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At least 163 records · Page 9

High-Pressure Minerals in Meteorites: Constraints on Shock Conditions and Duration

The objective of this research was to better understand the conditions and duration of shock metamorphism in meteorites through microstructural and microanalytical characterization of high-pressure minerals. A) Continue to investigate the mineralogy and microstructures of melt-veins in a suite of chondritic samples ranging from shock grades S3 through S6 to determine how the mineral assemblages that crystallize at high-pressure and are related to shock grade. B) Investigate the chemical, mineralogical, and microstructural heterogeneities that occur across melt veins to interpret crystallization histories. C) Use static high-pressure experiments to simulate crystallization of melt veins for mineralogical and textural comparisons with the melt veins of naturally shocked samples. D) Characterize the compositions and defect microstructures of polycrystalline ringwoodite, wadsleyite, majorite, (Mg,Fe)Si03-ilmenite and (Mg,Fe)SiO3-perovskite in S6 samples to understand the mechanisms of phase transformations that occur during shock. These results will combined with kinetic data to constrain the time scales of kinetic processes. E) Investigate the transformations of metastable high-pressure minerals back to low- pressure forms to constrain post-shock temperatures and estimates of the peak shock pressure. Of these objectives, we have obtained publishable data on A, B and D. I am currently doing difficult high-pressure melting and quench experiments on an L chondrite known as Mbale. These experiments will provide additional constraints on the mineral assemblages that are produced during rapid quench of an L chondrite at pressures of 16 to 25 GPa. Results from published or nearly published research is presented below. Lists of theses, dissertations and publications are given below.

Sharp, Thomas G.↗

Coronal Structures in Cool Stars

We have extended our study of the structure of coronas in cool stars to very young stars still accreting from their surrounding disks. In addition we are pursing the connection between coronal X-rays and a powerful diagnostic line in the infrared, the He I 10830Angstrom transition of helium. Highlights of these are summarized below including publications during this reporting period and presentations. Spectroscopy of the infrared He I (lambda10830) line with KECK/NIRSPEC and IRTF/CSHELL and of the ultraviolet C III (lambda977) and O VI (lambda1032) emission with FUSE reveals that the classical T Tauri star TW Hydrae exhibits P Cygni profiles, line asymmetries, and absorption indicative of a continuous, fast (approximately 400 kilometers per second), hot (approximately 300,000 K) accelerating outflow with a mass loss rate approximately 10(exp -11)-10(exp -12) solar mass yr(sup -1) or larger. Spectra of T Tauri N appear consistent with such a wind. The source of the emission and outflow seems restricted to the stars themselves. Although the mass accretion rate is an order of magnitude less for TW Hya than for T Tau, the outflow reaches higher velocities at chromospheric temperatures in TW Hya. Winds from young stellar objects may be substantially hotter and faster than previously thought. The ultraviolet emission lines, when corrected for absorption are broad. Emission associated with the accretion flow and shock is likely to show turbulent broadening. We note that the UV line widths are significantly larger than the X-ray line widths. If the X-rays from TW Hya are generated at the accretion shock, the UV lines may not be directly associated with the shock. On the other hand, studies of X-ray emission in young star clusters, suggest that the strength of the X-ray emission is correlated with stellar rotation, thus casting doubt on an accretion origin for the X-rays. We are beginning to access the infrared spectral region where the He I 108308Angstroms transition occurs. This line is particularly useful as a diagnostic of coronal radiation since it is formed by recombination following photoionization of neutral helium by coronal X-rays. Because the lower level of the transition is metastable, infrared radiation from the stellar photosphere is absorbed which provides a diagnostic of atmospheric dynamics. This transition is useful both in young stars in the T Tauri phase and in active cool star binaries. We will investigate the influence of coronal x-rays on the strength of this transition.

Oliversen, Ronald↗

Carbonate compositions in CM and CI chondrites, and implications for aqueous alteration

Carbonate minerals in fourteen CM chondrites and two CI chondrites have been analyzed by electron microprobe to provide a better understanding of the aqueous processes that affected carbonaceous chondrite parent bodies. Calcites in CM chondrites and dolomites and magnesites in CI chondrites display the compositions expected of stable phases formed at low temperatures. Dolomites in CM chondrites, identified here for the first time in five members of the group, have small amounts of excess Ca which may reflect metastable growth. The distribution of Fe between dolomite and coexisting serpentine differs in the two chondrite groups. If the distributions reflect an approach to chemical equilibrium, then the difference implies higher alteration temperatures for the CI group than the CM group in agreement with the results of previously published oxygen isotope thermometry and mineral solubility modeling of the alteration process. Dolomite Fe contents are relatively uniform in the two chondrite groups. Dolomite Mn contents, by contrast, vary widely. The variations may reflect transport-controlled coprecipitation of Mn resulting from a heterogeneous distribution of the element in the anhydrous precursor material. If this interpretation is correct, then the altering fluids were essentially immobile white hydration reactions proceeded on the meteorite parent bodies. The near closed-system character of the alteration process, long known from bulk chemical analyses of the meteorites, is a direct consequence of the limited mobility of dissolved species.

