Thermal Expansion and Thermal Conductivity of Rare Earth Silicates

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Lee, Kang N.; Bansal, Narottam P.

2006-01-01

Rare earth silicates are considered promising candidate materials for environmental barrier coatings applications at elevated temperature for ceramic matrix composites. High temperature thermophysical properties are of great importance for coating system design and development. In this study, the thermal expansion and thermal conductivity of hot-pressed rare earth silicate materials were characterized at temperatures up to 1400 C. The effects of specimen porosity, composition and microstructure on the properties were also investigated. The materials processing and testing issues affecting the measurements will also be discussed.

Mid-infrared interferometric variability of DG Tauri: Implications for the inner-disk structure

NASA Astrophysics Data System (ADS)

Varga, J.; Gabányi, K. É.; Ábrahám, P.; Chen, L.; Kóspál, Á.; Menu, J.; Ratzka, Th.; van Boekel, R.; Dullemond, C. P.; Henning, Th.; Jaffe, W.; Juhász, A.; Moór, A.; Mosoni, L.; Sipos, N.

2017-08-01

Context. DG Tau is a low-mass pre-main sequence star, whose strongly accreting protoplanetary disk exhibits a so-far enigmatic behavior: its mid-infrared thermal emission is strongly time-variable, even turning the 10 μm silicate feature from emission to absorption temporarily. Aims: We look for the reason for the spectral variability at high spatial resolution and at multiple epochs. Methods: Infrared interferometry can spatially resolve the thermal emission of the circumstellar disk, also giving information about dust processing. We study the temporal variability of the mid-infrared interferometric signal, observed with the VLTI/MIDI instrument at six epochs between 2011 and 2014. We fit a geometric disk model to the observed interferometric signal to obtain spatial information about the disk. We also model the mid-infrared spectra by template fitting to characterize the profile and time dependence of the silicate emission. We use physically motivated radiative transfer modeling to interpret the mid-infrared interferometric spectra. Results: The inner disk (r < 1-3 au) spectra exhibit a 10 μm absorption feature related to amorphous silicate grains. The outer disk (r > 1-3 au) spectra show a crystalline silicate feature in emission, similar to the spectra of comet Hale-Bopp. The striking difference between the inner and outer disk spectral feature is highly unusual among T Tauri stars. The mid-infrared variability is dominated by the outer disk. The strength of the silicate feature changed by more than a factor of two. Between 2011 and 2014 the half-light radius of the mid-infrared-emitting region decreased from 1.15 to 0.7 au. Conclusions: For the origin of the absorption we discuss four possible explanations: a cold obscuring envelope, an accretion heated inner disk, a temperature inversion on the disk surface and a misaligned inner geometry. The silicate emission in the outer disk can be explained by dusty material high above the disk plane, whose mass can change with time, possibly due to turbulence in the disk. Based on observations made with the ESO Very Large Telescope Interferometer at Paranal Observatory (Chile) under the programs 088.C-1007 (PI: L. Mosoni), 090.C-0040 (PI: Th. Ratzka), and 092.C-0086 (PI: Th. Ratzka).

Mechanical Properties and Durability of Advanced Environmental Barrier Coatings in Calcium-Magnesium-Alumino-Silicate Environments

NASA Technical Reports Server (NTRS)

Miladinovich, Daniel S.; Zhu, Dongming

2011-01-01

Environmental barrier coatings are being developed and tested for use with SiC/SiC ceramic matrix composite (CMC) gas turbine engine components. Several oxide and silicate based compositons are being studied for use as top-coat and intermediate layers in a three or more layer environmental barrier coating system. Specifically, the room temperature Vickers-indentation-fracture-toughness testing and high-temperature stability reaction studies with Calcium Magnesium Alumino-Silicate (CMAS or "sand") are being conducted using advanced testing techniques such as high pressure burner rig tests as well as high heat flux laser tests.

Discovery of Ni-smectite-rich saprolite at Loma Ortega, Falcondo mining district (Dominican Republic): geochemistry and mineralogy of an unusual case of "hybrid hydrous Mg silicate - clay silicate" type Ni-laterite

NASA Astrophysics Data System (ADS)

Tauler, Esperança; Lewis, John F.; Villanova-de-Benavent, Cristina; Aiglsperger, Thomas; Proenza, Joaquín A.; Domènech, Cristina; Gallardo, Tamara; Longo, Francisco; Galí, Salvador

2017-10-01

Hydrous Mg silicate-type Ni-laterite deposits, like those in the Falcondo district, Dominican Republic, are dominated by Ni-enriched serpentine and garnierite. Recently, abundant Ni-smectite in the saprolite zone have been discovered in Loma Ortega, one of the nine Ni-laterite deposits in Falcondo. A first detailed study on these Ni-smectites has been performed (μXRD, SEM, EPMA), in addition to a geochemical and mineralogical characterisation of the Loma Ortega profile (XRF, ICP-MS, XRD). Unlike other smectite occurrences in laterite profiles worldwide, the Loma Ortega smectites are trioctahedral and exhibit high Ni contents never reported before. These Ni-smectites may be formed from weathering of pyroxene and olivine, and their composition can be explained by the mineralogy and the composition of the Al-depleted, olivine-rich parent ultramafic rock. Our study shows that Ni-laterites are mineralogically complex, and that a hydrous Mg silicate ore and a clay silicate ore can be confined to the same horizon in the weathering profile, which has significant implications from a recovery perspective. In accordance, the classification of "hybrid hydrous Mg silicate - clay silicate" type Ni-laterite deposit for Loma Ortega would be more appropriate.

Metal-Silicate Partitioning of Various Siderophile Elements at High Pressure and High Temperatures: a Diamond Anvil Cell Study

NASA Astrophysics Data System (ADS)

Badro, J.; Blanchard, I.; Siebert, J.

2015-12-01

Core formation is the major chemical fractionation that occurred on Earth. This event is widely believed to have happened at pressures of at least 40 GPa and temperatures exceeding 3000 K. It has left a significant imprint on the chemistry of the mantle by removing most of the siderophile (iron-loving) elements from it. Abundances of most siderophile elements in the bulk silicate Earth are significantly different than those predicted from experiments at low P-T. Among them, vanadium, chromium, cobalt and gallium are four siderophile elements which abundances in the mantle have been marked by core formation processes. Thus, understand their respective abundance in the mantle can help bringing constraints on the conditions of Earth's differentiation. We performed high-pressure high-temperature experiments using laser heating diamond anvil cell to investigate the metal-silicate partitioning of those four elements. Homogeneous glasses doped in vanadium, chromium, cobalt and gallium were synthesized using a levitation furnace and load inside the diamond anvil cell along with metallic powder. Samples were recovered using a Focused Ion Beam and chemically analyzed using an electron microprobe. We investigate the effect of pressure, temperature and metal composition on the metal-silicate partitioning of V, Cr, Co and Ga. Three previous studies focused on V, Cr and Co partitioning at those conditions of pressure and temperature, but none explore gallium partitioning at the relevant extreme conditions of core formation. We will present the first measurements of gallium metal-silicate partitioning performed at the appropriate conditions of pressure and temperature of Earth's differentiation.

Metal/Silicate Partitioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition

NASA Technical Reports Server (NTRS)

Bailey, Edward; Drake, Michael J.

2004-01-01

The distinctive pattern of element concentrations in the upper mantle provides essential evidence in our attempts to understand the accretion and differentiation of the Earth (e.g., Drake and Righter, 2002; Jones and Drake, 1986; Righter et al., 1997; Wanke 1981). Core formation is best investigated through use of metal/silicate partition coefficients for siderophile elements. The variables influencing partition coefficients are temperature, pressure, the major element compositions of the silicate and metal phases, and oxygen fugacity. Examples of studies investigating the effects of these variables on partitioning behavior are: composition of the metal phase by Capobianco et al. (1999) and Righter et al. (1997); silicate melt composition by Watson (1976), Walter and Thibault (1995), Hillgren et al. (1996), Jana and Walker (1997), and Jaeger and Drake (2000); and oxygen fugacity by Capobianco et al. (1999), and Walter and Thibault (1995). Here we address the relative influences of silicate melt composition, pressure and temperature.

Low-temperature crystallization of silicate dust in circumstellar disks.

PubMed

Molster, F J; Yamamura, I; Waters, L B; Tielens, A G; de Graauw, T; de Jong, T; de Koter, A; Malfait, K; van den Ancker, M E; van Winckel, H; Voors, R H; Waelkens, C

1999-10-07

Silicate dust in the interstellar medium is observed to be amorphous, yet silicate dust in comets and interplanetary dust particles is sometimes partially crystalline. The dust in disks that are thought to be forming planets around some young stars also appears to be partially crystalline. These observations suggest that as the dust goes from the precursor clouds to a planetary system, it must undergo some processing, but the nature and extent of this processing remain unknown. Here we report observations of highly crystalline silicate dust in the disks surrounding binary red-giant stars. The dust was created in amorphous form in the outer atmospheres of the red giants, and therefore must be processed in the disks to become crystalline. The temperatures in these disks are too low for the grains to anneal; therefore, some low-temperature process must be responsible. As the physical properties of the disks around young stars and red giants are similar, our results suggest that low-temperature crystallization of silicate grains also can occur in protoplanetary systems.

Method of removing cesium from steam

DOEpatents

Carson, Jr., Neill J.; Noland, Robert A.; Ruther, Westly E.

1991-01-01

Method for removal of radioactive cesium from a hot vapor, such as high temperature steam, including the steps of passing input hot vapor containing radioactive cesium into a bed of silicate glass particles and chemically incorporating radioactive cesium in the silicate glass particles at a temperature of at least about 700.degree. F.

Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus.

PubMed

Shellnutt, J Gregory

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra.

Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus

PubMed Central

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra. PMID:29584745

Corrosion resistant thermal barrier coating. [protecting gas turbines and other engine parts

NASA Technical Reports Server (NTRS)

Levine, S. R.; Miller, R. A.; Hodge, P. E. (Inventor)

1981-01-01

A thermal barrier coating system for protecting metal surfaces at high temperature in normally corrosive environments is described. The thermal barrier coating system includes a metal alloy bond coating, the alloy containing nickel, cobalt, iron, or a combination of these metals. The system further includes a corrosion resistant thermal barrier oxide coating containing at least one alkaline earth silicate. The preferred oxides are calcium silicate, barium silicate, magnesium silicate, or combinations of these silicates.

The role of hydrothermal processes in concentrating high-field strength elements in the Strange Lake peralkaline complex, northeastern Canada

NASA Astrophysics Data System (ADS)

Salvi, Stefano; Williams-Jones, Anthony E.

1996-06-01

The middle-Proterozoic peralkaline pluton at Strange Lake, Quebec/Labrador, comprises hypersolvus to subsolvus phases which are unusually enriched in Zr, Y, REEs, Nb, Be, and F, as exotic alkali and alkaline-earth silicate minerals. The highest concentrations of these elements are in subsolvus granite, which underwent intense low temperature (≤200°C) hydrothermal alteration involving hematization and the replacement of alkali high-field strength element (HFSE) minerals by calcic equivalents. This alteration is interpreted to have been caused by meteoric or formational waters. High temperature (≥ 350°C) alteration, attributed to orthomagmatic fluids, is evident in other parts of the subsolvus granite by the replacement of arfvedsonite by aegirine. Comparisons of the chemical compositions of fresh and altered rocks indicate that rocks subjected to high temperature alteration were chemically unaffected, except for depletion in Zr, Y, and HREEs. These elements were appreciably enriched in rocks that underwent low temperature alteration. Other elements affected by low temperature alteration include Ca and Mg, which were added and Na, which was removed. Available data on HFSE speciation in aqueous fluids and the chemistry of the pluton, suggest that the HFSEs were transported as fluoride complexes. If this was the case, the low temperature fluid could not have been responsible for HFSE transport, because the high concentration of Ca and low solubility of fluorite would have buffered F - activity to levels too low to permit significant complexation. We propose that HFSE mineralization and accompanying alteration were the result of mixing, in the apical parts of the pluton, of a F-rich, essentially Ca-free orthomagmatic fluid containing significant concentrations of HFSEs, with an externally derived meteoric-dominated fluid, enriched in Ca as a result of interaction with calc-silicate gneisses and gabbros. According to this interpretation, the latter fluid was responsible for the exchange of Ca for alkalis, mainly Na, in HFSE-rich minerals and, by sharply reducing F - activity in the mixed fluid through fluorite precipitation and/or increasing pH, destabilised the HFSE-fluoride complexes, causing deposition of HFSE-bearing minerals. An important implication of this study is that major HFSE enrichment may be restricted to those rare cases where F-rich, Ca-free, metal leaching environments and Ca-rich depositional environments are juxtaposed.

Influence of Silicate Melt Composition on Metal/Silicate Partitioning of W, Ge, Ga and Ni

NASA Technical Reports Server (NTRS)

Singletary, S. J.; Domanik, K.; Drake, M. J.

2005-01-01

The depletion of the siderophile elements in the Earth's upper mantle relative to the chondritic meteorites is a geochemical imprint of core segregation. Therefore, metal/silicate partition coefficients (Dm/s) for siderophile elements are essential to investigations of core formation when used in conjunction with the pattern of elemental abundances in the Earth's mantle. The partitioning of siderophile elements is controlled by temperature, pressure, oxygen fugacity, and by the compositions of the metal and silicate phases. Several recent studies have shown the importance of silicate melt composition on the partitioning of siderophile elements between silicate and metallic liquids. It has been demonstrated that many elements display increased solubility in less polymerized (mafic) melts. However, the importance of silicate melt composition was believed to be minor compared to the influence of oxygen fugacity until studies showed that melt composition is an important factor at high pressures and temperatures. It was found that melt composition is also important for partitioning of high valency siderophile elements. Atmospheric experiments were conducted, varying only silicate melt composition, to assess the importance of silicate melt composition for the partitioning of W, Co and Ga and found that the valence of the dissolving species plays an important role in determining the effect of composition on solubility. In this study, we extend the data set to higher pressures and investigate the role of silicate melt composition on the partitioning of the siderophile elements W, Ge, Ga and Ni between metallic and silicate liquid.

The Chaunskij Meteorite: Mineralogical, Chemical and Isotope Data, Classification and Proposed Origin

NASA Astrophysics Data System (ADS)

Petaev, M. I.; Zaslavskaya, N. I.; Clarke, R. S., Jr.; Olsen, E. J.; Jarosewich, E.; Kononkova, N. N.; Holmberg, B. B.; Davis, A. M.; Ustinov, V. I.; Wood, J. A.

1992-07-01

The 1990 g Chaunskij meteorite was found in 1985 and classified as an anomalous ungrouped iron (Meteoritical Bulletin, 1988). The meteorite contains about 10 vol% mono- and polymineralic troilite-phosphate-silicate inclusions, microns to centimeters in size. STRUCTURE AND MINERALOGY. Chaunskij metal displays a mesosiderite structure with unusually high levels of shock damage in the kamacite. Tetrataenite borders 5-10 mm wide enclose large regions of cloudy taenite, which, in turn, sometimes enclose martensitic regions. Much of the tetrataenite has apparently been disordered by shock. Schreibersite occurs as occasional very small precipitates at tetrataenite borders, and infrequently as larger masses at grain boundaries. Shock-affected troilite in moderately large globules (up to several mm) and rounded phosphate inclusions are erratically distributed. Silicate areas of the polymineralic inclusions are, as a rule, irregular in shape. In larger inclusions, these areas are usually surrounded by phosphate rims. The groundmass of the polymineralic inclusions is a fine- grained intergrowth of low-Ca pyroxene (mg' = 28-31), whitlockite, and cordierite (mg' = 83-87), with rare large (50-100 mm) porphyritic grains of the first two minerals. Porphyritic pyroxene grain edges are generally rough. Minor minerals in the silicate inclusions are SiO2, kamacite, taenite, troilite, chromite, ilmenite, rutile, and small relict grains of plagioclase (An 83-95). The chromite and ilmenite vary in MgO, MnO, and Al2O3 contents. Rare grains of pyrophanite, alabandite, native copper, stanfieldite, and of a graftonite-farringtonite mineral are also observed in the meteorite. BULK CHEMISTRY. Bulk chemical data for the silicate-rich portion of one polymineralic inclusion (obtained by defocused beam analyses; Zaslavskaya et al.,1991) suggest a differentiated nature for the inclusions. High Al/Si (0.34) and Mn/Fe (0.029) ratios indicate a basalt-like precursor similar to HED and mesosiderite silicates. CLASSIFICATION. The proportion of metal suggests that Chaunskij should be classified as an iron with silicate inclusions. However, characteristics such as the mesosiderite-like structure of the metal, compositions of the pyroxene and plagioclase, and bulk Fe/Mn ratio all point to a relationship between Chaunskij and the mesosiderites, though the bulk Ni content in the metal (14.4 wt%; Zaslavskaya et al., 1991) is higher than previously observed in mesosiderites. In light of these data, Chaunskij may be tentatively classified as a highly-metamorphosed mesosiderite. Oxygen isotope data (R.N. Clayton, personal communication) for two Chaunskij inclusions plot outside the HED and mesosiderite clusters and lie between the terrestrial fractionation line and the silicates of the IAB irons. PROPOSED ORIGIN. The structural relationships of silicates and metal argue against simultaneous melting of these phases and suggest the incorporation of silicate fragments into plastic (molten?) metal. In such a scenario, the phosphate- silicate assemblage may be the result of a metamorphic reaction between silicates and phosphorus dissolved in the metal: Px + An + P [ss in metal] + O --> Cord + Q + Whit, which would take place under moderate temperatures (750-820 degrees C) and relatively high (for meteorites!) pressures (3.5-5.0 kbar) (Hess, 1969) in the interior of the Chaunskij parent body. REFERENCES Hess P.C.(1969) Contrib. Miner. Petrol., 24, 191- 207. The Meteoritical Bulletin (1988) Meteoritics, 23, 171- 173. Zaslavskaya N.I., Petaev M.I., Kononkova N.N., Barsukova L.D. (1991) Lunar Planet. Sci. (abstract), 22, 1545-1546.

Titanite chronology, thermometry, and speedometry of ultrahigh-temperature (UHT) calc-silicates from south Madagascar: U-Pb dates, Zr temperatures, and lengthscales of trace-element diffusion

NASA Astrophysics Data System (ADS)

Holder, R. M.; Hacker, B. R.

2017-12-01

Calc-silicate rocks are often overlooked as sources of pressure-temperature-time data in granulite-UHT metamorphic terranes due to the strong dependence of calc-silicate mineral assemblages on complex fluid compositions and a lack of thermodynamic data on common high-temperature calc-silicate minerals such as scapolite. In the Ediacaran-Cambrian UHT rocks of southern Madagascar, clinopyroxene-scapolite-feldspar-quartz-zircon-titanite calc-silicate rocks are wide-spread. U-Pb dates of 540-520 Ma from unaltered portions of titanite correspond to cooling of the rocks through upper-amphibolite facies and indicate UHT metamorphism occurred before 540 Ma. Zr concentrations in these domains preserve growth temperatures of 900-950 °C, consistent with peak temperatures calculated by pseudosection modeling of nearby osumilite-bearing gneisses. Younger U-Pb dates (510-490 Ma) correspond to fluid-mediated Pb loss from titanite grains, which occurred below their diffusive Pb-closure temperature, along fractures. The extent of fluid alteration is seen clearly in back-scattered electron images and Zr-, Al-, Fe-, Ce-, and Nb-concentration maps. Laser-ablation depth profiling of idioblastic titanite grains shows preserved Pb diffusion profiles at grain rims, but there is no evidence for Zr diffusion, indicating that it was effectively immobile even at UHT.

High-temperature silicate volcanism on Jupiter's moon Io

USGS Publications Warehouse

McEwen, A.S.; Keszthelyi, L.; Spencer, J.R.; Schubert, G.; Matson, D.L.; Lopes-Gautier, R.; Klaasen, K.P.; Johnson, T.V.; Head, J.W.; Geissler, P.; Fagents, S.; Davies, A.G.; Carr, M.H.; Breneman, H.H.; Belton, M.J.S.

1998-01-01

Infrared wavelength observations of Io by the Galileo spacecraft show that at last 12 different vents are erupting lavas that are probably hotter than the highest temperature basaltic eruptions on Earth today. In at least one case, the eruption near Pillan Patea, two independent instruments on Galileo show that the lava temperature must have exceeded 1700 kelvin and may have reached 2000 kelvin. The most likely explanation is that these lavas are ultramafic (magnesium-rich) silicates, and this idea is supported by the tentative identification of magnesium-rich orthopyroxene in lava flows associated with thse high-temperature hot spots.

Annealing of Silicate Dust by Nebular Shocks at 10 AU

NASA Technical Reports Server (NTRS)

Harker, David E.; Desch, Steven J.; DeVincenzi, D. (Technical Monitor)

2001-01-01

Silicate dust grains in the interstellar medium are known to be mostly amorphous, yet crystalline silicate grains have been observed in many long-period comets and in protoplanetary disks. Annealing of amorphous silicate grains into crystalline grains requires temperatures greater than or approximately equal to 1000 K, but exposure of dust grains in comets to such high temperatures is apparently incompatible with the generally low temperatures experienced by comets. This has led to the proposal of models in which dust grains were thermally processed near the protoSun, then underwent considerable radial transport until they reached the gas giant planet region where the long-period comets originated. We hypothesize instead that silicate dust grains were annealed in situ, by shock waves triggered by gravitational instabilities. We assume a shock speed of 5 km/s, a plausible value for shocks driven by gravitational instabilities. We calculate the peak temperatures of pyroxene grains under conditions typical in protoplanetary disks at 5-10 AU. We show that in situ annealing of micron-sized dust grains can occur, obviating the need for large-scale radial transport.

Anionic Pt in Silicate Melts at Low Oxygen Fugacity: Speciation, Partitioning and Implications for Core Formation Processes on Asteroids

NASA Technical Reports Server (NTRS)

Medard, E.; Martin, A. M.; Righter, K.; Malouta, A.; Lee, C.-T.

2017-01-01

Most siderophile element concentrations in planetary mantles can be explained by metal/ silicate equilibration at high temperature and pressure during core formation. Highly siderophile elements (HSE = Au, Re, and the Pt-group elements), however, usually have higher mantle abundances than predicted by partitioning models, suggesting that their concentrations have been set by late accretion of material that did not equilibrate with the core. The partitioning of HSE at the low oxygen fugacities relevant for core formation is however poorly constrained due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variables like temperature, pressure, and oxygen fugacity. To better understand the relative roles of metal/silicate partitioning and late accretion, we performed a self-consistent set of experiments that parameterizes the influence of oxygen fugacity, temperature and melt composition on the partitioning of Pt, one of the HSE, between metal and silicate melts. The major outcome of this project is the fact that Pt dissolves in an anionic form in silicate melts, causing a dependence of partitioning on oxygen fugacity opposite to that reported in previous studies.

Oxidation resistant Mo-Mo2B-silica and Mo-Mo2B-silicate composites for high temperature applications

NASA Astrophysics Data System (ADS)

Cochran, J. K.; Daloz, W. L.; Marshall, P. E.

2011-12-01

Development of Mo composites based on the Mo-Si-B system has been demonstrated as a possible new route to achieving a high temperature Mobased material. In this new system, the silicide phases are replaced directly with silica or other silicate materials. These composites avoid the high ductile to brittle transition temperature observed for Mo-Si-B alloys by removing the Si that exists in solid solution in Mo at equilibrium with its silicides. A variety of compositions is tested for room temperature ductility and oxidation resistance. A system based upon Mo, Mo2B, and SrO·Al2O3·(SiO2)2 is shown to possess both ductility at 80 vol.% Mo and oxidation resistance at 60 vol.%. These composites can be produced using a powder processing approach and fired to greater than 95% theoretical density with a desirable microstructure of isolated boride and silicate phases within a ductile Mo matrix.

Temperature and Oxygen Fugacity Constraints on CK and R Chondrites and Implications for Water and Oxidation in the Early Solar System

NASA Technical Reports Server (NTRS)

Righter, K.; Neff, K. E.

2007-01-01

Recent chondritic meteorite finds in Antarctica have included CB, CH, CK and R chondrites, the latter two of which are among the most oxidized materials found in meteorite collections. In this study we present petrographic and mineralogic data for a suite of CK and R chondrites, and compare to previous studies of CK and R, as well as some CV chondrites. In particular we focus on the opaque minerals magnetite, chromite, sulfides, and metal as well as unusual silicates hornblende, biotite, and plagioclase. Several mineral thermometers and oxy-barometers are utilized to calculate temperatures and oxygen fugacities for these unusual meteorites compared to other more common chondrite groups. R and CK chondrites show lower equilibrium temperatures than ordinary chondrites, even though they are at similar petrologic grades (e.g., thermal type 6). Oxygen fugacity calculated for CV and R chondrites ranges from values near the iron-wustite (IW) oxygen buffer to near the fayalite-magnetite-quartz (FMQ) buffer. In comparison, the fO2 recorded by ilmenite-magnetite pairs from CK chondrites are much higher, from FMQ+3.1 to FMQ+5.2. The latter values are the highest recorded for materials in meteorites, and place some constraints on the formation conditions of these magnetite-bearing chondrites. Differences between mineralogic and O isotopic compositions of CK and R chondrites suggest two different oxidation mechanisms, which may be due to high and low water: rock ratios during metamorphism, or to different fluid compositions, or both.

Evidence for seismogenic fracture of silicic magma.

PubMed

Tuffen, Hugh; Smith, Rosanna; Sammonds, Peter R

2008-05-22

It has long been assumed that seismogenic faulting is confined to cool, brittle rocks, with a temperature upper limit of approximately 600 degrees C (ref. 1). This thinking underpins our understanding of volcanic earthquakes, which are assumed to occur in cold rocks surrounding moving magma. However, the recent discovery of abundant brittle-ductile fault textures in silicic lavas has led to the counter-intuitive hypothesis that seismic events may be triggered by fracture and faulting within the erupting magma itself. This hypothesis is supported by recent observations of growing lava domes, where microearthquake swarms have coincided with the emplacement of gouge-covered lava spines, leading to models of seismogenic stick-slip along shallow shear zones in the magma. But can fracturing or faulting in high-temperature, eruptible magma really generate measurable seismic events? Here we deform high-temperature silica-rich magmas under simulated volcanic conditions in order to test the hypothesis that high-temperature magma fracture is seismogenic. The acoustic emissions recorded during experiments show that seismogenic rupture may occur in both crystal-rich and crystal-free silicic magmas at eruptive temperatures, extending the range of known conditions for seismogenic faulting.

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions.

PubMed

Bennett, Neil R; Brenan, James M; Fei, Yingwei

2015-06-13

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied.

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions

PubMed Central

Bennett, Neil R.; Brenan, James M.; Fei, Yingwei

2015-01-01

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied. PMID:26132380

Metal-silicate thermochemistry at high temperature - Magma oceans and the 'excess siderophile element' problem of the earth's upper mantle

NASA Technical Reports Server (NTRS)

Capobianco, Christopher J.; Jones, John H.; Drake, Michael J.

1993-01-01

Low-temperature metal-silicate partition coefficients are extrapolated to magma ocean temperatures. If the low-temperature chemistry data is found to be applicable at high temperatures, an important assumption, then the results indicate that high temperature alone cannot account for the excess siderophile element problem of the upper mantle. For most elements, a rise in temperature will result in a modest increase in siderophile behavior if an iron-wuestite redox buffer is paralleled. However, long-range extrapolation of experimental data is hazardous when the data contains even modest experimental errors. For a given element, extrapolated high-temperature partition coefficients can differ by orders of magnitude, even when data from independent studies is consistent within quoted errors. In order to accurately assess siderophile element behavior in a magma ocean, it will be necessary to obtain direct experimental measurements for at least some of the siderophile elements.

Alkali Silicate Vehicle Forms Durable, Fireproof Paint

NASA Technical Reports Server (NTRS)

Schutt, John B.; Seindenberg, Benjamin

1964-01-01

The problem: To develop a paint for use on satellites or space vehicles that exhibits high resistance to cracking, peeling, or flaking when subjected to a wide range of temperatures. Organic coatings will partially meet the required specifications but have the inherent disadvantage of combustibility. Alkali-silicate binders, used in some industrial coatings and adhesives, show evidence of forming a fireproof paint, but the problem of high surface-tension, a characteristic of alkali silicates, has not been resolved. The solution: Use of a suitable non-ionic wetting agent combined with a paint incorporating alkali silicate as the binder.

Silicate dust in a Vega-excess system

NASA Technical Reports Server (NTRS)

Skinner, C. J.; Barlow, M. J.; Justtanont, K.

1992-01-01

The 10-micron spectrum of the K5V star SAO 179815 (= HD 98800) is presented, and conclusively demonstrates the presence of small silicate dust grains around this star. The 9.7-micron silicate dust feature is unusually broad and shallow in this system. This, together with the slow fall-off of flux at longer wavelengths, constrains the size and density distributions of dust grains in models of the disk. It is found that there must be a significant population of small grains, as well as a population of large grains in order to explain all the observed properties of the disk.

Ion transport mechanism in glasses: non-Arrhenius conductivity and nonuniversal features.

PubMed

Murugavel, S; Vaid, C; Bhadram, V S; Narayana, C

2010-10-28

In this article, we report non-Arrhenius behavior in the temperature-dependent dc conductivity of alkali ion conducting silicate glasses well below their glass transition temperature. In contrast to the several fast ion-conducting and binary potassium silicate glasses, these glasses show a positive deviation in the Arrhenius plot. The observed non-Arrhenius behavior is completely reproducible in nature even after prolonged annealing close to the glass transition temperature of the respective glass sample. These results are the manifestation of local structural changes of the silicate network with temperature and give rise to different local environments into which the alkali ions hop, revealed by in situ high-temperature Raman spectroscopy. Furthermore, the present study provides new insights into the strong link between the dynamics of the alkali ions and different sites associated with it in the glasses.

SIZE AND SURFACE AREA OF ICY DUST AGGREGATES AFTER A HEATING EVENT AT A PROTOPLANETARY NEBULA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sirono, Sin-iti

2013-03-01

The activity of a young star rises abruptly during an FU Orionis outburst. This event causes a temporary temperature increase in the protoplanetary nebula. H{sub 2}O icy grains are sublimated by this event, and silicate cores embedded inside the ice are ejected. During the high-temperature phase, the silicate grains coagulate to form silicate core aggregates. After the heating event, the temperature drops, and the ice recondenses onto the aggregates. I determined numerically the size distribution of the ice-covered aggregates. The size of the aggregates exceeds 10 {mu}m around the snow line. Because of the migration of the ice to largemore » aggregates, only a small fraction of the silicate core aggregate is covered with H{sub 2}O ice. After the heating event, the surface of an ice-covered aggregate is totally covered by silicate core aggregates. This might reduce the fragmentation velocity of aggregates when they collide. It is possible that the covering silicate cores shield the UV radiation field which induces photodissociation of H{sub 2}O ice. This effect may cause the shortage of cold H{sub 2}O vapor observed by Herschel.« less

Experimental, in-situ carbon solution mechanisms and isotope fractionation in and between (C-O-H)-saturated silicate melt and silicate-saturated (C-O-H) fluid to upper mantle temperatures and pressures

NASA Astrophysics Data System (ADS)

Mysen, Bjorn

2017-02-01

Our understanding of materials transport processes in the Earth relies on characterizing the behavior of fluid and melt in silicate-(C-O-H) systems at high temperature and pressure. Here, Raman spectroscopy was employed to determine structure of and carbon isotope partitioning between melts and fluids in alkali aluminosilicate-C-O-H systems. The experimental data were recorded in-situ while the samples were at equilibrium in a hydrothermal diamond anvil cell at temperatures and pressures to 825 °C and >1300 MPa, respectively. The carbon solution equilibrium in both (C-O-H)-saturated melt and coexisting, silicate-saturated (C-O-H) fluid is 2CO3 + H2O + 2Qn + 1 = 2HCO3 + 2Qn. In the Qn-notation, the superscript, n, is the number of bridging oxygen in silicate structural units. At least one oxygen in CO3 and HCO3 groups likely is shared with silicate tetrahedra. The structural behavior of volatile components described with this equilibrium governs carbon isotope fractionation factors between melt and fluid. For example, the ΔH equals 3.2 ± 0.7 kJ/mol for the bulk 13C/12C exchange equilibrium between fluid and melt. From these experimental data, it is suggested that at deep crustal and upper mantle temperatures and pressures, the δ13C-differences between coexisting silicate-saturated (C-O-H) fluid and (C-O-H)-saturated silicate melts may change by more than 100‰ as a function of temperature in the range of magmatic processes. Absent information on temperature and pressure, the use of carbon isotopes of mantle-derived magma to derive isotopic composition of magma source regions in the Earth's interior, therefore, should be exercised with care.

Solubility of oxygen in liquid Fe at high pressure and consequences for the early differentiation of Earth and Mars

NASA Astrophysics Data System (ADS)

Rubie, D. C.; Gessmann, C. K.; Frost, D. J.

2003-04-01

Knowledge of the solubility of oxygen in liquid iron enables the partitioning of oxygen between metal and silicates and the oxidation state of residual silicates to be constrained during core formation in planetary bodies. We have determined oxygen solubility experimentally at 5--23 GPa, 2100--2700 K and oxygen fugacities 1--4 log units below the iron-wüstite buffer in samples of liquid Ni-Fe alloy contained in magnesiowüstite capsules using a multianvil apparatus. Results show that oxygen solubility increases with increasing temperature but decreases slightly with increasing pressure over the range of experimental conditions, at constant oxygen fugacity. Using an extrapolation of the results to higher pressures and temperatures, we have modeled the geochemical consequences of metal-silicate separation in magma oceans in order to explain the contrasting FeO contents of the mantles of Earth and Mars. We assume that both Earth and Mars accreted originally from material with a chondritic composition; because the initial oxidation state is uncertain, we vary this parameter by defining the initial oxygen content. Two metal-silicate fractionation models are considered: (1) Metal and silicate are allowed to equilibrate at fictive conditions that approximate the pressure and temperature at the base of a magma ocean. (2) The effect of settling Fe droplets in a magma ocean is determined using a simple polybaric metal-silicate fractionation model. We assume that the temperature at the base of a magma ocean is close to the peridotite liquidus. In the case of Earth, high temperatures in a magma ocean with a depth >1200 km would have resulted in significant quantities of oxygen dissolving in the liquid metal with the consequent extraction of FeO from the residual silicate. In contrast, on Mars, even if the magma ocean extended to the depth of the current core-mantle boundary, temperatures would not have been sufficiently high for oxygen solubility in liquid metal to be significant. The results show that Earth and Mars could have accreted from similar material, with an initial FeO content around 18 wt%. On Earth, oxygen was extracted from silicates by the segregating metal during core formation, leaving the mantle with its present FeO content of ˜8 wt%. On Mars, in contrast, the segregating metal extracted little or no oxygen and left the FeO content unaltered at ˜18 wt%. A consequence of this model is that oxygen should be an important light element in the Earth's core but not in the Martian core.

Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

NASA Technical Reports Server (NTRS)

King, C.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

2010-01-01

Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

Life in a temperate Polar sea: a unique taphonomic window on the structure of a Late Cretaceous Arctic marine ecosystem

PubMed Central

Chin, Karen; Bloch, John; Sweet, Arthur; Tweet, Justin; Eberle, Jaelyn; Cumbaa, Stephen; Witkowski, Jakub; Harwood, David

2008-01-01

As the earth faces a warming climate, the rock record reminds us that comparable climatic scenarios have occurred before. In the Late Cretaceous, Arctic marine organisms were not subject to frigid temperatures but still contended with seasonal extremes in photoperiod. Here, we describe an unusual fossil assemblage from Devon Island, Arctic Canada, that offers a snapshot of a ca 75 Myr ago marine palaeoecosystem adapted to such conditions. Thick siliceous biogenic sediments and glaucony sands reveal remarkably persistent high primary productivity along a high-latitude Late Cretaceous coastline. Abundant fossil faeces demonstrate that this planktonic bounty supported benthic invertebrates and large, possibly seasonal, vertebrates in short food chains. These ancient organisms filled trophic roles comparable to those of extant Arctic species, but there were fundamental differences in resource dynamics. Whereas most of the modern Arctic is oligotrophic and structured by resources from melting sea ice, we suggest that forested terrestrial landscapes helped support the ancient marine community through high levels of terrigenous organic input. PMID:18713718

High Pressure/Temperature Metal Silicate Partitioning of Tungsten

NASA Technical Reports Server (NTRS)

Shofner, G. A.; Danielson, L.; Righter, K.; Campbell, A. J.

2010-01-01

The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

Strong Eu2+ light emission in Eu silicate through Eu3+ reduction in Eu2O3/Si multilayer deposited on Si substrates

PubMed Central

2013-01-01

Eu2O3/Si multilayer nanostructured films are deposited on Si substrates by magnetron sputtering. Transmission electron microscopy and X-ray diffraction measurements demonstrate that multicrystalline Eu silicate is homogeneously distributed in the film after high-temperature treatment in N2. The Eu2+ silicate is formed by the reaction of Eu2O3 and Si layers, showing an intense and broad room-temperature photoluminescence peak centered at 610 nm. It is found that the Si layer thickness in nanostructures has great influence on Eu ion optical behavior by forming different Eu silicate crystalline phases. These findings open a promising way to prepare efficient Eu2+ materials for photonic application. PMID:23618344

Pt, Au, Pd and Ru Partitioning Between Mineral and Silicate Melts: The Role of Metal Nanonuggets

NASA Technical Reports Server (NTRS)

Malavergne, V.; Charon, E.; Jones, J.; Agranier, A.; Campbell, A.

2012-01-01

The partition coefficients of Pt and other Pt Group Elements (PGE) between metal and silicate D(sub Metal-Silicate) and also between silicate minerals and silicate melts D(sub Metal-Silicate) are among the most challenging coefficients to obtain precisely. The PGE are highly siderophile elements (HSE) with D(sub Metal-Silicate) >10(exp 3) due to the fact that their concentrations in silicates are very low (ppb to ppt range). Therefore, the analytical difficulty is increased by the possible presence of HSE-rich-nuggets in reduced silicate melts during experiments). These tiny HSE nuggets complicate the interpretation of measured HSE concentrations. If the HSE micro-nuggets are just sample artifacts, then their contributions should be removed before calculations of the final concentration. On the other hand, if they are produced during the quench, then they should be included in the analysis. We still don't understand the mechanism of nugget formation well. Are they formed during the quench by precipitation from precursor species dissolved homogeneously in the melts, or are they precipitated in situ at high temperature due to oversaturation? As these elements are important tracers of early planetary processes such as core formation, it is important to take up this analytical and experimental challenge. In the case of the Earth for example, chondritic relative abundances of the HSE in some mantle xenoliths have led to the concept of the "late veneer" as a source of volatiles (such as water) and siderophiles in the silicate Earth. Silicate crystal/liquid fractionation is responsible for most, if not all, the HSE variation in the martian meteorite suites (SNC) and Pt is the element least affected by these fractionations. Therefore, in terms of reconstructing mantle HSE abundances for Mars, Pt becomes a very important player. In the present study, we have performed high temperature experiments under various redox conditions in order to determine the abundances of Pt, Au, Ru and Pd in minerals (olivine and diopside) and in silicate melts, but also to characterize the sizes, density and chemistry of HSE nuggets when present in the samples.

Properties of zirconium silicate and zirconium-silicon oxynitride high-k dielectric alloys for advanced microelectronic applications: Chemical and electrical characterizations

NASA Astrophysics Data System (ADS)

Ju, Byongsun

2005-11-01

As the microelectronic devices are aggressively scaled down to the 1999 International Technology Roadmap, the advanced complementary metal oxide semiconductor (CMOS) is required to increase packing density of ultra-large scale integrated circuits (ULSI). High-k alternative dielectrics can provide the required levels of EOT for device scaling at larger physical thickness, thereby providing a materials pathway for reducing the tunneling current. Zr silicates and its end members (SiO2 and ZrO2) and Zr-Si oxynitride films, (ZrO2)x(Si3N 4)y(SiO2)z, have been deposited using a remote plasma-enhanced chemical vapor deposition (RPECVD) system. After deposition of Zr silicate, the films were exposed to He/N2 plasma to incorporate nitrogen atoms into the surface of films. The amount of incorporated nitrogen atoms was measured by on-line Auger electron spectrometry (AES) as a function of silicate composition and showed its local minimum around the 30% silicate. The effect of nitrogen atoms on capacitance-voltage (C-V) and leakage-voltage (J-V) were also investigated by fabricating metal-oxide-semiconductor (MOS) capacitors. Results suggested that incorporating nitrogen into silicate decreased the leakage current in SiO2-rich silicate, whereas the leakage increased in the middle range of silicate. Zr-Si oxynitride was a pseudo-ternary alloy and no phase separation was detected by x-ray photoelectron spectroscopy (XPS) analysis up to 1100°C annealing. The leakage current of Zr-Si oxynitride films showed two different temperature dependent activation energies, 0.02 eV for low temperature and 0.3 eV for high temperature. Poole-Frenkel emission was the dominant leakage mechanism. Zr silicate alloys with no Si3N4 phase were chemically separated into the SiO2 and ZrO2 phase as annealed above 900°C. While chemical phase separation in Zr silicate films with Si 3N4 phase (Zr-Si oxynitride) were suppressed as increasing the amount of Si3N4 phase due to the narrow bonding network m Si3N4 phase. (3.4 bonds/atom for Si3 N4 network, 2.67 bonds/atom for SiO2 network).

Effect of temperature on hydration kinetics and polymerization of tricalcium silicate in stirred suspensions of CaO-saturated solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grant, Steven A.; Boitnott, Ginger E.; Korhonen, Charles J.

2006-04-15

Tricalcium silicate was hydrated at 274, 278, 283, 298, and 313 K in stirred suspensions of saturated CaO solutions under a nitrogen-gas atmosphere until the end of deceleratory period. The suspension conductivities and energy flows were measured continuously. The individual reaction rates for tricalcium silicate dissolution, calcium silicate hydrate precipitation, and calcium hydroxide precipitation were calculated from these measurements. The results suggest that the proportion of tricalcium silicate dissolved was determined by the rate of tricalcium silicate dissolution and the time to very rapid calcium hydroxide precipitation. The time to very rapid calcium hydroxide precipitation was more sensitive to changesmore » in temperature than was the rate of tricalcium silicate dissolution, so that the proportion of tricalcium silicate hydration dissolved by the deceleratory period increased with decreasing temperature. The average chain length of the calcium silicate hydrate ascertained by magic-angle spinning nuclear magnetic resonance spectroscopy increased with increasing temperature.« less

Encapsulation of High Temperature Phase Change Materials for Thermal Energy Storage

NASA Astrophysics Data System (ADS)

Nath, Rupa

Thermal energy storage is a major contributor to bridge the gap between energy demand (consumption) and energy production (supply) by concentrating solar power. The utilization of high latent heat storage capability of phase change materials is one of the keys to an efficient way to store thermal energy. However, some of the limitations of the existing technology are the high volumetric expansion and low thermal conductivity of phase change materials (PCMs), low energy density, low operation temperatures and high cost. The present work deals with encapsulated PCM system, which operates at temperatures above 500°C and takes advantage of the heat transfer modes at such high temperatures to overcome the aforementioned limitations of PCMs. Encapsulation with sodium silicate coating on preformed PCM pellets were investigated. A low cost, high temperature metal, carbon steel has been used as a capsule for PCMs with a melting point above 500° C. Sodium silicate and high temperature paints were used for oxidation protection of steel at high temperatures. The emissivity of the coatings to enhance heat transfer was investigated.

SINTERING AND SULFATION OF CALCIUM SILICATE-ALUMINATE

EPA Science Inventory

The effect of sintering on the reactivity of solids at high temperature was studied. The nature of the interaction was studied with calcium silicate-aluminate reacting with SO2 between 665 and 800 C. The kinetics of the sintering and sulfation processes were measured independentl...

Fabrication and properties of aluminum silicate fibrous materials with in situ synthesized K2Ti6O13 whiskers

NASA Astrophysics Data System (ADS)

Liu, Hao; Wei, Nan; Wang, Zhou-fu; Wang, Xi-tang; Ma, Yan

2017-11-01

To improve their mechanical and thermal insulation properties, aluminum silicate fibrous materials with in situ synthesized K2Ti6O13 whiskers were prepared by firing a mixture of short aluminum silicate fibers and gel powders obtained from a sol-gel process. During the preparation process, the fiber surface was coated with K2Ti6O13 whiskers after the fibers were subjected to a heat treatment carried out at various temperatures. The effects of process parameters on the microstructure, compressive strength, and thermal conductivity were analyzed systematically. The results show that higher treatment temperatures and longer treatment durations promoted the development of K2Ti6O13 whiskers on the surface of aluminum silicate fibers; in addition, the intersection structure between whiskers modulated the morphology and volume of the multi-aperture structure among fibers, substantially increasing the fibers' compressive strength and reducing their heat conduction and convective heat transfer at high temperatures.

On the origin of the low-temperature band in depolarization current spectra of poled multicomponent silicate glasses

NASA Astrophysics Data System (ADS)

Brunkov, P. N.; Kaasik, V. P.; Lipovskii, A. A.; Tagantsev, D. K.

2018-04-01

Thermally stimulated depolarization current spectra of poled silicate multicomponent glasses in the vicinity of room temperature (220-320 K) have been recorded and two bands, typical for such glasses, have been observed. It was shown that the high-temperature band (at about 290 K) is related to the relaxation of poled glass structure in the bulk, while the low-temperature band (at about 230-270 K) should be attributed to the surface phenomenon—absorption/desorption of positive species of ambient atmosphere, supposedly, water cluster ions H+(H2O)n.

Metal/Silicate Partitioning at High Pressures and Temperatures

NASA Technical Reports Server (NTRS)

Shofner, G.; Campbell, A.; Danielson, L.; Righter, K.; Rahman, Z.

2010-01-01

The behavior of siderophile elements during metal-silicate segregation, and their resulting distributions provide insight into core formation processes. Determination of partition coefficients allows the calculation of element distributions that can be compared to established values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Moderately siderophile elements, including W, are particularly useful in constraining core formation conditions because they are sensitive to variations in T, P, oxygen fugacity (fO2), and silicate composition. To constrain the effect of pressure on W metal/silicate partitioning, we performed experiments at high pressures and temperatures using a multi anvil press (MAP) at NASA Johnson Space Center and laser-heated diamond anvil cells (LHDAC) at the University of Maryland. Starting materials consisted of natural peridotite mixed with Fe and W metals. Pressure conditions in the MAP experiments ranged from 10 to 16 GPa at 2400 K. Pressures in the LHDAC experiments ranged from 26 to 58 GPa, and peak temperatures ranged up to 5000 K. LHDAC experimental run products were sectioned by focused ion beam (FIB) at NASA JSC. Run products were analyzed by electron microprobe using wavelength dispersive spectroscopy. Liquid metal/liquid silicate partition coefficients for W were calculated from element abundances determined by microprobe analyses, and corrected to a common fO2 condition of IW-2 assuming +4 valence for W. Within analytical uncertainties, W partitioning shows a flat trend with increasing pressure from 10 to 16 GPa. At higher pressures, W becomes more siderophile, with an increase in partition coefficient of approximately 0.5 log units.

Experimental evidence for the absence of iron isotope fractionation between metal and silicate liquids at 1 GPa and 1250-1300 °C and its cosmochemical consequences

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Schmidt, Max W.; Bourdon, Bernard

2012-09-01

Iron isotope fractionation during metal-silicate differentiation has been proposed as a cause for differences in iron isotope compositions of chondrites, iron meteorites and the bulk silicate Earth. Stable isotope fractionation, however, rapidly decreases with increasing temperature. We have thus performed liquid metal-liquid silicate equilibration experiments at 1250-1300 °C and 1 GPa to address whether Fe isotope fractionation is resolvable at the lowest possible temperatures for magmatic metal-silicate differentiation. A centrifuging piston cylinder apparatus enabled quantitative metal-silicate segregation. Elemental tin or sulphur was used in the synthetic metal-oxide mixtures to lower the melting temperature of the metal. The analyses demonstrate that eight of the 10 experimental systems equilibrated in a closed isotopic system, as was assessed by varying run durations and starting Fe isotope compositions. Statistically significant iron isotope fractionation between quenched metals and silicates was absent in nine of the 10 experiments and all 10 experiments yield an average metal-silicate fractionation factor of 0.01 ± 0.04‰, independent of whether graphite or silica glass capsules were used. This implies that Fe isotopes do not fractionate during low pressure metal-silicate segregation under magmatic conditions. In large bodies such as the Earth, fractionation between metal and high pressure (>20 GPa) silicate phases may still be a possible process for equilibrium fractionation during metal-silicate differentiation. However, the 0.07 ± 0.02‰ heavier composition of bulk magmatic iron meteorites relative to the average of bulk ordinary/carbonaceous chondrites cannot result from equilibrium Fe isotope fractionation during core segregation. The up to 0.5‰ lighter sulphide than metal fraction in iron meteorites and in one ordinary chondrite can only be explained by fractionation during subsolidus processes.

Al Speciation in Silicate Melts: AlV a new Network Former?

