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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Ternary and quaternary oxides of Bi, Sr and Cu

Before the discovery of superconductivity in an oxide of Bi, Sr, and Cu, the system Bi-Sr-Cu-O had not been studied, although several solid phases had been identified in the two-component regions of the ternary system Bi2O3-Si-O-CuO. The oxides Sr2CuO3, SrCu2O2, SrCuO2, and Bi2CuO4 were then well known and characterized, and the phase diagram of the binary system Bi2O3-SrO had been established in the temperature range 620 to 1000 C. Besides nine solutions of compositions Bi(2-2x) Sr(x) O(3-2x) and different symmetries, this diagram includes three definite compounds of stoichiometries Bi(2)BrO4. Bi2Sr2O5, and Bi2Sr3O6 (x - 0.50, 0.67 and 0.75 respectively), only the second of which with known unit-cell of orthorhombic symmetry, dimensions (A) a = 14.293(2), b = 7.651(2), c = 6.172(1), and z = 4. The first superconducting oxide in the system Bi-Sr-Cu-O was initially formulated as Bi2Sr2Cu2O(7+x), with an orthorhombic unit-cell of parameters (A) a = 5.32, b = 26.6, c = 48.8. In a preliminary study the same oxide was formulated with half the copper content, Bi(2)Sr(2)CuO(6+x), and index its reflections assuming an orthorhombic unit-cell of dimensions (A) a = 5.390(2), b = 26.973(8), c = 24.69(4). Subsequent studies by diffraction techniques have confirmed the composition 2:2:1. A new family of oxygen-deficient perovskites, was characterized, after identifying by x ray diffraction the phases present in the products of thermal treatments of about 150 mixtures of analytical grade Bi2O3, Sr(OH)2-8H2O and CuO at different molar ratios. X ray diffraction data are presented for some other oxides of Bi and Sr, as well as for various quaternary oxides, among them an oxide of Bi, Sr, and Cu.

Casais, M. T.↗
NASA NTRS1991

High Tc superconductors: The scaling of Tc with the number of bound holes associated with charge transfer neutralizing the multivalence cations

It is observed that for the known high-T(sub c) Cu-, Tl-, and Bi-based superconductors, T(sub c) scales consistently with the number of bound holes per unit cell which arise from charge transfer excitations of frequency approximately = 3 x 10(exp 13) that neutralized the multivalence cations into diamagnetic states. The resulting holes are established on the oxygens. Extrapolation of this empirical fit in the up-temperature direction suggests a T(sub c) of about 220-230 K at a value of 25 holes/unit cell (approximately the maximum that can be materials-engineered into a high-T(sub c) K2MnF4 or triple Perovskite structure). In the down-temperature direction, the extrapolation gives a T(sub c) in the vicinity of 235 K for the Y-Ba-Cu-O system as well as the known maximum temperature of 23 K for low-T(sub c) materials shown by Nb3Ge. The approach is also consistent with the experimental findings that only multivalence ions which are diamagnetic in their atomic state (Cu, Tl, Bi, Pb, and Sb) associate with high-T(sub c) compounds.

Vezzoli, G. C.↗
NASA NTRS1992

Phase equilibria and trace element partitioning in a magma ocean to 260 kilobars

A magma ocean can solidify in a way that is intermediate between perfect equilibrium and perfect fractional crystallization. In order to model quantitatively any fractional crystallization scenario, it is necessary to understand the geochemical characteristics of the phases that crystallize from a magma ocean, and how they vary with pressure. The crystallizing phase is called the liquidus phase, and their identities were determined by numerous experiments utilizing the multianvil apparatus. For chondritic compositions the liquidus phases are as follows: olivine at 1 atmosphere to 100 kilobars; garnet from 100 to about 260 kilobars; silicate perovskite from 260 kilobars to possibly the core-mantle boundary in the Earth.

Herzberg, Claude↗
NASA NTRS1992

Material transport in laser-heated diamond anvil cell melting experiments

A previously undocumented effect in the laser-heated diamond anvil cell, namely, the transport of molten species through the sample chamber, over distances large compared to the laser beam diameter, is presented. This effect is exploited to determine the melting behavior of high-pressure silicate assemblages of olivine composition. At pressures where beta-spinel is the phase melted, relative strengths of partitioning can be estimated for the incompatible elements studied. Iron was found to partition into the melt from beta-spinel less strongly than calcium, and slightly more strongly than manganese. At higher pressures, where a silicate perovskite/magnesiowuestite assemblage is melted, it is determined that silicate perovskite is the liquidus phase, with iron-rich magnesiowuestite accumulating at the end of the laser-melted stripe.