Johnson, Craig A.↗

Liquid-metal atomization for hot working preforms

Rapid quenching of a liquid metal by atomization or splat cooling overcomes the major limitation of most solidification processes, namely, the segregation of alloying elements, impurities, and constituent phases. The cooling rates of different atomizing processes are related to the dendrite arm spacings and to the microstructure of the atomized powders. The increased solubility limits and the formation of metastable compounds in splat-cooled alloys are discussed. Consolidation of the powders by hot isostatic compaction, hot extrusion, or hot forging and rolling processes yields billets with properties equivalent to or better than those of the wrought alloys. The application of this powder processing technology to high-performance alloys is reviewed.

Grant, N. J.↗

Characterization of precipitates in a niobium-zirconium-carbon alloy

A niobium alloy with 1 percent zirconium and 0.063 percent carbon by weight was investigated in the as-rolled and annealed conditions, and after high-temperature (1350 and 1400 K) exposure with and without an applied stress. In the as-rolled and annealed conditions, large metastable carbides were observed in addition to a regular distribution of small particles. During the high-temperature exposure, the majority of the large carbides were dissolved and a more stable carbide phase formed. This finely dispersed phase had a composition determined to be approximately 70 percent ZrC and approximately 30 percent NbC and showed some evidence of an orientation relationship with the matrix. The precipitates appeared to coarsen slightly after approximately 5000 hr exposure in the presence of an applied stress resulted in a decrease in the size and in the interparticle spacing of the stable precipitates. However, the composition of the precipitate phase and its ability to pin dislocations were not affected by the temperature or stress conditions.

Grobstein, T. L.↗

Depressurization and two-phase flow of water containing high levels of dissolved nitrogen gas

Depressurization of water containing various concentrations of dissolved nitrogen gas was studied. In a nonflow depressurization experiment, water with very high nitrogen content was depressurized at rates from 0.09 to 0.50 MPa per second and a metastable behavior which was a strong function of the depressurization rate was observed. Flow experiments were performed in an axisymmetric, converging diverging nozzle, a two dimensional, converging nozzle with glass sidewalls, and a sharp edge orifice. The converging diverging nozzle exhibited choked flow behavior even at nitrogen concentration levels as low as 4 percent of the saturation level. The flow rates were independent of concentration level. Flow in the two dimensional, converging, visual nozzle appeared to have a sufficient pressure drop at the throat to cause nitrogen to come out of solution, but choking occurred further downstream. The orifice flow motion pictures showed considerable oscillation downstream of the orifice and parallel to the flow. Nitrogen bubbles appeared in the flow at back pressures as high as 3.28 MPa, and the level at which bubbles were no longer visible was a function of nitrogen concentration.

Simoneau, R. J.↗

Thermal Infrared Emission Spectroscopy of Synthetic Allophane and its Potential Formation on Mars

Allophane is a poorly-crystalline, hydrous aluminosilicate with variable Si/Al ratios approx.0.5-1 and a metastable precursor of clay minerals. On Earth, it forms rapidly by aqueous alteration of volcanic glass under neutral to slightly acidic conditions [1]. Based on in situ chemical measurements and the identification of alteration phases [2-4], the Martian surface is interpreted to have been chemically weathered on local to regional scales. Chemical models of altered surfaces detected by the Mars Exploration Rover Spirit in Gusev crater suggest the presence of an allophane-like alteration product [3]. Thermal infrared (TIR) spectroscopy and spectral deconvolution models are primary tools for determining the mineralogy of the Martian surface [5]. Spectral models of data from the Thermal Emission Spectrometer (TES) indicate a global compositional dichotomy, where high latitudes tend to be enriched in a high-silica material [6,7], interpreted as high-silica, K-rich volcanic glass [6,8]. However, later interpretations proposed that the high-silica material may be an alteration product (such as amorphous silica, clay minerals, or allophane) and that high latitude surfaces are chemically weathered [9-11]. A TIR spectral library of pure minerals is available for the public [12], but it does not contain allophane spectra. The identification of allophane on the Martian surface would indicate high water activity at the time of its formation and would help constrain the aqueous alteration environment [13,14]. The addition of allophane to the spectral library is necessary to address the global compositional dichotomy. In this study, we characterize a synthetic allophane by IR spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM) to create an IR emission spectrum of pure allophane for the Mars science community to use in Martian spectral models.

