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JSC Mars-1 Martian Soil Simulant: Melting Experiments and Electron Microprobe Studies

JSC Mars-1 has been developed as a Martian regolith simulant, and is the <1 mm size fraction of a palagonitic tephra (a glassy volcanic ash altered at low temperatures) from Pu'u Nene cinder cone on the Island of Hawaii. The Mars-1 simulant forms the basis for numerous terrestrial studies which aim to evaluate the suitability of Martian soil for materials processing. Martian soil may be sintered to form building materials for construction, and also melted or reacted to extract metals for various uses, as well as oxygen for life support.

Carpenter, P.↗

A Liquid-Liquid Transition in an Undercooled Ti-Zr-Ni Liquid

If crystallization can be avoided, liquids enter a metastable (undercooled) state below their equilibrium liquidus temperatures, TI, finally freezing into a glass below a characteristic temperature called the glass transition temperature, T,. In rare cases, the undercooled liquid may undergo a liquid-liquid phase transition (liquid polymorphism) before entering the glassy state. This has been suggested from experimental studies of HzO and Si4. Such phase transitions have been predicted in some stable liquids, i.e. above TI at atmospheric pressure, for Si02 and BeF;, but these have not been verified experimentally. They have been observed in liquids of P7, Sis and C9, but only under high pressure. All of these transitions are driven by an anomalous density change, i.e. change in local structure, with temperature or pressure. In this letter we present the first experimental evidence for a phase transition in a low viscosity liquid that is not driven by an anomalous density change, but by an approach to a constant configuration state. A maximum in the specific heat at constant pressure, similar to what is normally observed near T,, is reported here for undercooled low viscosity liquids of quasicrystal- forming Ti-Zr-Ni alloys. that includes cooperativity, by incorporating a temperature dependent excitation energy fits the data well, signaling a phase transition.

Lee, G. W.↗

Fe-57 Moessbauer Spectroscopy of Fulgurites: Implications for Chemical Reduction

The high temperature (superliquidus) processing of silicates often results in very reduced products, such as Si-bearing Fe metal in type-1 chondrules and in lunar regolith agglutinates. Previous work on fulgurites (the glassy products of the lightning strike fusion of sand, soil, or rock) found silicon metal and iron-silicon alloys inside the silicate glass. The mechanism for this extreme reduction is not yet understood. In this work, we begin a Fe-57 Moessbauer spectroscopy study as well as continuing a microprobe study of several fulgurites in order to better constrain the extent and process of Fe reduction.

Sheffer, A. A.↗

Chondrule Glass Alteration in Type IIA Chondrules in the CR2 Chondrites EET 87770 and EET 92105: Insights into Elemental Exchange Between Chondrules and Matrices

CR2 carbonaceous chondrites are a primitive group of meteorites that preserve evidence of a variety of processes that occurred in the solar nebula as well as on asteroidal parent bodies. CR2 chondrites are distinct from other carbonaceous chondrites by (among other properties) their relatively high abundance of chondrules (50-60 vol. %) and Fe,Ni metal (5-8 vol. %) [1]. Like the CM2 chondrites, the CRs have been affected by aqueous alteration and according to [2] show a range of degrees of alteration. In weakly- altered CR chondrites, fine-grained matrices and chondrule rims have been partially altered and chondrule mesostases show evidence of incipient aqueous alteration. In these meteorites, glassy mesostasis is still common. However, some CR chondrites, (e.g. Renazzo and Al Rais) show evidence of much more extensive alteration with complete replacement of chondrule mesostasis [2] by chlorite and serpentine. Although the general characteristics of alteration of the CR chondrites have been described, the details of alteration reactions in these meteorites remain unclear. In addition, the setting for aqueous alteration is poorly understood: both asteroidal and preaccretionary alteration scenarios have been proposed [2].