NASA Astrophysics Data System (ADS)

Neuville, D. R.; Florian, P.; de Ligny, D.; Montouillout, V.; Massiot, D.

2009-05-01

The first human glasses were made 3500 BC. It was essentially sodo-lime silicate glass. To improve the chemical resistance, the thermal properties and increase the viscosity it is interesting to add aluminum in these silicates. But what is the speciation of the aluminum and how it varies according to the chemical composition and to the temperature? The aluminum appears essentially in four or five fold coordination in glasses and melts melted. The proportion of [5]Al varies according to the alkaline or to the earth-alkaline content and to the temperature. We shall present in a first part the influence of the network-modifier on the proportion of [5]Al and then we shall present some new results of absorption of high-temperature using NMR and XANES spectroscopy at the Al K-edge. Finally, from glass transition temperature measurements we propose to explain that [5]Al can be a new network former.

High temperature calorimetric studies of heat of solution of NiO, CuO, La2O3, TiO2, HfO2 in sodium silicate liquids

NASA Astrophysics Data System (ADS)

Linard, Yannick; Wilding, Martin C.; Navrotsky, Alexandra

2008-01-01

The enthalpies of solution of La2O3, TiO2, HfO2, NiO and CuO were measured in sodium silicate melts at high temperature. When the heat of fusion was available, we derived the corresponding liquid-liquid enthalpies of mixing. These data, combined with previously published work, provide insight into the speciation reactions in sodium silicate melts. The heat of solution of La2O3 in these silicate solvents is strongly exothermic and varies little with La2O3 concentration. The variation of heat of solution with composition of the liquid reflects the ability of La(III) to perturb the transient silicate framework and compete with other cations for oxygen. The enthalpy of solution of TiO2 is temperature-dependent and indicates that the formation of Na-O-Si species is favored over Na-O-Ti at low temperature. The speciation reactions can be interpreted in terms of recent spectroscopic studies of titanium-bearing melts which identify a dual role of Ti4+ as both a network-former end network-modifier. The heats of solution of oxides of transition elements (Ni and Cu) are endothermic, concentration-dependent and reach a maximum with concentration. These indicate a charge balanced substitution which diminishes the network modifying role of Na+ by addition of Ni2+ or Cu2+. The transition metal is believed to be in tetrahedral coordination, charge balanced by the sodium cation in the melts.

View planetary differentiation process through high-resolution 3D imaging

NASA Astrophysics Data System (ADS)

Fei, Y.

2011-12-01

Core-mantle separation is one of the most important processes in planetary evolution, defining the structure and chemical distribution in the planets. Iron-dominated core materials could migrate through silicate mantle to the core by efficient liquid-liquid separation and/or by percolation of liquid metal through solid silicate matrix. We can experimentally simulate these processes to examine the efficiency and time of core formation and its geochemical signatures. The quantitative measure of the efficiency of percolation is usually the dihedral angle, related to the interfacial energies of the liquid and solid phases. To determine the true dihedral angle at high pressure and temperatures, it is necessary to measure the relative frequency distributions of apparent dihedral angles between the quenched liquid metal and silicate grains for each experiment. Here I present a new imaging technique to visualize the distribution of liquid metal in silicate matrix in 3D by combination of focus ion beam (FIB) milling and high-resolution SEM image. The 3D volume rendering provides precise determination of the dihedral angle and quantitative measure of volume fraction and connectivity. I have conducted a series of experiments using mixtures of San Carlos olivine and Fe-S (10wt%S) metal with different metal-silicate ratios, up to 25 GPa and at temperatures above 1800C. High-quality 3D volume renderings were reconstructed from FIB serial sectioning and imaging with 10-nm slice thickness and 14-nm image resolution for each quenched sample. The unprecedented spatial resolution at nano scale allows detailed examination of textural features and precise determination of the dihedral angle as a function of pressure, temperature and composition. The 3D reconstruction also allows direct assessment of connectivity in multi-phase matrix, providing a new way to investigate the efficiency of metal percolation in a real silicate mantle.

High Pressure and Temperature Core Formation as an Alternative to the "Late Veneer" Hypothesis

NASA Technical Reports Server (NTRS)

Righter, Kevin; Pando, K.; Humayun, M.; Danielson, L.

2011-01-01

The highly siderophile elements (HSE; Re, Au and the Platinum Group Elements - Pd Pt, Rh, Ru, Ir, Os) are commonly utilized to constrain accretion processes in terrestrial differentiated bodies due to their affinity for FeNi metal [1]. These eight elements exhibit highly siderophile behavior, but nonetheless have highly diverse metal-silicate partition coefficients [2]. Therefore the near chondritic relative concentrations of HSEs in the terrestrial and lunar mantles, as well as some other bodies, are attributed to late accretion rather than core formation [1]. Evaluation of competing theories, such as high pressure metal-silicate partitioning or magma ocean hypotheses has been hindered by a lack of relevant partitioning data for this group of eight elements. In particular, systematic studies isolating the effect of one variable (e.g. temperature or melt compositions) are lacking. Here we undertake new experiments on all eight elements, using Fe metal and FeO-bearing silicate melts at fixed pressure, but variable temperatures. These experiments, as well as some additional planned experiments should allow partition coefficients to be more accurately calculated or estimated at the PT conditions and compositions at which core formation is thought to have occurred.

Insights into Silicate and Oxide Melt Structure from Amorphous, Non-Glass-Forming Materials

NASA Astrophysics Data System (ADS)

Stebbins, J. F.

2015-12-01

Many silicate and oxide liquids of interest in the Earth sciences and in technology cannot readily be quenched to glasses, either because of low silica contents (and hence low viscosity at the melting point and accompanying liquid 'fragility') or because of liquid-liquid unmixing at high temperature. Although in-situ, high temperature structural tools have been in use for decades and are rapidly developing, many methods are still most informative for glass samples quenched to ambient pressure and temperature, e.g. high-resolution solid-state NMR. Amorphous oxides, including alumina and silicate compositions, have widespread technological applications. These are generally deposited by a variety of high-energy sputtering methods, as films of thicknesses of 10's to 100's of nm. Using Al-27, Si-29, and O-17 NMR, we have recently shown that for such films, very similar short-range structure is seen in materials made by very different kinetic pathways, such as sol-gel synthesis vs. ion-beam sputtering. This path-independent structure suggests that these materials pass through transient equilibrium states during their formation, probably that of deeply supercooled liquids just above glass transition temperatures. In the HfO2-SiO2 and ZrO2-SiO2 systems, for example, samples have well-resolved O-17 NMR spectra, allowing quantitation of O sites with only Hf(Zr) neighbors (so-called "free" oxide ions), with mixed Hf(Zr) and Si neighbors, and Si only. The observed oxygen speciation agrees well with a simple thermodynamic model of one of the most fundamental equilibria in silicate systems, namely the reaction of bridging (Si-O-Si) and "free" (e.g. OHf3 and OHf4) oxide ions to produce "non-bridging" oxygens (e.g. Si-OHf2). This new approach to sampling such structural equilibria in compositions far outside the range of normal glass-forming liquids may provide new insights into more geological compositions as well, as well as in more general models of silicate melt chemistry.

Float processing of high-temperature complex silicate glasses and float baths used for same

NASA Technical Reports Server (NTRS)

Cooper, Reid Franklin (Inventor); Cook, Glen Bennett (Inventor)

2000-01-01

A float glass process for production of high melting temperature glasses utilizes a binary metal alloy bath having the combined properties of a low melting point, low reactivity with oxygen, low vapor pressure, and minimal reactivity with the silicate glasses being formed. The metal alloy of the float medium is exothermic with a solvent metal that does not readily form an oxide. The vapor pressure of both components in the alloy is low enough to prevent deleterious vapor deposition, and there is minimal chemical and interdiffusive interaction of either component with silicate glasses under the float processing conditions. Alloys having the desired combination of properties include compositions in which gold, silver or copper is the solvent metal and silicon, germanium or tin is the solute, preferably in eutectic or near-eutectic compositions.

Infrared and Raman spectroscopic characterization of the carbonate bearing silicate mineral aerinite - Implications for the molecular structure

NASA Astrophysics Data System (ADS)

Frost, Ray L.; Scholz, Ricardo; López, Andrés

2015-10-01

The mineral aerinite is an interesting mineral because it contains both silicate and carbonate units which is unusual. It is also a highly colored mineral being bright blue/purple. We have studied aerinite using a combination of techniques which included scanning electron microscopy, energy dispersive X-ray analysis, Raman and infrared spectroscopy. Raman bands at 1049 and 1072 cm-1 are assigned to the carbonate symmetric stretching mode. This observation supports the concept of the non-equivalence of the carbonate units in the structure of aerinite. Multiple infrared bands at 1354, 1390 and 1450 cm-1 supports this concept. Raman bands at 933 and 974 cm-1 are assigned to silicon-oxygen stretching vibrations. Multiple hydroxyl stretching and bending vibrations show that water is in different molecular environments in the aerinite structure.

Uranium, thorium and REE partitioning into sulfide liquids at high pressure and high temperature: Implications for reduced, S-rich planetary bodies

NASA Astrophysics Data System (ADS)

Wohlers, A.; Wood, B. J.

2017-12-01

Based on models of the young solar nebula it is likely that the inner planets went through an early reduced phase of accretion with high metal/silicate ratio and low volatile element contents. Mercury is an existing example of a large planetary embryo with these characteristics but also with a very high S content. In order to investigate the geochemical evolution of Mercury-like bodies we experimentally determined the partitioning of lithophile elements (U, Th, Eu, Sm, Nd, Zr, La, Ce, Yb) between sulfide liquid, low-S metals and silicate melt at 1.5 GPa and 1400-2100˚C. Our results, when combined with those of Wohlers and Wood (2015) show that under highly reducing conditions (FeOsilicate<1wt%) U, Sm, Nd and other lithophile elements partition strongly into FeS liquids relative to silicate melts. The dependences of D's on the FeS contents of the metal and FeO contents of the silicate may be understood in terms of exchange reactions: UO2 + 2FeS = 2FeO + US2silicate sulfide silicate sulfideHigh concentrations of FeSmetal and low FeO contents of the silicate melts drive the reaction to the right, yielding high US2 in the sulfide and high DU. A second effect which raises DU (and other lithophile D's) is the S content of the silicate melt. The latter increases rapidly at low FeO contents and reaches 11wt %. This greatly reduces the activity coefficient of FeO, displacing the reaction further to the right. At 1.5GPa and 1400˚C we obtain sulfide-silicate partitioning with DNd/DSm 1.4 and DTh 0.1DU. As temperature increases to 2100˚C, DNd/DSm declines to 1.0 and DTh/DU increases to 0.3. We estimated the effects of accreting a reduced sulfur-rich component (with FeS core) added to early Earth. The results at 1400˚C imply the possibility of a significant ( 11ppm) 142Nd anomaly in silicate Earth and the addition of >8 ppb U to the core, but require an unreasonably high Th/U of silicate Earth (4.54). Results at 2100˚C lead to a 142Nd anomaly of 0 but addition of such a reduced sulfur-rich body could add up to 10 ppb of U to the core, together with 21 ppb Th. This combination would generate 3 TW of the energy required for the geodynamo. In this case, the Th/U ratio of silicate Earth would be 4.3, within the range of some estimates. Wohlers A. & Wood B.J. (2015) A Mercury-like component of early Earth yield uranium in the core and high mantle Nd142. Nature 520, 337-340

Influence of silica matrix composition and functional component additives on the bioactivity and viability of encapsulated living cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savage, Travis J.; Dunphy, Darren R.; Harbaugh, Svetlana

The remarkable impact encapsulation matrix chemistry can have on the bioactivity and viability of integrated living cells is reported. Two silica chemistries (aqueous silicate and alkoxysilane), and a functional component additive (glycerol), are employed to generate three distinct silica matrices. These matrices are used to encapsulate living E. coli cells engineered with a synthetic riboswitch for cell-based biosensing. Following encapsulation, membrane integrity, reproductive capability, and riboswitch-based protein expression levels and rates are measured over a 5 week period. Striking differences in E. coli bioactivity, viability, and biosensing performance are observed for cells encapsulated within the different matrices. E. coli cellsmore » encapsulated for 35 days in aqueous silicate-based (AqS) matrices showed relatively low membrane integrity, but high reproductive capability in comparison to cells encapsulated in glycerol containing sodium silicate-based (AqS + g) and alkoxysilane-based (PGS) gels. Further, cells in sodium silicate-based matrices showed increasing fluorescence output over time, resulting in a 1.8-fold higher fluorescence level, and a faster expression rate, over cells free in solution. Furthermore, this unusual and unique combination of biological properties demonstrates that careful design of the encapsulation matrix chemistry can improve functionality of the biocomposite material, and result in new and unexpected physiological states.« less

Influence of silica matrix composition and functional component additives on the bioactivity and viability of encapsulated living cells

DOE PAGES

Savage, Travis J.; Dunphy, Darren R.; Harbaugh, Svetlana; ...

2015-11-06

The remarkable impact encapsulation matrix chemistry can have on the bioactivity and viability of integrated living cells is reported. Two silica chemistries (aqueous silicate and alkoxysilane), and a functional component additive (glycerol), are employed to generate three distinct silica matrices. These matrices are used to encapsulate living E. coli cells engineered with a synthetic riboswitch for cell-based biosensing. Following encapsulation, membrane integrity, reproductive capability, and riboswitch-based protein expression levels and rates are measured over a 5 week period. Striking differences in E. coli bioactivity, viability, and biosensing performance are observed for cells encapsulated within the different matrices. E. coli cellsmore » encapsulated for 35 days in aqueous silicate-based (AqS) matrices showed relatively low membrane integrity, but high reproductive capability in comparison to cells encapsulated in glycerol containing sodium silicate-based (AqS + g) and alkoxysilane-based (PGS) gels. Further, cells in sodium silicate-based matrices showed increasing fluorescence output over time, resulting in a 1.8-fold higher fluorescence level, and a faster expression rate, over cells free in solution. Furthermore, this unusual and unique combination of biological properties demonstrates that careful design of the encapsulation matrix chemistry can improve functionality of the biocomposite material, and result in new and unexpected physiological states.« less

Development of a High Resolution-High Sensitivity Ion Microprobe Facility for Cosmochemical Applications

NASA Technical Reports Server (NTRS)

McKeegan, Kevin D.

1998-01-01

NASA NAGW-4112 has supported development of the CAMECA ims 1270 ion microprobe at UCLA for applications in cosmochemistry. The instrument has been brought to an operational status and techniques developed for accurate, precise microbeam analysis of oxygen isotope ratios in polished thin-sections. We made the first oxygen isotopic (delta(18)O and delta(17)O) measurements of rare mafic silicates in the most chemically primitive meteorites, the a chondrites (Leshin et al., 1997). The results have implications for both high temperature processing in the nebula and low-T aqueous alteration on the CI asteroid. We have performed measurements of oxygen isotopic compositions of magnetite and co-existing olivine from carbonaceous (Choi et al., 1997) and unequilibrated ordinary chondrites (Choi et al., in press). This work has identified a significant new oxygen isotope reservoir in the early solar system: water characterized by a very high Delta(17)) value of approx. 5 % per thousand. We have determined the spatial distributions of oxygen isotopic anomalies in all major mineral phases of a type B CAI from Allende. We have also studied an unusual fractionated CAI from Leoville and made the first oxygen isotopic measurements in rare CAIs from ordinary chondrites.

Genetic significance of the 867 cm- 1 out-of-plane Raman mode in graphite associated with V-bearing green grossular

NASA Astrophysics Data System (ADS)

Thomas, Rainer; Rericha, Adolf; Pohl, Walter L.; Davidson, Paul

2018-03-01

SE Kenya is the world's largest producer of green vanadium grossular gemstones (tsavorite). Samples from one of the mines near Mwatate, and of occurrences in Tanzania yielded remarkable new insights into the genesis of tsavorite. Graphite is intimately associated with V-grossular and is one of the keys to understanding its origin. In the course of this study we found five different types of graphite. Surprisingly, in one graphite type the "Raman-forbidden" and IR-active 867 cm- 1 band was observed. In this communication, we attempt to find an explanation for this unusual phenomenon. Additionally, our observations also address some of the issues pertaining to the origin of the green grossular-dominated rocks (grossularites), as well as the gem quality tsavorite crystals, since we propose that the anomalous spectroscopic behavior of the graphite is related to the unusual conditions during crystallization of both the grossular and graphite from a near-supercritical volatile- and sulfur-rich silicate melt. The massive green vanadium grossular contains abundant unequivocal crystallized melt inclusions, while the transparent gem quality grossular (tsavorite) displays only fluid inclusions. On the basis of inclusion studies we suggest that anatectic melts originated in the peculiar evaporitic host lithology of the tsavorite deposits. Near peak metamorphic temperatures ( 700 °C) these liquids occurred as a supercritical volatile-rich "fluid/melt phase" characterized by complete miscibility between H2O and silicate liquid. Relatively dry liquid batches precipitated non-transparent green grossular, whereas wet batches segregated fluids that formed transparent tsavorite.

Making mushy magma chambers in the lower continental crust: Cold storage and compositional bimodality

NASA Astrophysics Data System (ADS)

Jackson, Matthew; Blundy, Jon; Sparks, Steve

2017-04-01

Increasing geological and geophysical evidence suggests that crustal magma reservoirs are normally low melt fraction 'mushes' rather than high melt fraction 'magma chambers'. Yet high melt fractions must form within these mush reservoirs to explain the observed flow and eruption of low crystallinity magmas. In many models, crystallinity is linked directly to temperature, with higher temperature corresponding to lower crystallinity (higher melt fraction). However, increasing temperature yields less evolved (silicic) melt composition for a given starting material. If mobile, low crystallinity magmas require high temperature, it is difficult to explain how they can have evolved composition. Here we use numerical modelling to show that reactive melt flow in a porous and permeable mush reservoir formed by the intrusion of numerous basaltic sills into the lower continental crust produces magma in high melt fraction (> 0.5) layers akin to conventional magma chambers. These magma-chamber-like layers contain evolved (silicic) melt compositions and form at low (close to solidus) temperatures near the top of the mush reservoir. Evolved magma is therefore kept in 'cold storage' at low temperature, but also at low crystallinity so the magma is mobile and can leave the mush reservoir. Buoyancy-driven reactive flow and accumulation of melt in the mush reservoir controls the temperature and composition of magma that can leave the reservoir. The modelling also shows that processes in lower crustal mush reservoirs produce mobile magmas that contain melt of either silicic or mafic composition. Intermediate melt compositions are present but are not within mobile magmas. Silicic melt compositions are found at high melt fraction within the magma-chamber like layers near the top of the mush reservoir. Mafic melt compositions are found at high melt fraction within the cooling sills. Melt elsewhere in the reservoir has intermediate composition, but remains trapped in the reservoir because the local melt fraction is too low to form a mobile magma. The model results are consistent with geochemical data suggesting that lower crustal magma reservoirs supply silicic and mafic melts to arc volcanoes, but intermediate magmas are formed by mixing in shallower reservoirs. We suggest here that lower crustal magma chambers primarily form in response to changes in bulk composition caused by melt migration and chemical reaction in a mush reservoir. This process is different to the conventional and widely applied models of magma chamber formation. Similar processes are likely to operate in shallow mush reservoirs, but will likely be further complicated by the presence of volatile phases, and mixing of different melt compositions sourced from deeper mush reservoirs.

In Situ XANES of U and Th in Silicate Liquids at High Pressure and Temperature

NASA Astrophysics Data System (ADS)

Mallmann, G.; Wykes, J.; Berry, A.; O'Neill, H. S.; Cline, C. J., II; Turner, S.; Rushmer, T. A.

2016-12-01

Although the chemical environments of elements in silicate melts at specific conditions of temperature, pressure and oxygen fugacity (fO2) are often inferred from measurements after quenching the melts to glasses, it is widely recognized that changes may occur during the quenching process, making measurements in situ at high pressure and temperature highly desirable. A case of importance in geochemistry is the speciation of uranium in silicate melts as a function of pressure. Evidence from mineral-melt partitioning and XANES (X-ray Absorption Near-Edge Structure) spectroscopy of glasses suggests that U5+ may be stable at low pressures in the Earth's crust (along with U4+ or U6+, depending on fO2) where basaltic liquids crystallize, but not in the Earth's upper mantle where peridotite partially melts to produce such liquids. To test these observations we recorded in situ transmission U and Th L3-edge XANES spectra of U and Th-doped silicate liquids at 1.6 GPa and 1350°C using the D-DIA apparatus at the X-ray Absorption Spectroscopy Beamline of the Australian Synchrotron. Data for thorium, which occurs exclusively as a tetravalent cation under terrestrial fO2 conditions, were collected as a `control' to monitor for changes in coordination. The cell assembly consisted of a boron-epoxy cube as pressure medium, alumina sleeve and cylindrical graphite heater. The starting mix, a powdered synthetic average MORB silicate glass doped with 2 wt.% of U and Th, was loaded into San Carlos olivine capsules along with solid oxygen buffers (either Re-ReO2 or Ru-RuO2) in a sandwich arrangement. The capsule was then placed inside the graphite heater and insulated with crushable MgO powder. Temperature was monitored using a type D thermocouple. U and Th L3-edge XANES spectra were recorded throughout the heating/compression cycle and then after quenching. Our preliminary assessment indicates that the U-XANES spectra recorded for the liquid in situ at high pressure and temperature and subsequently for the quenched glass are very similar, which would suggest no apparent change in uranium coordination and/or valence state on cooling/decompression.

The solubility of carbon monoxide in silicate melts at high pressures and its effect on silicate phase relations. [in terrestrial and other planetary interiors

NASA Technical Reports Server (NTRS)

Eggler, D. H.; Mysen, B. O.; Hoering, T. C.; Holloway, J. R.

1979-01-01

Autoradiographic analysis and gas chromatography were used to measure the solubility in silicate melts of CO-CO2 vapors (30 to 40% CO by thermodynamic calculation) in equilibrium with graphite at temperatures up to 1700 deg C and pressures to 30 kbar. At near-liquidus temperatures CO-CO2 vapors were found to be slightly more soluble than CO2 alone. As a result of the apparently negative temperature dependence of CO solubility, the solubility of CO-CO2 at superliquidus temperatures is less than that of CO2. Melting points of two silicates were depressed more by CO than by CO2. Phase boundary orientations suggest that CO/CO + CO2 is greater in the liquid than in the vapor. The effect of the presence of CO on periodotite phase relations was investigated, and it was found that melts containing both CO and CO2 are nearly as polymerized as those containing only CO2. These results suggest that crystallization processes in planetary interiors can be expected to be about the same, whether the melts contain CO2 alone or CO2 and CO.

IN SITU INFRARED MEASUREMENTS OF FREE-FLYING SILICATE DURING CONDENSATION IN THE LABORATORY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ishizuka, Shinnosuke; Kimura, Yuki; Sakon, Itsuki

2015-04-20

We developed a new experimental system for infrared (IR) measurements on free-flying nucleating nanoparticles in situ and applied it to studies on silicate particles. We monitored the condensation of magnesium-bearing silicate nanoparticles from thermally evaporated magnesium and silicon monoxide vapor under an atmosphere of oxygen and argon. The IR spectrum of newly condensed particles showed a spectral feature for non-crystalline magnesium-bearing silicate that is remarkably consistent with the IR spectrum of astronomically observed non-crystalline silicate around oxygen-rich evolved stars. The silicate crystallized at <500 K and eventually developed a high crystallinity. Because of the size effects of nanoparticles, the silicatemore » would be expected to be like a liquid at least during the initial stages of nucleation and growth. Our experimental results therefore suggest decreasing the possible formation temperature of crystalline silicates in dust formation environments with relatively higher pressure.« less

The Activity of Trace Metals in Aqueous Systems and the Effect of Corrosion Control Inhibitors

DTIC Science & Technology

1975-10-01

corrosion product on metallic zinc 49 Uncombined slilica as quartz or cristobalite forms by the hydrothermal alteration of solid zilicates or by direct... hydrothermally . The com- position of the solids are dependent on temperature and pressure as well as on the relative concentrations of the dissolved...of the few anhydrous simple silicates formed hydrotherm - ally. The sodium silicates, Na2SiO 3 and BNa 2Si205, are somewhat soluble in high temperature

Effect of temperature on the hydration of Portland cement blended with siliceous fly ash

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deschner, Florian, E-mail: florian.deschner@gmail.com; Lothenbach, Barbara; Winnefeld, Frank

2013-10-15

The effect of temperature on the hydration of Portland cement pastes blended with 50 wt.% of siliceous fly ash is investigated within a temperature range of 7 to 80 °C. The elevation of temperature accelerates both the hydration of OPC and fly ash. Due to the enhanced pozzolanic reaction of the fly ash, the change of the composition of the C–S–H and the pore solution towards lower Ca and higher Al and Si concentrations is shifted towards earlier hydration times. Above 50 °C, the reaction of fly ash also contributes to the formation of siliceous hydrogarnet. At 80 °C, ettringitemore » and AFm are destabilised and the released sulphate is partially incorporated into the C–S–H. The observed changes of the phase assemblage in dependence of the temperature are confirmed by thermodynamic modelling. The increasingly heterogeneous microstructure at elevated temperatures shows an increased density of the C–S–H and a higher coarse porosity. -- Highlights: •The reaction of quartz powder at 80 °C strongly enhances the compressive strength. •Almost no strength increase of fly ash blended OPC at 80 °C was found after 2 days. •Siliceous hydrogarnet is formed upon the reaction of fly ash at high temperatures. •Temperature dependent change of the system was simulated by thermodynamic modelling. •Destabilisation of ettringite above 50 °C correlates with sulphate content of C–S–H.« less

Cs(2)K(UO)(2)Si(4)O(12): a mixed-valence uranium(IV,V) silicate.

PubMed

Lee, Cheng-Shiuan; Wang, Sue-Lein; Lii, Kwang-Hwa

2009-10-28

The first mixed-valence uranium(IV,V) silicate is synthesized under high-temperature, high-pressure hydrothermal conditions. The structure contains chains of corner-sharing U(IV,V)O(6) octahedra which are interconnected by Si(4)O(12) four-membered rings to form a 3-D framework. XPS and XANES spectra were measured to identify the valence state of uranium.

Biological and therapeutic effects of ortho-silicic acid and some ortho-silicic acid-releasing compounds: New perspectives for therapy.

PubMed

Jurkić, Lela Munjas; Cepanec, Ivica; Pavelić, Sandra Kraljević; Pavelić, Krešimir

2013-01-08

Silicon (Si) is the most abundant element present in the Earth's crust besides oxygen. However, the exact biological roles of silicon remain unknown. Moreover, the ortho-silicic acid (H4SiO4), as a major form of bioavailable silicon for both humans and animals, has not been given adequate attention so far. Silicon has already been associated with bone mineralization, collagen synthesis, skin, hair and nails health atherosclerosis, Alzheimer disease, immune system enhancement, and with some other disorders or pharmacological effects. Beside the ortho-silicic acid and its stabilized formulations such as choline chloride-stabilized ortho-silicic acid and sodium or potassium silicates (e.g. M2SiO3; M= Na,K), the most important sources that release ortho-silicic acid as a bioavailable form of silicon are: colloidal silicic acid (hydrated silica gel), silica gel (amorphous silicon dioxide), and zeolites. Although all these compounds are characterized by substantial water insolubility, they release small, but significant, equilibrium concentration of ortho-silicic acid (H4SiO4) in contact with water and physiological fluids. Even though certain pharmacological effects of these compounds might be attributed to specific structural characteristics that result in profound adsorption and absorption properties, they all exhibit similar pharmacological profiles readily comparable to ortho-silicic acid effects. The most unusual ortho-silicic acid-releasing agents are certain types of zeolites, a class of aluminosilicates with well described ion(cation)-exchange properties. Numerous biological activities of some types of zeolites documented so far might probably be attributable to the ortho-silicic acid-releasing property. In this review, we therefore discuss biological and potential therapeutic effects of ortho-silicic acid and ortho-silicic acid -releasing silicon compounds as its major natural sources.

Computational and experimental studies of iron-bearing carbonates and silicate glasses at lower mantle pressures

NASA Astrophysics Data System (ADS)

Solomatova, N. V.; Jackson, J. M.; Asimow, P. D.; Sturhahn, W.; Rossman, G. R.; Roskosz, M.

2017-12-01

Decomposition of carbonates may be responsible for creating silicate melts within the lower mantle by lowering the melting temperature of surrounding rock. Identifying and characterizing the stability of carbonates is therefore a necessary step towards understanding the transport of carbon in Earth's interior. Dolomite is one of the major mineral forms in which carbon is subducted into the Earth's mantle. Although iron-free dolomite is expected to break down upon compression, high-pressure polymorphs of iron-bearing dolomite may resist decomposition. Using a genetic algorithm that predicts crystal structures, we found a monoclinic phase with space group C2/c that has a lower energy than all previously reported dolomite structures at pressures above 15 GPa, where the substitution of iron for magnesium stabilizes monoclinic dolomite at certain pressures of the lower mantle. Thus, an iron-bearing dolomite polymorph may be an important carbon carrier in regions of Earth's lower mantle. The depth at which carbonates will decompose is dependent on the age, temperature and density of subducting slabs. Decarbonation reactions may lower the melting temperature of surrounding rocks to produce silicate melts. In regions of the mantle where silicate melts may exist, it is important to understand the physical properties and dynamic behavior of the melts because they affect the chemical and thermal evolution of its interior. Composition, degree of polymerization, and iron's spin state affect such properties. The behavior of iron in silicate melts is poorly understood but, in some cases, may be approximated by iron-bearing glasses. We measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to 120 GPa and 100 GPa, respectively, in a neon pressure medium using time-domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe2+-like sites with distinct quadrupole splittings, reflecting the influence of evolving coordination environments with pressure. With the assumption that coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically-complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle.

Electrochemistry and the Earth's Core-Mantle Boundary

NASA Astrophysics Data System (ADS)

Kavner, A.; Walker, D.

2001-12-01

The Earth's core-mantle boundary consists of a highly heterogeneous metal-oxide interface subjected to high temperatures, pressures, and additionally, to the presence of a temporally- and spatially-varying electrical field generated by the outer core dynamo. An understanding of the core-mantle boundary should include the nature of its electrical behavior, its electrically induced chemical partitioning, and any resultant core-mantle dynamic coupling. To this end, we have developed a method to measure the electrical behavior of metal-silicate interfaces at high pressures (15-25 kbar) and temperatures (1300-1400° C) in a piston-cylinder apparatus. Platinum electrical leads are placed at each end of the sample, which consists of a layer of iron and/or iron alloy below a layer of silicate. The sample is enclosed in a sintered MgO chamber which is then surrounded by a metal Faraday cage, allowing the sample to be electrically insulated from the AC field of the graphite heater. The platinum electric leads are threaded through the thermocouple tube and connected with an HP4284A LCR meter to measure AC impedance, or to a DC power supply to apply a field such that either the silicate or the metal end is the anode (+). AC impedance measurements performed in-situ on samples consisting of Fe, Fe-Ni-S, and a basalt-olivine mixture in series show that conductivity is strongly dependent on the electrical polarization of the silicate relative to the sulfide. When the silicate is positively charged (silicate is the anode) and when there is no applied charge, the probe-to-probe resistance displays semiconductor behavior, with conductivity ( ~10-2 S/cm) strongly thermally activated. However, when the electrical polarity is reversed, and the sulfide is the anode, the electrical conductivity between the two probes increases dramatically (to ~1 S/cm) over timescales of minutes. If the polarity is removed or reversed, the conductivity returns to its original values over similar timescales. A second set of experiments examined the behavior of iron-silicate interfaces subjected to electric fields of 1-10 V, applied for times ranging from several minutes to several days. The samples were quenched from high temperatures, mounted, and examined using both light and electron microscopy. When the iron/iron-sulfide end is charged positively (+1-2 V) with respect to the silicate, oxides form around the platinum electrode embedded within the iron metal, suggesting the reaction Fe->Fe+2+2e- occurs in the metal. When the electric field is reversed, the silicate and MgO surrounding the + electrode turns red, implying the reaction Fe+2\\rightarrowFe^{+3}+e^{-}$ occurs at the silicate (anode end) of the sample. The richness of electrical and electrically activated chemical behavior observed at metal-silicate interfaces may be relevant to the Earth's core mantle boundary.

Mineralogy and geochemistry of a Late Permian coal in the Dafang Coalfield, Guizhou, China: Influence from siliceous and iron-rich calcic hydrothermal fluids

USGS Publications Warehouse

Dai, S.; Chou, C.-L.; Yue, M.; Luo, K.; Ren, D.

2005-01-01

This paper describes the influence of siliceous and iron-rich calcic low-temperature hydrothermal fluids (LTHF) on the mineralogy and geochemistry of the Late Permian No. 11 Coal (anthracitic, Rr =2.85%) in the Dafang Coalfield in northwestern Guizhou Province, China. The No. 11 Coal has high contents of vein ankerite (10.2 vol.%) and vein quartz (11.4 vol.%), with formation temperatures of 85 and 180 ??C, respectively, indicating that vein ankerite and vein quartz were derived from low-temperature calcic and siliceous hydrothermal fluids in two epigenetic episodes. The vein quartz appears to have formed earlier than vein ankerite did, and at least three distinct stages of ankerite formation with different Ca/Sr and Fe/Mn ratios were observed. The two types of mineral veins are sources of different suites of major and trace metals. Scanning electron microscope and sequential extraction studies show that, in addition to Fe, Mg, and Ca, vein ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn in the coal, and the contents of these five elements are as high as 0.09% and 74.0, 33.6, 185, and 289 ??g/g, respectively. In contrast, vein quartz is the main carrier mineral for platinum-group elements (PGEs) Pd, Pt, and Ir in the coal, and the contents of Pd, Pt, and Ir are 1.57, 0.15, and 0.007 ??g/g, respectively. Sequential extraction showed a high PGE content in the silicate fraction, up to 10.4 ??g/g Pd, 1.23 ??g/g Pt, and 0.05 ??g/g Ir, respectively. It is concluded that the formation of ankerite and quartz and the anomalous enrichment of trace elements in the No. 11 Coal in the Dafang Coalfield, Guizhou, result from the influx of calcic and siliceous low-temperature hydrothermal fluids. ?? 2004 Elsevier B.V. All rights reserved.

Calcium-Magnesium-Alumino-Silicates (CMAS) Reaction Mechanisms and Resistance of Advanced Turbine Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Costa, Gustavo; Harder, Bryan J.; Wiesner, Valerie L.; Hurst, Janet B.; Puleo, Bernadette J.

2017-01-01

Environmental barrier coatings (EBCs) and SiC/SiC ceramic matrix composites (CMCs) systems will play a crucial role in future turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures, reduce engine weight and cooling requirements. The development of prime-reliant environmental barrier coatings is an essential requirement to enable the applications of the 2700-3000 F EBC - CMC systems. This presentation primarily focuses on the reaction mechanisms of advanced NASA environmental barrier coating systems, when in contact with Calcium-Magnesium Alumino-Silicates (CMAS) at high temperatures. Advanced oxide-silicate defect cluster environmental barrier coatings are being designed for ultimate balanced controls of the EBC temperature capability and CMAS reactivity, thus improving the CMAS resistance. Further CMAS mitigation strategies are also discussed.

Dielectric Constant Measurements on Lunar Soils and Terrestrial Minerals

NASA Technical Reports Server (NTRS)

Anderson, R. C.; Buehler, M. G.; Seshardri, S.; Schaap, M. G.

2004-01-01

The return to the Moon has ignited the need to characterize the lunar regolith using in situ methods. An examination of the lunar regolith samples collected by the Apollo astronauts indicates that only a few minerals (silicates and oxides) need be considered for in situ resource utilization (ISRU). This simplifies the measurement requirements and allows a detailed analysis using simple methods. Characterizing the physical properties of the rocks and soils is difficult because of many complex parameters such as soil temperature, mineral type, grain size, porosity, and soil conductivity. In this presentation, we will show that the dielectric constant measurement can provide simple detection for oxides such as TiO2, FeO, and water. Their presence is manifest by an unusually large imaginary permittivity.

High-temperature apparatus for chaotic mixing of natural silicate melts.

PubMed

Morgavi, D; Petrelli, M; Vetere, F P; González-García, D; Perugini, D

2015-10-01

A unique high-temperature apparatus was developed to trigger chaotic mixing at high-temperature (up to 1800 °C). This new apparatus, which we term Chaotic Magma Mixing Apparatus (COMMA), is designed to carry out experiments with high-temperature and high-viscosity (up to 10(6) Pa s) natural silicate melts. This instrument allows us to follow in time and space the evolution of the mixing process and the associated modulation of chemical composition. This is essential to understand the dynamics of magma mixing and related chemical exchanges. The COMMA device is tested by mixing natural melts from Aeolian Islands (Italy). The experiment was performed at 1180 °C using shoshonite and rhyolite melts, resulting in a viscosity ratio of more than three orders of magnitude. This viscosity ratio is close to the maximum possible ratio of viscosity between high-temperature natural silicate melts. Results indicate that the generated mixing structures are topologically identical to those observed in natural volcanic rocks highlighting the enormous potential of the COMMA to replicate, as a first approximation, the same mixing patterns observed in the natural environment. COMMA can be used to investigate in detail the space and time development of magma mixing providing information about this fundamental petrological and volcanological process that would be impossible to investigate by direct observations. Among the potentials of this new experimental device is the construction of empirical relationships relating the mixing time, obtained through experimental time series, and chemical exchanges between the melts to constrain the mixing-to-eruption time of volcanic systems, a fundamental topic in volcanic hazard assessment.

Calcium silicate insulation structure

DOEpatents

Kollie, Thomas G.; Lauf, Robert J.

1995-01-01

An insulative structure including a powder-filled evacuated casing utilizes a quantity of finely divided synthetic calcium silicate having a relatively high surface area. The resultant structure-provides superior thermal insulating characteristics over a broad temperature range and is particularly well-suited as a panel for a refrigerator or freezer or the insulative barrier for a cooler or a insulated bottle.

A-thermal elastic behavior of silicate glasses.

PubMed

Rabia, Mohammed Kamel; Degioanni, Simon; Martinet, Christine; Le Brusq, Jacques; Champagnon, Bernard; Vouagner, Dominique

2016-02-24

Depending on the composition of silicate glasses, their elastic moduli can increase or decrease as function of the temperature. Studying the Brillouin frequency shift of these glasses versus temperature allows the a-thermal composition corresponding to an intermediate glass to be determined. In an intermediate glass, the elastic moduli are independent of the temperature over a large temperature range. For sodium alumino-silicate glasses, the a-thermal composition is close to the albite glass (NaAlSi3O8). The structural origin of this property is studied by in situ high temperature Raman scattering. The structure of the intermediate albite glass and of silica are compared at different temperatures between room temperature and 600 °C. When the temperature increases, it is shown that the high frequency shift of the main band at 440 cm(-1) in silica is a consequence of the cristobalite-like alpha-beta transformation of 6-membered rings. This effect is stronger in silica than bond elongation (anharmonic effects). As a consequence, the elastic moduli of silica increase as the temperature increases. In the albite glass, the substitution of 25% of Si(4+) ions by Al(3+) and Na(+) ions decreases the proportion of SiO2 6-membered rings responsible for the silica anomaly. The effects of the silica anomaly balance the anharmonicity in albite glass and give rise to an intermediate a-thermal glass. Different networks, formers or modifiers, can be added to produce different a-thermal glasses with useful mechanical or chemical properties.

Spectroscopic and theoretical constraints on the differentiation of planetesimals

NASA Astrophysics Data System (ADS)

Moskovitz, Nicholas A.

The differentiation of small proto-planetary bodies into metallic cores, silicate mantles and basaltic crusts was a common occurrence in the first few million years of Solar System history. In this thesis, observational and theoretical methods are employed to investigate this process. Particular focus is given to the basaltic, crustal remnants of those differentiated parent bodies. A visible-wavelength spectroscopic survey was designed and performed to constrain the population of basaltic asteroids in the Main Belt. The results of this survey were used to provide statistical constraints on the orbital and size-frequency distributions of these objects. These distributions imply that basaltic material is rare in the Main Belt (particularly beyond the 3:1 mean motion resonance at 2.5 AU), however relic fragments of crust from multiple differentiated parent bodies are likely present. To provide insight on the mineralogical diversity of basaltic asteroids in the Main Belt, we performed a series of near-infrared spectroscopic observations. We find that V-type asteroids in the inner belt have spectroscopic properties consistent with an origin from a single parent body, most likely the asteroid Vesta. Spectroscopic differences (namely band area ratio) between these asteroids and basaltic meteorites here on Earth are best explained by space weathering of the asteroid surfaces. We also report the discovery of unusual spectral properties for asteroid 10537 (1991 RY16), a V-type asteroid in the outer Main Belt that has an ambiguous mineralogical interpretation. We conclude this thesis with a theoretical investigation of the relevant stages in the process of differentiation. We show that if partial silicate melting occurs within the interior of a planetesimal then both core and crust formation could have happened on sub-million year (Myr) time scales. However, it is shown that the high temperatures necessary to facilitate these processes may have been affected by the migration of molten silicates within these planetesimals and by chemical interactions between liquid water and silicate rock. Finally, a 1-dimensional model of heat conduction is used to explore whether differentiation would have occurred for planetesimals across a range of sizes (4-250 km) and times of accretion (0-3 Myr).

Multifunctional Composites for Improved Polyimide Thermal Stability

NASA Technical Reports Server (NTRS)

Miller, Sandi G.

2007-01-01

The layered morphology of silicate clay provides an effective barrier to oxidative degradation of the matrix resin. However, as resin thermal stability continues to reach higher limits, development of an organic modification with comparable temperature capabilities becomes a challenge. Typically, phyllosilicates used in polymer nanocomposites are modified with an alkyl ammonium ion. Such organic modifiers are not suited for incorporation into high temperature polymers as they commonly degrade below 200oC. Therefore, the development of nanoparticle specifically suited for high temperature applications is necessary. Several nanoparticles were investigated in this study, including pre-exfoliated synthetic clay, an organically modified clay, and carbon nanofiber. Dispersion of the layered silicate increases the onset temperature of matrix degradation as well as slows oxidative degradation. The thermally stable carbon nanofibers are also observed to significantly increase the resin thermal stability.

Peralkaline Rhyolite Achneliths with Evidence of Post-Emplacement Vesiculation at Aluto Volcano, Main Ethiopian Rift: What can these unusual pyroclasts tell us?

NASA Astrophysics Data System (ADS)

Calder, E.; Clarke, B. A.; Cortes, J. A.; Butler, I. B.; Yirgu, G.

2016-12-01

In peralkaline rhyolitic melts, Na+ and K+ combined with halogens act to disrupt silicate polymers reducing melt viscosity in comparison to other melts of equivalent silica content. As a result, such magmas are often associated with somewhat unusual deposits for which the associated eruptive behaviours are relatively poorly understood. We have discovered unusual globule-shaped clasts within an unconsolidated pyroclastic succession associated with a pumice cone at Aluto volcano in the Main Ethiopian Rift. The clasts are lapilli to ash sized, often have a droplet-like morphology and are characterised by a distinctive obsidian skin indicative of having been shaped by surface tension. We adopt Walker's term achneliths for these clasts. These achneliths however, unlike their mafic counterparts, are highly vesicular ( 78 vol %), and the glassy skin often shows a bread-crusted texture. Importantly, there is strong evidence for post-depositional, in-situ, inflation, including expanding against other clasts and in some cases fusing together. The unconsolidated nature of the deposit at Aluto means that these peralkaline achneliths are easily separated and investigated in 3D, providing an unprecedented opportunity to study their features in detail through the use of µCT, SEM and EPMA. Textural observations and preliminary 3D vesicle size distribution data suggest that surface tension is an important factor in shaping these clasts, and that vesiculation and degassing occurs over a prolonged period post-emplacement. MELTS model calculations on the EPMA analyses assuming dry conditions, suggest maximum liquidus temperatures of 1030 °C and minimum viscosities of 6 Log(poise). These observations have important implications for understanding the nature of late stage degassing, fragmentation and eruption style in peralkaline rhyolite systems as well as incipient welding in peralkaline pyroclastic units.

Amphibole and Phlogopite Formation on the R Chondrite Parent Body: An Experimental Investigation

NASA Astrophysics Data System (ADS)

Lunning, N. G.; Waters, L. E.; McCoy, T. J.

2017-07-01

High-temperature hydrated minerals can form at the pressures and the temperatures expected for the interiors of planetesimals. Under water-saturated conditions, minimum silicate melting can initiate at temperatures as low as 870°C at 40 MPa.

Platinum Partitioning at Low Oxygen Fugacity: Implications for Core Formation Processes

NASA Technical Reports Server (NTRS)

Medard, E.; Martin, A. M.; Righter, K.; Lanziroti, A.; Newville, M.

2016-01-01

Highly siderophile elements (HSE = Au, Re, and the Pt-group elements) are tracers of silicate / metal interactions during planetary processes. Since most core-formation models involve some state of equilibrium between liquid silicate and liquid metal, understanding the partioning of highly siderophile elements (HSE) between silicate and metallic melts is a key issue for models of core / mantle equilibria and for core formation scenarios. However, partitioning models for HSE are still inaccurate due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variable like temperature, pressure, and oxygen fugacity. In this abstract, we describe a self-consistent set of experiments aimed at determining the valence of platinum, one of the HSE, in silicate melts. This is a key information required to parameterize the evolution of platinum partitioning with oxygen fugacity.

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCammon, C.; Dubrovinsky, L.; Narygina, O.

We investigated the spin state of iron in Mg{sub 0.82}Fe{sub 0.18}SiO{sub 3} silicate perovskite using Moessbauer spectroscopy and nuclear forward scattering (NFS) at pressures up to 130 GPa and temperatures up to 1000 K. Majorite starting material was loaded into diamond anvil cells in three separate experiments, and transformed to silicate perovskite through laser heating. We found, in agreement with previous work, the predominance of a component with high isomer shift ({approx}1 mm/s relative to {alpha}-Fe) and high-quadrupole splitting (QS) (>4 mm/s) in Moessbauer and NFS spectra up to 115 GPa at room temperature, and in accordance with previous workmore » this component was assigned to intermediate-spin Fe{sup 2+}. At higher pressures, the intensity of the high QS component in the silicate perovskite spectrum decreased, while the intensity of a new component with low isomer shift ({approx}0 mm/s relative to {alpha}-Fe) and low quadrupole splitting (<0.5 mm/s) increased. This new component was assigned to low-spin Fe{sup 2+}, and its intensity increased with both increasing pressure and increasing temperature: at 120 GPa and 1000 K all Fe{sup 2+} was in the low-spin state. X-ray diffraction data showed well crystallized perovskite in all runs, and although the stable phase above 110 GPa is expected to be post-perovskite, sluggish transition kinetics likely preserved the perovskite phase in a metastable state. Our results combined with data in the literature and thermodynamic and topological considerations suggest that there may be a region where silicate perovskite containing low-spin Fe{sup 2+} is stable, which coincides with predicted pressure-temperature conditions near the D{double_prime} layer.« less

Giant siliceous spicules from the deep-sea glass sponge Monorhaphis chuni.

PubMed

Wang, Xiaohong; Schröder, Heinz C; Müller, Werner E G

2009-01-01

Only 13 years after realizing, during a repair of a telegraph cable pulled out from the deep sea, that the depth of the ocean is plentifully populated with a highly diverse fauna and flora, the Challenger expedition (1873-1876) treasured up a rich collection of vitreous sponges (Hexactinellida). They had been described by Schulze and represent the phylogenetically oldest class of siliceous sponges (phylum Porifera); they are eye-catching because of their distinct body plan, which relies on a filigree skeleton. It is constructed by an array of morphologically determined elements, the spicules. Soon after, during the German Deep Sea Expedition "Valdivia" (1898-1899), Schulze could describe the largest siliceous hexactinellid sponge on Earth, the up to 3-m high Monorhaphis chuni, which develops the equally largest bio-silica structure, the giant basal spicules (3 mx10 mm). Using these spicules as a model, basic knowledge on the morphology, formation, and development of the skeletal elements could be achieved. They are formed by a proteinaceous scaffold (composed of a 27-kDa protein), which mediates the formation of the siliceous lamellae, into which the proteins are encased. The high number of 800 of 5-10 microm thick lamellae is concentrically arranged around the axial canal. The silica matrix is composed of almost pure silicon oxide, providing it with unusually optophysical properties, which are superior to those of man-made waveguides. Experiments might suggest that the spicules function in vivo as a nonocular photoreception system. In addition, the spicules have exceptional mechanical properties, combining mechanical stability with strength and stiffness. Like demosponges, also the hexactinellids synthesize their silica enzymatically, via the enzyme silicatein (27-kDa protein). It is suggested that these basic insights will surely contribute to a further applied utilization and exploration of silica in bio-material/biomedical science.

Inclusions of Sulphide Immiscible Melts in Primitive Olivine Phenocrysts from Mantle-Derived Magmas; Preliminary Results

NASA Astrophysics Data System (ADS)

Danyushevsky, L.; Ryan, C.; Kamenetsky, V.; Crawford, A.