Rampe, E. B.↗

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.↗

On the ground state of metallic hydrogen

A proposed liquid ground state of metallic hydrogen at zero temperature is explored and a variational upper bound to the ground state energy is calculated. The possibility that the metallic hydrogen is a liquid around the metastable point (rs = 1.64) cannot be ruled out. This conclusion crucially hinges on the contribution to the energy arising from the third order in the electron-proton interaction which is shown here to be more significant in the liquid phase than in crystals.

Chakravarty, S.↗

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.↗

The growth of metastable peritectic compounds

The influence of gravitationally driven convection on the directional solidification of peritectic alloys was evaluated. The Pb-Bi peritectic was studied as a model solidification system. Analyses of directionally solidified Pb-Bi peritectic samples indicate that appreciable macrosegregation occurs due to thermosolutal convection and/or Soret diffusion. The macrosegregation results in sequantial change of phase and morphology as solidification progresses down the length of the sample. Banding was eliminated when furnace conditions were selected which resulted in a planar solidification interface. The directional solidification that occurs in the vicinity of the Pb-Bi peritectic isothermal was found to be isocompositional and to consist solely of the equilibrium terminal solid solution and peritectic phases on an extremely fine scale. Evidence was found to support the peritectic supercooling mechanism, but not the proposed peritectic superheat mechanism.

Larson, D. J., Jr.↗

Dynamics of binary phase separation in liquid He-3-He-4 mixtures

Binary phase-separation dynamics in liquid mixtures of He-3 and He-4 has been investigated near the tricritical point with laser-light scattering techniques. Rapid decompression of the mixtures results in quenches into the miscibility gap so that both the metastable and unstable (spinodal) regions can be probed. Quenches into the unstable region allowed measurements of the normalized dynamic structure factor S(k,t) that confirm the dynamical scaling hypotheses for spinodal decomposition. Measurements made for concentrations well away from the tricritical value show different behavior and suggest the presence of a spinodal boundary. Forward scattering intensities for shallow quenches probe nucleation phenomena and permit quantitative measurements of anomalous super-cooling as a function of quench rate. Comparisons with data in organic binary mixtures are given.

Hoffer, J. K.↗

The origin of chondrules - Experimental investigation of metastable liquids in the system Mg2SiO4-SiO2

Laser-melted magnesium silicate droplets were supercooled 400-750 C below their equilibrium liquidus temperatures before crystallization and their texture was compared with that of meteoritic and lunar chondrules. Crystal morphology, width and texture were studied in relation to nucleation temperature and bulk composition. It was found that the only phase to nucleate from the forsterite-enstatite normative melts was forsterite. Highly siliceous glass, about 65% SiO2 by weight, was identified interstitially to the forsterite crystals in seven of the MgSiO4 spherules and was thought to be present in all.

Blander, M.↗

Phase diagram of KHF2 and non-equilibrium effects

The equilibrium diagram for the KHF2-H2O system was constructed from cooling and heating curves for the compositions between 5 wt% and 40 wt% KHF2 and the results are shown. The phase diagrams shown is typical of that of a two component system with miscible liquid phases and whole solid phases consist of pure components. A eutectic point was found at approximately 15% KHF2 which remains completely liquid down to a temperature of -9.0 C. No hydrate formation was observed and no anomalous behavior such as the occurrence of solid transitions or metastable states was observed. The effect of rapid freezing on the equilibrium diagram did not appear, and cooling curves exhibited only one halt. Also, at rapid freezing rates, the supercooling of the solutions was smaller than those observed at the slow cooling rates. The existence of a eutectic composition and the slow rate of dissolution of the salt are used to interpret heat absorption behavior in practical applications of the KHF2-H2O system.

Hobson, M. C.↗

Pressure drop and temperature rise in He II flow in round tubes, Venturi flowmeters and valves

Pressure drops in highly turbulent He II flow were measured in round tubes, valves, and Venturi flowmeters. Results are in good agreement with single-phase flow correlations for classical fluids. The temperature rise in flow in a round tube was measured, and found to agree well with predictions for isenthalpic expansion. Cavitation was observed in the venturis under conditions of low back pressure and high flow rate. Metastable superheating of the helium at the venturi throat was observed before the helium made a transition to saturation pressure.