Burger, Paul V.↗

Applying state diagrams to food processing and development

The physical state of food components affects their properties during processing, storage, and consumption. Removal of water by evaporation or by freezing often results in formation of an amorphous state (Parks et al., 1928; Troy and Sharp, 1930; Kauzmann, 1948; Bushill et al., 1965; White and Cakebread, 1966; Slade and Levine, 1991). Amorphous foods are also produced from carbohydrate melts by rapid cooling after extrusion or in the manufacturing of hard sugar candies and coatings (Herrington and Branfield, 1984). Formation of the amorphous state and its relation to equilibrium conditions are shown in Fig. 1 [see text]. The most important change, characteristic of the amorphous state, is noticed at the glass transition temperature (Tg), which involves transition from a solid "glassy" to a liquid-like "rubbery" state. The main consequence of glass transition is an increase of molecular mobility and free volume above Tg, which may result in physical and physico-chemical deteriorative changes (White and Cakebread, 1966; Slade and Levine, 1991). We have conducted studies on phase transitions of amorphous food materials and related Tg to composition, viscosity, stickiness, collapse, recrystallization, and ice formation. We have also proposed that some diffusion-limited deteriorative reactions are controlled by the physical state in the vicinity of Tg (Roos and Karel, 1990, 1991a, b, c). The results are summarized in this article, with state diagrams based on experimental and calculated data to characterize the relevant water content, temperature, and time-dependent phenomena of amorphous food components.

Non-NASA Center↗

A Novel Liquid-Liquid Transition in Undercooled Ti-Zr-Ni Liquids

If crystallization can be avoided, liquids enter a metastable (undercooled) state below their equilibrium liquidus temperatures, T(sub l), finally 'freezing' into a glass below a characteristic temperature called the glass transition temperature, T(sub g). In rare cases, the undercooled liquid may undergo a liquid-liquid phase transition (liquid polymorphism) before entering the glassy state. This has been suggested from experimental studies of H2O and Si. Such phase transitions have been predicted in some stable liquids, ie. above T(sub l) at atmospheric pressure, for SiO2 and BeF2, but these have not been verified experimentally. They have been observed in liquids of P, Si and C, but only under high pressure. In this letter we present the first experimental evidence for a phase transition in a low viscosity metallic liquid that is driven by an approach to a constant entropy configuration state and correlated with a growing icosahedral order in the liquid. A maximum in the specific heat at constant pressure, similar to what is normally observed near T(sub g), is reported for undercooled liquids of quasicrystal-forming Ti-Zr-Ni alloys. A two-state excitation model that includes cooperativity by incorporating a temperature-dependent excitation energy, fits the specific heat data well, signaling a phase transition. An inflection in the liquid density with decreasing temperature instead of a discontinuity indicates that this is not a typical first order phase transition; it could be a weakly first order or higher order transition. While showing many similarities to a glass transition, this liquid-liquid phase transition occurs in a mobile liquid, making it novel.

Lee, G. W.↗

Glass and Glass-Ceramic Materials from Simulated Composition of Lunar and Martian Soils: Selected Properties and Potential Applications

In-situ resource processing and utilization on planetary bodies is an important and integral part of NASA's space exploration program. Within this scope and context, our general effort is primarily aimed at developing glass and glass-ceramic type materials using lunar and martian soils, and exploring various applications of these materials for planetary surface operations. Our preliminary work to date have demonstrated that glasses can be successfully prepared from melts of the simulated composition of both lunar and martian soils, and the melts have a viscosity-temperature window appropriate for drawing continuous glass fibers. The glasses are shown to have the potential for immobilizing certain types of nuclear wastes without deteriorating their chemical durability and thermal stability. This has a direct impact on successfully and economically disposing nuclear waste generated from a nuclear power plant on a planetary surface. In addition, these materials display characteristics that can be manipulated using appropriate processing protocols to develop glassy or glass-ceramic magnets. Also discussed in this presentation are other potential applications along with a few selected thermal, chemical, and structural properties as evaluated up to this time for these materials.