2001-12-01

Sulphide inclusions have been identified in olivine phenocrysts (and in one case in a spinel phenocryst) in primitive volcanic rocks from mid- ocean ridges, subduction-related island arcs and backarc basins. These inclusions represent droplets of an immiscible sulphide melt and are trapped by olivine crystals growing from silicate melts. Sulphide melt is usually trapped as separate inclusions, however combined inclusions of sulphide and silicate melts have also been observed. Sulphide inclusions have rounded shapes and vary in size from several up to 100 microns in diameter. At room temperature sulphide inclusions consist of several phases. These phases are formed as a result of crystallisation of the sulphide melt after it was trapped. Crystallisation occurs due to decreasing temperature in the magma chamber after trapping and/or when magma ascents from the magma chamber during eruptions. In all studied sulphides three different phases can be identified: a high- Fe, low-Ni, low-Cu phase; a high-Fe, high-Ni, low-Cu phase; and high-Fe, low-Ni, high-Cu phase. Low-Cu phases appear to be monomineralic, whereas the high-Cu phase is usually composed of a fine intergrowth of high- and low-Cu phases, resembling the quench 'spinifex' structure. Fe, Ni and Cu are the major elements in all sulphides studied. The amount of Ni decreases with decreasing forsterite content of the host olivine phenocryst, which is an index of the degree of silicate magma fractionation. Since Ni content of the silicate magma is decreasing during fractionation, this indicates either that the immiscible sulfide melt remains in equilibrium with the silicate melt continuously changing its composition during fractionation, or that the sulfide melt is continuously separated from the silicate melt during fractionation, with later formed droplets having lower Ni content due to the lower Ni content of the evolved, stronger fractionated silicate melt. Trace element contents of the sulfide inclusions have been analysed on the proton microprobe at CSIRO in Sydney. The main trace elements in the sulfide inclusions are Zn, Pb, Ag, and Se. Other trace elements are below detection limits, which are normally at a level of several ppm. Zn concentrations (120 +/- 40 ppm) in sulphides are similar to those in silicate melts. This indicates that separation of the sulfide melt does not affect Zn contents of silicate melts. On the contrary, Ag (30 +/- 10 ppm) and Pb (40 +/- 10 ppm) contents in sulphides are at least in order of magnitude higher than in the silicate melt, and thus separation of the immiscible sulfide melt can significantly decrease Pb and Ag contents of the silicate magma. The widespread occurrence of sulfide inclusions, which were also described in olivine phenocrysts from ocean island basalts, indicates common saturation at low pressure of mantle-derived magmas with reduced sulfur.

ALH85085: a unique volatile-poor carbonaceous chondrite with possible implications for nebular fractionation processes

USGS Publications Warehouse

Grossman, J.N.; Rubin, A.E.; MacPherson, G.J.

1988-01-01

Allan Hills 85085 is a unique chondrite with affinities to the Al Rais-Renazzo clan of carbonaceous chondrites. Its constituents are less than 50 ??m in mean size. Chondrules and microchondrules of all textures are present; nonporphyritic chondrules are unusually abundant. The mean compositions of porphyritic, nonporphyritic and barred olivine chondrules resemble those in ordinary chondrites except that they are depleted in volatile elements. Ca-, Al-rich inclusions are abundant and largely free of nebular alteration; they comprise types similar to those in CM and CO chondrites, as well as unique types. Calcium dialuminate occurs in several inclusions. Metal, silicate and sulfide compositions are close to those in CM-CO chondrites and Al Rais and Renazzo. C1-chondrite clasts and metal-rich "reduced" clasts are present, but opaque matrix is absent. Siderophile abundances in ALH85085 are extremely high (e.g., Fe Si = 1.7 ?? solar), and volatiles are depleted (e.g., Na Si = 0.25 ?? solar, S Si = 0.03 ?? solar). Nonvolatile lithophile abundances are similar to those in Al Rais, Renazzo, and CM and CO chondrites. ALH85085 agglomerated when temperatures in the nebula were near 1000 K, in the same region where Renazzo, Al Rais and the CI chondrites formed. Agglomeration of high-temperature material may thus be a mechanism by which the fractionation of refractory lithophiles occurred in the nebula. Chondrule formation must have occurred at high temperatures when clumps of precursors were small. After agglomeration, ALH85085 was annealed and lightly shocked. C1 and other clasts were subsequently incorporated during late-stage brecciation. ?? 1988.

Low-voltage bendable pentacene thin-film transistor with stainless steel substrate and polystyrene-coated hafnium silicate dielectric.

PubMed

Yun, Dong-Jin; Lee, Seunghyup; Yong, Kijung; Rhee, Shi-Woo

2012-04-01

The hafnium silicate and aluminum oxide high-k dielectrics were deposited on stainless steel substrate using atomic layer deposition process and octadecyltrichlorosilane (OTS) and polystyrene (PS) were treated improve crystallinity of pentacene grown on them. Besides, the effects of the pentacene deposition condition on the morphologies, crystallinities and electrical properties of pentacene were characterized. Therefore, the surface treatment condition on dielectric and pentacene deposition conditions were optimized. The pentacene grown on polystyrene coated high-k dielectric at low deposition rate and temperature (0.2-0.3 Å/s and R.T.) showed the largest grain size (0.8-1.0 μm) and highest crystallinity among pentacenes deposited various deposition conditions, and the pentacene TFT with polystyrene coated high-k dielectric showed excellent device-performance. To decrease threshold voltage of pentacene TFT, the polystyrene-thickness on high-k dielectric was controlled using different concentration of polystyrene solution. As the polystyrene-thickness on hafnium silicate decreases, the dielectric constant of polystyrene/hafnium silicate increases, while the crystallinity of pentacene grown on polystyrene/hafnium silicate did not change. Using low-thickness polystyrene coated hafnium silicate dielectric, the high-performance and low voltage operating (<5 V) pentacene thin film transistor (μ: ~2 cm(2)/(V s), on/off ratio, >1 × 10(4)) and complementary inverter (DC gains, ~20) could be fabricated.

Lunar oxygen and metal for use in near-earth space - Magma electrolysis

NASA Technical Reports Server (NTRS)

Colson, Russell O.; Haskin, Larry A.

1990-01-01

The unique conditions on the moon, such as vacuum, absence of many reagents common on the earth, and presence of very nontraditional 'ores', suggest that a unique and nontraditional process for extracting materials from the ores may prove the most practical. An investigation has begun into unfluxed silicate electrolysis as a method for extracting oxygen, Fe, and Si from lunar regolith. The advantages of the process include simplicity of concept, absence of need to supply reagents from the earth, and low power and mass requirements for the processing plant. Disadvantages include the need for uninterrupted high temperature and the highly corrosive nature of the high-temperature silicate melts, which has made identifying suitable electrode and container materials difficult.

Catalytic crystallization of ices by small silicate smokes at temperatures less than 20K

NASA Technical Reports Server (NTRS)

Moore, M.; Ferrante, R.; Hudson, R.; Tanabe, T.; Nuth, J.

1993-01-01

Samples of methanol and water ices condensed from the vapor onto aluminum substrates at low temperatures (below approximately 80 K) form amorphous ices; annealing at temperatures in excess of 140-155 K is usually required to convert such amorphous samples to crystalline ices. However, we have found that when either methanol or water vapor is deposited on to aluminum substrates that have been coated with a thin (0.1-0.5 mm) layer of amorphous silicate smoke, the ices condense in crystalline form. We believe that crystalline ice forms as the result of energy liberated at the ice/silicate interface perhaps due to weak bonding of the ice at defect sites on the grains and the very high surface to volume ratio and defect density of these smokes. Annealing of amorphous water ice mixed with more volatile components such as methane, carbon monoxide, etc., has been suggested as an efficient way to produce clatherates in the outer solar nebula and thus explain the volatile content of comets and icy satellites of the outer planets. This hypothesis may need to be re-examined if amorphous ice does not form on cold silicate grains.

The Influence of Sintering Method on Kaolin-Based Geopolymer Ceramics with Addition of Ultra High Molecular Weight Polyethylene as Binder

NASA Astrophysics Data System (ADS)

Romisuhani, A.; AlBakri, M. M.; Kamarudin, H.; Andrei, S. V.

2017-11-01

The influence of sintering method on kaolin-based geopolymer ceramics with addition of Ultra High Molecular Weight Polyethylene as binder were studied. Geopolymer were formed at room temperature from kaolin and sodium silicate in a highly alkaline medium, followed by curing and drying at 80 °C. 12 M of sodium hydroxide solution were mixed with sodium silicate at a ratio of 0.24 to form alkaline activator. Powder metallurgy technique were used in order to produce kaolin geopolymer ceramics with addition of Ultra High Molecular Weight Polyethylene. The samples were heated at temperature of 1200 °C with two different sintering method which are conventional method and two-step sintering method. The strength and density were tested.

High-temperature apparatus for chaotic mixing of natural silicate melts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morgavi, D.; Petrelli, M.; Vetere, F. P.

2015-10-15

A unique high-temperature apparatus was developed to trigger chaotic mixing at high-temperature (up to 1800 °C). This new apparatus, which we term Chaotic Magma Mixing Apparatus (COMMA), is designed to carry out experiments with high-temperature and high-viscosity (up to 10{sup 6} Pa s) natural silicate melts. This instrument allows us to follow in time and space the evolution of the mixing process and the associated modulation of chemical composition. This is essential to understand the dynamics of magma mixing and related chemical exchanges. The COMMA device is tested by mixing natural melts from Aeolian Islands (Italy). The experiment was performed atmore » 1180 °C using shoshonite and rhyolite melts, resulting in a viscosity ratio of more than three orders of magnitude. This viscosity ratio is close to the maximum possible ratio of viscosity between high-temperature natural silicate melts. Results indicate that the generated mixing structures are topologically identical to those observed in natural volcanic rocks highlighting the enormous potential of the COMMA to replicate, as a first approximation, the same mixing patterns observed in the natural environment. COMMA can be used to investigate in detail the space and time development of magma mixing providing information about this fundamental petrological and volcanological process that would be impossible to investigate by direct observations. Among the potentials of this new experimental device is the construction of empirical relationships relating the mixing time, obtained through experimental time series, and chemical exchanges between the melts to constrain the mixing-to-eruption time of volcanic systems, a fundamental topic in volcanic hazard assessment.« less

Glass formation, properties, and structure of soda-yttria-silicate glasses

NASA Technical Reports Server (NTRS)

Angel, Paul W.; Hann, Raiford E.

1991-01-01

The glass formation region of the soda yttria silicate system was determined. The glasses within this region were measured to have a density of 2.4 to 3.1 g/cu cm, a refractive index of 1.50 to 1.60, a coefficient of thermal expansion of 7 x 10(exp -6)/C, softening temperatures between 500 and 780 C, and Vickers hardness values of 3.7 to 5.8 GPa. Aqueous chemical durability measurements were made on select glass compositions while infrared transmission spectra were used to study the glass structure and its effect on glass properties. A compositional region was identified which exhibited high thermal expansion, high softening temperatures, and good chemical durability.

On the metallicity dependence of crystalline silicates in oxygen-rich asymptotic giant branch stars and red supergiants

NASA Astrophysics Data System (ADS)

Jones, O. C.; Kemper, F.; Sargent, B. A.; McDonald, I.; Gielen, C.; Woods, Paul M.; Sloan, G. C.; Boyer, M. L.; Zijlstra, A. A.; Clayton, G. C.; Kraemer, K. E.; Srinivasan, S.; Ruffle, P. M. E.

2012-12-01

We investigate the occurrence of crystalline silicates in oxygen-rich evolved stars across a range of metallicities and mass-loss rates. It has been suggested that the crystalline silicate feature strength increases with increasing mass-loss rate, implying a correlation between lattice structure and wind density. To test this, we analyse Spitzer Infrared Spectrograph and Infrared Space Observatory Short Wavelength Spectrometer spectra of 217 oxygen-rich asymptotic giant branch and 98 red supergiants in the Milky Way, the Large and Small Magellanic Clouds, and Galactic globular clusters. These encompass a range of spectral morphologies from the spectrally rich which exhibit a wealth of crystalline and amorphous silicate features to 'naked' (dust-free) stars. We combine spectroscopic and photometric observations with the GRAMS grid of radiative transfer models to derive (dust) mass-loss rates and temperature. We then measure the strength of the crystalline silicate bands at 23, 28 and 33 μm. We detect crystalline silicates in stars with dust mass-loss rates which span over 3 dex, down to rates of ˜10-9 M⊙ yr-1. Detections of crystalline silicates are more prevalent in higher mass-loss rate objects, though the highest mass-loss rate objects do not show the 23-μm feature, possibly due to the low temperature of the forsterite grains or it may indicate that the 23-μm band is going into absorption due to high column density. Furthermore, we detect a change in the crystalline silicate mineralogy with metallicity, with enstatite seen increasingly at low metallicity.

Experimental Investigation on the Topotaxy of Sulfide and Silicate Melts in Peridotite: Implications for the Origin of PGE-depleted Cu-Ni Sulfide Deposit

NASA Astrophysics Data System (ADS)

Wang, Z.; Zhang, J.; Jin, Z.

2016-12-01

Cu-Ni sulfide deposit is generally considered partial melt originated from the mantle which is usually PGE-enriched. However, the largest Cu-Ni sulfide deposits of China (the Jinchuan Cu-Ni deposit) is PGE-depleted. Comparing to silicate melt, the nature and topotaxy of sulfide melt have remained poorly understood. Here we report experimental investigation on the topotaxy of sulfide and silicate melts in peridotite using a piston-cylinder press and a 5GPa Griggs-type deformation apparatus. The starting material consists of polycrystalline olivine or pyrolite and 1 wt% Fe-Ni-Cu sulfide. Hydrostatic and deformation experiments were conducted at a pressure of 1.5 GPa and a temperature of 1250°. Under hydrostatic conditions, our results reveal that the apparent dihedral angle of sulfide melt in an olivine matrix( 96°) is much larger than that of silicate + sulfide melt in pyrolite(<60°) under hydrostatic conditions. The sulfide melt pockets appear mostly as blobs in triple junctions with an immiscible Ni-poor center surrounded by a Ni-rich layer. Under deformation conditions, olivine develops pronounced fabrics with the pole of the (010) forming high concentrations approximately normal to the foliation plane and the [100] axes forming a girdle in the foliation plane. EBSD phase mapping analyses reveal strong shape preferred orientations (SPO) of sulfide +silicate melt in the 45, 90, 135 degree directions for deformation experiments indicating complete wetting of grain boundaries and forming a favorable source for ore deposits. Deformation also causes mixing of the Ni-rich and the Ni-poor sulfide melts. As the platinum-group elements(PGE) prefer to concentrate in the Ni-rich sulfide melt at high temperatures, our results suggest that the metallogenetic source of the PGE-depleted Cu-Ni deposits may have formed under relatively intense deformation and low temperatures with a small fraction of mixed sulfide and silicate melts.

Earth's core-mantle boundary - Results of experiments at high pressures and temperatures

NASA Technical Reports Server (NTRS)

Knittle, Elise; Jeanloz, Raymond

1991-01-01

Laboratory experiments document that liquid iron reacts chemically with silicates at high pressures (above 2.4 x 10 to the 10th Pa) and temperatures. In particular, (Mg,Fe)SiO3 perovskite, the most abundant mineral of earth's lower mantle, is expected to react with liquid iron to produce metallic alloys (FeO and FeSi) and nonmetallic silicates (SiO2 stishovite and MgSiO3 perovskite) at the pressures of the core-mantle boundary, 14 x 10 to the 10th Pa. The experimental observations, in conjunction with seismological data, suggest that the lowermost 200 to 300 km of earth's mantle, the D-double-prime layer, may be an extremely heterogeneous region as a result of chemical reactions between the silicate mantle and the liquid iron alloy of earth's core. The combined thermal-chemical-electrical boundary layer resulting from such reactions offers a plausible explanation for the complex behavior of seismic waves near the core-mantle boundary and could influence earth's magnetic field observed at the surface.

Crystalline Silicates in Comets: Modeling Irregularly-Shaped Forsterite Crystals and Its Implications on Condensation Conditions

NASA Technical Reports Server (NTRS)

Wooden, Diane H.; Lindsay, Sean S.

2011-01-01

Crystalline silicates in comets are a product of the condensation in the hot inner regions (T > or approx. equals 1400 K [1]) of our proto-planetary disk or annealing at somewhat lower temperatures (T > or approx. equals 1000-1200 K) [2, 3, 4] in shocks coupled with disk evolutionary processes that include radial transport of crystals from their formation locations out to the cold outer regions where comet nuclei formed. The grain shape of forsterite (crystals) could be indicative of their formation pathways at high temperatures through vapor-solid condensation or at lower temperatures through vapor-liquid-solid formation and growth [5, 6, 7]. Experiments demonstrate that crystals that formed from a rapidly cooled highly supersaturated silicate vapor are characterized by bulky, platy, columnar/needle and droplet shapes for values of temperature and supersaturation, T and sigma, of 1000-1450 C and < 97, 700-1000 C and 97-161, 580-820 C and 131-230, and <500 C and > 230, respectively [7]. The experimental columnar/needle shapes, which form by vapor-liquid-solid at lower temperatures (<820 C), are extended stacks of plates, where the extension is not correlated with an axial direction: columnar/needles may be extended in the c-axis or a-axis direction, can change directions, and/or are off-kilter or a bit askew extending in a combination of the a- and c-axis direction.

Regularities in Low-Temperature Phosphatization of Silicates

NASA Astrophysics Data System (ADS)

Savenko, A. V.

2018-01-01

The regularities in low-temperature phosphatization of silicates are defined from long-term experiments on the interaction between different silicate minerals and phosphate-bearing solutions in a wide range of medium acidity. It is shown that the parameters of the reaction of phosphatization of hornblende, orthoclase, and labradorite have the same values as for clayey minerals (kaolinite and montmorillonite). This effect may appear, if phosphotization proceeds, not after silicate minerals with a different structure and composition, but after a secondary silicate phase formed upon interaction between silicates and water and stable in a certain pH range. Variation in the parameters of the reaction of phosphatization at pH ≈ 1.8 is due to the stability of the silicate phase different from that at higher pH values.

Partitioning of Mo, P and other siderophile elements (Cu, Ga, Sn, Ni, Co, Cr, Mn, V, and W) between metal and silicate melt as a function of temperature and silicate melt composition

NASA Astrophysics Data System (ADS)

Righter, K.; Pando, K. M.; Danielson, L.; Lee, Cin-Ty

2010-03-01

Metal-silicate partition coefficients can provide information about the earliest differentiation histories of terrestrial planets and asteroids. Systematic studies of the effects of key parameters such as temperature and melt composition are lacking for many elements. In particular, data for Mo is scarce, but given its refractory nature, is of great value in interpreting metal-silicate equilibrium. Two series of experiments have been carried out to study Mo and P partitioning between Fe metallic liquid and basaltic to peridotitic silicate melt, at 1 GPa and temperatures between 1500 and 1900 °C. Because the silicate melt utilized was natural basalt, there are also measurable quantities of 9 other siderophile elements (Ni, Co, W, Sn, Cu, Mn, V, Cr, Ga and Zn). The Ni and Co data can be used to assess consistency with previous studies. In addition, the new data also allow a first systematic look at the temperature dependence of Cu, Ga, Sn, Cr, Mn V and W for basaltic to peridotitic melts. Many elements exhibit an increase in siderophile behavior at higher temperature, contrary to popular belief, but consistent with predictions from thermodynamics. Using these new data we examine DMomet/sil and DPmet/sil in detail and show that increasing temperature causes a decrease in the former and an increase in the latter, whereas both increase with MgO content of the silicate melt. The depletions of Mo and P in the mantle of the Earth can be explained by metal-silicate equilibrium at magma ocean conditions — both elements are satisfied at PT conditions of an intermediate depth magma ocean for the Earth 22.5 GPa and 2400 °C.

Regenerable sorbents for CO.sub.2 capture from moderate and high temperature gas streams

DOEpatents

Siriwardane, Ranjani V [Morgantown, WV

2008-01-01

A process for making a granular sorbent to capture carbon dioxide from gas streams comprising homogeneously mixing an alkali metal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxide, alkali titanate, alkali zirconate, alkali silicate and combinations thereof with a binder selected from the group consisting of sodium ortho silicate, calcium sulfate dihydrate (CaSO.sub.4.2H.sub.2O), alkali silicates, calcium aluminate, bentonite, inorganic clays and organic clays and combinations thereof and water; drying the mixture and placing the sorbent in a container permeable to a gas stream.

Isotopic and trace element characteristics of an unusual refractory inclusion from Essebi

NASA Technical Reports Server (NTRS)

Deloule, E.; Kennedy, A. K.; Hutcheon, I. D.; Elgoresy, A.

1993-01-01

The isotopic and chemical properties of Ca-Al-rich inclusions (CAI) provide important clues to the early solar nebula environment. While the abundances of refractory major and trace elements are similar to those expected for high temperature condensates, the variety of textural, chemical, and isotopic signatures indicate most CAI experienced complex, multi-stage histories involving repeated episodes of condensation, evaporation, and metamorphism. Evidence of multiple processes is especially apparent in an unusual refractory inclusion from Essebi (URIE) described by El Goresy et al. The melilite (mel)-rich core of URIE contains polygonal framboids of spinel (sp) and hibonite (hb) or sp and fassaite (fas) and is surrounded by a rim sequence consisting of five layers. In contrast to rims on Allende, the mineralogy of the URIE rim layers becomes increasingly refractory from the core outwards, ending in a layer of spinel-Al2O3 solid solution + Sc-rich fassaite. The chemical and mineralogical features of URIE are inconsistent with crystallization from a homogeneous melt, and El Goresy et al. proposed a multi-step history involving condensation of sp + hb and aggregation into framboids, capture of framboids by a refractory silicate melt droplet, condensation of rim layers, and alteration of mel to calcite and feldspathoid. The PANURGE ion probe was used to investigate the isotopic and trace element characteristics of URIE to develop a more complete picture of the multiple processes leading to formation and metamorphism.

Lead recovery from waste CRT funnel glass by high-temperature melting process.

PubMed

Hu, Biao; Hui, Wenlong

2018-02-05

In this research, a novel and effective process for waste CRT funnel glass treatment was developed. The key to this process is removal of lead from the CRT funnel glass by high-temperature melting process. Sodium carbonate powder was used as a fusion agent, sodium sulfide serves as a catalytic agent and carbon powder acts as reducing agent. Experimental results showed that lead recovery rate increased with an increase in the amount of added sodium carbonate, sodium sulfide, carbonate, temperature and holding time initially, and then reached a stable value. The maximum lead recovery rate was approximately 94%, when the optimum adding amount of sodium carbonate, sodium sulfide, carbonate, temperature and holding time were 25%, 8%, 3.6%, 1200°C and 120min, respectively. In the high-temperature melting process, lead silicate in the funnel glass was firstly reduced, and then removed. The glass slag can be made into sodium and potassium silicate by hydrolysis process. This study proposed a practical and economical process for recovery of lead and utilization of waste glass slag. Copyright © 2017 Elsevier B.V. All rights reserved.

High-temperature hot spots on Io as seen by the Galileo solid state imaging (SSI) experiment

USGS Publications Warehouse

McEwen, A.S.; Simonelli, D.P.; Senske, D.R.; Klaasen, K.P.; Keszthelyi, L.; Johnson, T.V.; Geissler, P.E.; Carr, M.H.; Belton, M.J.S.

1997-01-01

High-temperature hot spots on Io have been imaged at ???50 km spatial resolution by Galileo's CCD imaging system (SSI). Images were acquired during eclipses (Io in Jupiter's shadow) via the SSI clear filter (???0.4-1.0 ??m), detecting emissions from both small intense hot spots and diffuse extended glows associated with Io's atmosphere and plumes. A total of 13 hot spots have been detected over ???70% of Io's surface. Each hot spot falls precisely on a low-albedo feature corresponding to a caldera floor and/or lava flow. The hot-spot temperatures must exceed ???700 K for detection by SSI. Observations at wavelengths longer than those available to SSI require that most of these hot spots actually have significantly higher temperatures (???1000 K or higher) and cover small areas. The high-temperature hot spots probably mark the locations of active silicate volcanism, supporting suggestions that the eruption and near-surface movement of silicate magma drives the heat flow and volcanic activity of Io. Copyright 1997 by the American Geophysical Union.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reimanis, Ivar; Cioabanu, Cristian

The study of materials with unusual properties offers new insight into structure-property relations as well as promise for the design of novel composites. In this spirit, the PIs seek to (1) understand fundamental mechanical phenomena in ceramics that exhibit pressure-induced phase transitions, negative coefficient of thermal expansion (CTE), and negative compressibility, and (2) explore the effect of these phenomena on the mechanical behavior of composites designed with such ceramics. The broad and long-term goal is to learn how to utilize these unusual behaviors to obtain desired mechanical responses. While the results are expected to be widely applicable to many ceramics,more » most of the present focus is on silicates, as they exhibit remarkable diversity in structure and properties. Eucryptite, a lithium aluminum silicate (LiAlSiO 4), is specifically targeted because it exhibits a pressure-induced phase transition at a sufficiently low pressure to be accessible during conventional materials processing. Thus, composites with eucryptite may be designed to exhibit a novel type of transformation toughening. The PIs have performed a combination of activities that encompass synthesis and processing to control structures, atomistic modeling to predict and understand structures, and characterization to study mechanical behavior. Several materials behavior discoveries were made. It was discovered that small amounts of Zn (as small as 0.1 percent by mol) reverse the sign of the coefficient of thermal expansion of beta-eucryptite from negative to slightly positive. The presence of Zn also significantly mitigates microcracking that occurs during thermal cycling of eucryptite. It is hypothesized that Zn disrupts the Li ordering in beta-eucryptite, thereby altering the thermal expansion behavior. A nanoindentation technique developed to characterize incipient plasticity was applied to examine the initial stages of the pressure induced phase transformation from beta to epsilon-eucryptite and show that the transformation nucleation is related to the motion of the tetrahedral units making up the structure. It was revealed that the conduction of Li ions through the structure is also dictated by the tetrahedral unit arrangement and how their positions change with temperature. The critical pressure to obtain the high pressure phase of eucryptite was shown to depend on the grain size. The structure of the high pressure phase was determined with a combination of atomistic modeling and in situ x-ray diffraction experiments.« less

Transesterification of palm oil using sodium silicate base catalyst from geothermal sludge

NASA Astrophysics Data System (ADS)

Perdana, I.; Nugrahanti, N.; Sofiyah; Bendiyasa, I. M.

2016-11-01

The use of solid base catalysts in biodiesel synthesis is becoming more preferable because of their superiority over homogeneous catalysts. In the present work, a strong base catalyst of sodium silicate synthesized from silica-rich geothermal sludge was used in a transesterification of palm oil with methanol. The catalyst was calcined at 400°C for three hours with a temperature ramp of 20°C/min. The transesterification was carried out at varying temperature in the range of 50 - 70°C for 60 minutes with a methanol-palm oil molar ratio of 8.8:1. The catalyst-palm oil ratio was varied in the range of 1 - 5% (w/w). In order to investigate kinetics of reaction, at a certain interval of time samples were taken consecutively during the reaction. Experimental results showed that the sodium silicate was very active in the transesterification of palm oil with methanol. Reaction temperature at 60°C was sufficient to reach a conversion level as high as 93% in a relatively short reaction period. Meanwhile, the high conversion was still achievable with the use of 1 % (w/w) catalyst. In addition, a lumped model of reaction kinetics was adequate to approach the experimental data with a calculated activation energy of 15.73 kcal/mole. Results of the present work suggested that sodium silicate synthesized from local resources of geothermal sludge would become potential solid base catalyst in biodiesel synthesis.

Monitoring of chlorophyll-a and sea surface silicate concentrations in the south part of Cheju island in the East China sea using MODIS data

NASA Astrophysics Data System (ADS)

Zhang, Yuanzhi; Huang, Zhaojun; Fu, Dongyang; Tsou, Jin Yeu; Jiang, Tingchen; Liang, X. San; Lu, Xia

2018-05-01

Continually supplied with nutrients, phytoplankton maintains high productivity under ideal illumination and temperature conditions. Data in the south part of Cheju Island in the East China Sea (ECS), which has experienced a spring bloom since the 2000s, were acquired during a research cruise in the spring of 2007. Compared with in-situ measurements, MODIS chlorophyll-a measurements showed high stability in this area. Excluding some invalid stations data, the relationships between nutrients and chlorophyll-a concentrations in the study area were examined and compared with the results in 2015. A high positive correlation between silicate and chlorophyll-a concentration was identified, and a regression relationship was proposed. MODIS chlorophyll-a measurements and sea surface temperature were utilized to determine surface silicate distribution. The silicate concentration retrieved from MODIS exhibited good agreement with in-situ measurements with R2 of 0.803, root mean square error (RMSE) of 0.326 μmol/L (8.23%), and mean absolute error (MAE) of 0.925 μmol/L (23.38%). The study provides a new solution to identify nutrient distributions using satellite data such as MODIS for water bodies, but the method still needs to be refined to determine the relationship of chlorophyll-a and nutrients during other seasons to monitor water quality in this and other areas.

Addressing Rare-Earth Element Criticality: An Example from the Aviation Industry

NASA Astrophysics Data System (ADS)

Ku, Anthony Y.; Dosch, Christopher; Grossman, Theodore R.; Herzog, Joseph L.; Maricocchi, Antonio F.; Polli, Drew; Lipkin, Don M.

2014-11-01

Rare-earth (RE) elements are enablers for a wide range of technologies, including high-strength permanent magnets, energy-efficient lighting, high-temperature thermal barrier coatings, and catalysts. While direct material substitution is difficult in many of these applications because of the specific electronic, optical, or electrochemical properties imparted by the individual rare-earth elements, we describe an example from the aviation industry where supply chain optimization may be an option. Ceramic matrix composite engine components require environmental barrier coatings (EBCs) to protect them from extreme temperatures and adverse reactions with water vapor in the hot gas path. EBC systems based on rare-earth silicates offer a unique combination of environmental resistance, thermal expansion matching, thermal conductivity, and thermal stability across the service temperature window. Several pure rare-earth silicates and solid solutions have been demonstrated in EBC applications. However, all rely on heavy rare-earth elements (HREEs) for phase stability. This article considers the possibility of using separation tailings containing a mixture of HREEs as a source material in lieu of using the high-purity HREE oxides. This option arises because the desired properties of RE-silicate EBCs derive from the average cation size rather than the electronic properties of the individual rare-earth cations. Because separation tailings have not incurred the costs associated with the final stages of separation, they offer an economical alternative to high-purity oxides for this emerging application.

Alkaline earth silicate wools - A new generation of high temperature insulation.

PubMed

Brown, Robert C; Harrison, Paul T C

2012-11-01

Intensive study of the natural asbestiform minerals that cause human diseases, and the consequent understanding of their hazardous characteristics, has enabled the development of manufactured fibres whose physical and/or chemical properties, in particular as they relate to biopersistence, have been adjusted to minimize possible harm to health. A strong driver for the developmentof new high temperature insulation materials wasthe perception of the toxicity of refractory ceramic fibres (RCF)and their classification in the EU as a category 2 carcinogen under Directive 67/548/EEC. Such classification carries with it the requirement for substitution by less hazardous materials. This paper focuses on the development of alkaline earth silicate (AES) wools as a new class of high temperature insulation with the capability of such substitution in a number of applications. These wools have only a low potential to cause harm because they do not persist in lung tissue once deposited, and have produced minimal effects in experimental test systems. AES wools are increasingly being used in a wide range of high temperature applications. Copyright © 2012 Elsevier Inc. All rights reserved.

Immiscible Transition from Carbonate-rich to Silicate-rich Melts in Eclogite+CO2 and Genesis of Ocean Island Melilitite

NASA Astrophysics Data System (ADS)

Dasgupta, R.; Stalker, K.; Hirschmann, M. M.

2004-12-01

Derivation of highly silica-undersaturated lavas such as olivine melilitites and melilite nephelinites from the mantle has been attributed to the effects of CO2. However, experimental studies have so far failed to demonstrate equilibrium of melilititic melts with a four-phase peridotite assemblage. Instead, the liquidus mineralogy of these silica-undersaturated magmas at high-pressures appears to be dominated by cpx1. Although, experimental partial melts from natural peridotite+CO2 span a continuum from carbonatite to alkali-basalts2, ocean-island melilitites have distinctly higher TiO2, FeO*, and CaO/(CaO+MgO)3,4 than compositions derived thus far from a carbonated lherzolite source. Partial melting experiments of a nominally anhydrous, natural eclogite with a small amount of added carbonate (SLEC1; 5 wt.% bulk CO2) were performed to investigate the transition between carbonate and silicate melts with increasing temperature. Experiments were conducted in a piston cylinder at 3 GPa from 1050 to 1400 ° C. Garnet and cpx appear in all the experiments and ilmenite is observed from 1075 to ˜1200 ° C. An Fe-bearing calcio-dolomitic melt is present from the solidus (1050-1075 ° C) up to 1375 ° C. Beginning at 1275 ° C, it coexists with a silica-poor silicate melt. Textural criteria indicate only a single CO2-rich silicate melt phase at 1400 ° C, coexisting with garnet and minor cpx. The liquidus temperature is estimated to be ˜1415 ° C from the melt fraction-temperature trend. With increasing temperature, the carbonate melt becomes richer in SiO2 ( ˜2 to 5 wt.%) and Al2O3 ( ˜0.75 to 2.25 wt.%) and poorer in CaO ( ˜30 to 25 wt.% from ˜1200 to 1375 ° C). Compositions of silicate partial melts change systematically with increasing temperature, increasing in SiO2 ( ˜36 to 41 wt.%), Al2O3 ( ˜4.5 to 9.5 wt.%), MgO ( ˜9.5 to 13 wt.%), CaO ( ˜8 to 14 wt.%) and decreasing in TiO2 ( ˜14 to 2.5 wt.%), FeO ( ˜20 to 13 wt.%), Na2O ( ˜3.3 to 1.7 wt.%). A wide temperature interval of coexisting carbonate and silicate partial melts of carbonated eclogite is distinct from the continuous transition from carbonate to silicate melts observed in carbonated peridotite systems2,5. At high-temperature, the silicate melts generated from SLEC1 are comparable to strongly silica-undersaturated, alkalic OIB lavas and closely resembles ocean island melilitite and nepheline melilitite3,4 in its SiO2, FeO*, MgO, CaO, TiO2, and Na2O content. They are also similar to melilite bearing lavas of continental affinity, though the match is not as close. Although the SLEC1 derived immiscible silicate melts are lower in Al2O3 than primitive alkalic OIB lavas, liquids richer in Al2O3 may be produced at slightly lower pressures. Geochemical and geodynamical investigations of carbonated eclogite sources for melilitic volcanic series thus merit consideration. 1. Brey, G and Green, D. H. 1977, CMP 61, 141-162. 2. Hirose, K. 1997, GRL 24, 2837-2840. 3. Clague, D. A. and Frey, F. A. 1982, JP 23, 447-504. 4. Hoernle, K. and Schmincke, H.-U. 1993, JP 34, 573-597. 5. Moore, K. R. and Wood, B. J. 1998, JP 39, 1943-1951.

Redox systematics of a magma ocean with variable pressure-temperature gradients and composition.

PubMed

Righter, K; Ghiorso, M S

2012-07-24

Oxygen fugacity in metal-bearing systems controls some fundamental aspects of the geochemistry of the early Earth, such as the FeO and siderophile trace element content of the mantle, volatile species that influence atmospheric composition, and conditions for organic compounds synthesis. Redox and metal-silicate equilibria in the early Earth are sensitive to oxygen fugacity (fO(2)), yet are poorly constrained in modeling and experimentation. High pressure and temperature experimentation and modeling in metal-silicate systems usually employs an approximation approach for estimating fO(2) that is based on the ratio of Fe and FeO [called "ΔIW (ratio)" hereafter]. We present a new approach that utilizes free energy and activity modeling of the equilibrium: Fe + SiO(2) + O(2) = Fe(2)SiO(4) to calculate absolute fO(2) and relative to the iron-wüstite (IW) buffer at pressure and temperature [ΔIW (P,T)]. This equilibrium is considered across a wide range of pressures and temperatures, including up to the liquidus temperature of peridotite (4,000 K at 50 GPa). Application of ΔIW (ratio) to metal-silicate experiments can be three or four orders of magnitude different from ΔIW (P,T) values calculated using free energy and activity modeling. We will also use this approach to consider the variation in oxygen fugacity in a magma ocean scenario for various thermal structures for the early Earth: hot liquidus gradient, 100 °C below the liquidus, hot and cool adiabatic gradients, and a cool subsolidus adiabat. The results are used to assess the effect of increasing P and T, changing silicate composition during accretion, and related to current models for accretion and core formation in the Earth. The fO(2) in a deep magma ocean scenario may become lower relative to the IW buffer at hotter and deeper conditions, which could include metal entrainment scenarios. Therefore, fO(2) may evolve from high to low fO(2) during Earth (and other differentiated bodies) accretion. Any modeling of core formation and metal-silicate equilibrium should take these effects into account.

Experimental Investigation of the Viscosity of Iron-rich Silicate Melts under Pressure

NASA Astrophysics Data System (ADS)

Edwards, P. M.; Lesher, C. E.; Pommier, A.; O'Dwyer Brown, L.

2017-12-01

The transport properties of silicate melts govern diffusive flow of momentum, heat, and mass in the interior of terrestrial planets. In particular, constraining melt viscosity is critical for dynamic modeling of igneous processes and is thus key to our understanding of magma convection and mixing, melt migration in the mantle, and crystal-liquid fractionation. Among the different constituents of silicate melts, iron is of significant importance as it highly influences some of their properties, such as surface tension, compressibility, and density. We present an experimental study of the viscosity of natural and synthetic iron-rich silicate melts under pressure. In situ falling-sphere measurements of viscosity have been conducted on hedenbergite (CaFeSi2O6) and iron-rich peridotite melts from 1 to 7 GPa and at temperatures between 1750 and 2100 K, using the multi-anvil apparatus at the GSECARS beamline at the Advanced Photon Source, Argonne National Lab. We used double reservoir capsules, with the bottom reservoir containing the sample, while a more refractory material is placed in the upper reservoir (e.g., diopside, enstatite, forsterite). This configuration allows the fall of two rhenium spheres across the sample at different temperatures. Melt viscosity is calculated using Stokes' law and the terminal velocity of the spheres. We observe that melt viscosity slightly decreases with increasing temperature and increasing pressure: for instance, the viscosity of the hedenbergite melt decreases from 1.26 Pa•s to 0.43 Pa•s over the 1 - 3.5 GPa pressure range and between 1820 and 1930 K. Our experimental data are used to develop a viscosity model of iron-rich silicate melts under pressure. Results will be compared with previous viscosity works on iron-free and iron-bearing silicate liquids in order to discuss the effect of iron on melt viscosity and structure at pressure and temperature conditions relevant to terrestrial mantles.

Thermochemistry of amorphous and crystalline zirconium and hafnium silicates.

NASA Astrophysics Data System (ADS)

Ushakov, S.; Brown, C. E.; Navrotsky, Alexandra; Boatner, L. A.; Demkov, A. A.; Wang, C.; Nguyen, B.-Y.

2003-03-01

Calorimetric investigation of amorphous and crystalline zirconium and hafnium silicates was performed as part of a research program on thermochemistry of alternative gate dielectrics. Amorphous hafnium and zirconium silicates with varying SiO2 content were synthesized by a sol-gel process. Crystalline zirconium and hafnium silicates (zircon and hafnon) were synthesized by solid state reaction at 1450 °C from amorphous gels and grown as single crystals from flux. High temperature oxide melt solution calorimetry in lead borate (2PbO.B2O3) solvent at 800 oC was used to measure drop solution enthalpies for amorphous and crystalline zirconium and hafnium silicates and corresponding oxides. Applying appropriate thermochemical cycles, formation enthalpy of crystalline ZrSiO4 (zircon) from binary oxides (baddeleite and quartz) at 298 K was calculated as -23 +/-2 kJ/mol and enthalpy difference between amorphous and crystalline zirconium silicate (vitrification enthalpy) was found to be 61 +/-3 kJ/mol. Crystallization onset temperatures of amorphous zirconium and hafnium silicates, as measured by differential scanning calorimetry (DSC), increased with silica content. The resulting crystalline phases, as characterized by X-ray diffraction (XRD), were tetragonal HfO2 and ZrO2. Critical crystallite size for tetragonal to monoclinic transformation of HfO2 in the gel was estimated as 6 +/-2 nm from XRD data Crystallization enthalpies per mole of hafnia and zirconia in gels decrease slightly together with crystallite size with increasing silica content, for example from -22 to -15 +/-1 kJ per mol of HfO2 crystallized at 740 and 1006 °C from silicates with 10 and 70 mol Applications of thermal analyses and solution calorimetry techniques together with first-principles density functional calculations to estimate interface and surface energies are discussed.

Residual stresses and phase transformations in Ytterbium silicate environmental barrier coatings

NASA Astrophysics Data System (ADS)

Stolzenburg, Fabian

Due to their high melting temperature, low density, and good thermomechanical stability, silicon-based ceramics (SiC, Si3N4) are some of the most promising materials systems for high temperature structural applications in gas turbine engines. However, their silica surface layer reacts with water vapor contained in combustion environments. The resulting hydroxide layer volatilizes, leading to component recession. Environmental barrier coatings (EBCs) have been developed to shield the substrate from degradation. Next generation coatings for silicon-based ceramics based on ytterbium silicates have shown a promising combination of very low and good thermomechanical properties. The focus of this thesis is threefold: In the first part, phase transformations in plasma sprayed ytterbium silicates were investigated. Plasma sprayed materials are known to contain large amounts of amorphous material. Phase changes during the conversion from amorphous to crystalline materials were investigated as they have been known to lead to failure in many coatings. The second part of this work focused on measuring residual stresses in multilayer EBCs using synchrotron X-ray diffraction (XRD). Strains were resolved spatially, with probe sizes as small as 20 um. Stresses were calculated using mechanical properties of ytterbium silicates, determined with in-situ loading and heating experiments. In-situ and ex-situ heating experiments allowed for the study of changes in stress states that occur in these EBC materials during heating and cooling cycles. Lastly, the interaction of ytterbium silicates with low-melting environmental calcium-magnesium-aluminosilicate (CMAS) glasses was studied. Synchrotron XRD was used to study the influence of CMAS on the stress state in the coating, X-ray computed tomography was used to provide 3D images of coatings, and EDS and TEM analysis were used to study the interactions at the CMAS/ytterbium silicate interface in detail.

High chloride content calcium silicate glasses.

PubMed

Chen, Xiaojing; Karpukhina, Natalia; Brauer, Delia S; Hill, Robert G

2017-03-08

Chloride is known to volatilize from silicate glass melts and until now, only a limited number of studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amounts of CaCl 2 . The CaCl 2 has been added to the calcium metasilicate composition (CaO·SiO 2 ). Glasses were produced via a melt quench route and an average of 70% of the chloride was retained after melting. Up to 31.6 mol% CaCl 2 has been successfully incorporated into these silicate glasses without the occurrence of crystallization. 29 Si MAS-NMR spectra showed the silicon being present mainly as a Q 2 silicate species. This suggests that chloride formed Cl-Ca(n) species, rather than Si-Cl bonds. Upon increasing the CaCl 2 content, the T g reduced markedly from 782 °C to 370 °C. Glass density and glass crystallization temperature decreased linearly with an increase in the CaCl 2 content. However, both linear regressions revealed a breakpoint at a CaCl 2 content just below 20 mol%. This might be attributed to a significant change in the structure and is also correlated with the nature of the crystallizing phases formed upon heat treatment. The glasses with less than 19.2 mol% CaCl 2 crystallized to wollastonite, whilst the compositions with CaCl 2 content equal to or greater than 19.2 mol% are thought to crystallize to CaCl 2 . In practice, the crystallization of CaCl 2 could not occur until the crystallization temperature fell below the melting point of CaCl 2 . The implications of the results along with the high chloride retention are discussed.

Effect of silicate ions on electrode overvoltage

NASA Technical Reports Server (NTRS)

Gras, J. M.; Seite, C.

1979-01-01

The influence of the addition of a silicate to a caustic solution (KOH) is studied in order to determine the degree to which silicates inhibit the corrosion of chrysotile under conditions of electrolysis at working temperatures of 100 C and above. In an alkaline solution containing various silicate concentrations, current density was increased and electrode overvoltage was measured. Results show that silicate ion concentrations in the electrolyte increase with temperature without effecting electrochemical performance up to 115 C at 700 MA/sqcm. At this point the concentration is about 0.5 g Si/100 g KOH. Beyond this limit, electrolytic performance rapidly degenerates due to severe oxidation of the electrodes.

Natural occurrence and significance of fluids indicating high pressure and temperature

USGS Publications Warehouse

Roedder, E.

1981-01-01

Most natural minerals have formed from a fluid phase such as a silicate melt or a saline aqueous solution. Fluid inclusions are tiny volumes of such fluids that were trapped within the growing crystals. These inclusions can provide valuable but sometimes ambiguous data on the temperature, pressure, and composition of these fluids, many of which are not available from any other source. They also provide "visual autoclaves" in which it is possible to watch, through the microscope, the actual phase changes take place as the inclusions are heated. This paper reviews the methods of study and the results obtained, mainly on inclusions formed from highly concentrated solutions, at temperatures ???500??C. Many such fluids have formed as a result of immiscibility with silicate melt in igneous or high-temperature metamorphic rocks. These include fluids consisting of CO2, H2O, or hydrosaline melts that were <50% H2O. From the fluid inclusion evidence it is clear that a boiling, very hot, very saline fluid was present during the formation of most of the porphyry copper deposits in the world. Similarly, from the inclusion evidence it is clear that early (common) pegmatites formed from essentially silicate melts and that the late, rare-element-bearing and chamber-type pegmatites formed from a hydrosaline melt or a more dilute water solution. The evidence on whether this change in composition from early to late solutions was generally continuous or involved immiscibility is not as clear. ?? 1981.

Metamorphic reactions in mesosiderites - Origin of abundant phosphate and silica

NASA Technical Reports Server (NTRS)

Harlow, G. E.; Delaney, J. S.; Prinz, M.; Nehru, C. E.

1982-01-01

In light of a study of the Emery mesosiderite, it is determined that the high modal abundances of merrillite and tridymite in most mesosiderites are attributable to redox reactions between silicates and P-bearing Fe-Ni metal within a limited T-fO2 range at low pressure. The recalculated amounts of dissolved P and S in the metallic portion of Emery reduce the metal liquidus temperature to less than 1350 C, and the solidus to less than 800 C, so that the mixing of liquid metal with cold silicates would have resulted in silicate metamorphism rather than melting. This redox reaction and redistribution of components between metal and silicates illuminates the complexities of mesosiderite processing, with a view to the recalculation of their original components.

The distribution of chromium among orthopyroxene, spinel and silicate liquid at atmospheric pressure

NASA Technical Reports Server (NTRS)

Barnes, S. J.

1986-01-01

The Cr distributions for a synthetic silicate melt equilibrated with bronzitic orthopyroxene and chromite spinel between 1334 and 1151 C over a range of oxygen fugacities between the nickel-nickel oxide and iron-wuestite buffers are studied. The occurrence, chemical composition, and structure of the orthopyroxene-silicate melt and the spinel-silicate melt are described. It is observed that the Cr content between bronzite and the melt increases with falling temperature along a given oxygen buffer and decreases with falling oxygen fugacity at a given temperature; however, the Cr content of the melt in equilibrium with spinel decreases with falling temperature and increases with lower oxygen fugacity.

Investigations on the crystal-structure and non-ambient behaviour of K2Ca2Si8O19 - a new potassium calcium silicate

NASA Astrophysics Data System (ADS)

Schmidmair, Daniela; Kahlenberg, Volker; Praxmarer, Alessandra; Perfler, Lukas; Mair, Philipp

2017-09-01

Within the context of a systematic re-investigation of phase relationships between compounds of the ternary system K2O-CaO-SiO2 a new potassium calcium silicate with the chemical formula K2Ca2Si8O19 was synthesized via solid state reactions as well as the flux method using KCl as a solvent. Its crystal structure was determined from single-crystal X-ray diffraction data by applying direct methods. The new compound crystallizes in the triclinic space group P 1 bar . Unit cell dimensions are a = 7.4231(7) Å, b = 10.7649(10) Å, c = 12.1252(10) Å, α = 70.193(8)°, β = 83.914(7)° and γ = 88.683(7)°. K2Ca2Si8O19 is built up of corner-connected, slightly distorted [SiO4]-tetrahedra forming double-sheets, which are linked by double-chains of edge-sharing [CaO6]-octahedra. Electroneutrality of the material is provided by additional potassium atoms that are located within the voids of the silicate layers and between adjacent [Ca2O6]-double-chains. Further characterization of the compound was performed by Raman spectroscopy and differential thermal analysis. The behaviour of K2Ca2Si8O19 under high-temperature and high-pressure was investigated by in-situ high-temperature powder X-ray diffraction up to a maximum temperature of 1125 °C and a piston cylinder experiment at 1.5 GPa and 1100 °C. Additionally an overview of known double-layer silicates is given as well as a comparison of K2Ca2Si8O19 to closely related structures.

