balances, kinetic rates, and simple fluid mechanical constraints. Assuming parent magmas of picritic compositions, we demonstrate the limits on the capacity of such magmas to melt and dissolve wall rock of anorthitic, troctolitic, noritic, and KREEP (quartz monzodiorite) compositions. Significant melting of the plagioclase-rich crustal lithologies requires turbulent convection in the assimilating magma and an efficient method of mixing in the relatively buoyant and viscous new melt. Even when this occurs, the major element chemistry of the picritic magmas will change by less than 1-2 wt %. Diffusion coefficients measured for Al2O3 from an iron-free basalt and an orange glass composition are 10(exp -12) sq m/s at 1340 C and 10(exp -11) sq m/s at 1390 C. These rates are too slow to allow dissolution of plagioclase to significantly affect magma compositions. Picritic magmas can melt significant quantities of KREEP, which suggests that their trace element chemistry may still be affected by assimilation processes; however, mixing viscous melts of KREEP composition with the fluid picritic magmas could be prohibitively difficult. We conclude that only a small part of the total major element chemical variation in the mare basalt and volcanic glass collection is due to assimilation/fractional crystallization processes near the lunar surface. Instead, most of the chemical variation in the lunar basalts and volcanic glasses must result from assimilation at deeper levels or from having distinct source regions in a heterogeneous lunar mantle.

Finnila, A. B.↗