Campbell, Andrew J.↗
NASA NTRS1992

The effects of Venusian mantle convection with multiple phase transitions

Recently there was a flurry of activities in studying the effects of phase transitions in the Earth's mantle. From petrological and geophysical considerations, phase-transitions would also play an important role in venusian dynamics. The basic differences between the two planets are the surface boundary conditions, both thermally and mechanically. In this vein we have studied time-dependent mantle convection with multiple phase transitions and depth-dependent thermal expansivity (alpha is approximately rho(exp -6)), based on high-pressure and temperature measurements. Both the olivine-spinel and spinel-perovskite transitions were simulated by introducing an effective thermal expansivity, as described. Used together with the extended Boussinesq Approximation this method serves as a powerful tool to examine the effects of phase transitions on convection at relatively low computational costs.

Steinbach, V.↗
NASA NTRS1992

Femtosecond resolution of soft mode dynamics in structural phase transitions

The microscopic pathway along which ions or molecules in a crystal move during structural phase transition can often be described in terms of a collective vibrational mode of the lattice. In many cases, this mode, called a 'soft' phonon mode because of its characteristically low frequency near the phase transition temperature, is difficult to characterize through conventional frequency-domain spectroscopies such as light or neutron scattering. A femtosecond time-domain analog of light-scattering spectroscopy called impulsive stimulated Raman scattering (ISRS) has been used to examine the soft modes of two perovskite ferroelectric crystals. The low-frequency lattice dynamics of KNbO3 and BaTiO3 are clarified in a manner that permits critical evaluation of microscopic models for their ferroelectric transitions. The results illustrate the advantages of ISRS over conventional Raman spectroscopy of low-frequency, heavily damped soft modes.

Dougherty, Thomas P.↗
NASA NTRS1993

Three-dimensional mantle dynamics with an endothermic phase transition

3D convection for the spinel to perovskite phase change has been simulated numerically. Results for Rayleigh (Ra) numbers of 0(10 exp 6) show intermittent layering with a strong robust plume rising through the phase boundary. Many descending instabilities are deflected but merging cold sheets come together at a junction. A pool of cold material accumulates underneath in the phase-transition zone. A strong gravitational instability results, which precipitates a rapid and massive discharge of upper-mantle material.

Honda, S.↗
NASA NTRS1992

X-ray photoelectron spectroscopy characterization of a nonsuperconducting Y-Ba-Cu-O superconductor-normal-metal-superconductor barrier material

A film of a novel nonsuperconducting Y-Ba-Cu-O (YBCO) barrier material was grown using conditions similar to those reported by Agostinelli et al. (1991) for forming a cubic semiconducting (c-YBCO) phase, and the material was characterized using X-ray photoelectron spectroscopy (XPS). A comparison of the XPS spectra of this material to those obtained from the orthorhombic and tetragonal phases of YBCO (o-YBCO and t-YBCO, respectively) showed that the barrier material had spectral characteristics different from those of o-YBCO and t-YBCO, particularly in the O 1s region. Features associated with the Cu-O chain and surface-reconstructed Cu-O planes were absent, consistent with expectations for the simple perovskite crystal structure of c-YBCO proposed by Agostinelli et al.

Vasquez, R. P.↗
NASA NTRS1993

Ca-,Al-rich inclusions in the unique chondrite ALH85085 - Petrology, chemistry, and isotopic compositions

A comprehensive study is performed for the Ca-,Al-rich inclusions (CAIs) in the unique chondrite ALH85085. The ALH85085 inclusions are smaller (5-80 microns) and more refractory than their counterparts in carbonaceous chondrites. The study includes 42 inclusions for petrography and mineralogy, 15 for bulk major and minor element chemical composition, six for Mg-Al isotopic systematics, 10 for Ca isotopes, nine for Ti isotopes, and six for trace element abundances. In addition, oxygen-isotopic compositions were determined in minerals from a single inclusion. No correlation is found between mineralogy, major element chemistry, and trace element abundances. It is further shown that the high-temperature geochemical behavior of ultrarefractory trace elements is decoupled from that of the major elements Ca and Ti (Ti is correlated with the relatively volatile elements Nb and Yb) implying that perovskite is of only minor importance as carrier of ultrarefractories.