High temperature crystal field spectra of transition metal-bearing minerals - Relevance to remote-sensed spectra of planetary surfaces

NASA Technical Reports Server (NTRS)

Parkin, K. M.; Burns, R. G.

1980-01-01

It is pointed out that transition metal ions in silicate minerals, glasses, and crystalline and amorphous oxyhydroxides and salts contribute to the visible-near infrared spectral profiles of planetary surfaces. Investigations are conducted to obtain spectral information which might be helpful in the interpretation of the remote-sensed spectra of planetary surfaces. A description is presented of the results of high temperature crystal field spectral measurements of a variety of heated minerals containing Cr(3+), Fe(3+), Fe(++), and Mn(++) ions in different coordination symmetries, taking into account a correlation of the temperature-induced variations with those previously observed for octahedrally coordinated Fe(++)-bearing silicates. The employed experimental methods are also discussed, giving attention to the preparation of the samples, the determination of the absorption spectra, electron microprobe analyses, and the curve fitting procedure.

High-temperature ultrasonic characterization of the mechanical and microstructural behavior of a fibrous composite with a magnesium lithium aluminum silicate glass-ceramic matrix

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cutard, T.; Huger, M.; Fargeot, D.

The mechanical behavior and the microstructural modifications of a SiC-fiber-reinforced magnesium lithium aluminum silicate glass-ceramic (SiC/MASL) have been characterized by ultrasonic measurement of uniaxial Young`s modulus at high temperature. Under vacuum, long isothermal agings in the 750--1,000 C temperature range have shown matrix modifications in terms of crystallization of residual glassy phases, and of phase transformations in the Li{sub 2}O-Al{sub 2}O{sub 3}-SiO{sub 2} system. In air, long isothermal agings performed under the same conditions have led to the same matrix transformations but in competition with oxidation mechanisms of the carbon fiber-matrix interphase. All of these matrix and/or interface transformations havemore » been confirmed by X-ray diffraction analysis, scanning electron microscopy, scanning acoustic microscopy, and microindentation tests.« less

A IAB-Complex Iron Meteorite Containing Low-Ca Clinopyroxene: Northwest Africa 468 and its Relationship to Iodranites and Formation by Impact Melting

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.

2002-01-01

Northwest Africa 468 (NWA 468) is a new ungrouped, silicate-rich member of the IAB complex of nonmagmatic iron meteorites. The silicates contain relatively coarse (approximately 300 micron-size) grains of low-Ca clinopyroxene with polysynthetic twinning and inclined extinction. Low-Ca clinopyroxene is indicative of quenching from high temperatures (either from protoenstatite in a few seconds or high-temperature clinoenstatite in a few hours). It seems likely that NWA 468 formed by impact melting followed by rapid cooling to less than or equal to 660 C. After the loss of a metal-sulfide melt from the silicates, sulfide was reintroduced, either from impact-mobilized FeS or as an S2 vapor that combined with metallic Fe to produce FeS. The O-isotopic composition (delta O-17 = -1.39 %) indicates that the precursor material of NWA 468 was a metal-rich (e.g., CR) carbonaceous chondrite. Lodranites are similar in bulk chemical and O-isotopic composition to the silicates in NWA 468; the MAC 88177 lodranite (which also contains low-Ca clinopyroxene) is close in bulk chemical composition. Both NWA 468 and MAC 88177 have relatively low abundances of REE (rare earth elements) and plagiophile elements. Siderophiles in the metal-rich areas of NWA 468 are similar to those in the MAC 88177 whole rock; both samples contain low Ir and relatively high Fe, Cu and Se. Most unweathered lodranites contain approximately 20 - 38 wt. % metallic Fe-Ni. These rocks may have formed in an analogous manner to NWA 468 (i.e., by impact melting of metal-rich carbonaceous-chondrite precursors) but with less separation of metal-rich melts from silicates.

Impact cratering: The process and its effects on planetary evolution. [and silicate-carbonate reactions on Venus

NASA Technical Reports Server (NTRS)

Grieve, R. A. F.

1984-01-01

The potential for silicate-carbon dioxide reactions as a geochemical weathering agent on Venus was studied. A tholetitic basalt close to the composition determined by the XRF experiment at the Venera 14 sites was subjected to high temperature and pressure (with pure CO2 as the pressure medium) for varying time durations. The starting basalt material and the run products were examined optically and by X-ray diffraction and electron microscopy. The kinetics of the silicate-carbonate reactions is discussed. A study to elucidate details of impact processes and to assess the effects of impact cratering on planetary evolution is mentioned.

Bonding by Hydroxide-Catalyzed Hydration and Dehydration

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung

2008-01-01

A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.

Ultrasonic Sound Velocity of Diopside Liquid Under High Pressure and High Temperature Conditions

NASA Astrophysics Data System (ADS)

Xu, M.; Jing, Z.; Chantel, J.; Yu, T.; Wang, Y.; Jiang, P.

2017-12-01

The equation of state (EOS) of silicate liquids is of great significance to the understanding of the dynamics and differentiation of the magmatic systems in Earth and other terrestrial planets. Sound velocity of silicate liquids measured at high pressure can provide direct information on the bulk modulus and its pressure derivative and hence tightly constrain the EOS of silicate liquids. In addition, the sound velocity data can be directly compared to seismic observations to infer the presence of melts in the mantle. While the sound velocity for silicate liquids at ambient pressure has been well established, the high-pressure sound velocity data are still lacking due to experimental challenges. In this study, we successfully determined the sound velocities of diopside (CaMgSi2O6) liquid in a multi-anvil apparatus under high pressure-high temperature conditions from 1 to 4 GPa and 1973 to 2473 K by the ultrasonic interferometry in conjunction with synchrotron X-ray techniques. Diopside was chosen to study because it is not only one of the most important phases in the Earth's upper mantle, but also an end-member composition of model basalt. It is thus an ideal simplified melt composition in the upper mantle. Besides, diopside liquid has been studied by ambient-pressure ultrasonic measurements (e.g., Ai and Lange, 2008) and shock-wave experiments at much higher pressure (e.g., Asimow and Ahrens, 2010), which allows comparison with our results over a large pressure range. Our high-pressure results on the sound velocity of Di liquid are consistent with the ambient-pressure data and show an increase of velocity with pressure (from 3039 m/s at 0.1 GPa to 4215 m/s at 3.5 GPa). Fitting to the Murnaghan EOS gives an isentropic bulk modulus (Ks) of 24.8 GPa and its pressure dependence (K'S) of 7.8. These are consistent with the results from shock-wave experiments on Di liquid (Asimow and Ahrens, 2010), indicating that the technique used in this study is capable to accurately determine the sound velocity of silicate liquids at high pressures. We will use these results to better constrain the hard sphere EOS model for silicate liquids (Jing and Karato, 2011), with implications to the stability of melt layers in the deep mantle under gravity and the presence of partial melts in low velocity zones in the mantle.

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

NASA Technical Reports Server (NTRS)

Blander, M.; Planner, H. N.; Keil, K.; Nelson, L. S.; Richardson, N. L.

1976-01-01

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.

Impact-melt origin for the Simondium, Pinnaroo, and Hainholz mesosiderites: implicatiions for impact processes beyond the Earth--Moon system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Floran, R J; Caulfield, J B.D.; Harlow, G E

The Simondium, Pinnaroo, and Hainholz mesosiderites are interpreted to be clast-laden impact melts that crystallized from immiscible silicate, metallic (Fe-FeS) liquids. The existence of silicate melts is shown by intergranular basaltic textures. Metallic melts are inferred on the basis of smooth boundaries between metal and troilite and the occurrence of troilite as anastomosing areas that radiate outward into the silicate fractions. These relations suggest that troilite crystallized after silicates, concentrating as a late-stage residuum. Evidence for impact melting includes: diversity and abundance of clast types (mineral, metal, lithic) in various stages of recrystallization and assimilation; differences in mineral chemistries betweenmore » clasts and igneous-textured matrix silicates; unusual metal plus silicate bulk composition. Silicate clasts consist primarily of orthopyroxene and minor olivine with a range of Fe/Fe + Mg ratios, anorthitic plagioclase, and rare orthopyroxenite (diogenite) fragments. Substantial amounts of Fe-Ni metal were melted during the impact events and minor amounts were incorporated into the melts as clasts. The clast populations suggest that at least four rock types were melted and mixed: (a) diogenite, (b) a plagioclase-rich source, possibly cumulate eucrite, (c) dunite, and (d) metal. Most orthopyroxene appears to have been derived from fragmentation of diogenites. Orthopyroxene (En/sub 82-61/) and olivine (Fo/sub 86-67/) clasts include much material unsampled as individual meteorites and probably represent a variety of source rocks.« less

Stable isotope compositions and water contents of boninite series volcanic rocks from Chichi-jima, Bonin Islands, Japan

USGS Publications Warehouse

Dobson, P.F.; O'Neil, J.R.

1987-01-01

Measurements of stable isotope compositions and water contents of boninite series volcanic rocks from the island of Chichi-jima, Bonin Islands, Japan, confirm that a large amount (1.6-2.4 wt.%) of primary water was present in these unusual magmas. An enrichment of 0.6??? in 18O during differentiation is explained by crystallization of 18O-depleted mafic phases. Silicic glasses have elevated ??18O values and relatively low ??D values indicating that they were modified by low-temperature alteration and hydration processes. Mafic glasses, on the other hand, have for the most part retained their primary isotopic signatures since Eocene time. Primary ??D values of -53 for boninite glasses are higher than those of MORB and suggest that the water was derived from subducted oceanic lithosphere. ?? 1987.

Size distributions and aerodynamic equivalence of metal chondrules and silicate chondrules in Acfer 059

NASA Technical Reports Server (NTRS)

Skinner, William R.; Leenhouts, James M.

1993-01-01

The CR2 chondrite Acfer 059 is unusual in that the original droplet shapes of metal chondrules are well preserved. We determined separate size distributions for metal chondrules and silicate chondrules; the two types are well sorted and have similar size distributions about their respective mean diameters of 0.74 mm and 1.44 mm. These mean values are aerodynamically equivalent for the contrasting densities, as shown by calculated terminal settling velocities in a model solar nebula. Aerodynamic equivalence and similarity of size distributions suggest that metal and silicate fractions experienced the same sorting process before they were accreted onto the parent body. These characteristics, together with depletion of iron in Acfer 059 and essentially all other chondrites relative to primitive CI compositions, strongly suggest that sorting in the solar nebula involved a radial aerodynamic component and that sorting and siderophile depletion in chondrites are closely related.

Sulfur and sulfides in chondrules

NASA Astrophysics Data System (ADS)

Marrocchi, Yves; Libourel, Guy

2013-10-01

The nature and distribution of sulfides within type I PO, POP and PP chondrules of the carbonaceous chondrite Vigarano (CV3) have been studied by secondary electron microscopy and electron microprobe. They occur predominantly as spheroidal blebs composed entirely of low-Ni iron sulfide (troilite, FeS) or troilite + magnetite but in less abundance in association with metallic Fe-Ni beads in opaque assemblages. Troilites are mainly located within the low-Ca pyroxene outer zone and their amounts increase with the abundance of low-Ca pyroxene within chondrules, suggesting co-crystallization of troilite and low-Ca pyroxene during high-temperature events. We show that sulfur concentration and sulfide occurrence in chondrules obey high temperature sulfur solubility and saturation laws. Depending on the fS2 and fO2 of the surrounding gas and on the melt composition, mainly the FeO content, sulfur dissolved in chondrule melts may eventually reach a concentration limit, the sulfur content at sulfide saturation (SCSS), at which an immiscible iron sulfide liquid separates from the silicate melt. The occurrence of both a silicate melt and an immiscible iron sulfide liquid is further supported by the non-wetting behavior of sulfides on silicate phases in chondrules due to the high interfacial tension between their precursor iron-sulfide liquid droplets and the surrounding silicate melt during the high temperature chondrule-forming event. The evolution of chondrule melts from PO to PP towards more silicic compositions, very likely due to high PSiO(g) of the surrounding nebular gas, induces saturation of FeS at much lower S content in PP than in PO chondrules, leading to the co-crystallization of iron sulfides and low-Ca pyroxenes. Conditions of co-saturation of low-Ca pyroxene and FeS are only achieved in non canonical environments characterized by high partial pressures of sulfur and SiO and redox conditions more oxidizing than IW-3. Fe and S mass balance calculations also suggest the occurrence of an external source of iron, very likely gaseous, during chondrule formation. We therefore propose that enrichments in sulfur (and other volatile and moderately volatile elements) from PO to PP type I bulk chondrule compositions towards chondritic values result from progressive reaction between partially depleted olivine-bearing precursors and a volatile-rich gas phase.

Development of an Integrated Thermocouple for the Accurate Sample Temperature Measurement During High Temperature Environmental Scanning Electron Microscopy (HT-ESEM) Experiments.

PubMed

Podor, Renaud; Pailhon, Damien; Ravaux, Johann; Brau, Henri-Pierre

2015-04-01

We have developed two integrated thermocouple (TC) crucible systems that allow precise measurement of sample temperature when using a furnace associated with an environmental scanning electron microscope (ESEM). Sample temperatures measured with these systems are precise (±5°C) and reliable. The TC crucible systems allow working with solids and liquids (silicate melts or ionic liquids), independent of the gas composition and pressure. These sample holder designs will allow end users to perform experiments at high temperature in the ESEM chamber with high precision control of the sample temperature.

Cometary crystalline silicate before and after perihelion passage II

NASA Astrophysics Data System (ADS)

Ootsubo, Takafumi

2014-01-01

Crystalline silicate is often observed in comets as an 11.3-micron resonant emission feature, and may be used for probing the early solar nebula. Because the formation of the crystalline silicate requires high temperature, they are thought to have been born from amorphous silicate at the inner region, and then transported toward the outer regions where comets were born. This transportation can produce the difference in the crystalline fraction in the cometary silicate dust between two dynamical types of comets, Oort-cloud comets (OCs) and Ecliptic comets (ECs), due to the different heliocentric distances of their birth places. The study of peak wavelengths in crystalline features is important to investigate the conditions of the crystalline silicate formation as well. Thus far, we don't have enough observational samples of OCs. Fortunately, we can observe comet C/2012 K1 (PanSTARRS) along with C/2013 A1 (Siding Spring) in this semester. In particular, the comet C/2012 K1 (PanSTARRS) is a bright and good target for this silicate peak feature study. Observations at pre- and post-perihelion provide us precious information on the dust evolution of the comet.

Silicon Carbide Nanotube Oxidation at High Temperatures

NASA Technical Reports Server (NTRS)

Ahlborg, Nadia; Zhu, Dongming

2012-01-01

Silicon Carbide Nanotubes (SiCNTs) have high mechanical strength and also have many potential functional applications. In this study, SiCNTs were investigated for use in strengthening high temperature silicate and oxide materials for high performance ceramic nanocomposites and environmental barrier coating bond coats. The high · temperature oxidation behavior of the nanotubes was of particular interest. The SiCNTs were synthesized by a direct reactive conversion process of multiwall carbon nanotubes and silicon at high temperature. Thermogravimetric analysis (TGA) was used to study the oxidation kinetics of SiCNTs at temperatures ranging from 800degC to1300degC. The specific oxidation mechanisms were also investigated.

Unusually high rotational temperature of the CN radical

NASA Astrophysics Data System (ADS)

Krełowski, J.; Galazutdinov, G.; Beletsky, Y.

2011-07-01

We analyse a high-resolution, high signal-to-noise spectrogram of the hot reddened star Trumpler 16 112 to find relationships between the physical parameters of the intervening interstellar medium (e.g., the rotational temperature of the CN radical) and the intensities of interstellar lines/bands. We report on the discovery of an interstellar cloud that shows an exceptionally high rotational temperature of CN (4.5 K) and unusually strong Ca I and Fe I interstellar lines. This rare CaFe-type cloud seemingly contains no diffuse band carriers. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere, Chile. Programs 073.D-0609(A) and 082.C-0566(A).

High temperature chemically resistant polymer concrete

DOEpatents

Sugama, T.; Kukacka, L.E.

High temperature chemically resistant, non-aqueous polymer concrete composites consist of about 12 to 20% by weight of a water-insoluble polymer binder. The binder is polymerized in situ from a liquid vinyl-type monomer or mixture of vinyl containing monomers such as triallylcyanurate, styrene, acrylonitrile, acrylamide, methacrylamide, methyl-methacrylate, trimethylolpropane trimethacrylate and divinyl benzene. About 5 to 40% by weight of a reactive inorganic filler selected from the group consisting of tricalcium silicate and dicalcium silicate and mixtures containing less than 2% free lime, and about 48 to 83% by weight of silica sand/ and a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, other orgaic peroxides and combinations to initiate polymerization of the monomer in the presence of the inorganic filers are used.

In situ study at high pressure and temperature of the environment of water in hydrous Na and Ca aluminosilicate melts and coexisting aqueous fluids

NASA Astrophysics Data System (ADS)

Le Losq, Charles; Dalou, Célia; Mysen, Bjorn O.

2017-07-01

The bonding and speciation of water dissolved in Na silicate and Na and Ca aluminosilicate melts were inferred from in situ Raman spectroscopy of the samples, in hydrothermal diamond anvil cells, while at crustal temperature and pressure conditions. Raman data were also acquired on Na silicate and Na and Ca aluminosilicate glasses, quenched from hydrous melts equilibrated at high temperature and pressure in a piston cylinder apparatus. In the hydrous melts, temperature strongly influences O-H stretching ν(O-H) signals, reflecting its control on the bonding of protons between different molecular complexes. Pressure and melt composition effects are much smaller and difficult to discriminate with the present data. However, the chemical composition of the melt + fluid system influences the differences between the ν(O-H) signals from the melts and the fluids and, hence, between their hydrogen partition functions. Quenching modifies the O-H stretching signals: strong hydrogen bonds form in the glasses below the glass transition temperature Tg, and this phenomenon depends on glass composition. Therefore, glasses do not necessarily record the O-H stretching signal shape in melts near Tg. The melt hydrogen partition function thus cannot be assessed with certainty using O-H stretching vibration data from glasses. From the present results, the ratio of the hydrogen partition functions of hydrous silicate melts and aqueous fluids mostly depends on temperature and the bulk melt + fluid system chemical composition. This implies that the fractionation of hydrogen isotopes between magmas and aqueous fluids in water-saturated magmatic systems with differences in temperature and bulk chemical composition will be different.

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

NASA Technical Reports Server (NTRS)

Ahlborg, Nadia L.; Zhu, Dongming

2013-01-01

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Modifying Silicates for Better Dispersion in Nanocomposites

NASA Technical Reports Server (NTRS)

Campbell, Sandi

2005-01-01

An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained.

From illite/smectite clay to mesoporous silicate adsorbent for efficient removal of chlortetracycline from water.

PubMed

Wang, Wenbo; Tian, Guangyan; Zong, Li; Zhou, Yanmin; Kang, Yuru; Wang, Qin; Wang, Aiqin

2017-01-01

A series of mesoporous silicate adsorbents with superior adsorption performance for hazardous chlortetracycline (CTC) were sucessfully prepared via a facile one-pot hydrothermal reaction using low-cost illite/smectite (IS) clay, sodium silicate and magnesium sulfate as the starting materials. In this process, IS clay was "teared up" and then "rebuilt" as new porous silicate adsorbent with high specific surface area of 363.52m 2 /g (about 8.7 folds higher than that of IS clay) and very negative Zeta potential (-34.5mV). The inert SiOSi (Mg, Al) bonds in crystal framework of IS were broken to form Si(Al) O - groups with good adsorption activity, which greatly increased the adsorption sites served for holding much CTC molecules. Systematic evaluation on adsorption properties reveals the optimal silicate adsorbent can adsorb 408.81mg/g of CTC (only 159.7mg/g for raw IS clay) and remove 99.3% (only 46.5% for raw IS clay) of CTC from 100mg/L initial solution (pH3.51; adsorption temperature 30°C; adsorbent dosage, 3g/L). The adsorption behaviors of CTC onto the adsorbent follows the Langmuir isotherm model, Temkin equation and pseudo second-order kinetic model. The mesopore adsorption, electrostatic attraction and chemical association mainly contribute to the enhanced adsorption properties. As a whole, the high-efficient silicate adsorbent could be candidates to remove CTC from the wastewater with high amounts of CTC. Copyright © 2016. Published by Elsevier B.V.

Synchrotron X-ray spectroscopic investigations of an Nb-bearing silicate melt in contact with an aqueous fluid

NASA Astrophysics Data System (ADS)

Mayanovic, R. A.; Anderson, A. J.; Bassett, W. A.; Chou, I.

2006-05-01

Understanding the structural properties of trace elements in hydrous silicate melts in contact with a hydrothermal fluid is fundamentally important for a better assessment of the role of such elements in silicate melts being subjected to hydrothermal processes. We describe the use of synchrotron x-ray microprobe techniques and the modified hydrothermal diamond-anvil cell for in-situ spectroscopic analysis of individual phases of a silicate-melt/fluid system. Synchrotron X-ray fluorescence (XRF) and Nb K-edge X-ray absorption fine structure (XAFS) measurements were made on sectors ID20 and ID13 at the Advanced Photon Source, at the Argonne National Laboratory, on a Nb-bearing granitic glass in H2O and separately in a 1 M Na2CO3 aqueous solution at temperatures ranging from 25 to 880 °C and at up to 700 MPa of pressure. Individual phases of the Nb-glass/fluid system (at low temperatures) or the hydrous-silicate-melt/fluid system (at elevated temperatures) were probed using an X-ray beam focused to a diameter of 5 μm at the location of the sample. XRF analysis shows that the Nb partitions selectively from the hydrous silicate melt into the aqueous fluid at high temperatures in the Nb-glass/Na2CO3/H2O system but not so in the Nb-glass/H2O system. Analysis of XAFS spectra measured from the hydrous silicate melt phase of the Nb-glass/H2O sample in the 450 to 700 °C range shows that the first shell contains six oxygen atoms at a distance of ~1.98 Å. Our results suggest that reorganization of the silicate structure surrounding Nb occurs in the melt when compared to that of the starting glass. The X-ray absorption near edge structure (XANES) spectra show a pre-edge peak feature located at ~18995 eV that exhibits sharpening and becomes more intensified in the 450 to 700 °C range. Fitting of the Nb K-edge XANES spectra measured from the melt is accomplished using FEFF8.28 and an atomic model NbSi4O6-4(Na, K). The model is based on the structure of fresnoite (Ba2TiSi2O8), in which an NbO6 octahedron unit is substituted for the TiO5 unit, four Na and four K atoms are placed alternately on nearby Ba atom sites, and four Si atoms are arranged in a single plane intersecting the NbO6 unit. The results from fitting indicate that the local structure of Nb in the silicate melt is altered from its local structure in the quenched glass before heating and in the glass after heating in the diamond anvil cell. The importance of in situ analysis of melts and hydrothermal fluids at various temperatures and pressures is discussed in the context of our study.

Texture related unusual phenomena in electrodeposition and vapor deposition

NASA Astrophysics Data System (ADS)

Lee, D. N.; Han, H. N.

2015-04-01

The tensile strength of electrodeposits generally decreases with increasing bath temperature because the grain size increases and the dislocation density decreases with increasing bath temperature. Therefore, discontinuities observed in the tensile strength vs. bath temperature curves in electrodeposition of copper are unusual. The tensile strength of electrodeposits generally increases with increasing cathode current density because the rate of nucleation in electrodeposits increases with increasing current density, which in turn gives rise to a decrease in the grain size and in turn an increase in the strength. Therefore, a decrease in the tensile strength of copper electrodeposits at a high current density is unusual. The grain size of vapor deposits is expected to decrease with decreasing substrate temperature. However, rf sputtered Co-Cr deposits showed that deposits formed on water-cooled polyimide substrates had a larger grain size than deposits formed on polyimide substrates at 200 °C. These unusual phenomena can be explained by the preferred growth model for deposition texture evolution.

Redox systematics of a magma ocean with variable pressure-temperature gradients and composition

PubMed Central

Righter, K.; Ghiorso, M. S.

2012-01-01

Oxygen fugacity in metal-bearing systems controls some fundamental aspects of the geochemistry of the early Earth, such as the FeO and siderophile trace element content of the mantle, volatile species that influence atmospheric composition, and conditions for organic compounds synthesis. Redox and metal-silicate equilibria in the early Earth are sensitive to oxygen fugacity (fO2), yet are poorly constrained in modeling and experimentation. High pressure and temperature experimentation and modeling in metal-silicate systems usually employs an approximation approach for estimating fO2 that is based on the ratio of Fe and FeO [called “ΔIW (ratio)” hereafter]. We present a new approach that utilizes free energy and activity modeling of the equilibrium: Fe + SiO2 + O2 = Fe2SiO4 to calculate absolute fO2 and relative to the iron-wüstite (IW) buffer at pressure and temperature [ΔIW (P,T)]. This equilibrium is considered across a wide range of pressures and temperatures, including up to the liquidus temperature of peridotite (4,000 K at 50 GPa). Application of ΔIW (ratio) to metal-silicate experiments can be three or four orders of magnitude different from ΔIW (P,T) values calculated using free energy and activity modeling. We will also use this approach to consider the variation in oxygen fugacity in a magma ocean scenario for various thermal structures for the early Earth: hot liquidus gradient, 100 °C below the liquidus, hot and cool adiabatic gradients, and a cool subsolidus adiabat. The results are used to assess the effect of increasing P and T, changing silicate composition during accretion, and related to current models for accretion and core formation in the Earth. The fO2 in a deep magma ocean scenario may become lower relative to the IW buffer at hotter and deeper conditions, which could include metal entrainment scenarios. Therefore, fO2 may evolve from high to low fO2 during Earth (and other differentiated bodies) accretion. Any modeling of core formation and metal-silicate equilibrium should take these effects into account. PMID:22778438

Sulfur Saturation Limits in Silicate Melts and their Implications for Core Formation Scenarios for Terrestrial Planets

NASA Technical Reports Server (NTRS)

Holzheid, Astrid; Grove, Timothy L.

2002-01-01

This study explores the controls of temperature, pressure, and silicate melt composition on S solubility in silicate liquids. The solubility of S in FeO-containing silicate melts in equilibrium with metal sulfide increases significantly with increasing temperature but decreases with increasing pressure. The silicate melt structure also exercises a control on S solubility. Increasing the degree of polymerization of the silicate melt structure lowers the S solubility in the silicate liquid. The new set of experimental data is used to expand the model of Mavrogenes and O'Neill(1999) for S solubility in silicate liquids by incorporating the influence of the silicate melt structure. The expected S solubility in the ascending magma is calculated using the expanded model. Because the negative pressure dependence of S solubility is more influential than the positive temperature dependence, decompression and adiabatic ascent of a formerly S-saturated silicate magma will lead to S undersaturation. A primitive magma that is S-saturated in its source region will, therefore, become S-undersaturated as it ascends to shallower depth. In order to precipitate magmatic sulfides, the magma must first cool and undergo fractional crystallization to reach S saturation. The S content in a metallic liquid that is in equilibrium with a magma ocean that contains approx. 200 ppm S (i.e., Earth's bulk mantle S content) ranges from 5.5 to 12 wt% S. This range of S values encompasses the amount of S (9 to 12 wt%) that would be present in the outer core if S is the light element. Thus, the Earth's proto-mantle could be in equilibrium (in terms of the preserved S abundance) with a core-forming metallic phase.

Effects of atmospheric composition on apparent activation energy of silicate weathering: I. Model formulation

NASA Astrophysics Data System (ADS)

Kanzaki, Yoshiki; Murakami, Takashi

2018-07-01

We have developed a weathering model to comprehensively understand the determining factors of the apparent activation energy of silicate weathering in order to better estimate the silicate-weathering flux in the Precambrian. The model formulates the reaction rate of a mineral as a basis, then the elemental loss by summing the reaction rates of whole minerals, and finally the weathering flux from a given weathering profile by integrating the elemental losses along the depth of the profile. The rate expressions are formulated with physicochemical parameters relevant to weathering, including solution and atmospheric compositions. The apparent activation energies of silicate weathering are then represented by the temperature dependences of the physicochemical parameters based on the rate expressions. It was found that the interactions between individual mineral-reactions and the compositions of solution and atmosphere are necessarily accompanied by those of temperature-dependence counterparts. Indeed, the model calculates the apparent activation energy of silicate weathering as a function of the temperature dependence of atmospheric CO2 (Δ HCO2‧) . The dependence of the apparent activation energy of silicate weathering on Δ HCO2‧ may explain the empirical dependence of silicate weathering on the atmospheric composition. We further introduce a compensation law between the apparent activation energy and the pre-exponential factor to obtain the relationship between the silicate-weathering flux (FCO2), temperature and the apparent activation energy. The model calculation and the compensation law enable us to predict FCO2 as a function of temperature, once Δ HCO2‧ is given. The validity of the model is supported by agreements between the model prediction and observations of the apparent activation energy and FCO2 in the modern weathering systems. The present weathering model will be useful for the estimation of FCO2 in the Precambrian, for which Δ HCO2‧ can be deduced from the greenhouse effect of atmospheric CO2.

Silicon based substrate with calcium aluminosilicate/thermal barrier layer

NASA Technical Reports Server (NTRS)

Eaton, Jr., Harry Edwin (Inventor); Allen, William Patrick (Inventor); Miller, Robert Alden (Inventor); Jacobson, Nathan S. (Inventor); Smialek, James L. (Inventor); Opila, Elizabeth J. (Inventor); Lee, Kang N. (Inventor); Nagaraj, Bangalore A. (Inventor); Wang, Hongyu (Inventor); Meschter, Peter Joel (Inventor)

2001-01-01

A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a calcium alumino silicate.

Silicon based substrate with environmental/thermal barrier layer

NASA Technical Reports Server (NTRS)

Eaton, Jr., Harry Edwin (Inventor); Allen, William Patrick (Inventor); Jacobson, Nathan S. (Inventor); Bansal, Narottam P. (Inventor); Opila, Elizabeth J. (Inventor); Smialek, James L. (Inventor); Lee, Kang N. (Inventor); Spitsberg, Irene T. (Inventor); Wang, Hongyu (Inventor); Meschter, Peter Joel (Inventor)

2002-01-01

A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a barium-strontium alumino silicate.

Silicon based substrate with environmental/ thermal barrier layer

NASA Technical Reports Server (NTRS)

Eaton, Jr., Harry Edwin (Inventor); Allen, William Patrick (Inventor); Jacobson, Nathan S. (Inventor); Bansal, Nanottam P. (Inventor); Opila, Elizabeth J. (Inventor); Smialek, James L. (Inventor); Lee, Kang N. (Inventor); Spitsberg, Irene T. (Inventor); Wang, Hongyu (Inventor); Meschter, Peter Joel (Inventor)

2002-01-01

A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a barium-strontium alumino silicate.

Precise new shock temperatures in forsterite and in silicate liquids: phase transitions and heat capacity at high pressure

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Fat'yanov, O. V.; Su, C.; Ma, X. J.

2017-12-01

Shock temperature measurements in transparent samples provide key constraints on the phase transitions and thermodynamic properties of materials at high pressure and temperature. Such measurements are necessary, for example, to allow equation of state measurements taken along the Hugoniot to be translated to P-V-T space. We have recently completed a detailed study of the accuracy and reproducibility of calibration of our 6-channel fast pyrometer. We have also introduced improved analysis procedures of the time-dependent multi-wavelength radiance signal that avoid the need for a greybody assumption and therefore have better precision than earlier results. This has motivated (a) renewed study of the shock temperature of forsterite in the superheating, partial melting, and complete melting regimes, (b) pre-heated diopside-anorthite glass shock temperature experiments for comparison to pre-heated silicate liquid equation of state results, and (c) new soda-lime glass shock temperature experiments. Single-crystal synthetic forsterite samples were shocked along (100) to pressures between 120 and 210 GPa on the Caltech two-stage light gas gun. Uncertainties on most results are 50 K. Results above the onset of partial melting at 130 GPa are consistent with Lyzenga and Ahrens (1980) data and show a low P-T slope consistent with a partial melting interval. Complete melting may occur, given sufficient time, at about 210 GPa. The experiment at 120-130 GPa is anomalous, showing two-wave structure and time- and wavelength-dependent scattering suggesting a subsolidus phase transition behind the shock front. The amount of super-heating, if any, is far smaller than claimed by Holland and Ahrens (1997). Steady radiation profiles, high emissivity, and consistency from channel to channel provide high precision (±40 K) in diopside-anorthite liquid shocked from just above the glass transition to high pressure. Temperatures are colder than expected for a model with constant heat capacity, providing direct evidence that multicomponent silicate liquids show a major increase in heat capacity in the P-T range appropriate to terrestrial magma oceans (<150 GPa, <5000 K).

Constraining the Depth of the Martian Magma Ocean during Core Formation using Element Partitioning

NASA Astrophysics Data System (ADS)

Wijbrans, Ineke; Tronche, Elodie; van Westrenen, Wim

2010-05-01

The depth of a planetary magma ocean places first order constraints on the thermal state of a young planet. For the Earth, the depth of the magma ocean is mostly constrained by the pressure-temperature conditions at which Fe-rich metal last equilibrated with the bulk silicate Earth (BSE). These equilibration conditions are thought to correspond to the conditions at the terrestrial magma ocean floor, as this is where the metal ponds before sinking to the core. This depth is estimated by combining the BSE contents of siderophile (iron-loving) elements with metal-silicate partition coefficients (D) at high temperatures and pressures [e.g. 1]. The extent and depth of a magma ocean on Mars are hotly debated. In the case of Mars, the sulphur content of the core is significantly higher than for Earth (10-16 wt% sulphur [2]). The presence of sulphur has been shown to have an effect on the metal-silicate partitioning of some siderophile elements [3], but the current data set is insufficient to be of use for direct application to Martian conditions. We have started an experimental programme to constrain siderophile element partition coefficients for Ni and Co between metal and silicate as a function of temperature, pressure and sulphur content in the metal-alloy. For the silicate composition we used a newly proposed bulk silicate Mars (BSM) [4]. We chose the above-mentioned siderophile elements because their BSM concentrations are reasonably known from studies of Martian meteorites. Our aim is to derive new constraints on the depth of the Martian magma ocean and the chemistry accompanying Martian core formation. Experimental methods: The starting material consisted of a 1:1 mixture of silicate glass + quench crystals in the FeO-CaO-MgO-Al2O3-SiO2 (FCMAS) system with a composition based on [4], and metal consisting of FeS, Fe, Ni, Co, FeP3. Four different metal compositions were used with sulphur contents of 0, 5, 15 and 25wt% respectively. Experiments were made in an end-loaded piston-cylinder using graphite-lined Pt capsules. Experiments were performed at 1, 2 and 3 GPa, and at temperatures of 1600 and 1650 °C, for 5hrs. Electron microprobe was used to determine the concentration of major and minor elements in each phase. Results: Preliminary results show that the sulfur content has an effect on the siderophile element partitioning, even within this small range of pressures and temperatures. With these experiments made with realistic conditions for a Martian magma ocean, we will present a new parameterization of metal-silicate D (Ni and Co) depending on pressure, temperature and sulfur content. References: [1] Righter (2003) Ann. Rev. Earth Planet. Sci. 31, 135-174 [2] Schubert (1990) JGR 95, 14095-14104. [3] Jana and Walker (1997) GCA 61, 5255-5277. [4] Khan and Connolly (2008) JGR, 113, E07003.

An unusual slowdown of fast diffusion in a room temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chathoth,; Mamontov, Eugene; Fulvio, Pasquale F

2013-01-01

Using quasielastic neutron scattering in the temperature range from 290 to 350 K, we show that the diffusive motions in a room temperature ionic liquid [H2NC(dma)2][BETI] become faster for a fraction of cations when the liquid is confined in a mesoporous carbon. This applies to both the localized and long-range translational diffusive motions of the highly mobile cations, although the former exhibit an unusual trend of slowing-down as the temperature is increased, until the localized diffusivity is reduced to the bulk ionic liquid value at a temperature of 350 K.

Competing covalent and ionic bonding in Ge-Sb-Te phase change materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Subedi, Alaska; Siegrist, Theo; Singh, David J.

Ge 2Sb 2Te 5 and related phase change materials are highly unusual in that they can be readily transformed between amorphous and crystalline states using very fast melt, quench, anneal cycles, although the resulting states are extremely long lived at ambient temperature. These states have remarkably different physical properties including very different optical constants in the visible in strong contrast to common glass formers such as silicates or phosphates. This behavior has been described in terms of resonant bonding, but puzzles remain, particularly regarding different physical properties of crystalline and amorphous phases. Here we show that there is a strongmore » competition between ionic and covalent bonding in cubic phase providing a link between the chemical basis of phase change memory property and origins of giant responses of piezoelectric materials (PbTiO 3, BiFeO 3). This has important consequences for dynamical behavior in particular leading to a simultaneous hardening of acoustic modes and softening of high frequency optic modes in crystalline phase relative to amorphous. As a result, this different bonding in amorphous and crystalline phases provides a direct explanation for different physical properties and understanding of the combination of long time stability and rapid switching and may be useful in finding new phase change compositions with superior properties.« less

Competing covalent and ionic bonding in Ge-Sb-Te phase change materials

DOE PAGES

Subedi, Alaska; Siegrist, Theo; Singh, David J.; ...

2016-05-19

Ge 2Sb 2Te 5 and related phase change materials are highly unusual in that they can be readily transformed between amorphous and crystalline states using very fast melt, quench, anneal cycles, although the resulting states are extremely long lived at ambient temperature. These states have remarkably different physical properties including very different optical constants in the visible in strong contrast to common glass formers such as silicates or phosphates. This behavior has been described in terms of resonant bonding, but puzzles remain, particularly regarding different physical properties of crystalline and amorphous phases. Here we show that there is a strongmore » competition between ionic and covalent bonding in cubic phase providing a link between the chemical basis of phase change memory property and origins of giant responses of piezoelectric materials (PbTiO 3, BiFeO 3). This has important consequences for dynamical behavior in particular leading to a simultaneous hardening of acoustic modes and softening of high frequency optic modes in crystalline phase relative to amorphous. As a result, this different bonding in amorphous and crystalline phases provides a direct explanation for different physical properties and understanding of the combination of long time stability and rapid switching and may be useful in finding new phase change compositions with superior properties.« less

Competing covalent and ionic bonding in Ge-Sb-Te phase change materials.

PubMed

Mukhopadhyay, Saikat; Sun, Jifeng; Subedi, Alaska; Siegrist, Theo; Singh, David J

2016-05-19

Ge2Sb2Te5 and related phase change materials are highly unusual in that they can be readily transformed between amorphous and crystalline states using very fast melt, quench, anneal cycles, although the resulting states are extremely long lived at ambient temperature. These states have remarkably different physical properties including very different optical constants in the visible in strong contrast to common glass formers such as silicates or phosphates. This behavior has been described in terms of resonant bonding, but puzzles remain, particularly regarding different physical properties of crystalline and amorphous phases. Here we show that there is a strong competition between ionic and covalent bonding in cubic phase providing a link between the chemical basis of phase change memory property and origins of giant responses of piezoelectric materials (PbTiO3, BiFeO3). This has important consequences for dynamical behavior in particular leading to a simultaneous hardening of acoustic modes and softening of high frequency optic modes in crystalline phase relative to amorphous. This different bonding in amorphous and crystalline phases provides a direct explanation for different physical properties and understanding of the combination of long time stability and rapid switching and may be useful in finding new phase change compositions with superior properties.

Isotopic Abundances as Tracers of the Processes of Lunar Formation

NASA Astrophysics Data System (ADS)

Pahlevan, K.

2011-12-01

Ever since Apollo, isotopic abundances have been used as tracers to study lunar formation, in particular, to study the sources of the lunar material. In the last decade, however, a number of isotopic similarities have been observed between the lunar samples and the Earth's mantle such that these two reservoirs are now known to be indistinguishable from one another to high precision for a variety of isotopic tracers. This occurs against the backdrop of a Solar System that exhibits widespread heterogeneity with respect to these tracers, a situation that strongly argues that the source of the lunar material is the silicate Earth. To reconcile this observation with the fact that the Moon is thought to result from the collision of two isotopically distinct planetary bodies, a scenario has emerged in which the material from the Moon-forming impactor and the proto-Earth are homogenized in the aftermath of the giant impact. This takes place via turbulent mixing in the time after the giant impact but before lunar accretion while the Earth-Moon system exists in the form of a continuous, high-temperature fluid. Importantly, this high-temperature phase of the evolution occurs in the presence of at least two phases (liquid + vapor) making possible chemical and isotopic fractionation. While equilibrium isotopic fractionation tends to zero at high temperatures, and the post giant impact environment experiences some of the highest temperatures encountered in the Earth sciences, there are several factors that nevertheless make equilibrium isotope effects important probes of this early evolution. (1) Because the vaporization of silicates involves decomposition reactions, the bonding environment for elements in the liquid is often very different from that in the vapor. This difference makes the magnitude of isotopic fractionation intrinsically large, even at the relevant temperatures. (2) Since the isotopic composition of a silicate liquid and co-existing vapor are distinctly different, if the Moon preferentially forms from the liquid or vapor relative to the Earth, mass-dependent isotopic differences at the planetary scale may arise. The large density contrast between liquid and vapor makes phase separation possible. (3) The precision with which planetary isotopic compositions can be determined has increased such that measurements are sensitive to even small degrees of high-temperature phase separation. Using thermodynamic models of silicate liquids to determine the partial vaporization behavior of the major elements, we will present calculations of isotopic fractionation due to liquid-vapor separation for the elements iron, magnesium, silicon, and oxygen. Improvements in analytical precision have largely settled the question of the source of the lunar material - the Earth's mantle - and isotopic measurements are now beginning to yield insight into the high-temperatures processes operating during lunar formation.

Igneous petrology of the new ureilites Nova 001 and Nullarbor 010

NASA Technical Reports Server (NTRS)

Triman, Allan H.; Berkley, John L.

1994-01-01

The Nova 001 (= Nuevo Mercurio (b)) and Nullarbor 010 meteorites are ureilites, both of which contain euhedral graphite crystals. The bulk of the meteorites are olivine (Fo79) and pyroxenes (Wo9En73Fs18, Wo3En77Fs20), with a few percent graphite and minor amounts of troilite, Ni-Fe metal, and possibly diamond. The rims of olivine grains are reduced (to Fo91) and contain abundant blebs of Fe metal. Silicate mineral grains are equant, anhedral, up to 2 mm across, and lack obvious preferred orientations. Euhedral graphite crystals (to 1 mm x 0.3 mm) are present at silicate grain boundaries, along boundaries and protruding into the silicates, and entirely within silicate mineral grains. Graphite euhedra are also present as radiating clusters and groups of parallel plates grains embedded in olivine; no other ureilite has comparable graphite textures. Minute lumps within graphite grains are possible diamond, inferred to be a result of shock. Other shock effects are limited to undulatory extinction and fracturing. Both ureilites have been weathered significantly. Considering their similar mineralogies, identical mineral compositions, and identical unusual textures, Nova 001 and Nullarbor 010 are probably paired. Based on olivine compositions, Nova 001 and Nullarbor 010 are in Group 1 (FeO-rich) of Berkley et al. (1980). Silicate mineral compositions are consistent with those of others known ureilites. The presence of euhedral graphite crystals within the silicate minerals is consistent with an igneous origin, and suggests that large proportions of silicate magma were present locally and crystallized in situ.

Calculation of Oxygen Fugacity in High Pressure Metal-Silicate Experiments and Comparison to Standard Approaches

NASA Technical Reports Server (NTRS)

Righter, K.; Ghiorso, M.

2009-01-01

Calculation of oxygen fugacity in high pressure and temperature experiments in metal-silicate systems is usually approximated by the ratio of Fe in the metal and FeO in the silicate melt: (Delta)IW=2*log(X(sub Fe)/X(sub FeO)), where IW is the iron-wustite reference oxygen buffer. Although this is a quick and easy calculation to make, it has been applied to a huge variety of metallic (Fe- Ni-S-C-O-Si systems) and silicate liquids (SiO2, Al2O3, TiO2, FeO, MgO, CaO, Na2O, K2O systems). This approach has surely led to values that have little meaning, yet are applied with great confidence, for example, to a terrestrial mantle at "IW-2". Although fO2 can be circumvented in some cases by consideration of Fe-M distribution coefficient, these do not eliminate the effects of alloy or silicate liquid compositional variation, or the specific chemical effects of S in the silicate liquid, for example. In order to address the issue of what the actual value of fO2 is in any given experiment, we have calculated fO2 from the equilibria 2Fe (metal) + SiO2 (liq) + O2 = Fe2SiO4 (liq).

Preparation of reactive beta-dicalcium silicate

DOEpatents

Shen, M.S.; Chen, J.M.; Yang, R.T.

1980-02-28

This invention relates to the preparation of fine particles of reactive beta-dicalcium silicate by means of a solid state process which comprises firing a mixture of calcium sulfate, silica, and a reducing additive selected from the group consisting of calcium sulfide, carbon, carbon monoxide, methane, and hydrogen, at a temperature of about 850 to 1000/sup 0/C. A carrier gas such as nitrogen or carbon dioxide may also be added, if desired. A high concentration of sulfur dioxide is a by-product of this process.

Preparation of reactive beta-dicalcium silicate

DOEpatents

Shen, Ming-Shing; Chen, James M.; Yang, Ralph T.

1982-01-01

This invention relates to the preparation of fine particles of reactive beta-dicalcium silicate by means of a solid state process which comprises firing a mixture of calcium sulfate, silica and a reducing additive selected from the group consisting of calcium sulfide, carbon, carbon monoxide, methane and hydrogen, at a temperature of about 850.degree.-1000.degree. C. A carrier gas such as nitrogen or carbon dioxide may also be added, if desired. A high concentration of sulfur dioxide is a by-product of this process.

Potential Applications of Alkali-Activated Alumino-Silicate Binders in Military Operations

DTIC Science & Technology

1985-11-01

Geopolymers for Reinforced Plastics/ Composits ," PACTEC 󈨓, Society of Plastic Engineers, Costa Mesa, CA, 1979, pp. 151-153. Davidovits, Joseph. 1983...34 Geopolymers II, Processing and Applications of Ultra-High Temperature, Inorganic Matrix Resin for Cast Composite Structures, Molds and Tools for RP/C and...alumino-silicate hydrates with an approximate composition of 3CaO - AI20 3 • 2i0 2 2120, begin to crystallize. As the gels begin to coalesce, bound water

Silicon based substrate with calcium aluminosilicate environmental/thermal barrier layer

NASA Technical Reports Server (NTRS)

Eaton, Jr., Harry Edwin (Inventor); Allen, William Patrick (Inventor); Miller, Robert Alden (Inventor); Jacobson, Nathan S. (Inventor); Smialek, James L. (Inventor); Opila, Elizabeth J. (Inventor); Lee, Kang N. (Inventor); Nagaraj, Bangalore A. (Inventor); Wang, Hongyu (Inventor); Meschter, Peter Joel (Inventor)

2001-01-01

A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a calcium alumino silicate.

Leakage conduction behavior in electron-beam-cured nanoporous silicate films

NASA Astrophysics Data System (ADS)

Liu, Po-Tsun; Tsai, T. M.; Chang, T. C.

2005-05-01

This letter explores the application of electron-beam curing on nanoporous silicate films. The electrical conduction mechanism for the nanoporous silicate film cured by electron-beam radiation has been studied with metal-insulator-semiconductor capacitors. Electrical analyses over a varying temperature range from room temperature to 150°C provide evidence for space-charge-limited conduction in the electron-beam-cured thin film, while Schottky-emission-type leaky behavior is seen in the counterpart typically cured by a thermal furnace. A physical model consistent with electrical analyses is also proposed to deduce the origin of conduction behavior in the nanoporous silicate thin film.

Core formation conditons in planetesimals: constraints from isotope fractionation experiments.

NASA Astrophysics Data System (ADS)

Guignard, J.; Quitté, G.; Toplis, M. J.; Poitrasson, F.

2016-12-01

Planetesimals are small objects (10 to 1000 km) early accreted in the history of the solar system which show a wide variety of thermal history due to the initial amount of radiogenic elements [1] (26Al and 60Fe), from a simple metamorphism to a complete metal-silicate differentiation. Moreover, isotope compositions of siderophile element, e.g. Fe, Ni, and W in meteorites spread on a range that can be attributed to the process of core-mantle segregation. We therefore performed isotope fractionation experiments of nickel and tungsten between metal and silicate in a gas-mixing (CO-CO2) vertical furnace, at different temperatures (from 1270°C to 1600°C), oxygen fugacity (from IW+2 to IW-6) and annealing times (from 20 minutes to 48 hours). The starting silicate is an anorthite-diopside eutectic composition glass, synthesize from the respective oxides. The starting metal is either a nickel or tungsten wire according to the element to study. After each experiment, metal and silicate are mechanically separated and digested in acids. Nickel and Tungsten separation have been made according to the methods developed by [2] and [3] and isotopes measurements have been made using a high resolution MC-ICP-MS (Neptune; Thermofisher©). Results show evidence for a strong kinetic isotope fractionation during the first annealing times with a faster diffusion of lightest isotopes than heaviest. Similar mechanism has been already highlighted for iron isotope fractionation between silicate and metal [4]. Chemical and isotopic equilibrium is also reached in our experiments but the time required dependent on the conditions of temperature and oxygen fugacity. Therefore, at equilibrium, metal-silicate isotope fractionation has also been quantified as well its temperature dependence. These experimental data can be used in order to bring new constraints on the metal silicate segregation in the planetesimals early accreted. [1] Lee T., et al., GRL, 3, 41-44 (1976) [2] Quitté G., and Oberli F., JAAS, 21, 1249-1255 (2006) [3] Breton T., and Quitté G., JAAS, 29, 2284-2293 (2014) [4] Roskosz M., et al., EPSL, 248, 851-867 (2006)

Transport and thermodynamic properties of hydrous melts in the system An-Di.