Walstrom, P. L.↗

Evolution of attached and detached slabs and their associated mantle dynamics

Over the two years of the NASA grant, this project has produced a significant amount of research results related to the plate subduction process and the surface crustal deformation at convergent boundaries (i.e., above subduction zones). While some research objectives are completely accomplished, other research tasks remain active and continue to be investigated at present. A steady state analytic thermal model for subducting slabs was used to examine the torques acting on a descending slab. It is found that gravitational torque vanishes when a slab is dipping either vertically or horizontally, unlike previous studies indicating that the magnitude of gravitational torque decreases as dip angle increases. Subsequently, a new time-dependent, analytic thermal model for a subducting slab was developed. The new model enables us to study transient phenomena associated with plate subduction analytically. On the basis of this model, the nature of slab dip angles was evaluated. Slab dip angles are found to be transient features. As they penetrate into the mantle and increase their lengths, the associated gravitational torque also increases resulting in a downward pulling of the slab to the steeper dip angle. This is especially true once a slab penetrates the olivine-spinel phase boundary at about 400 km depth. However, if the phase transformation does not follow the equilibrium condition, the gravitational torque may have a different behavior. This problem was investigated. Except for fast descending slabs, non-equilibrium phase transformation can only slow down the transient increase of slab dip angles discussed earlier. Its effect is not sufficiently strong to reverse the downward pulling for most of the slabs. However, when slabs subducting at 10 cm/yr or faster, a sufficient amount of metastable olivine can exist beneath 400 km. Because of its low density compared with the surrounding spinel, an upward buoyancy is produced resulting in an upward bending of the slab and possibly an upward rotation of the slab such that smaller dip angles are formed. Seismic studies of the Japanese Slab seem to support this interpretation. The development of oroclinal geometries at convergent boundaries was also examined to study plate obduction which is an important ingredient to the initiation of plate subduction. Although the study suggests that surface features are better modeled by block models, the large scale deformation can be adequately studied by viscous models. Such a model is now under development to complete our original objective to study the initiation of plate subduction. Finally, a three-dimensional, finite element, spherical convective model is developed to study dynamic plate subductions. The model development is now complete and it is being tested to ensure its proper operation. The model is able to generate convection results with a viscosity contrast of about 100. Our research continues to push the viscosity contrast to a level that is appropriate for a subducting slab.

Hsui, Albert T.↗

Ca-Rich Carbonate Melts: A Regular-Solution Model, with Applications to Carbonatite Magma + Vapor Equilibria and Carbonate Lavas on Venus

A thermochemical model of the activities of species in carbonate-rich melts would be useful in quantifying chemical equilibria between carbonatite magmas and vapors and in extrapolating liquidus equilibria to unexplored PTX. A regular-solution model of Ca-rich carbonate melts is developed here, using the fact that they are ionic liquids, and can be treated (to a first approximation) as interpenetrating regular solutions of cations and of anions. Thermochemical data on systems of alkali metal cations with carbonate and other anions are drawn from the literature; data on systems with alkaline earth (and other) cations and carbonate (and other) anions are derived here from liquidus phase equilibria. The model is validated in that all available data (at 1 kbar) are consistent with single values for the melting temperature and heat of fusion for calcite, and all liquidi are consistent with the liquids acting as regular solutions. At 1 kbar, the metastable congruent melting temperature of calcite (CaCO3) is inferred to be 1596 K, with (Delta)bar-H(sub fus)(calcite) = 31.5 +/- 1 kJ/mol. Regular solution interaction parameters (W) for Ca(2+) and alkali metal cations are in the range -3 to -12 kJ/sq mol; W for Ca(2+)-Ba(2+) is approximately -11 kJ/sq mol; W for Ca(2+)-Mg(2+) is approximately -40 kJ/sq mol, and W for Ca(2+)-La(3+) is approximately +85 kJ/sq mol. Solutions of carbonate and most anions (including OH(-), F(-), and SO4(2-)) are nearly ideal, with W between 0(ideal) and -2.5 kJ/sq mol. The interaction of carbonate and phosphate ions is strongly nonideal, which is consistent with the suggestion of carbonate-phosphate liquid immiscibility. Interaction of carbonate and sulfide ions is also nonideal and suggestive of carbonate-sulfide liquid immiscibility. Solution of H2O, for all but the most H2O-rich compositions, can be modeled as a disproportionation to hydronium (H3O(+)) and hydroxyl (OH(-)) ions with W for Ca(2+)-H3O(+) (approximately) equals 33 kJ/sq mol. The regular-solution model of carbonate melts can be applied to problems of carbonatite magma + vapor equilibria and of extrapolating liquidus equilibria to unstudied systems. Calculations on one carbonatite (the Husereau dike, Oka complex, Quebec, Canada) show that the anion solution of its magma contained an OH mole fraction of (approximately) 0.07, although the vapor in equilibrium with the magma had P(H2O) = 8.5 x P(CO2). F in carbonatite systems is calculated to be strongly partitioned into the magma (as F(-)) relative to coexisting vapor. In the Husereau carbonatite magma, the anion solution contained an F(-) mole fraction of (approximately) 6 x 10(exp -5).

Treiman, Allan H.↗

Electron microscopic determination of the metastable dissociation region in the system Li sub 2SiO3-SiO sub 2

Seven glasses with an alkali oxide content in the range 9.57 to 29.53 mole percent were investigated. The temperature at which the transition of microheterogeneous mixing to the condition of mutual solubility occurs on heating is found. It is found that the altered constituent composition results in the alteration in the percentage amount of the coexisting phases.

Marinov, M.↗