Ray, C. S.↗

On the Behavior of Phosphorus During the Aqueous Alteration of CM2 Carbonaceous Chondrites

During the earliest period of solar system formation, water played an important role in the evolution of primitive dust, both after accretion of planetesimals and possible before accretion within the protoplanetary disk. Many chondrites show evidence of variable degrees of aqueous alteration, the CM2 chondrites being among the most studied [1]. This group of chondrites is characterized by mineral assemblages of both primary and secondary alteration phases. Hence, these meteorites retain a particularly important record of the reactions that occurred between primary high temperature nebular phases and water. Studies of these chondrites can provide information on the conditions and environments of aqueous alteration and the mobility of elements during alteration. This latter question is at the core of a debate concerning the location of aqueous alteration, i.e. whether alteration occurred predominantly within a closed system after accretion (parent body alteration) or whether some degree of alteration occurred within the solar nebula or on ephemeral protoplanetary bodies prior to accretion. At the core of the parent body alteration model is the hypothesis that elemental exchange between different components, principally chondrules and matrix, must have occurred. chondrules and matrix, must have occurred. In this study, we focus on the behavior of the minor element, phosphorus. This study was stimulated by observations of the behavior of P during the earliest stages of alteration in glassy mesostasis in type II chondrules in CR chondrites and extends the preliminary observations of on Y791198 to other CM chondrites.

Brearley, Adrian J.↗

Silicone Contamination Camera for Developed for Shuttle Payloads

On many shuttle missions, silicone contamination from unknown sources from within or external to the shuttle payload bay has been a chronic problem plaguing experiment payloads. There is currently a wide range of silicone usage on the shuttle. Silicones are used to coat the shuttle tiles to enhance their ability to shed rain, and over 100 kg of RTV 560 silicone is used to seal white tiles to the shuttle surfaces. Silicones are also used in electronic components, potting compounds, and thermal control blankets. Efforts to date to identify and eliminate the sources of silicone contamination have not been highly successful and have created much controversy. To identify the sources of silicone contamination on the space shuttle, the NASA Lewis Research Center developed a contamination camera. This specially designed pinhole camera utilizes low-Earth-orbit atomic oxygen to develop a picture that identifies sources of silicone contamination on shuttle-launched payloads. The volatile silicone species travel through the aperture of the pinhole camera, and since volatile silicone species lose their hydrocarbon functionalities under atomic oxygen attack, the silicone adheres to the substrate as SiO_x. This glassy deposit should be spatially arranged in the image of the sources of silicone contamination. To view the contamination image, one can use ultrasensitive thickness measurement techniques, such as scanning variable-angle ellipsometry, to map the surface topography of the camera's substrate. The demonstration of a functional contamination camera would resolve the controversial debate concerning the amount and location of contamination sources, would allow corrective actions to be taken, and would demonstrate a useful tool for contamination documentation on future shuttle payloads, with near negligible effect on cost and weight.