Kimura, Makoto↗
NASA NTRS1993

The stability of hibonite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions

Phase fields in which hibonite (Hib) and silicate melt coexist with spinel (Sp), CaAl4O7 (CA2), gehlenitic melilite (Mel), anorthite (An), or corundum (Cor) in the system CaO-MgO-Al203-SiO2-TiO2 (CMAST) were determined and activity models developed for Mel and Hib solid solutions. Experimentally determined partition coefficients for Ti between Hib and coexisting melt, D sub t, vary from 0.8 to 2.1 and generally decrease with increasing TiO2 content in the liquid (L). Based on Ti partioning between Hib and melt, bulk inclusion compositions and Hib-saturated liquid use phase diagrams, the Hib in Fluffy Type A inclusions (FTA's) from Allende and at least some of the Hib from Hib-rich inclusions is relict; much of the Hib from Hib-glass spherules probably crystallized from a melt under nonequilibrium conditions. Bulk compositions for all of these Ca-Al-rich inclusions (CAI's) are consistent with an origin as Mel + Hib + Sp + perovskite (Pv) proto-inclusions in which Mel was partially altered. In some cases, the proto-inclusion was partially or completely melted with vaporization occurring over a period of time sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. If equilibration temperatures based on Hib-bearing CAI's reflect condensation in a cooling gas of solar composition, then Hib + Cor condensed at approximately 1260 C (referenced to 10 exp -3 atm) and Hib + Sp + Mel at approximately 1215 +/- 10 C. Simple thermochemical models for the substitution of trace elements into the Ca-site of meteoritic Hib suggest that virtually all Eu is divalent in early condensate Hibs but that Eu(2+)/Eu(3+) decreases by a factor of 20 or more during the course of condensation, primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phases condense. The relative sizes of Eu and Yb anomalies in meteoritic Hibs and CAI's may be influenced by this effect.

Beckett, J. R.↗
NASA NTRS1993

Trace element compositions of spinel-rich refractory inclusions from the Murchison meteorite

Three spinel-rich, perovskite-bearing, pyroxene-rimmed, hibonite-free inclusions from the Murchison C2 chondrite have volatility controlled, modified group II REE patterns. Two have high Eu/Yb ratios, two have small positive Ce anomalies and one has high refractory siderophiles for a group II inclusion. Two additional spinel-rich inclusions have subchondritic Ce/La ratios and negative Eu and Yb anomalies, the Eu anomalies being larger than the Yb ones. One of these inclusions is enriched in La relative to all HREE and the other is enriched in HREE relative to all LREE except La, possibly suggesting the presence of an ultrarefractory component in the latter. One hibonite-rich inclusion has a group III REE pattern with a negative Ce anomaly. A calcium dialuminate-bearing inclusion known to have crystallized from a melt at 2100-1800K has a modified group II REE pattern, rather than a pattern which would be predicted from the evaporation expected from such a droplet, e.g., a group III or ultrarefractory pattern. Volatile element contents of these inclusions are among the lowest found in any refractory inclusions.

Yoneda, S.↗
NASA NTRS1993

High temperature sensor/microphone development for active noise control

The industrial and scientific communities have shown genuine interest in electronic systems which can operate at high temperatures, among which are sensors to monitor noise, vibration, and acoustic emissions. Acoustic sensing can be accomplished by a wide variety of commercially available devices, including: simple piezoelectric sensors, accelerometers, strain gauges, proximity sensors, and fiber optics. Of the several sensing mechanisms investigated, piezoelectrics were found to be the most prevalent, because of their simplicity of design and application and, because of their high sensitivity over broad ranges of frequencies and temperature. Numerous piezoelectric materials are used in acoustic sensors today; but maximum use temperatures are imposed by their transition temperatures (T(sub c)) and by their resistivity. Lithium niobate, in single crystal form, has the highest operating temperature of any commercially available material, 650 C; but that is not high enough for future requirements. Only two piezoelectric materials show potential for use at 1000 C; AlN thin film reported to be piezoactive at 1150 C, and perovskite layer structure (PLS) materials, which possess among the highest T(sub c) (greater than 1500 C) reported for ferroelectrics. A ceramic PLS composition was chosen. The solid solution composition, 80% strontium niobate (SN) and 20% strontium tantalate (STa), with a T(sub c) approximately 1160 C, was hot forged, a process which concurrently sinters and renders the plate-like grains into a highly oriented configuration to enhance piezo properties. Poled samples of this composition showed coupling (k33) approximately 6 and piezoelectric strain constant (d33) approximately 3. Piezoactivity was seen at 1125 C, the highest temperature measurement reported for a ferroelectric ceramic. The high temperature piezoelectric responses of this, and similar PLS materials, opens the possibility of their use in electronic devices operating at temperatures up to 1000 C. Concurrent with the materials study was an effort to define issues involved in the development of a microphone capable of operation at temperatures up to 1000 C; important since microphones capable of operation above 260 C are not generally available. The distinguishing feature of a microphone is its diaphragm which receives sound from the atmosphere: whereas, most other acoustic sensors receive sound through the solid structure on which they are installed. In order to gain an understanding of the potential problems involved in designing and testing a high temperature microphone, a prototype was constructed using a commercially available lithium niobate piezoelectric element in a stainless steel structure. The prototype showed excellent frequency response at room temperature, and responded to acoustic stimulation at 670 C, above which temperature the voltage output rapidly diminished because of decreased resistivity in the element. Samples of the PLS material were also evaluated in a simulated microphone configuration, but their voltage output was found to be a few mV compared to the 10 output of the prototype.