NASA Astrophysics Data System (ADS)

Giordano, D.; Potuzak, M.; Romano, C.; Russell, J. K.; Nowak, M.; Dingwell, D. B.

2006-12-01

The thermodynamic and transport properties hydrous silicate melts are of fundamental importance for characterization of the dynamics and energetics associated with silicate melts in the Earth. The literature concerning the transport and calorimetric properties of hydrous silicate melts remains scarce. With few exceptions little has been effectively done in order to provide chemical models that bridge the gap between the description of both complex and simple systems. The An-Di system is of general interest to geochemists as well as petrologists because it serves as a simple analogue for basaltic compositions. It was chosen here due to the combination of its simple chemical description and the presence of an extensive database of published experimental data on both its transport and thermodynamic properties. We have measured the viscosity (η)), the glass transition temperatures (Tg) and the heat capacity (Cp) of silicate melts in the An-Di system containing up to 3 wt.% of dissolved H2O. Viscosity data were obtained by using the dilatometric method of micropenetration, whereas a differential scanning calorimeter (DSC) was employed to determine the glass transition temperatures and the heat capacities. In order to characterize the well-known cooling/heating rate dependence of the glass transition temperatures the calorimetric measurements were performed at heating/cooling rate of 5, 10, 15 and 20 K/min. These results together with those of previous experimental studies have been used to provide a compositional model capable of calculating the Newtonian viscosity of melts as well as the Tg and Cp values for the An- Di+H2O system. The non-Arrhenian T-dependence of viscosity is accounted for by the Vogel-Fulcher- Tammann (VFT) and the Adam Gibbs (AG) equations. Our optimizations assume a common, high-T limit (A) for silicate melt viscosity, consistent with values provided by both theoretical and experimental studies. In particular, we also show that glass transition temperatures taken at each single heating/cooling rate are associated to single viscosity values. The equivalence of the activation energy associated to viscous and enthalpic relaxation process at specific temperatures also allow us to calibrate a tool to predict the viscosity of silicate melts by using specific heat curves. The effect of water on the heat capacity of the glass (Cpglass), from dry to nearly 3 wt% H2O, ranges from almost absent up to 20% of the measured Cp,glass values.

Sensitivities of Earth's core and mantle compositions to accretion and differentiation processes

NASA Astrophysics Data System (ADS)

Fischer, Rebecca A.; Campbell, Andrew J.; Ciesla, Fred J.

2017-01-01

The Earth and other terrestrial planets formed through the accretion of smaller bodies, with their core and mantle compositions primarily set by metal-silicate interactions during accretion. The conditions of these interactions are poorly understood, but could provide insight into the mechanisms of planetary core formation and the composition of Earth's core. Here we present modeling of Earth's core formation, combining results of 100 N-body accretion simulations with high pressure-temperature metal-silicate partitioning experiments. We explored how various aspects of accretion and core formation influence the resulting core and mantle chemistry: depth of equilibration, amounts of metal and silicate that equilibrate, initial distribution of oxidation states in the disk, temperature distribution in the planet, and target:impactor ratio of equilibrating silicate. Virtually all sets of model parameters that are able to reproduce the Earth's mantle composition result in at least several weight percent of both silicon and oxygen in the core, with more silicon than oxygen. This implies that the core's light element budget may be dominated by these elements, and is consistent with ≤1-2 wt% of other light elements. Reproducing geochemical and geophysical constraints requires that Earth formed from reduced materials that equilibrated at temperatures near or slightly above the mantle liquidus during accretion. The results indicate a strong tradeoff between the compositional effects of the depth of equilibration and the amounts of metal and silicate that equilibrate, so these aspects should be targeted in future studies aiming to better understand core formation conditions. Over the range of allowed parameter space, core and mantle compositions are most sensitive to these factors as well as stochastic variations in what the planet accreted as a function of time, so tighter constraints on these parameters will lead to an improved understanding of Earth's core composition.

3D-Printed Bioactive Ca3SiO5 Bone Cement Scaffolds with Nano Surface Structure for Bone Regeneration.

PubMed

Yang, Chen; Wang, Xiaoya; Ma, Bing; Zhu, Haibo; Huan, Zhiguang; Ma, Nan; Wu, Chengtie; Chang, Jiang

2017-02-22

Silicate bioactive materials have been widely studied for bone regeneration because of their eminent physicochemical properties and outstanding osteogenic bioactivity, and different methods have been developed to prepare porous silicate bioactive ceramics scaffolds for bone-tissue engineering applications. Among all of these methods, the 3D-printing technique is obviously the most efficient way to control the porous structure. However, 3D-printed bioceramic porous scaffolds need high-temperature sintering, which will cause volume shrinkage and reduce the controllability of the pore structure accuracy. Unlike silicate bioceramic, bioactive silicate cements such as tricalcium silicate (Ca 3 SiO 5 and C 3 S) can be self-set in water to obtain high mechanical strength under mild conditions. Another advantage of using C 3 S to prepare 3D scaffolds is the possibility of simultaneous drug loading. Herein, we, for the first time, demonstrated successful preparation of uniform 3D-printed C 3 S bone cement scaffolds with controllable 3D structure at room temperature. The scaffolds were loaded with two model drugs and showed a loading location controllable drug-release profile. In addition, we developed a surface modification process to create controllable nanotopography on the surface of pore wall of the scaffolds, which showed activity to enhance rat bone-marrow stem cells (rBMSCs) attachment, spreading, and ALP activities. The in vivo experiments revealed that the 3D-printed C 3 S bone cement scaffolds with nanoneedle-structured surfaces significantly improved bone regeneration, as compared to pure C 3 S bone cement scaffolds, suggesting that 3D-printed C 3 S bone cement scaffolds with controllable nanotopography surface are bioactive implantable biomaterials for bone repair.

Partitioning of Ru, Rh, Pd, Re, Ir and Pt between liquid metal and silicate at high pressures and high temperatures - Implications for the origin of highly siderophile element concentrations in the Earth's mantle

NASA Astrophysics Data System (ADS)

Mann, Ute; Frost, Daniel J.; Rubie, David C.; Becker, Harry; Audétat, Andreas

2012-05-01

The apparent overabundance of the highly siderophile elements (HSEs: Pt-group elements, Re and Au) in the mantles of Earth, Moon and Mars has not been satisfactorily explained. Although late accretion of a chondritic component seems to provide the most plausible explanation, metal-silicate equilibration in a magma ocean cannot be ruled out due to a lack of HSE partitioning data suitable for extrapolations to the relevant high pressure and high temperature conditions. We provide a new data set of partition coefficients simultaneously determined for Ru, Rh, Pd, Re, Ir and Pt over a range of 3.5-18 GPa and 2423-2773 K. In multianvil experiments, molten peridotite was equilibrated in MgO single crystal capsules with liquid Fe-alloy that contained bulk HSE concentrations of 53.2-98.9 wt% (XFe = 0.03-0.67) such that oxygen fugacities of IW - 1.5 to IW + 1.6 (i.e. logarithmic units relative to the iron-wüstite buffer) were established at run conditions. To analyse trace concentrations of the HSEs in the silicate melt with LA-ICP-MS, two silicate glass standards (1-119 ppm Ru, Rh, Pd, Re, Ir, Pt) were produced and evaluated for this study. Using an asymmetric regular solution model we have corrected experimental partition coefficients to account for the differences between HSE metal activities in the multicomponent Fe-alloys and infinite dilution. Based on the experimental data, the P and T dependence of the partition coefficients (D) was parameterized. The partition coefficients of all HSEs studied decrease with increasing pressure and to a greater extent with increasing temperature. Except for Pt, the decrease with pressure is stronger below ˜6 GPa and much weaker in the range 6-18 GPa. This change might result from pressure induced coordination changes in the silicate liquid. Extrapolating the D values over a large range of potential P-T conditions in a terrestrial magma ocean (peridotite liquidus at P ⩽ 60-80 GPa) we conclude that the P-T-induced decrease of D would not have been sufficient to explain HSE mantle abundances by metal-silicate equilibration at a common set of P-T-oxygen fugacity conditions. Therefore, the mantle concentrations of most HSEs cannot have been established during core formation. The comparatively less siderophile Pd might have been partly retained in the magma ocean if effective equilibration pressures reached 35-50 GPa. To a much smaller extent this could also apply to Pt and Rh providing that equilibration pressures reached ⩾60 GPa in the late stage of accretion. With most of the HSE partition coefficients at 60 GPa still differing by 0.5-3 orders of magnitude, metal-silicate equilibration alone cannot have produced the observed near-chondritic HSE abundances of the mantles of the Earth as well as of the Moon or Mars. Our results show that an additional process, such as the accretion of a late veneer composed of some type of chondritic material, was required. The results, therefore, support recent hybrid models, which propose that the observed HSE signatures are a combined result of both metal-silicate partitioning as well as an overprint by late accretion.

Evidence for a Dying Magma Chamber at Rábida Island, Galápagos

NASA Astrophysics Data System (ADS)

Bercovici, H.; Geist, D.; Harpp, K. S.; Almeida, M.

2015-12-01

Rábida Island in the Galapagos has experienced both explosive and effusive volcanism. It is located to the east of the most active volcanoes of the Galapagos, and previously determined ages range from 0.9 to 1.1 Ma. An unusually curved escarpment cuts the western sector of the island, which might be part of a caldera wall, although its radius of curvature is much greater than that of the island. Lavas range from basalt to rhyolite, and there are also several intermediate compositions, which are unique in the archipelago. A welded ignimbrite crops out in northeast sector, the only such deposit known in the entire region. The volumetric proportion of evolved rocks is unusually high; 25% of the rocks in our comprehensive sample set are intermediate to felsic. The siliceous rocks occur in two clusters in the southern and southwestern sections of the island, suggesting two separate sources. The intermediate rocks are concentrated in the center and northwestern parts of the island. Despite these foci of more siliceous lavas, basalt is the most widespread rock type across the island. It is notable that Rabida is immediately east of Volcan Alcedo, which is the only active Galápagos volcano that has also erupted rhyolite, and south of Santiago Island, which erupted the trachyte dome observed by Charles Darwin in 1835. These observations, in conjunction with the cumulate xenoliths observed in Rábida explosive deposits, are consistent with the evolved rocks resulting from fractional crystallization of a dying magma chamber, as the volcano is carried away from the hotspot.

High temperature structural insulating material

DOEpatents

Chen, Wayne Y.

1987-01-06

A high temperature structural insulating material useful as a liner for cylinders of high temperature engines through the favorable combination of high service temperature (above about 800.degree. C.), low thermal conductivity (below about 0.2 W/m.degree. C.), and high compressive strength (above about 250 psi). The insulating material is produced by selecting hollow ceramic beads with a softening temperature above about 800.degree. C., a diameter within the range of 20-200 .mu.m, and a wall thickness in the range of about 2-4 .mu.m; compacting the beads and a compatible silicate binder composition under pressure and sintering conditions to provide the desired structural form with the structure having a closed-cell, compact array of bonded beads.

High temperature structural insulating material

DOEpatents

Chen, Wayne Y.

1987-01-01

A high temperature structural insulating material useful as a liner for cylinders of high temperature engines through the favorable combination of high service temperature (above about 800.degree. C.), low thermal conductivity (below about 0.2 W/m.degree. C.), and high compressive strength (above about 250 psi). The insulating material is produced by selecting hollow ceramic beads with a softening temperature above about 800.degree. C., a diameter within the range of 20-200 .mu.m, and a wall thickness in the range of about 2-4 .mu.m; compacting the beads and a compatible silicate binder composition under pressure and sintering conditions to provide the desired structural form with the structure having a closed-cell, compact array of bonded beads.

AC electrical breakdown phenomena of epoxy/layered silicate nanocomposite in needle-plate electrodes.

PubMed

Park, Jae-Jun; Lee, Jae-Young

2013-05-01

Epoxy/layered silicate nanocomposite for the insulation of heavy electric equipments were prepared by dispersing 1 wt% of a layered silicate into an epoxy matrix with a homogenizing mixer and then AC electrical treeing and breakdown tests were carried out. Wide-angle X-ray diffraction (WAXD) analysis and transmission electron microscopy (TEM) observation showed that nano-sized monolayers were exfoliated from a multilayered silicate in the epoxy matrix. When the nano-sized silicate layers were incorporated into the epoxy matrix, the breakdown rate in needle-plate electrode geometry was 10.6 times lowered than that of the neat epoxy resin under the applied electrical field of 520.9 kV/mm at 30 degrees C, and electrical tree propagated with much more branches in the epoxy/layered silicate nanocomposite. These results showed that well-dispersed nano-sized silicate layers retarded the electrical tree growth rate. The effects of applied voltage and ambient temperature on the tree initiation, growth, and breakdown rate were also studied, and it was found that the breakdown rate was largely increased, as the applied voltage and ambient temperature increased.

Venusian pancake domes: Insights from terrestrial voluminous silicic lavas and thermal modeling

NASA Technical Reports Server (NTRS)

Manley, Curtis R.

1993-01-01

The so-called 'pancake' domes, and several other volcanoes on Venus, appear to represent large extrusions of silicic lava. Similar voluminous rhyolite lava flows, often associated with mantle plumes, are known on Earth. Venus' high ambient temperature, and insulation by the dome's brecciated carapace, both act to prolong cooling of a dome's interior, allowing for episodic lava input over an extended period of time. Field relations and aspect ratios of terrestrial voluminous rhyolite lavas imply continuous, non-episodic growth, reflecting tapping of a large volume of dry, anatectic silicic magma. Petrogenetically, the venusian domes may be analogous to chains of small domes on Earth, which represent 'leakage' of evolved material from magma bodies fractionating from much more mafic liquids.

High temperature sorbents for oxygen

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor)

1994-01-01

A sorbent capable of removing trace amounts of oxygen (ppt) from a gas stream at a high temperature above 200 C comprising a porous alumina silicate support, such as zeolite, containing from 1 to 10 percent by weight of ion exchanged transition metal, such as copper or cobalt ions, and 0.05 to 1.0 percent by weight of an activator selected from a platinum group metal such as platinum is described. The activation temperature, oxygen sorption, and reducibility are all improved by the presence of the platinum activator.

Lunar and Planetary Science XXXV: Terrestrial Planets: Building Blocks and Differentiation

NASA Technical Reports Server (NTRS)

2004-01-01

The session "Terrestrial Planets: Building Blocks and Differentiation: included the following topics:Magnesium Isotopes in the Earth, Moon, Mars, and Pallasite Parent Body: High-Precision Analysis of Olivine by Laser-Ablation Multi-Collector ICPMS; Meteoritic Constraints on Collision Rates in the Primordial Asteroid Belt and Its Origin; New Constraints on the Origin of the Highly Siderophile Elements in the Earth's Upper Mantle; Further Lu-Hf and Sm-Nd Isotopic Data on Planetary Materials and Consequences for Planetary Differentiation; A Deep Lunar Magma Ocean Based on Neodymium, Strontium and Hafnium Isotope Mass Balance Partial Resetting on Hf-W System by Giant Impacts; On the Problem of Metal-Silicate Equilibration During Planet Formation: Significance for Hf-W Chronometry ; Solid Metal-Liquid Metal Partitioning of Pt, Re, and Os: The Effect of Carbon; Siderophile Element Abundances in Fe-S-Ni-O Melts Segregated from Partially Molten Ordinary Chondrite Under Dynamic Conditions; Activity Coefficients of Silicon in Iron-Nickel Alloys: Experimental Determination and Relevance for Planetary Differentiation; Reinvestigation of the Ni and Co Metal-Silicate Partitioning; Metal/Silicate Paritioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition; and Closure of the Fe-S-Si Liquid Miscibility Gap at High Pressure and Its Implications for Planetary Core Formation.

Formation of brucite and cronstedtite-bearing mineral assemblages on Ceres

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Yu.

2014-01-01

Dwarf planet Ceres is the largest body in the main asteroid belt with a rocky surface and uncertain internal structure. Spectra of Ceres in near- and mid-infrared wavelengths are consistent with the occurrence of brucite, Mg-bearing carbonates, and an Fe-rich phyllosilicate cronstedtite. Spectra of 10 Hygiea and 324 Bamberga imply similar compositions. Here, we considered stabilities of these minerals to constrain their origin. Cronstedtite is most stable at the temperature of ˜0 °C at moderately oxidizing aqueous conditions and at high water/rock ratios. Although cronstedtite could form on planetesimals, the apparent lack of serpentine may indicate its formation by Ceres' temporary surface solutions. Brucite forms at a low activity of dissolved SiO2, at a low fugacity of CO2, and at highly alkaline pH. Brucite and cronstedtite do not form together and may not form deep in the Ceres' interior. The absence of Mg serpentine from Ceres' surface materials and the unlikely occurrence of very olivine-rich rocks do not indicate a formation of brucite through serpentinization of such rocks. Brucite could form by transient near-surface fluids which do not equilibrate with silicates. Temporary fluids could deposit Mg carbonates before, after, or together with brucite at near-surface conditions that favor CO2 degassing. Regardless of Ceres' internal structure, internal thermal and aqueous processes may not affect cold near-surface layers. Percolation of interior fluids is not consistent with the lack of detection of low-solubility salts. However, impacts of ice-rich targets during the Late Heavy Bombardment could account for transient aqueous environments and unusual surface mineralogies of Ceres, Hygiea, and Bamberga. Brucite and Mg carbonates could have formed through hydration and carbonation of MgO evaporated from silicates. Apparently abundant carbonates may indicate an ample impact oxidation of organic matter, and the occurrence of brucite with cronstedtite may reflect turbulent and disequilibrium environments. Clay-like homogeneous surface materials on Ceres could be gravitationally sorted deposits of impact clouds.

Iron isotopic fractionation between silicate mantle and metallic core at high pressure

PubMed Central

Liu, Jin; Dauphas, Nicolas; Roskosz, Mathieu; Hu, Michael Y.; Yang, Hong; Bi, Wenli; Zhao, Jiyong; Alp, Esen E.; Hu, Justin Y.; Lin, Jung-Fu

2017-01-01

The +0.1‰ elevated 56Fe/54Fe ratio of terrestrial basalts relative to chondrites was proposed to be a fingerprint of core-mantle segregation. However, the extent of iron isotopic fractionation between molten metal and silicate under high pressure–temperature conditions is poorly known. Here we show that iron forms chemical bonds of similar strengths in basaltic glasses and iron-rich alloys, even at high pressure. From the measured mean force constants of iron bonds, we calculate an equilibrium iron isotope fractionation between silicate and iron under core formation conditions in Earth of ∼0–0.02‰, which is small relative to the +0.1‰ shift of terrestrial basalts. This result is unaffected by small amounts of nickel and candidate core-forming light elements, as the isotopic shifts associated with such alloying are small. This study suggests that the variability in iron isotopic composition in planetary objects cannot be due to core formation. PMID:28216664

CUMULATE ROCKS ASSOCIATED WITH CARBONATE ASSIMILATION, HORTAVÆR COMPLEX, NORTH-CENTRAL NORWAY

NASA Astrophysics Data System (ADS)

Barnes, C. G.; Prestvik, T.; Li, Y.

2009-12-01

The Hortavær igneous complex intruded high-grade metamorphic rocks of the Caledonian Helgeland Nappe Complex at ca. 466 Ma. The complex is an unusual mafic-silicic layered intrusion (MASLI) because the principal felsic rock type is syenite and because the syenite formed in situ rather than by deep-seated partial melting of crustal rocks. Magma differentiation in the complex was by assimilation, primarily of calc-silicate rocks and melts with contributions from marble and semi-pelites, plus fractional crystallization. The effect of assimilation of calcite-rich rocks was to enhance stability of fassaitic clinopyroxene at the expense of olivine, which resulted in alkali-rich residual melts and lowering of silica activity. This combination of MASLI-style emplacement and carbonate assimilation produced three types of cumulate rocks: (1) Syenitic cumulates formed by liquid-crystal separation. As sheets of mafic magma were loaded on crystal-rich syenitic magma, residual liquid was expelled, penetrating the overlying mafic sheets in flame structures, and leaving a cumulate syenite. (2) Reaction cumulates. Carbonate assimilation, illustrated by a simple assimilation reaction: olivine + calcite + melt = clinopyroxene + CO2 resulted in cpx-rich cumulates such as clinopyroxenite, gabbro, and mela-monzodiorite, many of which contain igneous calcite. (3) Magmatic skarns. Calc-silicate host rocks underwent partial melting during assimilation, yielding a Ca-rich melt as the principal assimilated material and permitting extensive reaction with surrounding magma to form Kspar + cpx + garnet-rich ‘cumulate’ rocks. Cumulate types (2) and (3) do not reflect traditional views of cumulate rocks but instead result from a series of melt-present discontinuous (peritectic) reactions and partial melting of calc-silicate xenoliths. In the Hortavær complex, such cumulates are evident because of the distinctive peritectic cumulate assemblages. It is unclear whether assimilation of ‘normal’ silicate rocks results in peritectic assemblages, or whether they could be identified as such if they exist.

Rapid thermal rejuvenation of high-crystallinity magma linked to porphyry copper deposit formation; evidence from the Koloula Porphyry Prospect, Solomon Islands

NASA Astrophysics Data System (ADS)

Tapster, S.; Condon, D. J.; Naden, J.; Noble, S. R.; Petterson, M. G.; Roberts, N. M. W.; Saunders, A. D.; Smith, D. J.

2016-05-01

Magmas containing the components needed to form porphyry copper deposits are relatively common within arcs, yet mineralising events are uncommon within the long-lived magmatic systems that host them. Understanding what causes the transition from barren to productive intrusions is critical to the development of conceptual deposit models. We have constrained the tempo of pre- and syn-mineralisation magmatic events in relationship to the thermal evolution of the plutonic body that underlies one of the world's youngest exposed plutonic-porphyry systems, the Inamumu Zoned Pluton, Koloula Porphyry Prospect, Solomon Islands. High precision ID-TIMS U-Pb dates of texturally and chemically characterised zircons indicate pluton emplacement over <150 kyr was superseded after ca. 50 kyr by two discrete episodes of mineralising porphyritic melt emplacement. Their associated hydrothermal systems initiated within ca. 30 kyrs of each other. Zircon populations within evolved intrusions contain resorbed cores that were recycled from the deeper magmatic system, yet their youngest dates are statistically indistinguishable from those yielded by crystals lacking resorption. Comparisons of Ti-in-zircon proxy temperatures, modelled zircon saturation temperatures and temperature-crystallinity relationships suggest that prior to being heated and emplaced within the shallow level pluton, magmas were stored at depth in a high-crystallinity (>50% crystals) state, past the point of rheological lock-up. We estimate that thermal rejuvenation of the deeper high-crystallinity magma and generation of a mobile melt fraction may have occurred ≤10 kyr before its transport and emplacement within the porphyry environment. The underlying pluton likely cooled and returned to high-crystallinity states prior to subsequent remobilisation-emplacement events. Titanium-in-zircon geothermometry and whole-rock geochemistry suggest pre-mineralisation intrusions were remobilised by mixing of a silicic magma with a high-temperature, less-evolved melt. In contrast, syn-mineralisation melts were most likely remobilised by the percolation of hot volatiles exsolved from contemporaneous less-evolved intrusions cooling beneath the crystalline silicic magma. The evidence for the rapid thermal rejuvenation and long term storage of highly crystalline silicic magmas is consistent with previous studies that indicate two components of exsolved volatiles contribute to ore forming fluids. We conclude that the liberation of crystal-rich porphyry copper deposit forming magmas, and the addition of the chemical components required for ore formation, are intrinsically linked to the volatiles released during the recharge of less-evolved melt into a highly crystalline silicic magma.

The effect of thermal and organic additive in morphology of ceramic based silicate

NASA Astrophysics Data System (ADS)

Ginting, J.; Bangun, N.; Sembiring, H. Br; Putri, N. K.

2017-04-01

M-Silicate (M = Mg, Ca) has been prepared by exchange metal reaction from M-Chloride salts and sodium silicate. The resulting white solid of chloride salts then heated at 700, 800, 900 and 1000 °C. Due to increase the porosity of M-Silicate, 1,2-propanediol, oleic acid and glycerol were added, then formed M-silicates were heated at 800 °C. Then, obtained white solid M-Silicates were characterized by Scanning Electron Microscopy (SEM). SEM images show the variance of surface morphology when the temperature increases. The addition of organic compounds is involved in surface modification.

MG Isotopic Measurement of FIB-Isolated Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

Messenger, Scott R.; Nguyen, A.; Ito, M.; Rahman, Z.

2010-01-01

The majority of presolar oxide and silicate grains are ascribed to origins in low-mass red giant and asymptotic giant branch (AGB) stars based on their O isotopic ratios. However, a minor population of these grains (< 10%) has O isotopic ratios incompatible with these sources. Two principle alternative sources are higher-than-solar metallicity (Z) stars or, more likely, supernovae (SN) [1-3]. These rare (Group 4) grains [3] are characterized by enrichments in O-18, and typically also enrichments in O-17. An even rarer subset of grains with extremely large enrichments in O-17 and smaller depletions in O-18 were suggested to come from binary star systems [2]. To establish the origins of these isotopically unusual grains, it is necessary to examine isotopic systems in addition to O. Presolar silicates offer several elements diagnostic of their stellar sources and nuclear processes, including O, Si, Mg, Fe and Ca. However, the database for minor element isotopic compositions in silicates is seriously lacking. To date only two silicate grains have been analyzed for Mg [4] or Fe [5]. One major complicating factor is their small size (average 230 nm), which greatly limits the number of measurements that can be performed on any one grain and makes it more difficult to obtain statistically relevant data. This problem is compounded because the grains are identified among isotopically solar silicates, which contribute a diluting signal in isotopic measurements [1]. Thus, relatively small isotopic anomalies are missed due to this dilution effect. By applying focused ion beam (FIB) milling, we obtain undiluted Mg isotopic ratios of isolated rare presolar silicate grains to investigate their sources.

Is Tridymite at Gale Crater Evidence for Silicic Volcanism on Mars?

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Vaniman, David T.; Ming, Douglas W.; Graff, Trevor G.; Downs, Robert T.; Fendrich, Kim; Mertzman, Stanley A.

2016-01-01

The X-ray diffraction (XRD) instrument (CheMin) onboard the MSL rover Curiosity detected 17 wt% of the SiO2 polymorph tridymite (relative to bulk sample) for the Buckskin drill sample (73 wt% SiO2) obtained from sedimentary rock in the Murray formation at Gale Crater, Mars. Other detected crystalline materials are plagioclase, sanidine, cristobalite, cation-deficient magnetite, and anhydrite. XRD amorphous material constitutes approx. 60 wt% of bulk sample, and the position of its broad diffraction peak near approx. 26 deg. 2-theta is consistent with opal-A. Tridymite is a lowpressure, high-temperature mineral (approx. 870 to 1670 deg. C) whose XRD-identified occurrence on the Earth is usually associated with silicic (e.g., rhyolitic) volcanism. High SiO2 deposits have been detected at Gale crater by remote sensing from martian orbit and interpreted as opal-A on the basis H2O and Si-OH spectral features. Proposed opal-A formation pathways include precipitation of silica from lake waters and high-SiO2 residues of acid-sulfate leaching. Tridymite is nominally anhydrous and would not exhibit these spectral features. We have chemically and spectrally analyzed rhyolitic samples from New Mexico and Iwodake volcano (Japan). The glassy (by XRD) NM samples have H2O spectral features similar to opal-A. The Iwodake sample, which has been subjected to high-temperature acid sulfate leaching, also has H2O spectral features similar to opal-A. The Iwodake sample has approx. 98 wt% SiO2 and 1% wt% TiO2 (by XRF), tridymite (>80 wt.% of crystalline material without detectable quartz by XRD), and H2O and Si-OH spectral features. These results open the working hypothesis that the opal-A-like high-SiO2 deposits at Gale crater detected from martian orbit are products of alteration associated with silicic volcanism. The presence or absence of tridymite will depend on lava crystallization temperatures (NM) and post crystallization alteration temperatures (Iwodake).

Partitioning of Oxygen During Core Formation on Earth and Mars

NASA Astrophysics Data System (ADS)

Rubie, D. C.; Gessmann, C. K.; Frost, D. J.

2003-12-01

Core formation on Earth and Mars involved the physical separation of Fe-Ni metal alloy from silicate, most likely in deep magma oceans. Although core-formation models explain many aspects of mantle geochemistry, they do not account for large differences between the compositions of the mantles of Earth ( ˜8 wt% FeO) and Mars ( ˜18 wt% FeO) or the much smaller mass fraction of the Martian core. Here we explain these differences using new experimental results on the solubility of oxygen in liquid Fe-Ni alloy, which we have determined at 5-23 GPa, 2100-2700 K and variable oxygen fugacities using a multianvil apparatus. Oxygen solubility increases with increasing temperature and oxygen fugacity and decreases with increasing pressure. Thus, along a high temperature adiabat (e.g. after formation of a deep magma ocean on Earth), oxygen solubility is high at depths up to about 2000 km but decreases strongly at greater depths where the effect of high pressure dominates. For modeling oxygen partitioning during core formation, we assume that Earth and Mars both accreted from oxidized chondritic material with a silicate fraction initially containing around 18 wt% FeO. In a terrestrial magma ocean, 1200-2000 km deep, high temperatures resulted in the extraction of FeO from the silicate magma ocean, due to the high solubility of oxygen in the segregating metal, leaving the mantle with its present FeO content of ˜8 wt%. Lower temperatures of a Martian magma ocean resulted in little or no extraction of FeO from the mantle, which thus remained unchanged at about 18 wt%. The mass fractions of segregated metal are consistent with the mass fraction of the Martian core being small relative to that of the Earth. FeO extracted from the Earth's magma ocean by segregating core-forming liquid may have contributed to chemical heterogeneities in the lowermost mantle, a FeO-rich D'' layer and the light element budget of the core.

Miocene silicic volcanism in southwestern Idaho: Geochronology, geochemistry, and evolution of the central Snake River Plain

USGS Publications Warehouse

Bonnichsen, B.; Leeman, W.P.; Honjo, N.; McIntosh, W.C.; Godchaux, M.M.

2008-01-01

New 40Ar-39Ar geochronology, bulk rock geochemical data, and physical characteristics for representative stratigraphic sections of rhyolite ignimbrites and lavas from the west-central Snake River Plain (SRP) are combined to develop a coherent stratigraphic framework for Miocene silicic magmatism in this part of the Yellowstone 'hotspot track'. The magmatic record differs from that in areas to the west and east with regard to its unusually large extrusive volume, broad lateral scale, and extended duration. We infer that the magmatic systems developed in response to large-scale and repeated injections of basaltic magma into the crust, resulting in significant reconstitution of large volumes of the crust, wide distribution of crustal melt zones, and complex feeder systems for individual eruptive events. Some eruptive episodes or 'events' appear to be contemporaneous with major normal faulting, and perhaps catastrophic crustal foundering, that may have triggered concurrent evacuations of separate silicic magma reservoirs. This behavior and cumulative time-composition relations are difficult to relate to simple caldera-style single-source feeder systems and imply complex temporal-spatial development of the silicic magma systems. Inferred volumes and timing of mafic magma inputs, as the driving energy source, require a significant component of lithospheric extension on NNW-trending Basin and Range style faults (i.e., roughly parallel to the SW-NE orientation of the eastern SRP). This is needed to accommodate basaltic inputs at crustal levels, and is likely to play a role in generation of those magmas. Anomalously high magma production in the SRP compared to that in adjacent areas (e.g., northern Basin and Range Province) may require additional sub-lithospheric processes. ?? Springer-Verlag 2007.

Spinodal decomposition in amorphous metal-silicate thin films: Phase diagram analysis and interface effects on kinetics

NASA Astrophysics Data System (ADS)

Kim, H.; McIntyre, P. C.

2002-11-01

Among several metal silicate candidates for high permittivity gate dielectric applications, the mixing thermodynamics of the ZrO2-SiO2 system were analyzed, based on previously published experimental phase diagrams. The driving force for spinodal decomposition was investigated in an amorphous silicate that was treated as a supercooled liquid solution. A subregular model was used for the excess free energy of mixing of the liquid, and measured invariant points were adopted for the calculations. The resulting simulated ZrO2-SiO2 phase diagram matched the experimental results reasonably well and indicated that a driving force exists for amorphous Zr-silicate compositions between approx40 mol % and approx90 mol % SiO2 to decompose into a ZrO2-rich phase (approx20 mol % SiO2) and SiO2-rich phase (>98 mol % SiO2) through diffusional phase separation at a temperature of 900 degC. These predictions are consistent with recent experimental reports of phase separation in amorphous Zr-silicate thin films. Other metal-silicate systems were also investigated and composition ranges for phase separation in amorphous Hf, La, and Y silicates were identified from the published bulk phase diagrams. The kinetics of one-dimensional spinodal decomposition normal to the plane of the film were simulated for an initially homogeneous Zr-silicate dielectric layer. We examined the effects that local stresses and the capillary driving force for component segregation to the interface have on the rate of spinodal decomposition in amorphous metal-silicate thin films.

Lattice thermal conductivity of silicate glasses at high pressures

NASA Astrophysics Data System (ADS)

Chang, Y. Y.; Hsieh, W. P.

2016-12-01

Knowledge of the thermodynamic and transport properties of magma holds the key to understanding the thermal evolution and chemical differentiation of Earth. The discovery of the remnant of a deep magma ocean above the core mantle boundary (CMB) from seismic observations suggest that the CMB heat flux would strongly depend on the thermal conductivity, including lattice (klat) and radiative (krad) components, of dense silicate melts and major constituent minerals around the region. Recent measurements on the krad of dense silicate glasses and lower-mantle minerals show that krad of dense silicate glasses could be significantly smaller than krad of the surrounding solid mantle phases, and therefore the dense silicate melts would act as a thermal insulator in deep lower mantle. This conclusion, however, remains uncertain due to the lack of direct measurements on the lattice thermal conductivity of silicate melts under relevant pressure-temperature conditions. Besides the CMB, magmas exist in different circumstances beneath the surface of the Earth. Chemical compositions of silicate melts vary with geological and geodynamic settings of the melts and have strong influences on their thermal properties. In order to have a better view of heat transport within the Earth, it is important to study compositional and pressure dependences of thermal properties of silicate melts. Here we report experimental results on lattice thermal conductivities of silicate glasses with basaltic and rhyolitic compositions up to Earth's lower mantle pressures using time-domain thermoreflectance coupled with diamond-anvil cell techniques. This study not only provides new data for the thermal conductivity of silicate melts in the Earth's deep interior, but is crucial for further understanding of the evolution of Earth's complex internal structure.

Enantioseparation of angiotensin II receptor type 1 blockers: evaluation of 6-substituted carbamoyl benzimidazoles on immobilized polysaccharide-based chiral stationary phases. Unusual temperature behavior.

PubMed

Su, Ran; Hou, Zhun; Sang, Lihong; Zhou, Zhi-Ming; Fang, Hao; Yang, Xinying

2017-09-15

Enantioseparation of thirteen 6-substituted carbamoyl benzimidazoles by high-performance liquid chromatography (HPLC) was investigated using two immobilized polysaccharide-based chiral stationary phases (CSPs), Chiralpak IC and Chiralpak IA, in normal-phase mode. Most of the examined compounds were completely resolved. The effects of a polar alcohol modifier, analyte structure, and column temperature on the chiral recognition were investigated. Furthermore, the structure-retention relationship was evaluated, and thermodynamic parameters were calculated from plots of ln k' or ln α versus 1/T. The thermodynamic parameters indicated that the separations were enthalpy-driven. Moreover, nonlinear van't Hoff plots were obtained on Chiralpak IA. However, two unusual phenomena were observed: (1) an unusual increase in retention with increasing temperature with linear van't Hoff plots on Chiralpak IC and (2) an extremely high T iso value (i.e., several thousand degrees centigrade). Copyright © 2017 Elsevier B.V. All rights reserved.

High temperature structural insulating material

DOEpatents

Chen, W.Y.

1984-07-27

A high temperature structural insulating material useful as a liner for cylinders of high temperature engines through the favorable combination of high service temperature (above about 800/sup 0/C), low thermal conductivity (below about 0.2 W/m/sup 0/C), and high compressive strength (above about 250 psi). The insulating material is produced by selecting hollow ceramic beads with a softening temperature above about 800/sup 0/C, a diameter within the range of 20-200 ..mu..m, and a wall thickness in the range of about 2 to 4 ..mu..m; compacting the beads and a compatible silicate binder composition under pressure and sintering conditions to provide the desired structural form with the structure having a closed-cell, compact array of bonded beads.

Lunar oxygen and metal for use in near-Earth space: Magma electrolysis

NASA Technical Reports Server (NTRS)

Colson, Russell O.; Haskin, Larry A.

1990-01-01

Because it is energetically easier to get material from the Moon to Earth orbit than from the Earth itself, the Moon is a potentially valuable source of materials for use in space. The unique conditions on the Moon, such as vacuum, absence of many reagents common on the Earth, and the presence of very nontraditional ores suggest that a unique and nontraditional process for extracting materials from the ores may prove the most practical. With this in mind, an investigation of unfluxed silicate electrolysis as a method for extracting oxygen, iron, and silicon from lunar regolith was initiated and is discussed. The advantages of the process include simplicity of concept, absence of need to supply reagents from Earth, and low power and mass requirements for the processing plant. Disadvantages include the need for uninterrupted high temperature and the highly corrosive nature of the high-temperature silicate melts which has made identifying suitable electrode and container materials difficult.

Pristine moon rocks - Apollo 17 anorthosites

NASA Technical Reports Server (NTRS)

Warren, P. H.; Jerde, E. A.; Kallemeyn, G. W.

1991-01-01

New chemical analyses and petrographic descriptions for 10 previously unanalyzed Apollo 17 rock samples are provided. Attention is focused on several that appear to be pristine. All samples were analyzed in INAA using a procedure based on that of Kallemeyn et al. (1989). One sample was found to be unambiguously pristine, and is the first pristine ferroan-anorthositic suite (FAS) sample from Apollo 17. It exhibits extremely low-mg(asterisk) mafic silicates, coupled with relatively sodic plagioclase. It has an unusually high augite/low-Ca pyroxene ratio and contains incompatible trace elements at levels unprecedentedly high compared to FAS anorthosites from the Apollo 14, 15, 16 sites. It is inferred that 74114.5, and Apollo 17 anorthosites in general, formed at a relatively late stage in the evolution of the primordial magmasphere.

The effects of sulfide composition on the solubility of sulfur in coexisting silicate melts

NASA Astrophysics Data System (ADS)

Smythe, Duane; Wood, Bernard; Kiseeva, Ekaterina

2016-04-01

The extent to which sulfur dissolves in silicate melts saturated in an immiscible sulfide phase is a fundamental question in igneous petrology and plays a primary role in the generation of magmatic ore deposits, volcanic degassing and planetary differentiation. Terrestrial sulfide melts often contain over 20 weight percent Ni + Cu, however, most experimental studies investigating sulfur solubility in silicate melt have been primarily concerned with the effects of silicate melt composition, and pure FeS has been use as the immiscible sulfide melt (O'Neill and Mavrogenes, 2002; Li and Ripley, 2005). To investigation of the effects of sulfide composition, in addition to those of temperature, pressure and silicate melt composition, on sulfur solubility in silicate melts, we have carried out a series of experiments done at pressures between 1.5 and 3 GPa and temperatures from 1400 to 1800C over a range of compositions of both the silicate and sulfide melt. We find that the solubility of sulfur in silicate melts drops significantly with the substitution of Ni and Cu for Fe in the immiscible sulfide melt, decreasing by approximately 40% at mole fractions of NiS + Cu2S of 0.4. Combining our results with those from the previous studies investigating sulfur solubility in silicate melts we have also found that solubility increases with increasing temperature and decreases pressure. These results show that without considering the composition of the immiscible sulfide phase the sulfur content of silicate melts can be significantly overestimated. This may serve to explain the relatively low sulfur concentrations in MORB melts, which previous models predict to be undersaturated in a sulfide phase despite showing chemical and textural evidence for sulfide saturation. Li, C. & Ripley, E. M. (2005). Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits. Mineralium Deposita 40, 218-230. O'Neill, H. S. C. & Mavrogenes, J. A. (2002). The Sulfide Capacity and the Sulfur Content at Sulfide Saturation of Silicate Melts at 1400°C and 1 bar. Journal of Petrology 43, 1049-1087.

Preparation and properties of isotropic Nd-Fe-B bonded magnets with sodium silicate binder

NASA Astrophysics Data System (ADS)

Liu, W. Q.; Hu, R. J.; Yue, M.; Yin, Y. X.; Zhang, D. T.

2017-08-01

In present study, sodium silicate, a kind of heat-resistant binder, was used to prepare bonded Nd-Fe-B magnets with improved thermal stability and mechanical strength. Effect of curing temperature and curing time of the new binder to the magnetic properties, microstructure, and mechanical strength of the magnets was systematically investigated. Fracture surface morphology observation show that sodium silicate in bonded magnets could completely be cured at 175 °C for 40 min, and the magnets prepared under this condition exhibit optimal properties. They exhibit usable magnetic properties of Br of 4.66 kGs, Hcj of 4.84 kOe, and (BH)max of 4.06 MGOe at 200 °C. Moreover, the magnets possess high compressive strength of 63 MPa.

Microscopic, Macroscopic, and Megascopic Melts: a simple model to synthesize simulation, spectroscopy, shock, and sink/float constraints on silicate melts and magma oceans

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Thomas, C.; Wolf, A. S.

2012-12-01

Silicate melts are the essential agents of planetary differentiation and evolution. Their phase relations, element partitioning preferences, density, and transport properties determine the fates of heat and mass flow in the high-temperature interior of active planets. In the early Earth and in extrasolar super-Earth-mass terrestrial planets it is these properties at very high pressure (> 100 GPa) that control the evolution from possible magma oceans to solid-state convecting mantles. Yet these melts are complex, dynamic materials that present many challenges to experimental, theoretical, and computational understanding or prediction of their properties. There has been encouraging convergence among various approaches to understanding the structure and dynamics of silicate melts at multiple scales: nearest- and next-nearest neighbor structural information is derived from spectroscopic techniques such as high-resolution multinuclear NMR; first-principles molecular dynamics probe structure and dynamics at scales up to hundreds of atoms; Archimedean, ultrasonic, sink/float, and shock wave methods probe macroscopic properties (and occasionally dynamics); and deformation and diffusion experiments probe dynamics at macroscopic scale and various time scales. One challenge that remains to integrating all this information is a predictive model of silicate liquid structure that agrees with experiments and simulation both at microscopic and macroscopic scale. In addition to our efforts to collect macroscopic equation of state data using shock wave methods across ever-wider ranges of temperature, pressure, and composition space, we have introduced a simple model of coordination statistics around cations that can form the basis of a conceptual and predictive link across scales and methods. This idea is explored in this presentation specifically with regard to the temperature dependence of sound speed in ultramafic liquids. This is a highly uncertain quantity and yet it is key, in many models, to extrapolating the equation of state up or down temperature to geophysically relevant conditions. Ultrasonic data on felsic to basaltic melts, across a fairly narrow temperature range from their liquidi to ≤1650 °C, suggest either no temperature dependence or sound speeds that increase with temperature. Simulations, conducted at much higher temperature to obtain relaxation, suggest a strong decrease in sound speed with temperature. Our shock wave data on Mg2SiO4 liquid at 2000 °C yield a sound speed significantly lower than that predicted from data on less mafic liquids collected at lower temperatures where Mg2SiO4 liquid is not stable. The same shock method applied to melt compositions that are stable at 1300-1550 °C, however, yields sound speeds comparable to the ultrasonic results. Although each of these methods has its shortcomings, we show that considerable insight can be obtained in the context of a predictive model of Mg2+ and Si4+ coordination statistics as functions of temperature and pressure. We suggest that this can explain the difference between results obtained at ordinary upper mantle magmatic temperatures and those expected for magma oceans.

The lunar core can be a major reservoir for volatile elements S, Se, Te and Sb.

PubMed

Steenstra, Edgar S; Lin, Yanhao; Dankers, Dian; Rai, Nachiketa; Berndt, Jasper; Matveev, Sergei; van Westrenen, Wim

2017-11-06

The Moon bears a striking compositional and isotopic resemblance to the bulk silicate Earth (BSE) for many elements, but is considered highly depleted in many volatile elements compared to BSE due to high-temperature volatile loss from Moon-forming materials in the Moon-forming giant impact and/or due to evaporative loss during subsequent magmatism on the Moon. Here, we use high-pressure metal-silicate partitioning experiments to show that the observed low concentrations of volatile elements sulfur (S), selenium (Se), tellurium (Te), and antimony (Sb) in the silicate Moon can instead reflect core-mantle equilibration in a largely to fully molten Moon. When incorporating the core as a reservoir for these elements, their bulk Moon concentrations are similar to those in the present-day bulk silicate Earth. This suggests that Moon formation was not accompanied by major loss of S, Se, Te, Sb from Moon-forming materials, consistent with recent indications from lunar carbon and S isotopic compositions of primitive lunar materials. This is in marked contrast with the losses of other volatile elements (e.g., K, Zn) during the Moon-forming event. This discrepancy may be related to distinctly different cosmochemical behavior of S, Se, Te and Sb within the proto-lunar disk, which is as of yet virtually unconstrained.

Petrology and physical conditions of metamorphism of calcsilicate rocks from low- to high-grade transition area, Dharmapuri District, Tamil Nadu

NASA Technical Reports Server (NTRS)

Narayana, B. L.; Natarajan, R.; Govil, P. K.

1988-01-01

Calc-silicate rocks comprising quartz, plagioclase, diopside, sphene, scapolite, grossularite-andradite and wollastonite occur as lensoid enclaves within the greasy migmatitic and charnockitic gneisses of the Archaean amphibolite- to granulite-facies transition zone in Dharmapuri district, Tamil Nadu. The calc-silicate rocks are characterized by the absence of K-feldspar and primary calcite, presence of large modal quartz and plagioclase and formation of secondary garnet and zoisite rims around scapolite and wollastonite. The mineral distributions suggest compositional layering. The chemical composition and mineralogy of the calc-silicate rocks indicate that they were derived from impure silica-rich calcareous sediments whose composition is similar to that of pelite-limestone mixtures. From the mineral assemblages the temperature, pressure and fluid composition during metamorphism were estimated. The observed mineral reaction sequences require a range of X sub CO2 values demonstrating that an initially CO2-rich metamorphic fluid evolved with time towards considerably more H2O-rich compositions. These variations in fluid composition suggest that there were sources of water-rich fluids external to the calc-silicate rocks and that mixing of these fluids with those of calc-silicate rocks was important in controlling fluid composition in calc-silicate rocks and some adjacent rock types as well.

Acoustic Levitation Containerless Processing

NASA Technical Reports Server (NTRS)

Whymark, R. R.; Rey, C. A.

1985-01-01

This research program consists of the development of acoustic containerless processing systems with applications in the areas of research in material sciences, as well as the production of new materials, solid forms with novel and unusual microstructures, fusion target spheres, and improved optical fibers. Efforts have been focused on the containerless processing at high temperatures for producing new kinds of glasses. Also, some development has occurred in the areas of containerlessly supporting liquids at room temperature, with applications in studies of fluid dynamics, potential undercooling of liquids, etc. The high temperature area holds the greatest promise for producing new kinds of glasses and ceramics, new alloys, and possibly unusual structural shapes, such as very uniform hollow glass shells for fusion target applications. High temperature acoustic levitation required for containerless processing has been demonstrated in low-g environments as well as in ground-based experiments. Future activities include continued development of the signals axis acoustic levitator.

A vaporization model for iron/silicate fractionation in the Mercury protoplanet

NASA Technical Reports Server (NTRS)

Fegley, Bruce, Jr.; Cameron, A. G. W.

1987-01-01

A study has been carried out on the vaporization of a totally molten silicate magma of chondritic composition heated into the range 2500-3500 K. The motivation for this was to determine the changes in the composition of the mantle that would occur in the Mercury protoplanet should that body have been subjected to the high-temperature phase in the evolution of the primitive solar nebula, but the results are of more general interest. An empirical model based on ideal mixing of complex components was used to describe the nonideal magma. It is found that vaporization of about 70-80 percent of the original amount of silicate from a chondritic planet is required to produce an iron-rich body with a mean uncompressed density equal to that deduced for Mercury. At this point the silicate is depleted in the alkalis, FeO, and SiO2, and enriched in CaO, MgO, Al2O3, and TiO2 relative to chondritic material.