Source record↗

Physics of Hard Spheres Experiment: Significant and Quantitative Findings Made

Direct examination of atomic interactions is difficult. One powerful approach to visualizing atomic interactions is to study near-index-matched colloidal dispersions of microscopic plastic spheres, which can be probed by visible light. Such spheres interact through hydrodynamic and Brownian forces, but they feel no direct force before an infinite repulsion at contact. Through the microgravity flight of the Physics of Hard Spheres Experiment (PHaSE), researchers have sought a more complete understanding of the entropically driven disorder-order transition in hard-sphere colloidal dispersions. The experiment was conceived by Professors Paul M. Chaikin and William B. Russel of Princeton University. Microgravity was required because, on Earth, index-matched colloidal dispersions often cannot be density matched, resulting in significant settling over the crystallization period. This settling makes them a poor model of the equilibrium atomic system, where the effect of gravity is truly negligible. For this purpose, a customized light-scattering instrument was designed, built, and flown by the NASA Glenn Research Center at Lewis Field on the space shuttle (shuttle missions STS 83 and STS 94). This instrument performed both static and dynamic light scattering, with sample oscillation for determining rheological properties. Scattered light from a 532- nm laser was recorded either by a 10-bit charge-coupled discharge (CCD) camera from a concentric screen covering angles of 0 to 60 or by sensitive avalanche photodiode detectors, which convert the photons into binary data from which two correlators compute autocorrelation functions. The sample cell was driven by a direct-current servomotor to allow sinusoidal oscillation for the measurement of rheological properties. Significant microgravity research findings include the observation of beautiful dendritic crystals, the crystallization of a "glassy phase" sample in microgravity that did not crystallize for over 1 year in 1g (Earth's gravity), and the emergence of face-centered-cubic (FCC) crystals late in the coarsening process (as small crystallites lost particles to the slow ripening of large crystallites). Significant quantitative findings from the microgravity experiments have been developed describing complex interactions among crystallites during the growth process, as concentration fields overlap in the surrounding disordered phase. Time-resolved Bragg scattering under microgravity captures one effect of these interactions quite conclusively for the sample at a volume fraction of 0.528. From the earliest time until the sample is almost fully crystalline, the size and overall crystallinity grow monotonically, but the number of crystallites per unit volume (number density) falls. Apparently nucleation is slower than the loss of crystallites because of the transfer of particles from small to large crystals. Thus, coarsening occurs simultaneously with growth, rather than following the completion of nucleation and growth as is generally assumed. In the same sample, an interesting signature appears in the apparent number density of crystallites and the volume fraction within the crystallites shortly before full crystallinity is reached. A brief upturn in both indicates the creation of more domains of the size of the average crystallite simultaneous with the compression of the crystallites. Only the emergence of dendritic arms offers a reasonable explanation. The arms would be "seen" by the light scattering as separate domains whose smaller radii of curvature would compress the interior phase. In fiscal year 1999, numerous papers, a doctoral dissertation, and the PHaSE final report were produced. Although this flight project has been completed, plans are in place for a follow-on colloid experiment by Chaikin and Russel that employs a light microscope within Glenn's Fluids and Combustion Facility on the International Space Station. PHaSE is providing us with a deeper understanding of the nure of phase transitions. The knowledge derived has added to the understanding of condensed matter. In addition, the burgeoning study of the dynamics of colloidal self-assembly may lead to the development of a range of photonic materials that control the desirable properties of light. Thus, applications of ordered colloidal structures include not only ultrastructure ceramics, but also photonic crystals and photothermal nanosecond light-switching devices. Industries dealing with semiconductors, electro-optics, ceramics, and composites stand to benefit from such advancements.

Doherty, Michael P.↗

Atomic Oxygen Interactions With Silicone Contamination on Spacecraft in Low Earth Orbit Studied

Silicones have been widely used on spacecraft as potting compounds, adhesives, seals, gaskets, hydrophobic surfaces, and atomic oxygen protective coatings. Contamination of optical and thermal control surfaces on spacecraft in low Earth orbit (LEO) has been an ever-present problem as a result of the interaction of atomic oxygen with volatile species from silicones and hydrocarbons onboard spacecraft. These interactions can deposit a contaminant that is a risk to spacecraft performance because it can form an optically absorbing film on the surfaces of Sun sensors, star trackers, or optical components or can increase the solar absorptance of thermal control surfaces. The transmittance, absorptance, and reflectance of such contaminant films seem to vary widely from very transparent SiOx films to much more absorbing SiOx-based films that contain hydrocarbons. At the NASA Glenn Research Center, silicone contamination that was oxidized by atomic oxygen has been examined from LEO spacecraft (including the Long Duration Exposure Facility and the Mir space station solar arrays) and from ground laboratory LEO simulations. The findings resulted in the development of predictive models that may help explain the underlying issues and effects. Atomic oxygen interactions with silicone volatiles and mixtures of silicone and hydrocarbon volatiles produce glassy SiOx-based contaminant coatings. The addition of hydrocarbon volatiles in the presence of silicone volatiles appears to cause much more absorbing (and consequently less transmitting) contaminant films than when no hydrocarbon volatiles are present. On the basis of the LDEF and Mir results, conditions of high atomic oxygen flux relative to low contaminant flux appear to result in more transparent contaminant films than do conditions of low atomic oxygen flux with high contaminant flux. Modeling predictions indicate that the deposition of contaminant films early in a LEO flight should depend much more on atomic oxygen flux than it does later in a mission.