Shrout, Thomas R.↗
NASA NTRS1994

Scientific objectives of the primitive body sample return missions: An approach from the light-induced effect on water vapor

Water is undoubtedly one of the most crucial components of the solar nebula for determining planetary composition: planets were formed from the accretion of the dust particles in the nebula, and the redox state of Fe in the particles can be determined by the reaction of Fe with water vapor diffused into the interior of the particle in the early stage of solar system formation. It has been discussed from various observations that the cores of Mercury, Venus, and the Earth might be metallic Fe, although the core of the Earth may be somewhat oxidized by the high pressure and temperature reaction of liquid Fe with perovskite at the boundary of the mantle and the core, whereas the core of Mars may be highly oxidized, as suggested by its low density. Isotopic anomalies of various elements have frequently been observed in the solar system (in planetary atmospheres and in meteorites) and some of them can be attributed to the injection of exotic particles formed in other stars into the solar nebula. Hydrogen and D anomalies in planetary atmospheres were frequently believed to correlate with the differential escape of H and D from the exospheres of Venus and Mars, although no one knows the primordial D/H ratios before thermal escape. This paper explains the decrease of the observed D/H ratios with distance from the sun by considering the light-induced drift effect to displace H2(16)O alone to the outside in the solar nebula.

Shimizu, Mikio↗
NASA NTRS1994

A ceramic/slag interface as an analog for accretion of hot refractory objects and rim formation

Refractory inclusions or Ca-Al-rich inclusions (CAI's) from carbonaceous chondrites span a wide range of bulk compositions that cannot be explained either by segregation from a gas of solar composition at different points in the condensation sequence or by fractional crystallization from a parent liquid. CAI's are commonly rimmed by Wark-Lovering (W-L) rims, a series of nearly monomineralic layers that have been a source of controversy since the variety of rim sequences occurring on different types of CAI's from Allende were described. The origin of these distinctive features has not yet been resolved, with proponents of accretion, condensation, flash heating, ablation, evaporation, etc. Rims have generated considerable interest because they potentially contain clues to conditions experienced by CAI's after the formation of the inclusion and prior to incorporation into the parent body. Ceramic bricks in contact with hot steel slag may produce reaction products in rimlike fashion similar to those found in CAI's. The similarity between the mineralogy of blast furnace slags and CAI's has long been recognized, with both containing unusual phases not found in terrestrial materials. We provide here a comparison between a ceramic brick/slag multiple-layered interface and a multiple-layered interface between a melilite-perovskite object and a melilite-spinel object in the Allende inclusion USNM 4691-1. These results have implications in interpreting the origin of rims and the textures and compositions of CAI's.

Paque, J. M.↗
NASA NTRS1994

Subduction and volatile recycling in Earth's mantle

The subduction of water and other volatiles into the mantle from oceanic sediments and altered oceanic crust is the major source of volatile recycling in the mantle. Until now, the geotherms that have been used to estimate the amount of volatiles that are recycled at subduction zones have been produced using the hypothesis that the slab is rigid and undergoes no internal deformation. On the other hand, most fluid dynamical mantle flow calculations assume that the slab has no greater strength than the surrounding mantle. Both of these views are inconsistent with laboratory work on the deformation of mantle minerals at high pressures. We consider the effects of the strength of the slab using two-dimensional calculations of a slab-like thermal downwelling with an endothermic phase change. Because the rheology and composition of subducting slabs are uncertain, we consider a range of Clapeyron slopes which bound current laboratory estimates of the spinel to perovskite plus magnesiowustite phase transition and simple temperature-dependent rheologies based on an Arrhenius law diffusion mechanism. In uniform viscosity convection models, subducted material piles up above the phase change until the pile becomes gravitationally unstable and sinks into the lower mantle (the avalanche). Strong slabs moderate the 'catastrophic' effects of the instabilities seen in many constant-viscosity convection calculations; however, even in the strongest slabs we consider, there is some retardation of the slab descent due to the presence of the phase change.