Glass formation and crystallization in high-temperature glass-ceramics and Si3N4

NASA Technical Reports Server (NTRS)

Drummond, Charles H., III

1991-01-01

The softening of glassy grain boundaries in ceramic matrix composites and Si3N4 at high temperatures reduces mechanical strength and the upper-use temperature. By crystallizing this glass to a more refractory crystalline phase, a material which performs at higher temperatures may result. Three systems were examined: a cordierite composition with ZrO2 as a nucleating agent; celsian compositions; and yttrium silicate glasses both in bulk and intergranular in Si3N4. For the cordierite compositions, a series of metastable phases was obtained. The crystallization of these compositions was summarized in terms of metastable ternary isothermal sections. Zircon formed at the expense of ZrO2 and spinel. In SiC composites, the transformations were slower. In celsian, two polymorphs were crystallized. One phase, hexacelsian, which always crystallized, even when metastable, had an undesirable volume change. The other phase, celsian, was very difficult to crystallize. In yttrium silicate bulk glasses, similar in composition to the intergranular glass in Si3N4, a number of polymorphs of Y2Si2O7 were crystallized. The conditions under which these polymorphs formed are compared with crystallization in Si3N4.

High temperature alkali corrosion of ceramics in coal gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pickrell, G.R.; Sun, T.; Brown, J.J.

1992-02-24

The high temperature alkali corrosion kinetics of SiC have been systematically investigated from 950 to 1100[degrees]C at 0.63 vol % alkali vapor concentration. The corrosion rate in the presence of alkaliis approximately 10[sup 4] to 10[sup 5] times faster than the oxidation rate of SiC in air. The activation energy associated with the alkali corrosion is 406 kJ/mol, indicating a highly temperature-dependent reaction rate. The rate-controlling step of the overall reaction is likely to be the dissolution of silica in the sodium silicate liquid, based on the oxygen diffusivity data.

Formation of Metal and Silicate Globules in Gujba: A New Bencubbin-like Meteorite Fall

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.; Clayton, Robert N.; Mayeda, Toshiko; Grady, Monica; Verchovsky, Alexander B.; Eugster, Otto; Lorenzetti, Silvio

2006-01-01

Gujba is a coarse-grained meteorite fall composed of 41 vol% large kamacite globules, 20 vol% large light-colored silicate globules with cryptocrystalline, barred pyroxene and barred olivine textures, 39 vol% dark-colored, silicate-rich matrix, and rare refractory inclusions. Gujba resembles Bencubbin and Weatherford in texture, oxygen-isotopic composition and in having high bulk delta N-15 values (approximately +685%0). The He-3 cosmic-ray exposure age of Gujba (26 +/- 7 Ma) is essentially identical to that of Bencubbin, suggesting that they were both reduced to meter-size fragments in the same parent-body collision. The Gujba metal globules exhibit metal-troilite quench textures and vary in their abundances of troilite and volatile siderophile elements. We suggest that the metal globules formed as liquid droplets either via condensation in an impact-generated vapor plume or by evaporation of preexisting metal particles in a plume. The lower the abundance of volatile elements in the metal globules, the higher the globule quench temperature. We infer that the large silicate globules also formed from completely molten droplets; their low volatile-element abundances indicate that they also formed at high temperatures, probably by processes analogous to those that formed the metal globules. The coarse-grained Bencubbin-Weatherford-Gujba meteorites may represent a depositional component from the vapor cloud enriched in coarse and dense particles. A second class of Bencubbin-like meteorites (represented by Hammadah a1 Hamra 237 and QUE 94411) may be a finer fraction derived from the same vapor cloud

Rb3In(H2O)Si5O13: a novel indium silicate with a CdSO4-topological-type structure.

PubMed

Hung, Ling-I; Wang, Sue-Lein; Chen, Chia-Yi; Chang, Bor-Chen; Lii, Kwang-Hwa

2005-05-02

A novel indium silicate, Rb3In(H2O)Si5O13, has been synthesized using a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. The structure consists of five-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to four adjacent five-membered rings to form a 3D silicate framework that belongs to the CdSO4 topological type. The InO6 octahedron shares five of its corners with five different SiO4 tetrahedra to form a 3D frame-work that delimits two types of channels to accommodate the rubidium cations. The sixth corner of InO6 is coordinated H2O. The structure is related to that of the titanium silicate ETS-10, and these are the only two metal silicates that have the CdSO4-topological-type structure. In addition, the crystal of Rb3In(H2O)Si5O13 shows an intense second harmonic generation signal. Crystal data: H2Rb3InSi5O14, monoclinic, space group Cc (No. 9), a = 9.0697(5) A, b = 11.5456(6) A, c = 13.9266(8) A, beta = 102.300(1) degrees, V = 1424.8(1) A3, and Z = 4.

High Temperature Sorbents for Oxygen

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor)

1996-01-01

A sorbent capable of removing trace amounts of oxygen (ppt) from a gas stream at a high temperature above 200 C is introduced. The sorbent comprises a porous alumina silicate support such as zeolite containing from 1 to 10 percent by weight of ion exchanged transition metal such as copper or cobalt ions and 0.05 to 1.0 percent by weight of an activator selected from a platinum group metal such as platinum. The activation temperature, oxygen sorption and reducibility are all improved by the presence of the platinum activator.

X-ray Raman scattering study of MgSiO3 glass at high pressure: Implication for triclustered MgSiO3 melt in Earth's mantle

PubMed Central

Lee, Sung Keun; Lin, Jung-Fu; Cai, Yong Q.; Hiraoka, Nozomu; Eng, Peter J.; Okuchi, Takuo; Mao, Ho-kwang; Meng, Yue; Hu, Michael Y.; Chow, Paul; Shu, Jinfu; Li, Baosheng; Fukui, Hiroshi; Lee, Bum Han; Kim, Hyun Na; Yoo, Choong-Shik

2008-01-01

Silicate melts at the top of the transition zone and the core-mantle boundary have significant influences on the dynamics and properties of Earth's interior. MgSiO3-rich silicate melts were among the primary components of the magma ocean and thus played essential roles in the chemical differentiation of the early Earth. Diverse macroscopic properties of silicate melts in Earth's interior, such as density, viscosity, and crystal-melt partitioning, depend on their electronic and short-range local structures at high pressures and temperatures. Despite essential roles of silicate melts in many geophysical and geodynamic problems, little is known about their nature under the conditions of Earth's interior, including the densification mechanisms and the atomistic origins of the macroscopic properties at high pressures. Here, we have probed local electronic structures of MgSiO3 glass (as a precursor to Mg-silicate melts), using high-pressure x-ray Raman spectroscopy up to 39 GPa, in which high-pressure oxygen K-edge features suggest the formation of tricluster oxygens (oxygen coordinated with three Si frameworks; [3]O) between 12 and 20 GPa. Our results indicate that the densification in MgSiO3 melt is thus likely to be accompanied with the formation of triculster, in addition to a reduction in nonbridging oxygens. The pressure-induced increase in the fraction of oxygen triclusters >20 GPa would result in enhanced density, viscosity, and crystal-melt partitioning, and reduced element diffusivity in the MgSiO3 melt toward deeper part of the Earth's lower mantle. PMID:18535140

The W-W02 Oxygen Fugacity Buffer at High Pressures and Temperatures: Implications for f02 Buffering and Metal-silicate Partitioning

NASA Technical Reports Server (NTRS)

Shofner, G. A.; Campbell, A. J.; Danielson, L.; Righter, K.

2013-01-01

Oxygen fugacity (fO2) controls multivalent phase equilibria and partitioning of redox-sensitive elements, and it is important to understand this thermodynamic parameter in experimental and natural systems. The coexistence of a metal and its oxide at equilibrium constitutes an oxygen buffer which can be used to control or calculate fO2 in high pressure experiments. Application of 1-bar buffers to high pressure conditions can lead to inaccuracies in fO2 calculations because of unconstrained pressure dependencies. Extending fO2 buffers to pressures and temperatures corresponding to the Earth's deep interior requires precise determinations of the difference in volume (Delta) V) between the buffer phases. Synchrotron x-ray diffraction data were obtained using diamond anvil cells (DAC) and a multi anvil press (MAP) to measure unit cell volumes of W and WO2 at pressures and temperatures up to 70 GPa and 2300 K. These data were fitted to Birch-Murnaghan 3rd-order thermal equations of state using a thermal pressure approach; parameters for W are KT = 306 GPa, KT' = 4.06, and aKT = 0.00417 GPa K-1. Two structural phase transitions were observed for WO2 at 4 and 32 GPa with structures in P21/c, Pnma and C2/c space groups. Equations of state were fitted for these phases over their respective pressure ranges yielding the parameters KT = 190, 213, 300 GPa, KT' = 4.24, 5.17, 4 (fixed), and aKT = 0.00506, 0.00419, 0.00467 GPa K-1 for the P21/c, Pnma and C2/c phases, respectively. The W-WO2 buffer (WWO) was extended to high pressure by inverting the W and WO2 equations of state to obtain phase volumes at discrete pressures (1-bar to 100 GPa, 1 GPa increments) along isotherms (300 to 3000K, 100 K increments). The slope of the absolute fO2 of the WWO buffer is positive with increasing temperature up to approximately 70 GPa and is negative above this pressure. The slope is positive along isotherms from 1000 to 3000K with increasing pressure up to at least 100 GPa. The WWO buffer is at a higher fO2 than the IW buffer at pressures lower than 40 GPa, and the magnitude of this difference decreases at higher pressures. This qualitatively indicates an increasingly lithophile character for W at higher pressures. The WWO buffer was quantitatively applied to W metal-silicate partitioning by using the WWO-IW buffer difference in combination with literature data on W metal-silicate partitioning to model the exchange coefficient (KD) for the Fe-W exchange reaction. This approach captures the pressure dependence of W metal-silicate partitioning using the WWO-IW buffer difference and models the activities of the components in the silicate and metallic phases using an expression of the Gibbs excess energy of mixing. Calculation of KD along a peridotite liquidus predicts a decrease in W siderophility at higher pressures that supports the qualitative behavior predicted by the WWO-IW buffer difference, and agrees with findings of others. Comparing the competing effects of temperature and pressure on W metal-silicate partitioning, our results indicate that pressure exerts a greater effect.

Models of a partially hydrated Titan interior with clathrate crust

NASA Astrophysics Data System (ADS)

Lunine, J. I.; Castillo-Rogez, J.

2012-04-01

We present an updated model of the interior evolution of Titan over time, assuming the silicate core was hydrated early in Titan's history and is dehydrating over time. The original model presented in Castillo-Rogez and Lunine (2010) was motivated by a Cassini-derived moment of inertia (Iess et al., 2010) for Titan too large to be accommodated by classical fully differentiated models in which an anhydrous silicate core was overlain by a water ice (with possible perched ocean) mantle. Our model consisted of a silicate core still in the process of dehydrating today, a situation made possible by the leaching of radiogenic potassium from the silicates into the liquid water ocean. The crust of Titan was assumed to be pure water ice I. The model was consistent with the moment of inertia of Titan, but neglected the presence of large amounts of methane in the upper crust invoked to explain methane's persistence at present and through geologic time (Tobie et al. 2006). We have updated our model with such a feature. We have also improved our modeling with a better physical model for the dehydration of antigorite and other hydrated minerals. In particular our modeling now simulates heat advection resulting from water circulation (e.g., Seipold and Schilling 2003), rather than the purely conductive heat transfer regime assumed in the first version of our model. The modeling proceeds as in Castillo-Rogez and Lunine (2010), with the thermal conductivity of the methane clathrate crust rather than that of ice I. The former is several times lower than that of the latter, and the two have rather different temperature dependences (English and Tse, 2009). The crust turns out to have essentially no bearing on the temperature of the silicate core and hence the timing of dehydration, but it profoundly affects the thickness of the high-pressure ice layer beneath the ocean. Indeed, with the insulating methane clathrate crust, there must be a liquid water ocean beneath the methane clathrate crust and in contact with the silicates beneath for most of Titan's history. Although a high-pressure ice layer is likely in place today, it is thin enough that plumes of hot water from the dehydrating core probably breach the high pressure ice layer maintaining contact between the ocean and the silicate core. Part of this work has been performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. Government sponsorship acknowledged.

The evolution of grain mantles and silicate dust growth at high redshift

NASA Astrophysics Data System (ADS)

Ceccarelli, Cecilia; Viti, Serena; Balucani, Nadia; Taquet, Vianney

2018-05-01

In dense molecular clouds, interstellar grains are covered by mantles of iced molecules. The formation of the grain mantles has two important consequences: it removes species from the gas phase and promotes the synthesis of new molecules on the grain surfaces. The composition of the mantle is a strong function of the environment that the cloud belongs to. Therefore, clouds in high-zeta galaxies, where conditions - like temperature, metallicity, and cosmic ray flux - are different from those in the Milky Way, will have different grain mantles. In the last years, several authors have suggested that silicate grains might grow by accretion of silicon-bearing species on smaller seeds. This would occur simultaneously with the formation of the iced mantles and be greatly affected by its composition as a function of time. In this work, we present a numerical study of the grain mantle formation in high-zeta galaxies, and we quantitatively address the possibility of silicate growth. We find that the mantle thickness decreases with increasing redshift, from about 120 to 20 layers for z varying from 0 to 8. Furthermore, the mantle composition is also a strong function of the cloud redshift, with the relative importance of CO, CO2, ammonia, methane, and methanol highly varying with z. Finally, being Si-bearing species always a very minor component of the mantle, the formation of silicates in molecular clouds is practically impossible.

Solubility of copper in silicate melts as function of oxygen and sulfur fugacities, temperature, and silicate composition

NASA Astrophysics Data System (ADS)

Holzheid, A.; Lodders, K.

2001-06-01

The solubility of Cu in silicate melts coexisting with liquid Cu(Fe) metal and liquid Cu(Fe) sulfide was determined experimentally at oxygen fugacities ranging from 10 -9.1 to 10 -13.6 bar and sulfur fugacities ranging from 10 -2.5 to 10 -6.3 bar at 1300°C. An iron oxide-free silicate of anorthite-diopside eutectic composition and a synthetic MgO-rich basaltic silicate (FeO-bearing) were used in the partitioning experiments. In S-containing systems, some of the metal reacted to metal sulfide. The silicates in the four systems investigated (Fe-free and S-free; Fe-containing and S-free; Fe-free and S-containing; Fe-containing and S-containing) had different colors depending on the dissolved Cu species and the presence of iron and/or sulfur. Irrespective of the presence of sulfur, the solubility of Cu in the silicate increases with increasing oxygen fugacity and metal/silicate partition coefficients for Cu decrease. Increasing the temperature from 1300°C to 1514°C increases the Cu solubility (decreases the metal/silicate partition coefficient) at an oxygen fugacity 0.5 log units below the iron-wüstite (IW) equilibrium in the Fe-free, S-free and Fe-containing, S-free systems. We infer the presence of monovalent Cu + ("CuO 0.5") in the silicate melt on the basis of the solubility of Cu as function of oxygen fugacity. Experiments containing iron yield a formal valence of ˜0.5 for Cu at very low oxygen fugacities, which is not observed in Fe-free systems. The low formal valence is explained by redox reactions between iron and copper in the silicate melts. There is no evidence for sulfidic dissolution of Cu in the silicates but sulfur has indirect effects on Cu partitioning. Iron metal/silicate partition coefficients depend on oxygen fugacity and on sulfur fugacity. Sulfidic dissolution of iron and oxide-sulfide exchange reactions with Cu cause a small increase in Cu metal/silicate partition coefficients. We derive an activity coefficient (γ CuO 0.5) of 10 ± 1 for liquid CuO 0.5 at 1300°C for the silicate melts used here. A comparison with literature data shows that log γ CuO 0.5 increases in proportion to the mass percentages [CaO +(Al 2O 3)/2] in silicate melts. We recommend the following equations for Cu metal/silicate and sulfide/silicate partitioning for geochemical and cosmochemical modeling if silicate composition and the activity of Cu in the metal or sulfide is known: log D met/sil = -0.48 - 0.25 · log fO 2 - log γ Cu metal + 0.02 · [CaO + (Al 2O 3)/2; wt%] silicate logD sul/sil=+0.76-0.25 · logfO 2+0.25logfS 2-logγ CS 0.5,sulfide +0.02 · [CaO+Al 2O 3/2;wt%] silicate. The derived Cu metal/silicate and metal/sulfide partition coefficients are applied to core formation in the Earth and Mars. The observed Cu abundances in the Earth cannot be easily explained by simple core-mantle equilibrium, but the observed Cu abundances for Mars are consistent with core-mantle equilibrium at low pressure and temperatures.

PREFACE: 5th Baltic Conference on Silicate Materials

NASA Astrophysics Data System (ADS)

Mezinskis, G.; Bragina, L.; Colombo, P.; Frischat, G. H.; Grabis, J.; Greil, P.; Deja, J.; Kaminskas, R.; Kliava, J.; Medvids, A.; Nowak, I.; Siauciunas, R.; Valancius, Z.; Zalite, I.

2011-12-01

Logo This Volume of IOP Conference Series: Materials Science and Engineering presents a selection of the contributions to the 5th Baltic Conference on Silicate Materials (BaltSilica2011) held at Riga Technical University, Riga, Latvia from 23-25 May 2011. The conference was organized by Riga Technical University (Latvia) and Kaunas University of Technology (Lithuania). The series of Baltic conferences on silicate materials was started since 2004: the first conference was held in Riga, Latvia, 2004; the second conference was held in Kaunas, Lithuania 2005; the third was held again in Riga, Latvia, 2007, and the fourth was held in Kaunas, Lithuania 2009. BaltSilica 2011 was attended by around 50 participants from Latvia, Lithuania, Estonia, Germany, Poland, Italy, France, Ukraine and Russia. In comparison with previous silicate materials conferences, the broadening of participating countries is an indication of the interest of scientists, engineers and students to exchange research ideas, latest results, and to find new research topics for cooperation in the fields of silicate, high temperature materials, and inorganic nanomaterials. The scientific programme included 8 invited plenary lectures 23 oral presentations and 25 posters [1]. Scientific themes covered in the conference and in this special issue: Natural and Artificial Stone Materials; Traditional and New Ceramic and Glass-Like Materials; Nanoparticles and Nanomaterials. This volume consists of 23 selected proceeding papers. The Editor of this special issue is grateful to all the contributors to BaltSilica 2011. I am also very grateful to the scientific committee, the local organizing committee, the session chairs, the referees who refereed the submitted articles to this issue, and to students from the Department of Silicate, High Temperature and Inorganic Nanomaterials Technology of the Riga Technical University who ensured the smooth running of the conference. Particular thanks goes to eight plenary speakers who provided interesting findings and thoughtful overviews in the scientific themes of the conference. Special thanks go to Prof., Dr.rer.nat. Günther Heinz Frischat (Germany) who encouraged and supported the organization of these scientific meetings from the very first BaltSilica conferences. With warm regards and best wishes for the next BaltSilica conference. The Conference Chairman Gundars Mezinskis Reference [1] Baltic Conference on Silicate Materials. Book of abstracts of the 5th Baltic Conference on Silicate Materials BaltSilica 2011 : 23-25 May 2011, Riga, Latvia ed G Mezinskis, G Sedmale, J Setina, I Sperberga, L Krage, I Pavlovska, D Andersone (Riga: RTU Publishing House) p 94

A GEOCLIM simulation of climatic and biogeochemical consequences of Pangea breakup

NASA Astrophysics Data System (ADS)

Donnadieu, Y.; GoddéRis, Y.; Pierrehumbert, R.; Dromart, G.; Fluteau, F.; Jacob, R.

2006-11-01

Large fluctuations in continental configuration occur throughout the Mesozoic. While it has long been recognized that paleogeography may potentially influence atmospheric CO2 via the continental silicate weathering feedback, no numerical simulations have been done, because of the lack of a spatially resolved climate-carbon model. GEOCLIM, a coupled numerical model of the climate and global biogeochemical cycles, is used to investigate the consequences of the Pangea breakup. The climate module of the GEOCLIM model is the FOAM atmospheric general circulation model, allowing the calculation of the consumption of atmospheric CO2 through continental silicate weathering with a spatial resolution of 7.5°long × 4.5°lat. Seven time slices have been simulated. We show that the breakup of the Pangea supercontinent triggers an increase in continental runoff, resulting in enhanced atmospheric CO2 consumption through silicate weathering. As a result, atmospheric CO2 falls from values above 3000 ppmv during the Triassic down to rather low levels during the Cretaceous (around 400 ppmv), resulting in a decrease in global mean annual continental temperatures from about 20°C to 10°C. Silicate weathering feedback and paleogeography both act to force the Earth system toward a dry and hot world reaching its optimum over the last 260 Myr during the Middle-Late Triassic. In the super continent case, given the persistent aridity, the model generates high CO2 values to produce very warm continental temperatures. Conversely, in the fragmented case, the runoff becomes the most important contributor to the silicate weathering rate, hence producing a CO2 drawdown and a fall in continental temperatures. Finally, another unexpected outcome is the pronounced fluctuation in carbonate accumulation simulated by the model in response to the Pangea breakup. These fluctuations are driven by changes in continental carbonate weathering flux. Accounting for the fluctuations in area available for carbonate platforms, the simulated ratio of carbonate deposition between neritic and deep sea environments is in better agreement with available data.

Experimental high strain-rate deformation products of carbonate-silicate rocks: Comparison with terrestrial impact materials

NASA Astrophysics Data System (ADS)

van der Bogert, C. H.; Schultz, P. H.; Spray, J. G.

2008-09-01

Introduction. The response of carbonate to impact processes has thus far been investigated using a combination of thermodynamic modelling, shock experiments, and impact experiments. Localized shear deformation was suggested to play an important role in the failure of carbonate during some shock experiments [1,2], and was invoked to explain significant degassing of carbonates during oblique impact experiments [3]. The results of the impact experiments are at odds with experiments [4] that show back-reaction of CO2 with CaO and MgO could significantly reduce CO2 degassing during impact events. We performed a frictional-welding experiment in order to investigate the effects of high strain-rate deformation on carbonate-silicate target materials, exclusive of shock deformation effects, and to investigate the differing results of other experiments. Samples and Techniques. A frictional melting experiment was performed using dolomitic marble and quartzite samples to simulate conditions during an impact into carbonate-silicate target rocks. The experiment followed the method of Spray (1995) [5]. The 1.5 cm3 samples were mounted onto separate steel cylinders with epoxy. Using a Blacks FWH-3 axial friction-welding rig, the samples were brought into contact at room temperature and under dry conditions with ~5 MPa applied pressure. Contact was maintained for two seconds at 750 rpm for a sustained strain-rate of 102 to 103 s-1. Results. Vapor or fine dust escaped from the interface during the experiment. Immediately after sample separation, the interfaces were incandescent. Once cooled, opaque white material adhered to both the quartzite and dolomitic marble samples. Quartzite sample. Material was injected into cracks that formed in the quartzite sample. Cooling and crystallization of the friction products resulted in the formation of submicron-sized minerals such as periclase and Ca- and Ca,Mg-silicates (Fig. 1) including merwinite and åkermanite. While periclase was observed as an individual mineral species, no pure lime was observed to be present. In the quartzite sample, CaO is present only as a component of the Ca- and Ca,Mg-silicates. In the fine-grained shear zone materials, however, elemental mapping and EMP analyses reveal an overall segregation of MgO and CaO [6], suggesting that CaO is mostly present in Casilicates and Ca,Mg-silicates with low MgO contents. Dolomitic marble sample. The dolomitic marble section exhibited thinner, shorter fractures than the quartzite sample. Mechanical twinning was induced by the deformation. The adhered friction products were very fine-grained material with larger, untwinned calcite (Fig. 2), and dendritic carbonates with a composition similar to huntite. Most of the secondary calcite had rounded margins, which suggested that they were molten during the experiment. The dendritic huntite-like carbonate, with a CO2 content higher than of these secondary carbonate grains (Fig. 3). However, calcite was the dominant secondary mineral. The finegrained portion of the shear zone material contained pervasive vesicles. The vesicles immediately adjacent to the secondary calcite grains were smaller than those adjacent to the dolomitic marble. This suggests that incorporation of CO2 near the calcite grains facilitated their growth. Discussion. The textures and compositions of the experimental products indicate that the dolomitic marble decarbonated in response to the high temperatures generated during experimental deformation. Simultaneously, the liberated CaO recombined with CO2 to form molten calcite in the shear zone. This effect, in part, is due to the lower decarbonation temperature for dolomite versus calcite [c.f., 7], which allows calcite to survive at higher temperatures than dolomite. In addition, the confining pressure during the experiment was high enough to allow calcite to be present as a liquid [c.f., 8]. Both the calcite and dendritic carbonate are likely products of back-reaction of CaO and MgO with CO2. However, both CaO and MgO were also incorporated into secondary silicates, which reduced the total amount available to back-react with CO2. It appears that all CaO released from the dolomitic marble formed secondary minerals (carbonates and silicates), because it is not present as pure CaO. The MgO released from the dolomitic marble primarily formed secondary silicates, periclase, and minor secondary carbonate. As a result, the secondary carbonates cannot be a sink for all the CO2 gas released from the dolomitic marble, unless a much higher proportion of the huntite-like phase was present. Thus, there was a net release of CO2 gas from the original dolomitic marble. A portion of this CO2 remained trapped in vesicles, but CO2 gas also escaped from the shear zone. This is consistent with compositional measurements of the shear zone that suggest a release of at least 5 wt% CO2 relative to the original dolomitic marble. Comparison with terrestrial craters. Many of the descriptions of deformation features in carbonates at terrestrial craters, such as mechanical twinning and bent fractures [9-11], are similar to those seen in our experimental products. Carbonates that survive impact seem to accommodate both shock and shear deformation primarily through mechanical fracturing and twinning. Impact melts at craters in carbonate-rich targets have been found to contain both silicic and carbonatitic melts [e.g., 12], with mineral phases that are indicative of high temperature reactions between carbonate and silicate rocks [e.g., 9]. Our experiments also showed these characteristics, however, the mineral phases produced were slightly different and we have not observed silicate glass in our experimental products. The segregation of MgO from CaO has been observed, for example, at Haughton [12] and Popigai [13], and was also seen in our experimental products [6]. Implications. The products of high strain-rate deformation experiments with carbonate-silicate rocks are similar in many aspects to impact products at terrestrial craters in mixed carbonate-silicate targets. The experiments show that decarbonation of carbonate targets and high temperature reactions between carbonate and silicates in the target rocks are not exclusive effects of shock deformation. Shear deformation alone can generate temperature and pressure conditions necessary to decarbonate dolomitic marble and generate calcitic melts. Thus, high strain-rate deformation is a potentially major contributor to the total impact-related energy deposited into the target, especially for oblique impacts. Shear deformation occuring during and after shock deformation could, in fact, enhance the release of CO2 as a gas, by creating pathways that allow gases to escape from target materials. Understanding the relative importance and interaction of each CO2 releasing or trapping mechanism is important for the determination of the environmental significance of impacts in targets containing carbonates. References. [1] Lange M. A. and Ahrens T. J. (1986) EPSL 77, 409-418. [2] Tyburczy J. A. and Ahrens T. J. (1986) JGR 91, 4730-4744. [3] Schultz P. H. (1996) GSA Abstracts, A384. [4] Agrinier P., et al. (2001) GCA 65, 2615-2632. [5] Spray J. G. (1995) Geology 23, 1119-1122. [6] van der Bogert C. H., et al. (2007) LPI Contribution No. 1360, 123-124. [7] Martinez I., et al. (1995) JGR 100, 15456-15476. [8] Ivanov B. A. and Deutsch A. (2002) Phys. Earth Planet. Int. 129, 131-143. [9] Martinez I., et al. (1994) EPSL 121, 559-574. [10] Redeker H.-J. and Stöffler D. (1988) Meteoritics 23, 185-196. [11] Skála R. and Jakes P. (1999). In Large Meteorite Impacts and Planetary Evolution II (eds. B. O. Dressler and V. L. Sharpton), pp. 205-214. [12] Osinski G. R. and Spray J. G. (2001) EPSL 194, 17-29. [13] Kenkmann T., et al. (1999) LPS XXX, Abstract #1561.

Co-settling of Chromite and Sulfide Melt Droplets and Trace Element Partitioning between Sulfide and Silicate Melts

NASA Astrophysics Data System (ADS)

Manoochehri, S.; Schmidt, M. W.; Guenther, D.

2013-12-01

Gravitational settling of immiscible, dense sulfide melt droplets together with other cumulate phases such as chromite, combined with downward percolation of these droplets through a cumulate pile, is thought to be one of the possible processes leading to the formation of PGE rich sulfide deposits in layered mafic intrusions. Furthermore some chromitite seams in the Merensky Reef (Bushveld Complex) are considered to be acting as a filter or barrier for further downward percolation of sulfide melts into footwall layers. To investigate the feasibility of such mechanical processes and to study the partitioning behavior of 50 elements including transition metals and REEs (but not PGEs) between a silicate and a sulfide melt, two separate series of high temperature (1250-1380 °C) centrifuge-assisted experiments at 1000 g, 0.4-0.6 GPa were conducted. A synthetic silicate glass with a composition representative of the parental magma of the Bushveld Complex (~ 55 wt% SiO2) was mixed with pure FeS powder. For the first series of experiments, 15 or 25 wt% natural chromite with average grain sizes of ~ 5 or 31 μm were added to a mixture of silicate glass and FeS (10 wt%) adding 1 wt% water. For the second series, a mixture of the same glass and FeS was doped with 50 trace elements. These mixtures were first statically equilibrated and then centrifuged. In the first experimental series, sulfide melt droplets settled together with, but did not segregate from chromite grains even after centrifugation at 1000 g for 12 hours. A change in initial chromite grain size and proportions didn't have any effect on segregation. Without chromite, the starting mixture resulted in the formation of large sulfide melt pools together with finer droplets still disseminated through the silicate glass and both at the bottom of the capsule. The incomplete segregation of sulfide melt is interpreted as being due to high interfacial energies between sulfide and silicate melts/crystals which hinder both, the nucleation of newly formed sulfide droplets and the interconnectivity of separate droplets. The interfacial energies between sulfide melt and silicate or oxide crystals is even higher than for silicate melt, consequently in experiments with chromite, sulfide segregation is even more hindered. Partition coefficients of 50 elements between a sulfide and a silicate melt are determined as a function of differing temperature between 1250 - 1380 °C. As a proxy to investigate the bond strength of network modifier cations, the relation between the partition coefficients and ionic potentials of different groups of elements has been determined.

The largest Bio-Silica Structure on Earth: The Giant Basal Spicule from the Deep-Sea Glass Sponge Monorhaphis chuni.

PubMed

Wang, Xiaohong; Gan, Lu; Jochum, Klaus P; Schröder, Heinz C; Müller, Werner E G

2011-01-01

The depth of the ocean is plentifully populated with a highly diverse fauna and flora, from where the Challenger expedition (1873-1876) treasured up a rich collection of vitreous sponges [Hexactinellida]. They have been described by Schulze and represent the phylogenetically oldest class of siliceous sponges [phylum Porifera]; they are eye-catching because of their distinct body plan, which relies on a filigree skeleton. It is constructed by an array of morphologically determined elements, the spicules. Later, during the German Deep Sea Expedition "Valdivia" (1898-1899), Schulze could describe the largest siliceous hexactinellid sponge on Earth, the up to 3 m high Monorhaphis chuni, which develops the equally largest bio-silica structures, the giant basal spicules (3 m × 10 mm). With such spicules as a model, basic knowledge on the morphology, formation, and development of the skeletal elements could be elaborated. Spicules are formed by a proteinaceous scaffold which mediates the formation of siliceous lamellae in which the proteins are encased. Up to eight hundred 5 to 10 μm thick lamellae can be concentrically arranged around an axial canal. The silica matrix is composed of almost pure silicon and oxygen, providing it with unusual optophysical properties that are superior to those of man-made waveguides. Experiments indicated that the spicules function in vivo as a nonocular photoreception system. In addition, the spicules have exceptional mechanical properties, combining mechanical stability with strength and stiffness. Like demosponges the hexactinellids synthesize their silica enzymatically, via the enzyme silicatein. All these basic insights will surely contribute also to a further applied utilization and exploration of bio-silica in material/medical science.

The largest Bio-Silica Structure on Earth: The Giant Basal Spicule from the Deep-Sea Glass Sponge Monorhaphis chuni

PubMed Central

Wang, Xiaohong; Gan, Lu; Jochum, Klaus P.; Schröder, Heinz C.; Müller, Werner E. G.

2011-01-01

The depth of the ocean is plentifully populated with a highly diverse fauna and flora, from where the Challenger expedition (1873–1876) treasured up a rich collection of vitreous sponges [Hexactinellida]. They have been described by Schulze and represent the phylogenetically oldest class of siliceous sponges [phylum Porifera]; they are eye-catching because of their distinct body plan, which relies on a filigree skeleton. It is constructed by an array of morphologically determined elements, the spicules. Later, during the German Deep Sea Expedition “Valdivia” (1898-1899), Schulze could describe the largest siliceous hexactinellid sponge on Earth, the up to 3 m high Monorhaphis chuni, which develops the equally largest bio-silica structures, the giant basal spicules (3 m × 10 mm). With such spicules as a model, basic knowledge on the morphology, formation, and development of the skeletal elements could be elaborated. Spicules are formed by a proteinaceous scaffold which mediates the formation of siliceous lamellae in which the proteins are encased. Up to eight hundred 5 to 10 μm thick lamellae can be concentrically arranged around an axial canal. The silica matrix is composed of almost pure silicon and oxygen, providing it with unusual optophysical properties that are superior to those of man-made waveguides. Experiments indicated that the spicules function in vivo as a nonocular photoreception system. In addition, the spicules have exceptional mechanical properties, combining mechanical stability with strength and stiffness. Like demosponges the hexactinellids synthesize their silica enzymatically, via the enzyme silicatein. All these basic insights will surely contribute also to a further applied utilization and exploration of bio-silica in material/medical science. PMID:21941585

Discovery of hydrothermally active and extinct talc mounds on the Mid-Cayman Rise

NASA Astrophysics Data System (ADS)

Hodgkinson, M.; Murton, B. J.; Roberts, S.

2013-12-01

Since 1977, hydrothermal vents have been the subject of intense scientific interest due to their role in cooling the oceanic crust and global geochemical cycles. Until now, two types of hydrothermal system have been identified: one, driven by magmatic heat extruding ';black smoker' fluids; and another, involving serpentinisation of ultramafic rocks and the precipitation of carbonate/brucite chimneys. Here, we present details of a new, off-axis type of hydrothermal system consisting of mounds of predominately botryoidal talc (a magnesium-silicate) with accessory silica and copper sulphides, and chimneys exhaling fluids of moderate temperature and pH. Discovered on the Mid-Cayman Rise (MCR) in 2010, the Von Damm Vent Field (VDVF) features a NNW-ESE-trending line of four overlapping cones, the largest of which is 75 m high by 150 m in diameter. The VDVF is hosted in the gabbroic footwall of the Mount Dent Oceanic Core Complex (MDOCC), which includes serpentinised peridotite at depth. The largest cone vents clear fluids from two main orifices at its summit, with primary temperatures of 215°C. Elsewhere, both focussed and diffuse flow areas emit fluids with temperatures of up to 150°C. The surrounding ~1 m thick pelagic sediment contains abundant pockmarks that emit methane-rich fluids at temperatures of less than 10°C. During the return to the MCR in early 2013, several other talc mounds were discovered within a kilometre of the active VDVF. These inactive mounds also comprise an assemblage of botryoidal talc, silica, disseminated sulphides (including chalcopyrite) and sulphates. One of these mounds (Mystic Mount) is double the volume of the active VDVF. The unique dominance of talc as the major mineral forming the hydrothermal structures indicates unusual vent fluid compositions that are able to carry both copper (at high-temperatures) and precipitate magnesium silicate. Thermodynamic modelling indicates that talc precipitates on mixing a moderately acidic, silica rich fluid (e.g. the primary VDVF fluids) with only 2% of seawater. At lower pH (e.g. typical ';black smoker' fluids), the ratio jumps to over 90% while at high pH (e.g. ';Lost City' fluids) brucite and carbonate dominate. Estimates using recently measured vent temperatures and fluid fluxes indicate a heat flux of ~800 MW for the active VDVF. Assuming the primary vent fluid has remained largely unchanged, the VDVF could have grown in under 1000 years and Mystic Mount in ~2000 years. Both the hydrothermal mounds and faults in the surrounding gabbro share a NNW-ESE orientation that is consistent with a brittle structural control imposed by the flexural curvature of the MDOCC in response to the uplift of the lower oceanic crust along a low-angle detachment fault. We propose that these flexural faults provide pathways for fluids to ingress deep into the MDOCC where they react with both mafic rocks (producing high-temperature, low pH, sulphide and copper-bearing fluids), peridotites and carbonates (increasing the pH) resulting in a moderate pH, silica-rich fluid that precipitates talc on mixing with seawater. The presence of further, inactive, talc mounds within 1 km of the VDVF indicates hydrothermal activity on OCCs has been widespread and represents a significant but hitherto overlooked mechanism of crustal heat loss and chemical interaction with the ocean at slow-spreading ridges.

Cloud Chemistry of Fallout Formation

DTIC Science & Technology

1968-01-31

SILICATES ....... 19 LEACHING STUDIES ..... ............................ 26 HIGH-TEMPERATURE MASS SPECTROMETRY ............... 31 Rare-Earth Oxide ...reactions between technetium oxides ................. 39 TABLES 1 . Small Boy particle size-weight fraction description (each particle size fraction...29 9. Rare-earth oxide thermodynamics (Reaction 15) ............... 32 10. Enthalpies for gas-phase reactions

Experimental study of the electrolysis of silicate melts

NASA Technical Reports Server (NTRS)

Keller, R.; Larimer, K. T.

1991-01-01

To produce oxygen from lunar resources, it may be feasible to melt and electrolyze local silicate ores. This possibility was explored experimentally with synthesized melts of appropriate compositions. Platinum electrodes were employed at a melt temperature of 1425 C. When silicon components of the melt were reduced, the platinum cathode degraded rapidly, which prompted the substitution of a graphite cathode substrate. Discrete particles containing iron or titanium were found in the solidified electrolyte after three hours of electrolysis. Electrolyte conductivities did not decrease substantially, but the escape of gas bubbles, in some cases, appeared to be hindered by high viscosity of the melt.

Thermochromic platinum complexes

DOEpatents

Kostic, Nenad M.; Zhou, Xia-Ying

1990-05-29

Thermochromic compounds containing the [Pt(dipic)Cl].sup.- anion. These compounds are yellow and monomeric at high temperatures or in low concentrations and abruptly change to red and polymeric at low temperatures or higher solution concentrations. This unusual property allows them to be used as temperature sensors.

Thermochromic platinum complexes

DOEpatents

Kostic, Nenad M.; Zhou, Xia-Ying

1989-08-15

Thermochromic compounds containing the [Pt(dipic)Cl].sup.- anion. These compounds are yellow and monomeric at high temperatures or in low concentrations and abruptly change to red and polymeric at low temperatures or higher solution concentrations. This unusual property allows them to be used as temperature sensors.

Anomalous glassy dynamics in simple models of dense biological tissue

NASA Astrophysics Data System (ADS)

Sussman, Daniel M.; Paoluzzi, M.; Marchetti, M. Cristina; Manning, M. Lisa

2018-02-01

In order to understand the mechanisms for glassy dynamics in biological tissues and shed light on those in non-biological materials, we study the low-temperature disordered phase of 2D vertex-like models. Recently it has been noted that vertex models have quite unusual behavior in the zero-temperature limit, with rigidity transitions that are controlled by residual stresses and therefore exhibit very different scaling and phenomenology compared to particulate systems. Here we investigate the finite-temperature phase of two-dimensional Voronoi and Vertex models, and show that they have highly unusual, sub-Arrhenius scaling of dynamics with temperature. We connect the anomalous glassy dynamics to features of the potential energy landscape associated with zero-temperature inherent states.

Energy saving effect of desiccant ventilation system using Wakkanai siliceous shale

NASA Astrophysics Data System (ADS)

Nabeshima, Yuki; Togawa, Jun-ya; Nagano, Katsunori; Kazuyo, Tsuzuki

2017-10-01

The nuclear power station accident resulting from the Great East Japan Earthquake disaster has resulted in a constrained electricity supply. However, in this Asian region there is high temperature and high humidity and consequently dehumidification process requires a huge amount of energy. This is the reason for the increasing energy consumption in the residential and commercial sectors. Accordingly, a high efficiency air-conditioning system is needed to be developed. The desiccant ventilation system is effective to reduce energy consumption for the dehumidification process. This system is capable of dehumidifying without dew condensing unlike a conventional air-conditioning system. Then we focused on Wakkanai Siliceous Shale (WSS) as a desiccant material to develop a new desiccant ventilation system. This is low priced, high performance, new type of thing. The aim of this study is to develop a desiccant ventilation unit using the WSS rotor which can be regenerated with low-temperature by numerical calculation. The results of performance prediction of the desiccant unit, indicate that it is possible to regenerate the WSS rotor at low-temperature of between 35 - 45 °C. In addition, we produced an actual measurement for the desiccant unit and air-conditioning unit. This air-conditioning system was capable to reduce roughly 40 % of input energy consumption.

Change in Unusually Hot and Cold Temperatures in the Contiguous 48 States, 1948-2015

EPA Pesticide Factsheets

This map shows trends in unusually hot and cold temperatures at individual weather stations that have operated consistently since 1948. In this case, the term ??unusually hot?? refers to a daily maximum temperature that is hotter than the 95th percentile temperature during the 1948??2015 period. Thus, the maximum temperature on a particular day at a particular station would be considered ??unusually hot?? if it falls within the warmest 5 percent of measurements at that station during the 1948??2015 period. The map shows changes in the total number of days per year that were hotter than the 95th percentile. Red upward-pointing symbols show where these unusually hot days are becoming more common. Blue downward-pointing symbols show where unusually hot days are becoming less common. For more information: www.epa.gov/climatechange/science/indicators

Sulfide Melts and Chalcophile Element Behavior in High Temperature Systems

NASA Astrophysics Data System (ADS)

Wood, B. J.; Kiseeva, K.

2016-12-01

We recently found that partition coefficients (Di) of many weakly and moderately chalcophile elements (e.g., Cd, Zn, Co, Cr, Pb, Sb, In) between sulfide and silicate melts are simple functions of the FeO content of the silicate liquid: logDi A-Blog[FeO] where [FeO] is the FeO concentration in the silicate, A and B are constants and the latter is related to the valency of the element of interest. In contrast, some strongly chalcophile (e.g Cu, Ni, Ag) and lithophile elements (e.g Mn) show marked deviations from linearity on a plot of logDi vs log[FeO]. More recent experiments show that linear behavior is confined to elements whose affinities for S and O are similar to those of Fe. In the case of elements more strongly lithophile than Fe (Ti, U, REE, Zr, Nb, Ta, Mn) a plot of logDi versus log[FeO] describes a U-shape with the element partitioning strongly into the sulfide at very low FeO and again at very high FeO content of the silicate melt. In contrast, strongly chalcophile elements (Cu, Ni, Ag) describe an n-shape on the plot of logD vs log[FeO]. The result is that lithophile elements such as Nb become more "chalcophile" than Cu at very low and very high FeO contents of the silicate melt. The reasons for this surprising behavior are firstly that, at very low FeO contents the silicate melt dissolves substantial amounts of sulfur, which drives down the activity of FeO and, from mass-action "pulls" the lihophile element into the sulfide. At high FeO contents of the silicate the sulfide itself starts to dissolve substantial amounts of oxygen and lithophile elements follow the oxygen into the sulfide. Given the principles which we have established, we are able to describe the patterns of chalcophile element behavior during partial melting and fractional crystallisation on Earth and also on bodies such as Mercury and Mars which are, respectively, strongly reduced relative to Earth and more oxidised than Earth.

Crystal structures and infrared spectra of two Fe-bearing hydrous magnesium silicates synthesized at high temperature and pressure

NASA Technical Reports Server (NTRS)

Yang, H.; Prewitt, C. T.; Liu, Z.

2002-01-01

The synthesis and characterization of Fe-bearing phase E and phase E' demonstrate that the phase E-type structures can be rather compliant and complex, and that as we further explore the temperature-pressure-composition space, other types of structures that are similar to or related to the structure of phase E may be discovered.

Investigation of the H7 ordinary chondrite, Watson 012: Implications for recognition and classification of Type 7 meteorites

NASA Astrophysics Data System (ADS)

Tait, Alastair W.; Tomkins, Andrew G.; Godel, Bélinda M.; Wilson, Siobhan A.; Hasalova, Pavlina

2014-06-01

Despite the fact that the number of officially classified meteorites is now over 45,000, we lack a clearly defined sequence of samples from a single parent body that records the entire range in metamorphic temperatures from pristine primitive meteorites up to the temperatures required for extensive silicate partial melting. Here, we conduct a detailed analysis of Watson 012, an H7 ordinary chondrite, to generate some clarity on the textural and chemical changes associated with equilibrium-based silicate partial melting in chondritic meteorites. To do this we compare the textures in the meteorite with those preserved in metamorphic contact aureoles on Earth. The most distinctive texture generated by the partial melting that affected Watson 012 is an extensively interconnected plagioclase network, which is clearly observable with a petrographic microscope. Enlarged metal-troilite grains are encapsulated at widenings in this plagioclase network, and this is clearly visible in reflected light. Together with these features, we define a series of other characteristics that can be used to more clearly classify chondritic meteorites as being of petrologic Type 7. To provide comprehensive evidence of silicate partial melting and strengthen the case for using simple petrographic observations to classify similar meteorites, we use high-resolution X-ray computed tomography to demonstrate that the plagioclase network has a high degree of interconnectedness and crystallised as large (cm-scale) skeletal crystals within an olivine-orthopyroxene-clinopyroxene framework, essentially pseudomorphing a melt network. Back-scattered electron imaging and element mapping are used to show that some of the clino- and orthopyroxene in Watson 012 also crystallised from silicate melt, and the order of crystallisation was orthopyroxene → clinopyroxene → plagioclase. X-ray diffraction data, supported by bulk geochemistry, are used to show that plagioclase and ortho- and clinopyroxene were added to the Watson 012 sample by through-flowing basaltic melt. Along with the absence of glass and granophyre, this interconnected network of coarse-grained skeletal plagioclase indicates that the sample cooled slowly at depth within the parent body. The evidence of melt flux indicates that Watson 012 formed in the presence of a gravitational gradient, and thus at significant distance from the centre of the H chondrite parent body (the gravitational gradient at the centre would be zero). Our interpretation is that incipient silicate partial melting in Watson 012 occurred when a region of radiogenically heated H6 material located at considerable depth (possibly at ∼15-20 km from surface) was heated by an additional ca. 200-300 °C in association with a large shock event. Due to insulation at depth within an already hot parent body, the post-shock temperature equilibrated and remained above the solidus long enough for widespread equilibrium-based silicate partial melting, and for melt to migrate. Although the observed melting may have been facilitated by additional heating from an impact event, this is not an example of instantaneous shock melting, which produces thermal disequilibrium at short length scales and distinctly different textures. A small number of H, L and LL chondrites have been previously classified as being of petrologic Type 7; with our new criteria to support that classification, these represent our best opportunity to explore the transition from high temperature sub-solidus metamorphism through the onset of silicate partial melting in three different parent bodies.

Geographic variation in the relationships of temperature, salinity or sigma sub t versus plant nutrient concentrations in the world ocean. [silicic acid, nitrate, and phosphate concentration

NASA Technical Reports Server (NTRS)

Kamykowski, D.; Zentara, S. J.

1985-01-01

A NODC data set representing all regions of the world ocean was analyzed for temperature and sigma-t relationships with nitrate, phosphate or silicic acid. Six cubic regressions were for each ten degree square of latitude and longitude containing adequate data. World maps display the locations that allow the prediction of plant nutrient concentrations from temperature or sigma-t. Geographic coverage improves along the sequence: nitrate, phosphate, and silicic acid and is better for sigma-t than for temperature. Contour maps of the approximate temperature of sigma-t at which these nitrients are no longer measurable in a parcel of water are generated, based on a percentile analysis of the temperature or sigma-t at which less than a selected amount of plant nutrient occurs. Results are stored on magnetic tape in tabular form. The global potential to predict plant nutrient concentrations from remotely sensed temperature of sigma-t and to emphasize the latitudinally and longitudinally changing phytoplankton growth environment in present and past oceans is demonstrated.

Planetesimal core formation with partial silicate melting using in-situ high P, high T, deformation x-ray microtomography

NASA Astrophysics Data System (ADS)

Anzures, B. A.; Watson, H. C.; Yu, T.; Wang, Y.