Banks, Bruce A.↗

Formation of Nanophase Iron in Lunar Soil Simulant for Use in ISRU Studies

For the prospective return of humans to the Moon and the extensive amount of premonitory studies necessary, large quantities of lunar soil simulants are required, for a myriad of purposes from construction/engineering purposes all the way to medical testing of its effects from ingestion by humans. And there is only a limited and precious quantity of lunar soil available on Earth (i.e., Apollo soils) - therefore, the immediate need for lunar soil simulants. Since the Apollo era, there have been several simulants; of these JSC-1 (Johnson Space Center) and MLS-1 (Minnesota Lunar Simulant) have been the most widely used. JSC-1 was produced from glassy volcanic tuff in order to approximate lunar soil geotechnical properties; whereas, MLS-1 approximates the chemistry of Apollo 11 high-Ti soil, 10084. Stocks of both simulants are depleted, but JSC-1 has recently gone back into production. The lunar soil simulant workshop, held at Marshall Space Flight Center in January 2005, identified the need to make new simulants for the special properties of lunar soil, such as nanophase iron (np-Fe(sup 0). Hill et al. (2005, this volume) showed the important role of microscale Fe(sup 0) in microwave processing of the lunar soil simulants JSC-1 and MLS-1. Lunar soil is formed by space weathering of lunar rocks (e.g., micrometeorite impact, cosmic particle bombardment). Glass generated during micrometeorite impact cements rock and mineral fragments together to form aggregates called agglutinates, and also produces vapor that is deposited and coats soil grains. Taylor et al. (2001) showed that the relative amount of impact glass in lunar soil increases with decreasing grain size and is the most abundant component in lunar dust (less than 20 micrometer fraction). Notably, the magnetic susceptibility of lunar soil also increases with the decreasing grain size, as a function of the amount of nanophase-sized Fe(sup 0) in impact-melt generated glass. Keller et al. (1997, 1999) also discovered the presence of abundant np-Fe(sup 0) particles in the glass patinas coating most soil particles. Therefore, the correlation of glass content and magnetic susceptibility can be explained by the presence of the np-Feo particles in glass: small particles contain relatively more np-Fe(sup 0) as glass coatings because the surface area versus mass ratio of the grain size is so increased. The magnetic properties of lunar soil are important in dust mitigation on the Moon (Taylor et al. 2005). Thus material simulating this property is important for testing mitigation methods using electromagnetic field. This np- Fe(sup 0) also produces a unique energy coupling to normal microwaves, such as present in kitchen microwave ovens. Effectively, a portion of lunar soil placed in a normal 2.45 GHz oven will melt at greater than 1200 C before your tea will boil at 100 C, a startling and new discovery reported by Taylor and Meek (2004, 2005). Several methods have been investigated in attempts to make nanophase-sized Feo dispersed within silicate glass; like in the lunar glass. We have been successful in synthesizing such a product and continue to improve on our recipe. We have performed extensive experimentation on this subject to date. Ultimately it will probably be necessary to add this np-Fe(sup 0) bearing silicate glass to lunar soil stimulant, like JSC-1, to actually produce the desired magnetic and microwave coupling properties for use in appropriate ISRU experimentation.

Liu, Yang↗

Mineralogy of nakhlite Martian meteorites: Implications for their relative burial depths