King, S. D.↗
NASA NTRS1994

Hydrogen storage in Earth's mantle and core

Two different approaches to explaining how hydrogen might be stored in the mantle are illustrated by a number of papers published over the past 25-30 years, but there has been little attempt to provide objective comparisons of the two. One approach invokes the presence in the mantle of dense hydrous magnesium silicates (DHMS) stable at elevated pressures and temperatures. The other involves nominally anhydrous minerals (NAM) that contain hydrogen as a minor constituent on the ppm level. Experimental studies on DHMS indicate these phases may be stable to pressures and temperatures as high at 16 GPa and 1200 C. This temperature is lower than that indicated by a mantle geotherm at 16 GPa, but may be reasonable for a subducting slab. It is possible that other DHMS could be stable to even higher pressures, but little is known about maximum temperature limits. For NAM, small amounts of hydrogen (up to several hundred ppm) have been detected in olivine, orthopyroxene, clinopyroxene, and garnet recovered from xenoliths in kimberlites, eclogites, and alkali basalts; it has been demonstrated that synthetic wadsleyite and perovskite can accommodate significant amounts of hydrogen. A number of problems are associated with each possibility. For NAM originating in the mantle, one would like to assume that the hydrogen measured in samples recovered on Earth's surface was incorporated when the phase-crystallized at high temperatures and pressures, but it could have been introduced during transport to the surface. Major problems for the DHMS proponents are that none of these phases have been found as minerals and little is yet known about their stabilities in systems containing other cations such as Fe, Al, and Ca.

Prewitt, Charles T.↗
NASA NTRS1994

Lower mantle thermal structure deduced from seismic tomography, mineral physics and numerical modelling

The long-wavelength thermal anomalies in the lower mantle have been mapped out using several seismic tomographic models in conjunction with thermodynamic parameters derived from high-pressure mineral physics experiments. These parameters are the depth variations of thermal expansivity and of the proportionality factor between changes in density and seismic velocity. The giant plume-like structures in the lower mantle under the Pacific Ocean and Africa have outer fringes with thermal anomalies around 300-400 K, but very high temperatures are found in the center of the plumes near the base of the core-mantle boundary. These extreme values can exceed +1500 K and may reflect large hot thermal anomalies in the lower mantle, which are supported by recent measurements of high melting temperatures of perovskite and iron. Extremely cold anomalies, around -1500 K, are found for anomalies in the deep mantle around the Pacific rim and under South America. Numerical simulations show that large negative thermal anomalies in the mid-lower mantle have modest magnitudes of around -500 K. correlation pattern exists between the present-day locations of cold masses in the lower mantle and the sites of past subduction since the Cretaceous. Results from correlation analysis show that the slab mass-flux in the lower mantle did not conform to a steady-state nature but exhibited time-dependent behavior.

Cadek, O.↗
NASA NTRS1994

An ion microprobe study of CAIs from CO3 meteorites

When attempting to interpret the history of Ca, Al-rich inclusions (CAIs) it is often difficult to distinguish between primary features inherited from the nebula and those produced during secondary processing on the parent body. We have undertaken a systematic study of CAIs from 10 CO chondrites, believed to represent a metamorphic sequence with the goal of distinguishing primary and secondary features. ALHA 77307 (3.0), Colony (3.0), Kainsaz (3.1), Felix (3.2), ALH 82101 (3.3), Ornans (3.3), Lance (3.4), ALHA 77003 (3.5), Warrenton (3.6), and Isna (3.7) were examined by Scanning Electron Microscopy (SEM) and optical microscopy. We have identified 141 CAIs within these samples, and studied in detail the petrology of 34 inclusions. The primary phases in the lower petrologic types are spinel, melilite, and hibonite. Perovskite, FeS, ilmenite, anorthite, kirschsteinite, and metallic Fe are present as minor phases. Melilite becomes less abundant in higher petrologic types and was not detected in chondrites of type 3.5 and above, confirming previous reports that this mineral easily breaks down during heating. Iron, an element that would not be expected to condense at high temperatures, has a lower abundance in spinel from low-petrologic-type meteorites than those of higher grade, and CaTiO3 is replaced by FeTiO3 in meteorites of higher petrologic type. The abundance of CAIs is similar in each meteorite. Eight inclusions have been analyzed by ion probe. The results are summarized. The results obtained to date show that CAIs in CO meteorites, like those from other meteorite classes, contain Mg* and that Mg in some inclusions has been redistributed.

Russell, S. S.↗