2017-12-01

Differentiation is a defining moment in formation of terrestrial planets and asteroids. Smaller planetesimals likely didn't reach high enough temperatures for widescale melting. However, we infer that core formation must have occurred within a few million years from Hf-W dating. In lieu of a global magma ocean, planetesimals likely formed through inefficient percolation. Here, we used in-situ high temperature, high pressure, x-ray microtomography to track the 3-D evolution of the sample at mantle conditions as it underwent shear deformation. Lattice-Boltzmann simulations for permeability were used to characterize the efficiency of melt percolation. Mixtures of KLB1 peridotite plus 6.0 to 12.0 vol% FeS were pre-sintered to achieve an initial equilibrium microstructure, and then imaged through several consecutive cycles of heating and deformation. The maximum calculated melt segregation velocity was found to be 0.37 cm/yr for 6 vol.% FeS and 0.61 cm/year for 12 vol.% FeS, both below the minimum velocity of 3.3 cm/year required for a 100km planetesimal to fully differentiate within 3 million years. However, permeability is also a function of grain size and thus the samples having smaller grains than predicted for small planetesimals could have contributed to low permeability and also low migration velocity. The two-phase (sulfide melt and silicate melt) flow at higher melt fractions (6 vol.% and 12 vol.% FeS) was an extension of a similar study1 containing only sulfide melt at lower melt fraction (4.5 vol.% FeS). Contrary to the previous study, deformation did result in increased permeability until the sample was sheared by twisting the opposing Drickamer anvils by 360 degrees. Also, the presence of silicate melt caused the FeS melt to coalesce into less connected pathways as the experiment with 6 vol.% FeS was found to be less permeable than the one with 4.5 vol.% FeS but without any partial melt. The preliminary data from this study suggests that impacts as well as higher temperature leading to partial melting of the silicate portion of the mantle could have contributed to fast enough core formation. 1. Todd, K.A., Watson, H.C., Yu, T., Wang, Y., American Mineralogist, 101.9, 1996-2004, 2016

The crystalline revolution :ISO's finding opens a new research field, "astro-mineralogy"

NASA Astrophysics Data System (ADS)

2000-02-01

Silicate minerals were known to be a main component of dust in space, but detecting them in a crystallised state has been a surprise. It allows the identification of precise silicates in astronomical objects, which will open "a totally new field in astronomy: astro-mineralogy. This is the crystalline revolution", said the author, Dutch astronomer Rens Waters of Amsterdam university. "It's really fantastic, this possibility of identifying the silicates. Before ISO everybody thought that all silicates in space were amorphous, without a well-ordered internal structure; that means you cannot differentiate among the many different silicates existing. Now we can try to identify them and track their presence in different regions. A whole new research field is starting", said Rens Waters, who brought to the press conference samples of several terrestrial crystalline silicates: olivine and pyroxene, the most common silicates on Earth. Crystals give key clues about the physical conditions and evolutionary history of crystal-bearing objects. The precise mechanisms for crystal-making are now being researched now very actively in the laboratories, although some working-hypotheses are already being used. For instance, crystals can be made by heating the material to temperatures above 1 300 degrees Centigrade and then cooling it down slowly. Those found so far by ISO are at -170 degrees Centigrade, both in stellar envelopes and in protoplanetary discs. In the case of the old stars -red giant stars, where crystals are found to account for as much as 20% of all the surrounding dust, astronomers think that that the high temperatures near the star triggered the crystallisation of the silicates. In the protoplanetary discs some experts postulate that electric shocks - like lightning flashes - heated the dust, which cooled afterwards. "The crystals detected by ISO in these discs have a size of about a thousandth of a millimetre. They collide with each other, forming bigger and bigger bodies. Models predict that in about ten to one hundred million years they will make planets", Waters says. "In fact, crystalline silicates are very common in our own Solar System. You also have them in the comet Hale Bopp!". The reason why crystalline silicates had not been detected before in stars has to do with their low temperatures. Cold material emits mostly infrared light, which means an infrared space telescope like ESA's ISO was needed. The two high-resolution spectrometers on-board the satellite, able to detect the 'chemical fingerprint' of the crystals, did the rest. Astronomers are sure about the discovery because those chemical fingerprints, the spectra, can be compared in laboratories with spectra from crystalline silicates found on Earth. This method has demonstrated the crystalline structure and has even already allowed the identification of some of the crystals, such as forsterite and enstatite. However, crystalline silicates are a large family and their chemical signatures can be very similar; to enlarge the list of precise crystals more work will be needed, say experts in space chemistry. That is just one of the open questions requiring lab work. There's at least another one: crystalline silicates are found around old stars, in protoplanetary disks and in our own Solar System, but not in the space among the stars; astronomers can't explain it yet. "Crystalline silicates are synthesised around the stars; then that dust goes into the interstellar space, and enriches the raw material out of which more stars and planets will form. So you would expect crystals also to be in the interstellar medium! Crystals will certainly make us learn a lot...", says Waters. "This finding shows that ISO is really unveiling the chemistry of the Universe", says ESA astronomer Alberto Salama, chairman of the workshop about ISO results in spectroscopy held this week at ESA's Villafranca station in Madrid where the results were presented to the scientific community. "This is becoming more and more a 'hot field' of research. Initially we intended to organise a modest workshop, but we have had 150 astronomers coming from all over Europe!".

Plasma technologies application for building materials surface modification

NASA Astrophysics Data System (ADS)

Volokitin, G. G.; Skripnikova, N. K.; Volokitin, O. G.; Shehovtzov, V. V.; Luchkin, A. G.; Kashapov, N. F.

2016-01-01

Low temperature arc plasma was used to process building surface materials, such as silicate brick, sand lime brick, concrete and wood. It was shown that building surface materials modification with low temperature plasma positively affects frost resistance, water permeability and chemical resistance with high adhesion strength. Short time plasma processing is rather economical than traditional processing thermic methods. Plasma processing makes wood surface uniquely waterproof and gives high operational properties, dimensional and geometrical stability. It also increases compression resistance and decreases inner tensions level in material.

Whisker/Cone growth on the thermal control surfaces experiment no. S0069

NASA Technical Reports Server (NTRS)

Zwiener, James M.; Coston, James E., Jr.; Miller, Edgar R.; Mell, Richard J.; Wilkes, Donald R.

1995-01-01

An unusual surface 'growth' was found during scanning electron microscope (SEM) investigations of the Thermal Control Surface Experiment (TCSE) S0069 front thermal cover. This 'growth' is similar to the cone type whisker growth phenomena as studied by G. K. Wehner beginning in the 1960's. Extensive analysis has identified the most probable composition of the whiskers to be a silicate type glass. Sources of the growth material are outgassing products from the experiment and orbital atomic oxygen, which occurs naturally at the orbital altitudes of the LDEF mission in the form of neutral atomic oxygen. The highly ordered symmetry and directionality of the whiskers are attributed to the long term (5.8 year) stable flight orientation of the LDEF.

Deep-Earth Equilibration between Molten Iron and Solid Silicates

NASA Astrophysics Data System (ADS)

Brennan, M.; Zurkowski, C. C.; Chidester, B.; Campbell, A.

2017-12-01

Elemental partitioning between iron-rich metals and silicate minerals influences the properties of Earth's deep interior, and is ultimately responsible for the nature of the core-mantle boundary. These interactions between molten iron and solid silicates were influential during planetary accretion, and persist today between the mantle and liquid outer core. Here we report the results of diamond anvil cell experiments at lower mantle conditions (40 GPa, >2500 K) aimed at examining systems containing a mixture of metals (iron or Fe-16Si alloy) and silicates (peridotite). The experiments were conducted at pressure-temperature conditions above the metallic liquidus but below the silicate solidus, and the recovered samples were analyzed by FIB/SEM with EDS to record the compositions of the coexisting phases. Each sample formed a three-phase equilibrium between bridgmanite, Fe-rich metallic melt, and an oxide. In one experiment, using pure Fe, the quenched metal contained 6 weight percent O, and the coexisting oxide was ferropericlase. The second experiment, using Fe-Si alloy, was highly reducing; its metal contained 10 wt% Si, and the coexisting mineral was stishovite. The distinct mineralogies of the two experiments derived from their different starting metals. These results imply that metallic composition is an important factor in determining the products of mixed phase iron-silicate reactions. The properties of deep-Earth interfaces such as the core-mantle boundary could be strongly affected by their metallic components.

Experimental and Theoretical Studies on the Viscosity-Structure Correlation for High Alumina-Silicate Melts

NASA Astrophysics Data System (ADS)

Talapaneni, Trinath; Yedla, Natraj; Pal, Snehanshu; Sarkar, Smarajit

2017-06-01

Blast furnaces are encountering high Alumina (Al2O3 > 25 pct) in the final slag due to the charging of low-grade ores. To study the viscosity behavior of such high alumina slags, synthetic slags are prepared in the laboratory scale by maintaining a chemical composition of Al2O3 (25 to 30 wt pct) CaO/SiO2 ratio (0.8 to 1.6) and MgO (8 to 16 wt pct). A chemical thermodynamic software FactSage 7.0 is used to predict liquidus temperature and viscosity of the above slags. Experimental viscosity measurements are performed above the liquidus temperature in the range of 1748 K to 1848 K (1475 °C to 1575 °C). The viscosity values obtained from FactSage closely fit with the experimental values. The viscosity and the slag structure properties are intent by Fourier Transform Infrared (FTIR) and Raman spectroscopy. It is observed that increase in CaO/SiO2 ratio and MgO content in the slag depolymerizes the silicate structure. This leads to decrease in viscosity and activation energy (167 to 149 kJ/mol) of the slag. Also, an addition of Al2O3 content increases the viscosity of slag by polymerization of alumino-silicate structure and activation energy from 154 to 161 kJ/mol. It is witnessed that the activation energy values obtained from experiment closely fit with the Shankar model based on Arrhenius equation.

Chinese Journal of Lasers (Selected Articles),

DTIC Science & Technology

1986-04-22

properties We first investigated silicate based glasses, then the other inorganic glasses such as borate, phosphate, germanate. tellurate ...of the growth of high melting temperature I.~ oxides, several upward pulling single crystal furnaces with nigh precision mechanical movement and high...automatic electronic weighting systems, and programmable automatic movement correction systems. The reliability of most of these control systems

Experimental evidence for Mo isotope fractionation between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Burkhardt, Christoph; Schmidt, Max W.; Bourdon, Bernard; Kleine, Thorsten

2013-10-01

Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to <1400 °C, while variable Fe-oxide contents were used to vary oxygen fugacity in graphite and MgO capsules. Isotopic analyses were performed using a double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

Atomic layer deposition of zirconium silicate films using zirconium tetrachloride and tetra-n-butyl orthosilicate

NASA Astrophysics Data System (ADS)

Kim, Won-Kyu; Kang, Sang-Woo; Rhee, Shi-Woo; Lee, Nae-In; Lee, Jong-Ho; Kang, Ho-Kyu

2002-11-01

Atomic layer chemical vapor deposition of zirconium silicate films with a precursor combination of ZrCl4 and tetra-n-butyl orthosilicate (TBOS) was studied for high dielectric gate insulators. The effect of deposition conditions, such as deposition temperature, pulse time for purge and precursor injection on the deposition rate per cycle, and composition of the film were studied. At 400 °C, the growth rate saturated to 1.35 Å/cycle above 500 sccm of the argon purge flow rate. The growth rate, composition ratio ((Zr/Zr+Si)), and impurity contents (carbon and chlorine) saturated with the increase of the injection time of ZrCl4 and TBOS and decreased with the increased deposition temperature from 300 to 500 °C. The growth rate, composition ratio, carbon, and chlorine contents of the Zr silicate thin films deposited at 500 °C were 1.05 Å/cycle, 0.23, 1.1 at. %, and 2.1 at. %, respectively. It appeared that by using only zirconium chloride and silicon alkoxide sources, the content of carbon and chlorine impurities could not be lowered below 1%. It was also found that the incorporation rate of metal from halide source was lower than alkoxide source.

Solubility of tungsten in a haplobasaltic melt as a function of temperature and oxygen fugacity

NASA Astrophysics Data System (ADS)

Ertel, W.; O'Neill, H. St. C.; Dingwell, D. B.; Spettel, B.

1996-04-01

The solubility of tungsten (W) in a haplobasaltic melt has been determined as a function of oxygen fugacity in the temperature range 1300-1500°C using the mechanically assisted equilibrium technique of Dingwell et al. (1994), and at 1600-1700°C by the wire loop method. Quenched samples were analysed for W by using ICP-AES as well as INAA, and sample major element compositions were checked by electron microprobe. W concentrations ranged from 20 ppm to 17 wt%, and the solution of WO 2 in the melt may be described by Henry's Law up to remarkably high concentrations (e.g., 14 wt% at 1500°C). W dissolves in the melt with a quadrivalent (4+) formal oxidation state over the entire range of oxygen fugacity and temperature investigated. The solubility of W decreases strongly with increasing temperature at constant oxygen fugacity. The solubility data have been used to calculate trace distribution coefficients for W between Fe-rich metal and silicate melt, using literature values for the activity coefficient of W in liquid Fe. Comparison of our data with the distribution coefficients for Mo calculated from the analogous Mo solubility data of Holzheid et al. (1994) shows that the ratio of the metal-silicate distribution coefficient DMomet/sil/ DWmet/sil remains very high (~10 3) at all T-fO 2 conditions. However, in the Earth's mantle, Mo is relatively more depleted than W only by a factor of three. The relative abundances of W and Mo in the Earth's mantle cannot, therefore, be explained by core formation from a homogeneously accreted Earth whatever the temperature at which metal/silicate equilibrium may have ocurred might have been. Their abundances may be quantitatively accounted for by a heterogeneous accretion model such as that of O'Neill (1991).

Interplay of superconductivity and magnetic fluctuations in single crystals of BaFe2-xCoxAs2

NASA Astrophysics Data System (ADS)

Bag, Biplab; Kumar, Ankit; Banerjee, S. S.; Vinod, K.; Bharathi, A.

2018-04-01

We report unusual pinning response in optimally doped and overdoped single crystals of BaFe2-xCoxAs2. Here we use magneto-optical imaging technique to measure the local magnetization response which shows an unusual transformation from low temperature diamagnetic state to high temperature positive magnetization response. Our data suggests coexistence of magnetic fluctuation along with superconductivity in the optimally doped crystal. The strength of magnetic fluctuations is the strongest in the optimally doped compound with the highest Tc.

Voluminous lava-like precursor to a major ash-flow tuff: Low-column pyroclastic eruption of the Pagosa Peak Dacite, San Juan volcanic field, Colorado

USGS Publications Warehouse

Bachmann, Olivier; Dungan, M.A.; Lipman, P.W.

2000-01-01

The Pagosa Peak Dacite is an unusual pyroclastic deposit that immediately predated eruption of the enormous Fish Canyon Tuff (~5000 km3) from the La Garita caldera at 28 Ma. The Pagosa Peak Dacite is thick (to 1 km), voluminous (>200 km3), and has a high aspect ratio (1:50) similar to those of silicic lava flows. It contains a high proportion (40-60%) of juvenile clasts (to 3-4 m) emplaced as viscous magma that was less vesiculated than typical pumice. Accidental lithic fragments are absent above the basal 5-10% of the unit. Thick densely welded proximal deposits flowed rheomorphically due to gravitational spreading, despite the very high viscosity of the crystal-rich magma, resulting in a macroscopic appearance similar to flow-layered silicic lava. Although it is a separate depositional unit, the Pagosa Peak Dacite is indistinguishable from the overlying Fish Canyon Tuff in bulk-rock chemistry, phenocryst compositions, and 40Ar/39Ar age. The unusual characteristics of this deposit are interpreted as consequences of eruption by low-column pyroclastic fountaining and lateral transport as dense, poorly inflated pyroclastic flows. The inferred eruptive style may be in part related to synchronous disruption of the southern margin of the Fish Canyon magma chamber by block faulting. The Pagosa Peak eruptive sources are apparently buried in the southern La Garita caldera, where northerly extensions of observed syneruptive faults served as fissure vents. Cumulative vent cross-sections were large, leading to relatively low emission velocities for a given discharge rate. Many successive pyroclastic flows accumulated sufficiently rapidly to weld densely as a cooling unit up to 1000 m thick and to retain heat adequately to permit rheomorphic flow. Explosive potential of the magma may have been reduced by degassing during ascent through fissure conduits, leading to fracture-dominated magma fragmentation at low vesicularity. Subsequent collapse of the 75 x 35 km2 La Garita caldera and eruption of the Fish Canyon Tuff were probably triggered by destabilization of the chamber roof as magma was withdrawn during the Pagosa Peak eruption. (C) 2000 Elsevier Science B.V. All rights reserved.

Rietveld refinement of the crystal structures of Rb2 XSi5O12 (X = Ni, Mn).

PubMed

Bell, Anthony M T; Henderson, C Michael B

2016-02-01

The synthetic leucite silicate framework mineral analogues Rb2 XSi5O12 {X = Ni [dirubidium nickel(II) penta-silicate] and Mn [dirubidium manganese(II) penta-silicate]} have been prepared by high-temperature solid-state synthesis. The results of Rietveld refinements, using X-ray powder diffraction data collected using Cu Kα X-rays, show that the title compounds crystallize in the space group Pbca and adopt the cation-ordered structure of Cs2CdSi5O12 and other leucites. The structures consist of tetra-hedral SiO4 and XO4 units sharing corners to form a partially substituted silicate framework. Extraframework Rb(+) cations sit in channels in the framework. All atoms occupy the 8c general position for this space group. In these refined structures, silicon and X atoms are ordered onto separate tetra-hedrally coordinated sites (T-sites). However, the Ni displacement parameter and the Ni-O bond lengths suggest that for the X = Ni sample, there may actually be some T-site cation disorder.

Rietveld refinement of the crystal structures of Rb2 XSi5O12 (X = Ni, Mn)

PubMed Central

Bell, Anthony M. T.; Henderson, C. Michael B.

2016-01-01

The synthetic leucite silicate framework mineral analogues Rb2 XSi5O12 {X = Ni [dirubidium nickel(II) penta­silicate] and Mn [dirubidium manganese(II) penta­silicate]} have been prepared by high-temperature solid-state synthesis. The results of Rietveld refinements, using X-ray powder diffraction data collected using Cu Kα X-rays, show that the title compounds crystallize in the space group Pbca and adopt the cation-ordered structure of Cs2CdSi5O12 and other leucites. The structures consist of tetra­hedral SiO4 and XO4 units sharing corners to form a partially substituted silicate framework. Extraframework Rb+ cations sit in channels in the framework. All atoms occupy the 8c general position for this space group. In these refined structures, silicon and X atoms are ordered onto separate tetra­hedrally coordinated sites (T-sites). However, the Ni displacement parameter and the Ni—O bond lengths suggest that for the X = Ni sample, there may actually be some T-site cation disorder. PMID:26958399

High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of mixed-alkali metals uranyl silicates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Yi-Hsin; Liu, Hsin-Kuan; Chang, Wen-Jung

2016-04-15

Three mixed-alkali metals uranyl silicates, Na{sub 3}K{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}]·2H{sub 2}O (1), Na{sub 3}Rb{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}] (2), and Na{sub 6}Rb{sub 4}[(UO{sub 2}){sub 4}Si{sub 12}O{sub 33}] (3), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 °C and 1440 bar, and characterized by single-crystal X-ray diffraction, photoluminescence, and thermogravimetric analysis. Compound 1 and 2 are isostructural and contain layers of uranyl disilicate. The smaller cation, Na{sup +}, is located in the intralayer channels, whereas the larger cations, K{sup +} and Rb{sup +}, and water molecule are located in the interlayer region. The absencemore » of lattice water in 2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate. Compound 3 adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain with the structural formula {uB,4"1_∞}[{sup 3}Si{sub 12}O{sub 33}] formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. The connectivity of the Si atoms in the Si{sub 12}O{sub 33}{sup 18−} anion can be interpreted on the basis of Zintl–Klemm concept. Crystal data for compound 1: triclinic, P-1, a=5.7981(2) Å, b=7.5875(3) Å, c=12.8068(5) Å, α=103.593(2)°, β=102.879(2)°, γ=90.064(2)°, V=533.00(3) Å{sup 3}, Z=1, R1=0.0278; compound 2: triclinic, P-1, a=5.7993(3) Å, b=7.5745(3) Å, c=12.9369(6) Å, α=78.265(2)°, β=79.137(2)°, γ=89.936(2)°, V=546.02(4) Å{sup 3}, Z=1, R1=0.0287; compound 3: monoclinic, C2/m, a=23.748(1) Å, b=7.3301(3) Å, c=15.2556(7) Å, β=129.116(2)°, V=2060.4(2) Å{sup 3}, Z=2, R1=0.0304. - Graphical abstract: Three mixed-alkali metals uranyl silicates were synthesized under hydrothermal conditions at 550 °C and 1400 bar and structurally characterized by single-crystal X-ray diffraction. Two of them have a layer structure with the alkali metal cations within and between the layers. The third one adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. - Highlights: • Three new mixed-alkali metals uranyl silicates were synthesized by high-T, high-P hydrothermal method and structurally. • Two compounds adopt a layer structure and the third one has a 3D framework structure. • The 3D framework structure contains a unique unbranched dreier fourfold silicate chain formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si.« less

Evolution of Titan's High-Pressure Ice layer

NASA Astrophysics Data System (ADS)

Sotin, C.; Kalousova, K.

2016-12-01

Constraints on the present interior structure of Titan come from the gravity science experiment onboard the Cassini spacecraft and from the interpretation of the Extremely Low Frequency (ELF) wave observed by the Huygens probe [1, 2]. From the surface to the center, Titan would be composed of 4 layers: an icy crust, a global salty ocean, a layer of high-pressure ice (HP ice) and a core made of hydrated silicates [2, 3, 4]. The presence of a large amount of 40Ar in Titan's atmosphere argues for a geologically recent exchange process between the silicate core, where 40Ar is produced by the decay of 40K, and the atmosphere. Argon must then be able to be transported from the silicate core to the surface. This study investigates how volatiles can be transported through the HP ice layer.Recent numerical simulations [5] have demonstrated that the dynamics of the HP ice layer is controlled by convection processes in a two-phase material (water and high-pressure ice). The silicate / HP ice interface is maintained at the melting temperature, which might allow for the incorporation of volatiles such as 40Ar into the convecting HP ice. Above the hot thermal boundary layer, the temperature of the convecting HP ice is below the melting temperature, except for the upwelling plumes when they approach the cold thermal boundary layer. The upper part of the HP ice layer is at the melting point and permeable for water transport, providing a path for the transfer of volatiles trapped in the ice towards the ocean.Scaling laws are inferred from the numerical simulations [5]. They are then used to model the evolution of the HP ice layer. Specifically, we look at the effect of (i) ice viscosity, (ii) heat flux at the silicate/HP ice interface, and (iii) presence of anti-freeze compounds in the ocean, on the thickness of the HP ice layer. In addition, our results provide insights on possible resurfacing processes that could explain the geologically young age of Titan's surface. This work has been performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. [1] Iess et al. (2012) Science, 337, 457-461. [2] Beghin et al. (2012) Icarus, 1028-1042. [3] Mitri et al. (2014) Icarus, 236, 169-177. [4] Castillo and Lunine (2010) Geophys. Res. Lett., 37, L20205. [5] Kalousova et al. (2015) Fall AGU, P31C-2078.

Multidiffusion mechanisms for noble gases (He, Ne, Ar) in silicate glasses and melts in the transition temperature domain: Implications for glass polymerization

NASA Astrophysics Data System (ADS)

Amalberti, Julien; Burnard, Pete; Laporte, Didier; Tissandier, Laurent; Neuville, Daniel R.

2016-01-01

Noble gases are ideal probes to study the structure of silicate glasses and melts as the modifications of the silicate network induced by the incorporation of noble gases are negligible. In addition, there are systematic variations in noble gas atomic radii and several noble gas isotopes with which the influence of the network itself on diffusion may be investigated. Noble gases are therefore ideally suited to constrain the time scales of magma degassing and cooling. In order to document noble gas diffusion behavior in silicate glass, we measured the diffusivities of three noble gases (4He, 20Ne and 40Ar) and the isotopic diffusivities of two Ar isotopes (36Ar and 40Ar) in two synthetic basaltic glasses (G1 and G2; 20Ne and 36Ar were only measured in sample G1). These new diffusion results are used to re-interpret time scales of the acquisition of fractionated atmospheric noble gas signatures in pumices. The noble gas bearing glasses were synthesized by exposing the liquids to high noble gas partial pressures at high temperature and pressure (1750-1770 K and 1.2 GPa) in a piston-cylinder apparatus. Diffusivities were measured by step heating the glasses between 423 and 1198 K and measuring the fraction of gas released at each temperature step by noble gas mass spectrometry. In addition we measured the viscosity of G1 between 996 and 1072 K in order to determine the precise glass transition temperature and to estimate network relaxation time scales. The results indicate that, to a first order, that the smaller the size of the diffusing atom, the greater its diffusivity at a given temperature: D(He) > D(Ne) > D(Ar) at constant T. Significantly, the diffusivities of the noble gases in the glasses investigated do not display simple Arrhenian behavior: there are well-defined departures from Arrhenian behavior which occur at lower temperatures for He than for Ne or Ar. We propose that the non-Arrhenian behavior of noble gases can be explained by structural modifications of the silicate network itself as the glass transition temperature is approached: as the available free volume (available site for diffusive jumps) is modified, noble gas diffusion is no longer solely temperature-activated but also becomes sensitive to the kinetics of network rearrangements. The non-Arrhenian behavior of noble gas diffusion close to Tg is well described by a modified Vogel-Tammann-Fulcher (VTF) equation: Finally, our step heating diffusion experiments suggest that at T close to Tg, noble gas isotopes may suffer kinetic fractionation at a degree larger than that predicted by Graham's law. In the case of 40Ar and 36Ar, the traditional assumption based on Graham's law is that the ratio D40Ar/D36Ar should be equal to 0.95 (the square root of the ratio of the mass of 36Ar over the mass of 40Ar). In our experiment with glass G1, D40Ar/D36Ar rapidly decreased with decreasing temperature, from near unity (0.98 ± 0.14) at T > 1040 K to 0.76 when close to Tg (T = 1003 K). Replicate experiments are needed to confirm the strong kinetic fractionation of heavy noble gases close to the transition temperature.

Spin crossover in liquid Fe2SiO4 at high pressures: an ab initio Molecular Dynamics study

NASA Astrophysics Data System (ADS)

Munoz Ramo, D.; Stixrude, L. P.

2010-12-01

Liquid iron silicate (Fe2SiO4) is an important component of natural silicate liquids appearing in Earth’s interior. The effect of iron in the properties of these melts is a crucial issue, as it displays a high-spin to low-spin transition at high pressures which is accompanied by volume reduction and changes in the optical absorption spectrum. This phenomenon has a major influence on properties like the buoyancy or the thermal conductivity of the melt, and ultimately on the chemical and thermal evolution of our planet. Computer simulations using ab initio methods have proven to be a powerful approach to the study of liquid silicate systems[1,2], although not yet including Fe. In this paper, we report ab initio molecular dynamics studies of liquid iron silicate at high pressure (up to 300 GPa) and high temperatures (from 3000K to 6000K) that allow us to predict different properties of the system. We use mainly the GGA density functional for the calculation of the electronic structure. We also perform simulations with the GGA+U formalism to estimate the impact of strong electron correlation effects in the properties of the system at high pressures. The spin-polarized formalism is also used in order to keep track of the evolution of the iron magnetic moments in the system. By means of these simulations we predict the short and medium-range structure and thermodynamic properties of the liquid. We compute the theoretical Hugoniot for the system and find very good agreement between the GGA results and the equation of state values obtained from shock experiments [3], while the GGA+U results overestimate the Hugoniot curve at high pressures. Density crossover with the solid is obtained at about 110 GPa at 3000 K. Our calculations show that the spin crossover in this system takes place at a wide pressure interval, dependent on temperature. At 3000K, the spin transition starts at around 10 GPa and finishes at pressures around 250 Gpa. Increase of the temperature to 6000K reduces the interval of the transition to 180 GPa. [1] N. P. de Koker, L. Stixrude, B. B. Karki, Geochim Cosmochim Acta 2008, 72, 1427. [2] B. B. Karki, D. Bhattarai, L. Stixrude, Phys. Rev. B 2007, 76, 104205. [3] G. Q. Chen, T. J. Ahrens, E. M. Stolper, Phys. Earth Planet. Inter. 2002, 134, 35.

Trapping of water vapor from an atmosphere by condensed silicate matter formed by high-temperature pulse vaporization

NASA Technical Reports Server (NTRS)

Gerasimov, M. V.; Dikov, Yu. P.; Yakovlev, O. I.; Wlotzka, F.

1993-01-01

The origin of planetary atmospheres is thought to be the result of bombardment of a growing planet by massive planetesimals. According to some models, the accumulation of released water vapor and/or carbon dioxide can result in the formation of a dense and hot primordial atmosphere. Among source and sink processes of atmospheric water vapor the formation of hydroxides was considered mainly as rehydration of dehydrated minerals (foresterite and enstatite). From our point of view, the formation of hydroxides is not limited to rehydration. Condensation of small silicate particles in a spreading vapor cloud and their interaction with a wet atmosphere can also result in the origin of hydrated phases which have no genetic connections with initial water bearing minerals. We present results of two experiments of a simulated interaction of condensed silicate matter which originated during vaporization of dry clinopyroxene in a wet helium atmosphere.

Experimental determination of the Mo isotope fractionation factor between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, R. C.; Burkhardt, C.; Schmidt, M. W.; Bourdon, B.

2011-12-01

The conditions and chemical consequences of core formation have mainly been reconstructed from experimentally determined element partition coefficients between metal and silicate liquids. However, first order questions such as the mode of core formation or the nature of the light element(s) in the Earth's core are still debated [1]. In addition, the geocentric design of most experimental studies leaves the conditions of core formation on other terrestrial planets and asteroids even more uncertain than for Earth. Through mass spectrometry, records of mass-dependent stable isotope fractionation during high-temperature processes such as metal-silicate segregation are detectable. Stable isotope fractionation may thus yield additional constrains on core formation conditions and its consequences for the chemical evolution of planetary objects. Experimental investigations of equilibrium mass-dependent stable isotope fractionation have shown that Si isotopes fractionate between metal and silicate liquids at temperatures of 1800°C and pressures of 1 GPa, while Fe isotopes leave no resolvable traces of core formation processes [2,3]. Molybdenum is a refractory and siderophile trace element in the Earth, and thus much less prone to complications arising from mass balancing core and mantle and from potential volatile behaviour than other elements. To determine equilibrium mass-dependent Mo isotope fractionation during metal-silicate segregation, we have designed piston cylinder experiments with a basaltic silicate composition and an iron based metal with ~8 wt% Mo, using both graphite and MgO capsules. Metal and silicate phases are completely segregated by the use of a centrifuging piston cylinder at ETH Zurich, thus preventing analysis of mixed metal and silicate signatures. Molybdenum isotope compositions were measured using a Nu Instruments 1700 MC-ICP-MS at ETH Zurich. To ensure an accurate correction of analytical mass fractionation a 100Mo-97Mo double spike was admixed before chemical purification. Initial results provide an equilibrium 98Mo/95Mo isotope fractionation factor between metal and silicate liquids of -0.18±0.10% (2σ) at 1400°C and 1 GPa. Although the relative mass difference of these Mo isotopes is smaller than for Fe isotopes, this result implies that metal-silicate segregation may have led to mass-dependent stable Mo isotope fractionation, as opposed to Fe isotopes. A possible explanation is that the bonding environment of Mo may counterbalance its relatively small mass separation. At reducing conditions, Mo occurs in 4+ valence state in silicates [4] and thus its bond strength difference between metal and silicate may be more similar to that of Si than Fe. Stable Mo isotopes may thus become an important tool for constraining the conditions of core formation in asteroids and terrestrial planets. [1] Rubie et al. (2011) EPSL 301, 31-42. [2] Shahar et al. (2009) EPSL 288, 228-234. [3] Poitrasson et al. (2009) EPSL 278, 376-385. [4] Farges et al. (2006) Can. Min. 44, 731-753.

Hydrothermal Synthesis of Dicalcium Silicate Based Cement

NASA Astrophysics Data System (ADS)

Dutta, N.; Chatterjee, A.

2017-06-01

It is imperative to develop low energy alternative binders considering the large amounts of energy consumed as well as carbon dioxide emissions involved in the manufacturing of ordinary Portland cement. This study is on the synthesis of a dicalcium silicate based binder using a low temperature hydrothermal route.The process consists of synthesizing an intermediate product consisting of a calcium silicate hydrate phase with a Ca:Si ratio of 2:1 and further thermal treatment to produce the β-Ca2SiO4 (C2S) phase.Effect of various synthesis parameters like water to solid ratio, dwell time and temperature on the formation of the desired calcium silicate hydrate phase is reported along with effect of heating conditions for formation of the β-C2S phase. Around 77.45% of β-C2S phase was synthesized by thermal treatment of the intermediate phase at 820°C.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

PubMed

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H 2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

NASA Astrophysics Data System (ADS)

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

Experimental investigations of influence of pressure on the solubility of sulfur in silicate melts.

NASA Astrophysics Data System (ADS)

Kostyuk, Anastasia; Gorbachev, Nikolay

2010-05-01

Sulfide-silicate demixing of silicate melts on immiscible silicate and sulfide liquids occurs at magma sulfur saturation. This type of liquation plays an important role in geochemistry of mantle magmas, in processes of magmatic differentiation, and in ore deposit formation. The major parameter defining sulfide-silicate stratification of silicate melts is solubility of sulfur in magmas. It is considered that «solubility of sulfur» is concentration of sulfur in silicate melts. The previous researches have established positive dependence of solubility of sulphur on temperature [1, 2], melt composition [3, 4], oxidation-reduction conditions [5, 6] and our experimental data confirm it. However, available data does not give a simple answer about dependence of solubility of sulfur from pressure in modelling and natural "dry" sulfide-saturated silicate melts. The reason of difference in experiments remains not clear and further work is needed on this topic. In this paper, we report our findings on the influence of pressure on the solubility of sulfur in hydrous magnesian melts. This melts are represent by olivine basalt - picrite, coexisting with Fe-Cu-Ni sulfide melt and harzburgite (Ol+Opx) and it was investigated in a temperature range from 1200 to 1350°С and a pressure range from 0.2 to 2.5 GPa. Experiments were carried out on the piston-cylinder at Р=1-2.5GPa and in an internal-heated pressure vessels at P=0.2-0.6 GPa by a quenching technique. Our findings disagree with all previous studies demonstrating the positive [7] or negative [8, 9] influence of pressure on the solubility of sulfur in silicate melts. Our researches have shown complicated influence of pressure. Concentration of sulfur in glasses increases with increase in pressure from 0.2 to 0.6 GPa in experiments where andesite was used as a starting material. The sulfur concentration increases from 0.09 wt.% at 0.2 GPa to 0.4 wt.% at 0.6 GPa and Т=1200°С. In hydrous magnesian basalts (12-18 % MgO), we observe an extremum around 1.5 GPa. Solubility of sulfur increases from 0.31 wt.% to 1.01 wt.% at P=1-1.5 GPa, T=1300°С and decreases till 0.19 wt.% at P=2.5 GPa, T=1350°С. At ultrahigh (>4GPa) pressure concentration of sulfur in magmas will change slightly, considering increase of magnesian basalt liquidus in temperature and positive influence of temperature on the solubility of sulfur. Extreme character of the pressure dependences plays an important role in transportation of sulfide-silicate melts from the deep magmatic centers into the modern magmatic chambers where most of open deposits of hypabyssal ore-bearing magmas are localized. Possible explanation of an extremum in the field of 1.5-2.0 GPa is character of dissolution of water in silicate melts. Supported by grant RFBR 09-05-01131, 10-05-00928. References: 1.Luhr, J. F. Experimental phase relations of water- and sulphur-saturated arc magmas and the 1982 eruptions of El Chichòn Volcano. Journal of Petrology 31, 1990, p. 1071-1114. 2.Carroll, M. R. & Rutherford, M. J. The stability of igneous anhydrite: experimental results and implications for sulphur behavior in the 1982 El Chichòn trachyandesite and other evolved magmas. Journal of Petrology 28, 1987. p. 781-801. 3.Haughton, D. R., Roeder, P. L. & Skinner, B. J. Solubility of sulphur in mafic magmas. Economic Geology 69, 1974. p. 451-466 4.Wallace P., and Carmachael L.S.E. Sulfur in basaltic magmas. Geochim. Cosmochim. Acta 56, 1992. p. 1863-1874. 5.Fincham, C. J. B. & Richardson, F. D. Behaviour of sulphur in silicate and aluminate melts. Proceedings of the Royal Society of London 223, 1954. p. 40-62. 6.Carroll M.R. and Webster J.D. Solubilities of sulfur, noble gases, nitrogen, chlorine and fluorine in magmas. In Volatiles in Magmas (1994); pp. 231-279. Rev. mineral. 30, Mineralogical Society of America. 7.Mysen B.O., Popp R.N. Amer.J.Sci. V. 280. № 2. 1980 P.788-792. 8.Wendlandt R.F. Sulfide saturation of basalt and andesite melts at high pressure and temperature. Amer. Mineral. V. 67. № 7. 1982 P. 877-885. 9.Mavrogenes J.A., O'Neill H.S. The relative effects of pressure, temperature and oxygen fugacity on the solubility of sulfide in mafic magmas // Geochim. Cosmochim. Acta. 1999. V.63. № 7/8. P.1173-1180.

Optical Properties of Iron Silicates in the Infrared to Millimeter as a Function of Wavelength and Temperature

NASA Technical Reports Server (NTRS)

Richey, C. R.; Kinzer, R. E.; Cataldo, G.; Wollack, E. J.; Nuth, J. A.; Benford, D. J.; Silverberg, R. F.; Rinhart, S. A.

2013-01-01

The Optical Properties of Astronomical Silicates with Infrared Techniques program utilizes multiple instruments to provide spectral data over a wide range of temperatures and wavelengths. Experimental methods include Vector Network Analyzer and Fourier transform spectroscopy transmission, and reflection/scattering measurements. From this data, we can determine the optical parameters for the index of refraction, n, and the absorption coefficient, k. The analysis of the laboratory transmittance data for each sample type is based upon different mathematical models, which are applied to each data set according to their degree of coherence. Presented here are results from iron silicate dust grain analogs, in several sample preparations and at temperatures ranging from 5 to 300 K, across the infrared and millimeter portion of the spectrum (from 2.5 to 10,000/micron or 4000 to 1/cm).

Aqua de Ney, California, a spring of unique chemical character

USGS Publications Warehouse

Feth, J.H.; Rogers, S.M.; Roberson, C.E.

1961-01-01

The chemistry of water of Aqua de Ney, a cold spring of unusual character located in Siskiyou County, Calif., has been re-examined as part of a study of the relation of water chemistry to rock environment. The water has a pH of 11??6 and a silica content of 4000 parts per million (p.p.m.), the highest values known to occur in natural ground waters. The rocks exposed nearby consist of two volcanic sequences, one predominantly basaltic in composition, the other highly siliceous. Neither these rocks nor the sedimentary and igneous rocks presumed to underlie the area at depth seem to offer explanation of the unusual mineralization which includes 240 p.p.m. of boron, 1000 p.p.m. of sulphide (as H2S), and 148 p.p.m. of ammonia nitrogen (as NH4) in a water that is predominantly sodium chloride and sodium carbonate in character. By analogy, it is assumed that water from Aqua de Ney is the product of an initial mixture of connate sea water with a calcium magnesium sulphate water. It is postulated that ion exchange has increased the content of sodium and reduced that of calcium and magnesium, and that sulphate reduction has brought about the high alkalinity, high pH, and high content of sulphide. The large silica value is explained as the result of solution of silica by water having the high pH observed. ?? 1961.

Superheat in magma oceans

NASA Technical Reports Server (NTRS)

Jakes, Petr

1992-01-01

The existence of 'totally molten' planets implies the existence of a superheat (excess of heat) in the magma reservoirs since the heat buffer (i.e., presence of crystals having high latent heat of fusion) does not exist in a large, completely molten reservoir. Any addition of impacting material results in increase of the temperature of the melt and under favorable circumstances heat is stored. The behavior of superheat melts is little understood; therefore, we experimentally examined properties and behavior of excess heat melts at atmospheric pressures and inert gas atmosphere. Highly siliceous melts (70 percent SiO2) were chosen for the experiments because of the possibility of quenching such melts into glasses, the slow rate of reaction in highly siliceous composition, and the fact that such melts are present in terrestrial impact craters and impact-generated glasses. Results from the investigation are presented.

A Hydrothermal Origin for the Sulfate-rich Ocean of Europa

NASA Technical Reports Server (NTRS)

Zolotov, M. Yu.; Shock, E. L.

2001-01-01

Thermodynamic calculations show that formation of a sulfate-rich ocean on Europa might require high-temperature alkaline hydrothermal processes in the oxidized silicate mantle. The ocean on Europa could be thought of as a cooled hydrothermal fluid. Additional information is contained in the original extended abstract.

Rock weathering by indigenous heterotrophic bacteria of Bacillus spp. at different temperature: a laboratory experiment

NASA Astrophysics Data System (ADS)

Štyriaková, I.; Štyriak, I.; Oberhänsli, H.

2012-07-01

The bio-weathering of basalt, granite and gneiss was experimentally investigated in this study. These rock-forming minerals weathered more rapidly via the ubiquitous psychrotrophic heterotrophic bacteria . With indigenous bacteria of Bacillus spp. from sediments of Lake Baikal, we traced the degradation process of silicate minerals to understand the weathering processes occurring at the change temperature in the subsurface environment with organic input. The bacteria mediated dissolution of minerals was monitored with solution and solid chemistry, X-ray analyses as well as microscopic techniques. We determined the impact of the bacteria on the mineral surface and leaching of K, Ca, Mg, Si, Fe, and Al from silicate minerals. In the samples the release of major structural elements of silicates was used as an overall indicator of silicate mineral degradation at 4°C and 18°C from five medium exchanges over 255 days of rock bioleaching. The increase of temperature importantly affected the efficiency of Fe extraction from granite and basalt as well as Si extraction from granite and gneiss. In comparison with elemental extraction order at 4°C, Ca was substituted first by Fe or Si. It is evident that temperature influences rock microbial weathering and results in a change of elements extraction.

Habitability constraints on water-rich exoplanets

NASA Astrophysics Data System (ADS)

Noack, Lena; Höning, Dennis; Rivoldini, Attilio; Heistracher, Clemens; Zimov, Nastasia; Journaux, Baptiste; Lammer, Helmut; Van Hoolst, Tim; Hendrik Bredehöft, Jan

2016-04-01

This research addresses the characterization, modelling, thermal evolution and possible habitability of water-rich exoplanets. Water is necessary for the origin and survival of life as we know it. In the search for habitable worlds, water-rich planets therefore seem obvious candidates. The water layer on such planets could be hundreds of kilometers deep. Depending on the temperature profile and the pressure gradient, it is likely that at great depths a significant part of the water layer is solid high pressure ice. Whether the solid ice layer extends to the bottom of the water layer, or if a shallow lower ocean forms above the silicate mantle, depends amongst others on the thermal state of the planet. We therefore model the thermal evolution of water-rich planets with a 1D parameterized model. Depth-dependent profiles for thermodynamic properties as well as pressure and gravity are obtained by solving the Poisson equation for the gravity and the hydrostatic pressure equation for pre-defined mass and composition (in terms of iron, silicates and water) [1]. For density, equations of state are applied. For the simulation of the thermal evolution of water-rich planets, several parameters (as initial temperatures or layer thicknesses) are unknown. We therefore employ a quantitatve study with more than 20'000 simulations, where we investigated which parameters have the largest influence on the appearance of a lower ocean, i.e. the possible melting of high-pressure ice by heat flowing out of the silicate mantle [2]. We find that the surface temperature has the largest influence on the thickness of water layers, for which a lower ocean can still form between the high-pressure ice layer and the silicate mantle. For higher surface temperatures, not only entirely liquid oceans are possible for deeper water shells, also a liquid ocean can form under high-pressure ice layers of hundreds of kilometer thickness (for a 1 Earth-mass planet). Deeper down, the lower ocean can still appear episodically at the water-mantle boundary (WMB). We also investigated the main paramters influencing the existence of volcanic activity and silicate crust formation. Under deep water layers, the high pressure from the overlying water layer can inhibit melting in the mantle. The main parameters influencing the maximal water layer depth, for which melting is still possible, are indeed the parameters influencing the mantle energy budget, which are the amount of radioactive heat sources and the initial upper mantle temperature. Plate tectonics also has a strong influence on the existence of volcanism. Crustal parameters (initial thickness or heat sources enrichment factor) as well as the ice rheology (i.e. the isolating effect of the ice shell on the mantle) have only a small influence on melting processes in the interior and the formation of crust. [1] L. Noack, A. Rivoldini and T. Van Hoolst 2015: CHIC - Coupling Habitability, Interior and Crust: A new Code for Modeling the Thermal Evolution of Planets and Moons. INFOCOMP 2015, ISSN 2308-3484, ISBN 978-1-61208-416-9, pp. 84-90, IARIA, 2015. [2] L. Noack, D. Höning, A. Rivoldini, C. Heistracher, N. Zimov, B. Journaux, H. Lammer, T. Van Hoolst and J.H. Bredehöft: Water-rich planets: how habitable is a water layer deeper than on Earth? Submitted to Icarus.

Partitioning of Nb, Mo, Ba, Ce, Pb, Th and U between immiscible carbonate and silicate liquids: Evaluating the effects of P2O5,F, and carbonate composition

NASA Technical Reports Server (NTRS)

Jones, J. H.; Walker, D.

1993-01-01

Previously we have reported carbonate liq./silicate liq. partition coefficients (D) for a standard suite of trace elements (Nb, Mo, Ba, Ce, Pb, Th, and U) and Ra and Pa as well. In brief, we have found that immiscible liquid partitioning is a strong function of temperature. As the critical temperature of the carbonate-silicate solvus is approached, all partition coefficients approach unity. Additionally, for the overwhelming majority of the partitioning elements, InD is a linear function of 'ionic field strength,' z/r, where z is the charge of the partitioned cation and r is its ionic radius.

Experimentally determined Si isotope fractionation between silicate and Fe metal and implications for Earth's core formation

NASA Astrophysics Data System (ADS)

Shahar, Anat; Ziegler, Karen; Young, Edward D.; Ricolleau, Angele; Schauble, Edwin A.; Fei, Yingwei

2009-10-01

Stable isotope fractionation amongst phases comprising terrestrial planets and asteroids can be used to elucidate planet-forming processes. To date, the composition of the Earth's core remains largely unknown though cosmochemical and geophysical evidence indicates that elements lighter than iron and nickel must reside there. Silicon is often cited as a light element that could explain the seismic properties of the core. The amount of silicon in the core, if any, can be deduced from the difference in 30Si/ 28Si between meteorites and terrestrial rocks if the Si isotope fractionation between silicate and Fe-rich metal is known. Recent studies (e.g., [Georg R.B., Halliday A.N., Schauble E.A., Reynolds B.C., 2007. Silicon in the Earth's core. Nature 447 (31), 1102-1106.]; [Fitoussi, C., Bourdon, B., Kleine, T., Oberli, F., Reynolds, B. C., 2009. Si isotope systematics of meteorites and terrestrial peridotites: implications for Mg/Si fractionation in the solar nebula and for Si in the Earth's core. Earth Planet. Sci. Lett. 287, 77-85.]) showing (sometimes subtle) differences between 30Si/ 28Si in meteorites and terrestrial rocks suggest that Si missing from terrestrial rocks might be in the core. However, any conclusion based on Earth-meteorite comparisons depends on the veracity of the 30Si/ 28Si fractionation factor between silicates and metals at appropriate conditions. Here we present the first direct experimental evidence that silicon isotopes are not distributed uniformly between iron metal and rock when equilibrated at high temperatures. High-precision measurements of the silicon isotope ratios in iron-silicon alloy and silicate equilibrated at 1 GPa and 1800 °C show that Si in silicate has higher 30Si/ 28Si than Si in metal, by at least 2.0‰. These findings provide an experimental foundation for using isotope ratios of silicon as indicators of terrestrial planet formation processes. They imply that if Si isotope equilibrium existed during segregation of Earth's core-forming metal and silicate mantle, there should be an isotopic signature of Si in the core. Our experiments, combined with previous measurements of Si isotope ratios in meteorites and rocks representing the bulk silicate Earth, suggest that the formation of the Earth's core imparted a high 30Si/ 28Si signature to the bulk silicate Earth due to dissolution of ~ 6 wt% Si into the early core.

High-performance polymer/layered silicate nanocomposites

NASA Astrophysics Data System (ADS)

Heidecker, Matthew J.