Nakhlites are Martian cumulate rocks mainly composed of augite with variable amounts of olivine and groundmass (mesostasis). Currently seven samples are known: Nakhla (Nak), Governador Valadares (GV), Lafayette (Laf), NWA817, Y000593 (Y), NWA998 and MIL03346 (MIL). All the nakhlites show a similar unbrecciated cumulate texture, and their identical crystallization and exposure ages suggest that they originated from the same igneous body on Mars and were ejected by the same impact event. It is important to study difference of their mineralogy to reconstruct the igneous body from which nakhlites originated. Augite grains in all nakhlites have a nearly identical core composition (En39Fs22Wo39) and have thin Fe-rich rims. These Fe-rich rims are zoned to Ca-poor pyroxene compositions and the degree of chemical zoning varies from one sample to another. NWA998 has the most Mg-rich edge composition. The edge composition becomes more Fe-rich in the order of Laf, Nak/GV, Y and NWA817. Unlike other samples, the Fe-rich edge of MIL augite is zoned to the hedenbergite composition. Olivine grains in all samples except Laf and NWA998 show extensive chemical zoning whose degree is clearly related to the chemical zoning of pyroxenes. MIL and NWA817 have the widest compositional ranges (Fa54-93). Y has a slightly narrower compositional range of Fa58-85. Nak and GV have even narrower ranges (Fa58-72). In contrast to these samples, olivines in Laf and NWA998 are homogeneous (Fa66-67 and Fa61-62, respectively). Such chemical zoning (Fa and Ca) can be used to quantitatively estimate their cooling rates (burial depths) because it was clearly formed by interaction with the intercumulus melt. The obtained burial depths are 1-2 m for NWA817, 4 m for MIL, 7 m for Y, approx.10 m for Nak and GV, and >30 m for Laf and NWA998. This order is clearly related to the degree of pyroxene chemical zoning. The abundance and mineralogy of nakhlite groundmass are also consistent with this order. In Nak, GV and Laf, the groundmass abundance is about 7-8%. Y and NWA998 have a slightly higher abundance (10%), while NWA817 and MIL have much higher abundance (20-24%). The groundmass texture is also related to its abundance. The groundmass of Nak, GV, Laf and Y is mainly composed of feldspar laths. In contrast, NWA817 and MIL have glassy mesostasis without feldspar crystals. In NWA998, feldspar is a large blocky crystal with clear twinning, suggesting that it is even deeper than Laf.

Mikouchi, T.↗

The Selicate Material In Comets

Silicates in comets appear to be a mix of high-temperature crystalline enstatite and forsterite plus glassy or amorphous grains that formed at lower temperatures.

comets Hale-Bopp silicates infrared spectra↗

(abstract) Undercooling Studies of the Bulk Metallic Glass Forming Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) Alloy During Containerless Electrostatic Levitation Processing

Bulk glass forming metallic alloys have long been desired for technological applications and for investigation into liquid undercooling, solidification processes, and thermophysical properties. A glass forming alloy Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) was used to investigate the thermal treatments affecting undercooling and vitrification. The experiments were performed using the high temperature high vacuum electrostatic levitator at JPL. A sample approximately 3 mm in diameter was melted, superheated, undercooled, and solidified while levitated in high vacuum. The results show that when the sample was held above its melting temperature for a sufficient period of time to dissolve oxides and then cooled faster than a critical cooling rate, it undercooled to the glass transition temperature, T(sub g), and formed a glassy alloy. The required critical cooling rate for metallic glass formation was obtained to be between 0.9 K per second and 1.2 K per second for the 42.4 mg sample.

levitation vitrification↗

Ru(sub 2)Ge(sub 3): Crystal Growth and Come Properties

Large samples of Ru(sub 2)Ge(sub 3) were grown from Ge-rich off-stoichiometric melts at a temperature close to 1460 C by a vertical gradient freeze method in graphite and glassy carbon crucibles.

off-stoichiometric melt twinning crack formation h↗

Development of Standardized Lunar Regolith Simulant Materials

Lunar exploration requires studies using standardized testing procedures. Previous lunar simulants focused on physical aspects of the lunar regolith. Renewed lunar exploration requires standardized lunar regolith simulant (SLRS) materials that simulate the physical, chemical, and mineralogical properties of the regolith [l]. A root simulant models an end-member, and a derivative is formed by addition of material [2]. The 2005 Workshop recommended a low-Ti mare basalt and a high-Ca highland anorthosite set of roots. Derivatives involve addition of ilmenite and glassy agglutinates [3]. An ideal SLRS material is homogeneous. Geochemical standards are finely-ground to reduce chemical variability, but lunar simulants have a grain size variation and mineralogy that must match the lunar regolith. The simulant homogeneity is monitored using major, minor, and trace element data of progressively smaller samples compared to bulk material. Both chemical and geotechnical properties depend on the contrast from grain to grain. The variability of simulant material is an inherent property that must be taken into account. Simulant production requires monitoring of adherence to simulant requirements and homogeneity during production. Quality control establishes a traceability to a master set of reference standards.

Carpenter, P.↗