High-performance layered-silicate nanocomposites of Polycarbonate (PC), poly(ethylene terephthalate) (PET), and their blends were produced via conventional melt-blending techniques. The focus of this thesis was on the fundamentals of dispersion, control of thermal stability, maintenance of melt-blending processing conditions, and on optimization of the composites' mechanical properties via the design of controlled and thermodynamically favorable nano-filler dispersions within the polymer matrices. PET and PC require high temperatures for melt-processing, rendering impractical the use of conventional/commercial organically-modified layered-silicates, since the thermal degradation temperatures of their ammonium surfactants lies below the typical processing temperatures. Thus, different surfactant chemistries must be employed in order to develop melt-processable nanocomposites, also accounting for polymer matrix degradation due to water (PET) or amine compounds (PC). Novel high thermal-stability surfactants were developed and employed in montmorillonite nanocomposites of PET, PC, and PC/PET blends, and were compared to the respective nanocomposites based on conventional quaternary-ammonium modified montmorillonites. Favorable dispersion was achieved in all cases, however, the overall material behavior -- i.e., the combination of crystallization, mechanical properties, and thermal degradation -- was better for the nanocomposites based on the thermally-stable surfactant fillers. Studies were also done to trace, and ultimately limit, the matrix degradation of Polycarbonate/montmorillonite nanocomposites, through varying the montmorillonite surfactant chemistry, processing conditions, and processing additives. Molecular weight degradation was, maybe surprisingly, better controlled in the conventional quaternary ammonium based nanocomposites -- even though the thermal stability of the organically modified montmorillonites was in most cases the lowest. Dependence of the resultant nanocomposites' mechanical properties on the preferential alignment of the montmorillonite nano-platelet was also evaluated. Highly aligned filler platelets did not result in an additional enhancement in mechanical properties. PC/PET blends and their respective PC/PET/montmorillonite nanocomposites were synthesized and compared. The dispersion of the organically modified nano-fillers in the PC/PET blends was controlled via thermodynamic considerations, realized through proper surfactant choice: Nanocomposites in which the layered silicate was preferentially sequestered in the PET phase were designed and synthesized. This preferential dispersion of the nano-filler in the PET phase of the PC/PET blend was insensitive to processing conditions, including approaches employing a master-batch (filler concentrate); regardless of the master-batch matrix, both PC and PET were employed, thermodynamics drove the layered silicate to preferentially migrate to the PET phase of the PC/PET blend. In a second approach, the development of a nanocomposite with controlled PC/PET compatibilization near the montmorillonite platelets, in absence of appreciable transesterification reactions, led to the formation of very high performance nanocomposites. These latter systems, point to an exciting new avenue of future considerations for nanocomposite blends with selective nano-filler dispersions, where performance can be tailored via the controlled preferential dispersion of nano-fillers in one phase, or by filler-induced polymer compatibilization.

Chemical Reactions in the Processing of Mosi2 + Carbon Compacts

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Lee, Kang N.; Maloy, Stuart A.; Heuer, Arthur H.

1993-01-01

Hot-pressing of MoSi2 powders with carbon at high temperatures reduces the siliceous grain boundary phase in the resultant compact. The chemical reactions in this process were examined using the Knudsen cell technique. A 2.3 wt pct oxygen MoSi2 powder and a 0.59 wt pct oxygen MoSi2 powder, both with additions of 2 wt pct carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1350 K and the resultant P(SiO)/P(CO) ratios interpreted in terms of the SiO(g) and CO(g) isobars on the Si-C-O predominance diagram. The MoSi2 + carbon mixtures were then heated at the hot-pressing temperature of 2100 K. Large weight losses were observed and could be correlated with the formation of a low-melting eutectic and the formation and vaporization of SiC.

Creep Behavior of Hafnia and Ytterbium Silicate Environmental Barrier Coating Systems on SiC/SiC Ceramic Matrix Composites

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Fox, Dennis S.; Ghosn, Louis J.; Harder, Bryan

2011-01-01

Environmental barrier coatings will play a crucial role in future advanced gas turbine engines because of their ability to significantly extend the temperature capability and stability of SiC/SiC ceramic matrix composite (CMC) engine components, thus improving the engine performance. In order to develop high performance, robust coating systems for engine components, appropriate test approaches simulating operating temperature gradient and stress environments for evaluating the critical coating properties must be established. In this paper, thermal gradient mechanical testing approaches for evaluating creep and fatigue behavior of environmental barrier coated SiC/SiC CMC systems will be described. The creep and fatigue behavior of Hafnia and ytterbium silicate environmental barrier coatings on SiC/SiC CMC systems will be reported in simulated environmental exposure conditions. The coating failure mechanisms will also be discussed under the heat flux and stress conditions.

Relationships Between HED's, Mesosiderites, and Ungrouped Achondrites: Trace Element Analyses of Mesosiderite RKPA 79015 and Ungrouped Achondrite QUE 93148

NASA Technical Reports Server (NTRS)

Righter, M.; Lapen, T.; Righter, K.

2008-01-01

Achondritic meteorites are a diverse group of meteorites that formed by igneous activity in asteroids. These meteorites can provide important information about early differentiation processes on asteroidal bodies. The howardite-eucrite-diogenite (HED) meteorites, the largest group of achondrites, are the only group of meteorites for which a potential parent body has been identified (4 Vesta) [e.g., 1]. Mesosiderites are stony-iron meteorites composed of roughly equal amounts of metal and silicates and silicates are broadly similar to HED meteorites [2]. They may have been formed by impact-mixing of crustal and core materials of differentiated meteorite parent bodies. Chemical and oxygen isotopic compositional data suggest that the HED meteorites and silicate portions of mesosiderites originated on the same or closely related parent bodies. Pallasites and IIIAB irons also have similar oxygen isotope compositions and have been thought to be related to the HEDs [3,4]. However, recent high resolution analyses have shown that pallasites and HED's have different oxygen isotopic values, but mesosiderites and HED s have the same isotope compositions implying a close connection [5]. QUE 93148 is a small (1.1g) olivine-rich (mg 86) achondrite that contains variable amounts of orthopyroxenene (mg 87) and kamacite (6.7 wt% Ni), with minor augite [6]. This meteorite was originally classified as a lodranite [7], but it s oxygen isotopic composition precludes a genetic relationship to the acapulcoites and lodranites. And also this meteorite has a lower Mn/Mg ratio than any major group of primitive or evolved achondrites and suggested that QUE 93148 may be a piece of the deep mantle of the HED parent body [6]. To better understand the relationship between HED s, mesosiderites and related achondrites, we have measured trace elements in the individual metallic and silicate phases. In this study, abundances of a suite of elements were measured for the unusual mesosiderite RKPA 79015 and a ungrouped achondrite QUE93148.

Constraints on the origin of Os-isotope disequilibrium in included and interstitial sulfides in mantle peridotites: Implications for the interpretation of Os-isotope signatures in MORB and Abyssal Peridotites

NASA Astrophysics Data System (ADS)

Lassiter, J. C.

2016-12-01

The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting (Hofmann & Hart, 1978). However, several studies report Os-isotope disequilibrium in distinct populations of sulfides in some peridotites. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable Re/Os, or partial re-equilibration of low-Re/Os sulfides with high-Re/Os silicate phases along grain boundaries during mantle melting (e.g., Alard et al., 2005). Both cases require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long ( Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed to the armoring effect of low-[Os] silicates, which limit diffusive exchange between isolated Os-rich phases. This raises the prospect that peridotite-derived melts may not inherit the Os-isotope composition of their source. The timescale required for diffusive equilibration between separate sulfide grains or between Os-rich sulfides and Os-poor silicates is a function of average sulfide size and spacing, Os diffusivity in armoring silicate minerals, and Os partitioning between silicate and sulfide phases. For typical sulfide abundances and sizes in mantle peridotites, neighboring sulfides are expected to re-equilibrate in less than a few 10s of m.y. at adiabatic mantle temperatures, even for very high (>106) sulfide/silicate KD values. Maintenance of disequilibrium requires very large sulfides (>100 um) separated by several mm and diffusion rates (D < 10-20 m2/s) slower than for most other elements in olivine. Equilibration timescales between sulfides and surrounding silicates are similar, so that large-scale isotopic disequilibrium between sulfides and silicates is also unlikely within the convecting mantle. Instead, observed grain-scale Os-isotope disequilibrium in mantle peridotites likely reflects recent sulfide metasomatism linked to interaction with eclogite- or pyroxenite-derived melts. Interstitial sulfides with radiogenic Os-isotopes provide further evidence for a role of eclogite melting in MORB genesis.

Simulation of the planetary interior differentiation processes in the laboratory.

PubMed

Fei, Yingwei

2013-11-15

A planetary interior is under high-pressure and high-temperature conditions and it has a layered structure. There are two important processes that led to that layered structure, (1) percolation of liquid metal in a solid silicate matrix by planet differentiation, and (2) inner core crystallization by subsequent planet cooling. We conduct high-pressure and high-temperature experiments to simulate both processes in the laboratory. Formation of percolative planetary core depends on the efficiency of melt percolation, which is controlled by the dihedral (wetting) angle. The percolation simulation includes heating the sample at high pressure to a target temperature at which iron-sulfur alloy is molten while the silicate remains solid, and then determining the true dihedral angle to evaluate the style of liquid migration in a crystalline matrix by 3D visualization. The 3D volume rendering is achieved by slicing the recovered sample with a focused ion beam (FIB) and taking SEM image of each slice with a FIB/SEM crossbeam instrument. The second set of experiments is designed to understand the inner core crystallization and element distribution between the liquid outer core and solid inner core by determining the melting temperature and element partitioning at high pressure. The melting experiments are conducted in the multi-anvil apparatus up to 27 GPa and extended to higher pressure in the diamond-anvil cell with laser-heating. We have developed techniques to recover small heated samples by precision FIB milling and obtain high-resolution images of the laser-heated spot that show melting texture at high pressure. By analyzing the chemical compositions of the coexisting liquid and solid phases, we precisely determine the liquidus curve, providing necessary data to understand the inner core crystallization process.

Simulation of the Planetary Interior Differentiation Processes in the Laboratory

PubMed Central

Fei, Yingwei

2013-01-01

A planetary interior is under high-pressure and high-temperature conditions and it has a layered structure. There are two important processes that led to that layered structure, (1) percolation of liquid metal in a solid silicate matrix by planet differentiation, and (2) inner core crystallization by subsequent planet cooling. We conduct high-pressure and high-temperature experiments to simulate both processes in the laboratory. Formation of percolative planetary core depends on the efficiency of melt percolation, which is controlled by the dihedral (wetting) angle. The percolation simulation includes heating the sample at high pressure to a target temperature at which iron-sulfur alloy is molten while the silicate remains solid, and then determining the true dihedral angle to evaluate the style of liquid migration in a crystalline matrix by 3D visualization. The 3D volume rendering is achieved by slicing the recovered sample with a focused ion beam (FIB) and taking SEM image of each slice with a FIB/SEM crossbeam instrument. The second set of experiments is designed to understand the inner core crystallization and element distribution between the liquid outer core and solid inner core by determining the melting temperature and element partitioning at high pressure. The melting experiments are conducted in the multi-anvil apparatus up to 27 GPa and extended to higher pressure in the diamond-anvil cell with laser-heating. We have developed techniques to recover small heated samples by precision FIB milling and obtain high-resolution images of the laser-heated spot that show melting texture at high pressure. By analyzing the chemical compositions of the coexisting liquid and solid phases, we precisely determine the liquidus curve, providing necessary data to understand the inner core crystallization process. PMID:24326245

Unusual Entropy of Adsorbed Methane on Zeolite-Templated Carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stadie, Nicholas P.; Murialdo, Maxwell; Ahn, Channing C.

2015-11-25

Methane adsorption at high pressures and across a wide range of temperatures was investigated on the surface of three porous carbon adsorbents with complementary structural properties. The measured adsorption equilibria were analyzed using a method that can accurately account for nonideal fluid properties and distinguish between absolute and excess quantities of adsorption, and that also allows the direct calculation of the thermodynamic potentials relevant to adsorption. On zeolite-templated carbon (ZTC), a material that exhibits extremely high surface area with optimal pore size and homogeneous structure, methane adsorption occurs with unusual thermodynamic properties that are greatly beneficial for deliverable gas storage:more » an enthalpy of adsorption that increases with site occupancy, and an unusually low entropy of the adsorbed phase. The origin of these properties is elucidated by comparison of the experimental results with a statistical mechanical model. The results indicate that temperature-dependent clustering (i.e., reduced configurations) of the adsorbed phase due to enhanced lateral interactions can account for the peculiarities of methane adsorbed on ZTC.« less

Understanding Vesuvius magmatic processes: Evidence from primitive silicate-melt inclusions in medieval scoria clinopyroxenes (Terzigno formation)

USGS Publications Warehouse

Lima, A.; Belkin, H.E.; Torok, K.

1999-01-01

Microthermometric investigations of silicate-melt inclusions and electron microprobe analyses were conducted on experimentally homogenized silicate-melt inclusions and on the host clinopyroxenes from 4 scoria samples of different layers from the Mt. Somma-Vesuvius medieval eruption (Formazione di Terzigno, 893 A.D.). The temperature of homogenization, considered the minimum trapping temperature, ranges from 1190 to 1260??5 ??C for all clinopyroxene-hosted silicate melt inclusions. The major and minor-element compositional trends shown by Terzigno scoria and matrix glass chemical analysis are largely compatible with fractional crystallization of clinopyroxene and Fe-Ti oxides. Sulfur contents of the homogenized silicate-melt inclusions in clinopyroxene phenocrysts compared with that in the host scoria show that S has been significantly degassed in the erupted products; whereas, Cl has about the same abundance in the inclusions and in host scoria. Fluorine is low (infrequently up to 800 ppm) in the silicate-melt inclusions compared to 2400 ppm in the bulk scoria. Electron microprobe analyses of silicate-melt inclusions show that they have primitive magma compositions (Mg# = 75-91). The composition of the host clinopyroxene phenocrysts varies from typical plinian-related (Mg#???85) to non-plinian related (Mg#???85). The mixed source of the host clinopyroxenes and primitive nature of the silicate-melt inclusions implies that these phenocrysts, in part, may be residual and/or have a polygenetic origin. The similar variation trends of major and minor-elements between homogenized silicate-melt inclusions from the Terzigno scoria, and silicate-melt inclusions in olivine and diopside phenocrysts from plinian eruptions (Marianelli et al., 1995) suggest that the trapped inclusions represent melts similar to those that supplied the plinian and sub-plinian magma chambers. These geochemical characteristics suggest that the Vesuvius magmatic system retained a vestige of the most recent plinian event.

New insights into the early stages of silica-controlled barium carbonate crystallisation

NASA Astrophysics Data System (ADS)

Eiblmeier, Josef; Schürmann, Ulrich; Kienle, Lorenz; Gebauer, Denis; Kunz, Werner; Kellermeier, Matthias

2014-11-01

Recent work has demonstrated that the dynamic interplay between silica and carbonate during co-precipitation can result in the self-assembly of unusual, highly complex crystal architectures with morphologies and textures resembling those typically displayed by biogenic minerals. These so-called biomorphs were shown to be composed of uniform elongated carbonate nanoparticles that are arranged according to a specific order over mesoscopic scales. In the present study, we have investigated the circumstances leading to the continuous formation and stabilisation of such well-defined nanometric building units in these inorganic systems. For this purpose, in situ potentiometric titration measurements were carried out in order to monitor and quantify the influence of silica on both the nucleation and early growth stages of barium carbonate crystallisation in alkaline media at constant pH. Complementarily, the nature and composition of particles occurring at different times in samples under various conditions were characterised ex situ by means of high-resolution electron microscopy and elemental analysis. The collected data clearly evidence that added silica affects carbonate crystallisation from the very beginning (i.e. already prior to, during, and shortly after nucleation), eventually arresting growth on the nanoscale by cementation of BaCO3 particles within a siliceous matrix. Our findings thus shed light on the fundamental processes driving bottom-up self-organisation in silica-carbonate materials and, for the first time, provide direct experimental proof that silicate species are responsible for the miniaturisation of carbonate crystals during growth of biomorphs, hence confirming previously discussed theoretical models for their formation mechanism.Recent work has demonstrated that the dynamic interplay between silica and carbonate during co-precipitation can result in the self-assembly of unusual, highly complex crystal architectures with morphologies and textures resembling those typically displayed by biogenic minerals. These so-called biomorphs were shown to be composed of uniform elongated carbonate nanoparticles that are arranged according to a specific order over mesoscopic scales. In the present study, we have investigated the circumstances leading to the continuous formation and stabilisation of such well-defined nanometric building units in these inorganic systems. For this purpose, in situ potentiometric titration measurements were carried out in order to monitor and quantify the influence of silica on both the nucleation and early growth stages of barium carbonate crystallisation in alkaline media at constant pH. Complementarily, the nature and composition of particles occurring at different times in samples under various conditions were characterised ex situ by means of high-resolution electron microscopy and elemental analysis. The collected data clearly evidence that added silica affects carbonate crystallisation from the very beginning (i.e. already prior to, during, and shortly after nucleation), eventually arresting growth on the nanoscale by cementation of BaCO3 particles within a siliceous matrix. Our findings thus shed light on the fundamental processes driving bottom-up self-organisation in silica-carbonate materials and, for the first time, provide direct experimental proof that silicate species are responsible for the miniaturisation of carbonate crystals during growth of biomorphs, hence confirming previously discussed theoretical models for their formation mechanism. Electronic supplementary information (ESI) available: Additional titration data (Fig. S1 and S2) and further results from TEM-EDX analyses (Fig. S3-S8). See DOI: 10.1039/c4nr05436a

A SIMS study of lunar 'komatiitic glasses' - Trace element characteristics and possible origin

NASA Technical Reports Server (NTRS)

Shearer, C. K.; Papike, J. J.; Galbreath, K. C.; Wentworth, S. J.; Shimizu, N.

1990-01-01

In Apollo 16 regolith breccias, Wentworth and McKay (1988) identified a suite of minute (less than 120 microns) 'komatiitic glass beads'. The wide major element compositional range, and ultra-Mg-prime character of the glasses suggest a variety of possible origins from complex impact processes to complex volcanic processes involving rather unusual and primitive magmatism. The extent of trace element depletion or enrichment in these glasses appears to be correlated to the siderophile character of the element (ionization potential or experimentally determined silicate melt/Fe metal partition coefficients. The ultra-Mg-prime glasses are depleted in Co relative to a bulk Moon Mg/Co exhibited by many lunar samples (volcanic glasses, basalts, regolith breccia, estimated upper mantle). The low Co and high incompatible element concentrations diminish the possibility that these glasses are a product of lunar komatiitic volcanism or impact, excavation, and melting of a very high Mg-prime plutonic unit.

Geologic map of upper Eocene to Holocene volcanic and related rocks in the Cascade Range, Washington

USGS Publications Warehouse

Smith, James G.

1993-01-01

For geothermal reasons, the maps emphasize Quaternary volcanic rocks. Large igneous-related geothermal systems that have high temperatures are associated with Quaternary volcanic fields, and geothermal potential declines rapidly as age increases (Smith and Shaw, 1975). Most high-grade recoverable geothermal energy is likely to be associated with silicic volcanism less than 1 Ma. Lower grade (= lower temperature) geothermal resources may be associated with somewhat older rocks; however, volcanic rocks older than about 2 Ma are unlikely geothermal targets (Smith and Shaw, 1975).

Improving the electrical properties of lanthanum silicate films on ge metal oxide semiconductor capacitors by adopting interfacial barrier and capping layers.

PubMed

Choi, Yu Jin; Lim, Hajin; Lee, Suhyeong; Suh, Sungin; Kim, Joon Rae; Jung, Hyung-Suk; Park, Sanghyun; Lee, Jong Ho; Kim, Seong Gyeong; Hwang, Cheol Seong; Kim, HyeongJoon

2014-05-28

The electrical properties of La-silicate films grown by atomic layer deposition (ALD) on Ge substrates with different film configurations, such as various Si concentrations, Al2O3 interfacial passivation layers, and SiO2 capping layers, were examined. La-silicate thin films were deposited using alternating injections of the La[N{Si(CH3)3}2]3 precursor with O3 as the La and O precursors, respectively, at a substrate temperature of 310 °C. The Si concentration in the La-silicate films was further controlled by adding ALD cycles of SiO2. For comparison, La2O3 films were also grown using [La((i)PrCp)3] and O3 as the La precursor and oxygen source, respectively, at the identical substrate temperature. The capacitance-voltage (C-V) hysteresis decreased with an increasing Si concentration in the La-silicate films, although the films showed a slight increase in the capacitance equivalent oxide thickness. The adoption of Al2O3 at the interface as a passivation layer resulted in lower C-V hysteresis and a low leakage current density. The C-V hysteresis voltages of the La-silicate films with Al2O3 passivation and SiO2 capping layers was significantly decreased to ∼0.1 V, whereas the single layer La-silicate film showed a hysteresis voltage as large as ∼1.0 V.

A GEOCLIM Simulation Of Climatic And Biogeochemical Consequences Of Pangea Break Up

NASA Astrophysics Data System (ADS)

Donnadieu, Y.; Godderis, Y.; Pierrehumbert, R.; Dromart, G.; Jacob, R.

2006-12-01

Large fluctuations in continental configuration occur all along the Mesozoic times. While it has long been recognized that paleogeography may potentially influence atmospheric CO2 via the continental silicate weathering feedback, no numerical simulation have been done given the lack of a spatially resolved climate- carbon model. GEOCLIM, a coupled numerical model of the climate and global biogeochemical cycles, is used to investigate the consequences of the Pangea break up. The climate module of the GEOCLIM model is the FOAM atmospheric general circulation model, allowing the calculation of the consumption of atmospheric CO2 through continental silicate weathering with a spatial resolution of 7.5°long 4.5°lat. Seven time slices have been simulated. We show that the break up of the Pangea supercontinent triggers an increase in continental runoff, resulting in enhanced atmospheric CO2 consumption through silicate weathering. As a result, atmospheric CO2 falls from values above 3000 ppmv during the Triassic, down to rather low levels during the Cretaceous (around 400 ppmv), resulting in a decrease in continental temperatures from about 20°C to 10°C. Silicate weathering feedback and paleogeography both act to force the Earth system toward a dry and hot world reaching its optimum over the last 260 Ma during the Middle-Late Triassic. In the super continent case, given the relative aridity that cannot be climatically overwhelmed, the model generates high CO2 values to produce very warm continental temperatures compensating for the lack of continental humidity. Conversely, in the fragmented case, the runoff becomes the most important contributor to the silicate weathering rate, hence, producing a CO2 drawdown and a fall in continental temperatures. Finally, an other unexpected outcome is the pronounced fluctuations in carbonate accumulation simulated by the model in response to the Pangea break up. These fluctuations are driven by changes in continental carbonate weathering flux. Accounting for the fluctuations in area available for carbonate platforms, the simulated ratio of carbonate deposition between neritic and deep sea environments is in better agreement with available data.

Materials properties of hafnium and zirconium silicates: Metal interdiffusion and dopant penetration studies

NASA Astrophysics Data System (ADS)

Quevedo Lopez, Manuel Angel

Hafnium and Zirconium based gate dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in CMOS processing. Furthermore, the addition of nitrogen into this pseudo-binary alloy has been shown to improve their thermal stability, electrical properties, and reduce dopant penetration. Because CMOS processing requires high temperature anneals (up to 1050°C), it is important to understand the diffusion properties of any metal associated with the gate dielectric in silicon at these temperatures. In addition, dopant penetration from the doped polysilicon gate into the Si channel at these temperatures must also be studied. Impurity outdiffusion (Hf, Zr) from the dielectric, or dopant (B, As, P) penetration through the dielectric into the channel region would likely result in deleterious effects upon the carrier mobility. In this dissertation extensive thermal stability studies of alternate gate dielectric candidates ZrSixOy and HfSixO y are presented. Dopant penetration studies from doped-polysilicon through HfSixOy and HfSixOyNz are also presented. Rutherford Backscattering Spectroscopy (RBS), Heavy Ion RBS (HI-RBS), X-ray Photoelectron Spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HR-TEM), and Time of Flight and Dynamic Secondary Ion Mass Spectroscopy (ToF-SIMS, D-SIMS) methods were used to characterize these materials. The dopant diffusivity is calculated by modeling of the dopant profiles in the Si substrate. In this disseration is reported that Hf silicate films are more stable than Zr silicate films, from the metal interdiffusion point of view. On the other hand, dopant (B, As, and P) penetration is observed for HfSixO y films. However, the addition of nitrogen to the Hf - Si - O systems improves the dopant penetration properties of the resulting HfSi xOyNz films.

Density Measurement for MORB Melts by X-ray Absorption Method

NASA Astrophysics Data System (ADS)

Sakamaki, T.; Urakawa, S.; Suzuki, A.; Ohtani, E.; Katayama, Y.

2006-12-01

Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the top anvil sizes of 6 mm and 4 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 5 GPa, from 300 to 2000 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

Density Measurement for MORB Melts by X-ray Absorption Method

NASA Astrophysics Data System (ADS)

Sakamaki, T.; Urakawa, S.; Ohtani, E.; Suzuki, A.; Katayama, Y.

2005-12-01

Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the edge-length of 6 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 4 GPa, from 300 to 2200 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

Galileo Chain Thermometer

ERIC Educational Resources Information Center

Ucke, C.; Schlichting, H. J.

2017-01-01

This relatively rare thermometer has a rather unusual display: lower temperatures are located at the top of the scale, higher ones at the bottom. A sphere on a chain floats in a suitable liquid, sinking at high temperatures when the density of the liquid decreases and rising in the increased density at low temperatures. With reasonable effort and…

Optical Properties of Iron Silicates in the Infrared to Millimeter as a Function of Wavelength and Temperature

NASA Technical Reports Server (NTRS)

Richey, C. R.; Kinzer, R. E.; Cataldo, G.; Wollack, E. J.; Nuth, J. A.; Benford, D. J.; Silverberg, R. F.; Rinehart, S. A.

2013-01-01

The Optical Properties of Astronomical Silicates with Infrared Techniques (OPASI-T) program utilizes multiple instruments to provide spectral data over a wide range of temperature and wavelengths. Experimental methods include Vector Network Analyzer (VNA) and Fourier Transform Spectroscopy (FTS) transmission, and reflection/scattering measurements. From this data, we can determine the optical parameters for the index of refraction, n, and the absorption coefficient, k. The analysis of the laboratory transmittance data for each sample type is based upon different mathematical models, which are applied to each data set according to their degree of coherence. Presented here are results from iron silicate dust grain analogs, in several sample preparations and at temperatures ranging from 5-300 K, across the infrared and millimeter portion of the spectrum (from 2.5-10,000 m or 4,000-1 cm(exp-1).

Optical Properties of Iron Silicates in the Infrared to Millimeter as a Function of Wavelength and Temperature

NASA Technical Reports Server (NTRS)

Richey, Christina Rae; Kinzer, R. E.; Cataldo, R. E. G.; Wollack, E. J.; Nuth, J. A.; Benford, D. J.; Silverberg, R. F.; Rinehart, S. A.

2013-01-01

The Optical Properties of Astronomical Silicates with Infrared Techniques (OPASI-T) program utilizes multiple instruments to provide spectral data over a wide range of temperature and wavelengths. Experimental methods include Vector Network Analyzer (VNA) and Fourier Transform Spectroscopy (FTS) transmission, and reflection/scattering measurements. From this data, we can determine the optical parameters for the index of refraction, n, and the absorption coefficient, k. The analysis of the laboratory transmittance data for each sample type is based upon different mathematical models, which are applied to each data set according to their degree of coherence. Presented here are results from iron silicate dust grain analogs, in several sample preparations and at temperatures ranging from 5-300 K, across the infrared and millimeter portion of the spectrum (from 2.5-10,000 µm or 4,000-1 cm(exp -1).

7 CFR 3201.41 - Metalworking fluids.

Code of Federal Regulations, 2013 CFR

2013-01-01

... feedstock during grinding and machining operations involving unusually high temperatures or corrosion... prevention when applied to metal feedstock during normal grinding and machining operations. (iii) High... percent. (3) High performance soluble, semi-synthetic, and synthetic oils—40 percent. (c) Preference...

7 CFR 3201.41 - Metalworking fluids.

Code of Federal Regulations, 2012 CFR

2012-01-01

... feedstock during grinding and machining operations involving unusually high temperatures or corrosion... prevention when applied to metal feedstock during normal grinding and machining operations. (iii) High... percent. (3) High performance soluble, semi-synthetic, and synthetic oils—40 percent. (c) Preference...

7 CFR 3201.41 - Metalworking fluids.

Code of Federal Regulations, 2014 CFR

2014-01-01

... feedstock during grinding and machining operations involving unusually high temperatures or corrosion... prevention when applied to metal feedstock during normal grinding and machining operations. (iii) High... percent. (3) High performance soluble, semi-synthetic, and synthetic oils—40 percent. (c) Preference...

Experimental constraints on the degree of melting beneath tectonic plates

NASA Astrophysics Data System (ADS)

Clark, A. N.; Lesher, C. E.

2017-12-01

Determining the volume and geometric distribution of silicate melts is fundamentally important to understand the current structure of the Earth as well as the dynamics of the Earth's interior. Regions in the upper mantle and crust that have lower velocities than the 1D global average are commonly attributed to the presence of silicate melts. Constraining melt fraction and distribution from seismic data requires a robust equation of state for silicate melts. Commonly, silicate melts are modeled at high pressure using equations of state developed for crystalline materials (e.g. the Birch-Murnaghan equation of state). However, amorphous silicates (glasses and melts), which lack long-range ordering, violate Birch's law at high pressures and high temperatures (Clark et al., 2016). We present a new model for seismic velocity reductions that accounts for the violation of Birch's law (anomalous compressibility) observed in amorphous silicates, rendering compressional wave velocities more sensitive to melt fraction and distribution than previous estimates. Forward modeling that combines our experimental data with the analytical solution of Takei (2002) predicts comparable velocity reductions for compressional and shear waves for partially molten mantle. Additionally, models that use crystalline equations of state to determine melt fraction at high pressure may overestimate melt fraction by 20% at pressures corresponding to the lithosphere-asthenosphere boundary (LAB) with the overestimation increasing with depth (e.g. a factor of 2 at the transition zone). By applying our results to recent seismic studies below the western Pacific plate that have reported low velocity regions associated with the lithosphere - asthenosphere boundary (LAB), we predict melt present at <5% distributed in near-textural equilibrium. These findings reconcile seismic observations for the LAB regionally and locally, and favor models of strong coupling across the LAB rather than melt channeling due to shear deformation. Clark, A. N., Lesher, C. E., Jacobsen, S. D., and Wang, Y., 2016, Journal of Geophysical Research: Solid Earth, v. 121, no. 6, p. 4232-4248. Takei, Y., 2002, Journal of Geophysical Research: Solid Earth (1978-2012), v. 107, no. B2, p. 6-12.

Metal/Silicate Partitioning, Melt Speciation, Accretion, and Core Formation in the Earth

NASA Astrophysics Data System (ADS)

Drake, M. J.; Hillgren, V. J.; Dearo, J. A.; Capobianco, C. J.

1993-07-01

Core formation in terrestrial planets was concomitant with accretion. Siderophile and chalcophile element signatures in the mantles of planets are the result of these processes. For Earth, abundances of most siderophile and chalcophile elements are elevated relative to predictions from simple metal/silicate equilibria at low pressures [1]. This observation has led to three hypotheses for how these abundances were established: heterogeneous accretion [2], inefficient core formation [3], and metal/silicate equilibria at magma ocean pressures and temperatures [4]. Knowledge of speciation of siderophile elements in silicate melts in equilibrium with metal may help distinguish between these hypotheses. But there is some uncertainty regarding speciation. For example, Ni and Co have been reported to be present as 1+ or zero valence species in silicate melts at redox states appropriate to planetary accretion, rather than the expected 2+ state [5-7]. Independent metal/silicate partitioning experiments by three members of this group using two different experimental designs on both synthetic and natural compositions do not show evidence for Ni and Co in valence states other than 2+ over a wide range of redox states. For example, solid metal/silicate melt partition coefficients for Ni at 1260 degrees C obtained by VJH from experiments investigating the partitioning of Ni, Co, Mo, W, and P are indistinguishable from those obtained by JAD in similar experiments investigating the partitioning of Ni, Ge, and Sn. Both datasets define a line with the equation: log D(Ni) = - 0.54log fO2 - 3.14 with r^2 > 0.995. (Note that fO2 was calculated in both studies from thermodynamic data and phase compositions. A small, systematic offset from the true fO2 as measured by a solid electrolyte cell affects both equations similarly, but does not diminish their close agreement.) The valence of Ni in the silicate melt is obtained by multiplying the slope of the line by -4, indicating divalent Ni in both studies. Experiments by [8] between 1300 degrees C and 1550 degrees C and fO2 from air to just below iron-wustite in which Ni and Co are partitioned between Pt metal and CaO-Al2O3-SiO2 silicate melt also show evidence only for 2+ valence. Capobianco et al. [1] have noted that reliable extrapolation from current laboratory temperatures (1190 degrees C-1600 degrees C) to magma ocean temperatures is not possible. The hypothesis that siderophile and chalcophile element abundances in the mantle of Earth were established by metal/silicate equilibria at magma ocean pressures and temperatures needs to be tested using direct experimental measurements at magma ocean temperatures and pressures. Such experiments are currently being conducted. References: [1] Capobianco et al. (1993) J. Geophys. Res., 98, 5433. [2] Wanke (1981) Phil. Trans. R. Soc. London, A303, 287. [3] Jones and Drake (1986) Nature, 322, 221. [4] Murthy (1991) Science, 253, 303. [5] Schmitt et al. (1989) GCA, 53, 173. [6] Ehlers et al. (1993) GCA, 56, 3733. [7] Colson (1992) Nature, 357, 65. [8] Capobianco and Amelin (1993) GCA, 56 (in press).

Unusual olivine and pyroxene composition in interplanetary dust and unequilibrated ordinary chondrites

NASA Technical Reports Server (NTRS)

Klock, W.; Mckay, D. S.; Thomas, K. L.; Palme, H.

1989-01-01

The presence, in both a number of interplanetary dust particles (IDPs) and in meteorite matrices, of olivine and orthopyroxene grains, low in FeO but containing up to 5 wt pct MnO, is reported. The majority of olivines and pyroxenes in meteorites contain less than 0.5 wt pct MnO. The presence of these low-iron, manganese-enriched (LIME) olivines and pyroxenes in IDPs and meteorites may indicate a link between the origin and history of IDPs and the matrix material of primitive meteorites. The origin of the LIME silicates could be explained by condensation from a gas of solar composition. Forsterite is the first major silicate phase to condense from a solar nebula gas, and Mn, which is not stable as a metal under solar nebula conditions, would condense at about 1100 K as Mn2SiO4 in solid solution with forsterite.

Core Formation on Asteroid 4 Vesta: Iron Rain in a Silicate Magma Ocean

NASA Astrophysics Data System (ADS)

Kiefer, W. S.; Mittlefehldt, D. W.

2017-07-01

Initially small liquid metal drops must grow to about 10 cm in size before sinking through the convecting silicate magma ocean to form a core. The required magma temperature is consistent with moderately siderophile element abundances in eucrites.

The Brittle-Ductile Transition in Crystal and Bubble-bearing Magmas

NASA Astrophysics Data System (ADS)

Caricchi, L.; Pistone, M.; Cordonnier, B.; Tripoli, B.; Ulmer, P.; Reusser, E.; Marone, F.; Burlini, L.

2011-12-01

The strain response of magma is critically dependent upon its viscosity, the magnitude of the applied stress and the experimental time-scale. The brittle-ductile transition in pure silicate melts is expected for an applied stress approaching 108±0.5 Pa (Dingwell, 1997). However, magmas are mostly mixture of crystal and bubble-bearing silicate melts. To date, there are no data to constrain the ductile-brittle transition for three-phase magmas. Thus, we conducted consistent torsion experiments at high temperature (673-973 K) and high pressure (200 MPa), in the strain rate range 1*10-5-4*10-3 s-1, using a HT-HP internally-heated Paterson-type rock deformation apparatus. The samples are composed of hydrous haplogranitic glass, quartz crystals (24-65 vol%) and CO2-rich gas-pressurized bubbles (9-12 vol%). The applied strain rate was increased until brittle failure occurred; micro-fracturing and healing processes commonly occurred before sample macroscopic fracturing. The experimental results highlight a clear relationship between the effective viscosity of the three-phase magmas, strain rate, temperature and the onset of brittle-ductile behavior. Crystal- and bubble-free melts at high viscosity (1011-1011.6 Pa*s at 673 K) show brittle behavior in the strain rate range between 1*10-4 and 5*10-4 s-1. For comparable viscosities crystal and bubble-bearing magmas show a transition to brittle behavior at lower strain rates. Synchrotron-based 3D imaging of fractured samples, show the presence of fractures with an antithetic trend with respect to shear strain directions. The law found in this study expresses the transition from ductile to brittle behavior for real magmas and could significantly improve our understanding of the control of brittle processes on extrusion of high-viscosity magmas and degassing at silicic volcanoes.

Water and carbon in rusty lunar rock 66095

USGS Publications Warehouse

Friedman, I.; Hardcastle, Kenneth G.; Gleason, J.D.

1974-01-01

Lunar rock 66095 contains a hydrated iron oxide and has an unusual amount of water for a lunar rock (140 to 750 parts per million), 90 percent of which is released below 690??C. The ??D of water released at these low temperatures varies from -75 to -140 per mil relative to standard mean ocean water (SMOW). The small amount of water released between 690?? and 1300??C has a ??D of about -175 ?? 25 per mil SMOW. These ??D values are not unusual for terrestrial water. The ??18O of water extracted from 110?? to 400??C has a value of + 5 ?? 1 per mil SMOW, similar to the value for lunar silicates from rock 66095 and different from the value of -4 to -22 per mil found for samples of terrestrial rust including samples of rusted meteoritic iron. The amount of carbon varies from 11 to 59 parts per million with a ??13C from -20 to -30 per mil relative to Pee Dee belemnite. Only very small amounts of reduced species (such as hydrogen, carbon monoxide, and methane) were found, in contrast to the analyses of other lunar rocks. Although it is possible that most of the water in the iron oxide (goethite) may be terrestrial in origin or may have exchanged with terrestrial water during sample return and handling, evidence presented herein suggests that this did not happen and that some lunar water may have a ??D that is indistinguishable from that of terrestrial water.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bozovic, I.; Wu, J.; He, X.

Over the course of three decades of intense study, apart from the exceptionally high critical temperature, many unusual properties of cuprates have been discovered, notably including resistivity linear in temperature, electronic Raman continuum and optical absorption extending throughout the infrared region, pseudogap, hour-glass spin excitation spectrum, etc. However, each of these features have been also observed in other materials, including some that are not even superconducting at all. Here, we describe an extensive experiment in which over 2,000 films of the La 2-xSr xCuO 4 have been synthesized and studied in detail over the course of the last twelve years.more » We argue here that, uniquely, in the cuprates an unusual superconducting state, that defies the standard BCS description, develops from an unusual metallic state, in which the rotational symmetry of the electron fluid is spontaneously broken.« less

Big Jump of Record Warm Global Mean Surface Temperature in 2014-2016 Related to Unusually Large Oceanic Heat Releases

NASA Astrophysics Data System (ADS)

Yin, Jianjun; Overpeck, Jonathan; Peyser, Cheryl; Stouffer, Ronald

2018-01-01

A 0.24°C jump of record warm global mean surface temperature (GMST) over the past three consecutive record-breaking years (2014-2016) was highly unusual and largely a consequence of an El Niño that released unusually large amounts of ocean heat from the subsurface layer of the northwestern tropical Pacific. This heat had built up since the 1990s mainly due to greenhouse-gas (GHG) forcing and possible remote oceanic effects. Model simulations and projections suggest that the fundamental cause, and robust predictor of large record-breaking events of GMST in the 21st century, is GHG forcing rather than internal climate variability alone. Such events will increase in frequency, magnitude, and duration, as well as impact, in the future unless GHG forcing is reduced.

Lanthanide-based oxides and silicates for high-kappa gate dielectric applications

NASA Astrophysics Data System (ADS)

Jur, Jesse Stephen

The ability to improve performance of the high-end metal oxide semiconductor field effect transistor (MOSFET) is highly reliant on the dimensional scaling of such a device. In scaling, a decrease in dielectric thickness results in high current leakage between the electrode and the substrate by way of direct tunneling through the gate dielectric. Observation of a high leakage current when the standard gate dielectric, SiO2, is decreased below a thickness of 1.5 nm requires engineering of a replacement dielectric that is much more scalable. This high-kappa dielectric allows for a physically thicker oxide, reducing leakage current. Integration of select lanthanide-based oxides and silicates, in particular lanthanum oxide and silicate, into MOS gate stack devices is examined. The quality of the high-kappa dielectrics is monitored electrically to determine properties such as equivalent oxide thickness, leakage current density and defect densities. In addition, analytical characterization of the dielectric and the gate stack is provided to examine the materialistic significance to the change of the electrical properties of the devices. In this work, lanthanum oxide films have been deposited by thermal evaporation on to a pre-grown chemical oxide layer on silicon. It is observed that the SiO2 interfacial layer can be consumed by a low-temperature reaction with lanthanum oxide to produce a high-quality silicate. This is opposed to depositing lanthanum oxide directly on silicon, which can possibly favor silicide formation. The importance of oxygen regulation in the surrounding environment of the La2O3-SiO2 reaction-anneal is observed. By controlling the oxygen available during the reaction, SiO2 growth can be limited to achieve high stoichiometric ratios of La2O 3 to SiO2. As a result, MOS devices with an equivalent oxide thickness (EOT) of 5 A and a leakage current density of 5.0 A/cm 2 are attained. This data equals the best value achieved in this field and is a substantial improvement over SiO(N) dielectrics, allowing for increased device scaling. High-temperature processing, consistent with the source/drain activation anneal in MOSFET processing, is performed on lanthanum-silicate based MOS devices with Ta or TaN gate electrodes and a W metal capping layer. The thermal limit of Ta is observed to be less than 800°C, resulting in a phase transformation that can result in uncontrolled shifting of the MOS device flat-band voltage. TaN is observed to be more thermally stable (up to 1000°C) and results in an increase in the capacitance density suggesting that it impedes oxygen reaction with silicon to produce SiO2. It is later observed that a W metal capping layer can serve as a high-oxygen source, which results in an increased interfacial SiO2 formation. By limiting the oxygen content in the W capping layer and by utilizing a thermally stable TaN gate electrode, control over the electrical properties of the MOS device is acquired. To determine the stability of amorphous lanthanum-silicate in contact with investigated by means of back-side secondary ion mass spectroscopy profiling. The results are the first reported data showing that the lanthanum incorporated in the silica matrix doe not diffuse into the silicon substrate after high temperature processing. The decrease in the device effective work function (φM,eff ) observed in these samples is examined in detail. First, as a La 2O3 capping layer on HfSiO(N), the shift yields ideal-φ M,eff values for nMOSFET deices (4.0 eV) that were previously inaccessible. Other lanthanide oxides (Dy, Ho and Yb) used as capping layers show similar effects. It is also shown that tuning of φM,eff can be realized by controlling the extent of lanthanide-silicate formation. This research, conducted in conjunction with SEMATECH and the SRC, represents a significant technological advancement in realizing 45 and sub-45 nm MOSFET device nodes.

Carbonate-silicate liquid immiscibility in the mantle propels kimberlite magma ascent

NASA Astrophysics Data System (ADS)

Kamenetsky, Vadim S.; Yaxley, Gregory M.

2015-06-01

Kimberlite is a rare volcanic rock renowned as the major host of diamonds and originated at the base of the subcontinental lithospheric mantle. Although kimberlite magmas are dense in crystals and deeply-derived rock fragments, they ascend to the surface extremely rapidly, enabling diamonds to survive. The unique physical properties of kimberlite magmas depend on the specific compositions of their parental melts that, in absence of historical eruptions and due to pervasive alteration of kimberlite rocks, remain highly debatable. We explain exceptionally rapid ascent of kimberlite magma from mantle depths by combining empirical data on the essentially carbonatite composition of the kimberlite primary melts and experimental evidence on interaction of the carbonate liquids with mantle minerals. Our experimental study shows that orthopyroxene is completely dissolved in a Na2CO3 melt at 2.0-5.0 GPa and 1000-1200 °C. The dissolution of orthopyroxene results in homogeneous silicate-carbonate melt at 5.0 GPa and 1200 °C, and is followed by unmixing of carbonate and carbonated silicate melts and formation of stable magmatic emulsion at lower pressures and temperatures. The dispersed silicate melt has a significant capacity for storing a carbonate component in the deep mantle (13 wt% CO2 at 2.0 GPa). We envisage that this component reaches saturation and is gradually released as CO2 bubbles, as the silicate melt globules are transported upwards through the lithosphere by the carbonatite magma. The globules of unmixed, CO2-rich silicate melt are continuously produced upon further reaction between the natrocarbonatite melt and mantle peridotite. On decompression the dispersed silicate melt phase ensures a continuous supply of CO2 bubbles that decrease density and increase buoyancy and promote rapid ascent of the magmatic emulsion.

Silicates Eroded under Simulated Martian Conditions Effectively Kill Bacteria—A Challenge for Life on Mars

PubMed Central

Bak, Ebbe N.; Larsen, Michael G.; Moeller, Ralf; Nissen, Silas B.; Jensen, Lasse R.; Nørnberg, Per; Jensen, Svend J. K.; Finster, Kai

2017-01-01

The habitability of Mars is determined by the physical and chemical environment. The effect of low water availability, temperature, low atmospheric pressure and strong UV radiation has been extensively studied in relation to the survival of microorganisms. In addition to these stress factors, it was recently found that silicates exposed to simulated saltation in a Mars-like atmosphere can lead to a production of reactive oxygen species. Here, we have investigated the stress effect induced by quartz and basalt abraded in Mars-like atmospheres by examining the survivability of the three microbial model organisms Pseudomonas putida, Bacillus subtilis, and Deinococcus radiodurans upon exposure to the abraded silicates. We found that abraded basalt that had not been in contact with oxygen after abrasion killed more than 99% of the vegetative cells while endospores were largely unaffected. Exposure of the basalt samples to oxygen after abrasion led to a significant reduction in the stress effect. Abraded quartz was generally less toxic than abraded basalt. We suggest that the stress effect of abraded silicates may be caused by a production of reactive oxygen species and enhanced by transition metal ions in the basalt leading to hydroxyl radicals through Fenton-like reactions. The low survivability of the usually highly resistant D. radiodurans indicates that the effect of abraded silicates, as is ubiquitous on the Martian surface, would limit the habitability of Mars as well as the risk of forward contamination. Furthermore, the reactivity of abraded silicates could have implications for future manned missions, although the lower effect of abraded silicates exposed to oxygen suggests that the effects would be reduced in human habitats. PMID:28955310

Silicates Eroded under Simulated Martian Conditions Effectively Kill Bacteria-A Challenge for Life on Mars.

PubMed

Bak, Ebbe N; Larsen, Michael G; Moeller, Ralf; Nissen, Silas B; Jensen, Lasse R; Nørnberg, Per; Jensen, Svend J K; Finster, Kai

2017-01-01

The habitability of Mars is determined by the physical and chemical environment. The effect of low water availability, temperature, low atmospheric pressure and strong UV radiation has been extensively studied in relation to the survival of microorganisms. In addition to these stress factors, it was recently found that silicates exposed to simulated saltation in a Mars-like atmosphere can lead to a production of reactive oxygen species. Here, we have investigated the stress effect induced by quartz and basalt abraded in Mars-like atmospheres by examining the survivability of the three microbial model organisms Pseudomonas putida, Bacillus subtilis , and Deinococcus radiodurans upon exposure to the abraded silicates. We found that abraded basalt that had not been in contact with oxygen after abrasion killed more than 99% of the vegetative cells while endospores were largely unaffected. Exposure of the basalt samples to oxygen after abrasion led to a significant reduction in the stress effect. Abraded quartz was generally less toxic than abraded basalt. We suggest that the stress effect of abraded silicates may be caused by a production of reactive oxygen species and enhanced by transition metal ions in the basalt leading to hydroxyl radicals through Fenton-like reactions. The low survivability of the usually highly resistant D. radiodurans indicates that the effect of abraded silicates, as is ubiquitous on the Martian surface, would limit the habitability of Mars as well as the risk of forward contamination. Furthermore, the reactivity of abraded silicates could have implications for future manned missions, although the lower effect of abraded silicates exposed to oxygen suggests that the effects would be reduced in human habitats.

Silicate melts density, buoyancy relations and the dynamics of magmatic processes in the upper mantle

NASA Astrophysics Data System (ADS)

Sanchez-Valle, Carmen; Malfait, Wim J.

2016-04-01

Although silicate melts comprise only a minor volume fraction of the present day Earth, they play a critical role on the Earth's geochemical and geodynamical evolution. Their physical properties, namely the density, are a key control on many magmatic processes, including magma chamber dynamics and volcanic eruptions, melt extraction from residual rocks during partial melting, as well as crystal settling and melt migration. However, the quantitative modeling of these processes has been long limited by the scarcity of data on the density and compressibility of volatile-bearing silicate melts at relevant pressure and temperature conditions. In the last decade, new experimental designs namely combining large volume presses and synchrotron-based techniques have opened the possibility for determining in situ the density of a wide range of dry and volatile-bearing (H2O and CO2) silicate melt compositions at high pressure-high temperature conditions. In this contribution we will illustrate some of these progresses with focus on recent results on the density of dry and hydrous felsic and intermediate melt compositions (rhyolite, phonolite and andesite melts) at crustal and upper mantle conditions (up to 4 GPa and 2000 K). The new data on felsic-intermediate melts has been combined with in situ data on (ultra)mafic systems and ambient pressure dilatometry and sound velocity data to calibrate a continuous, predictive density model for hydrous and CO2-bearing silicate melts with applications to magmatic processes down to the conditions of the mantle transition zone (up to 2773 K and 22 GPa). The calibration dataset consist of more than 370 density measurements on high-pressure and/or water-and CO2-bearing melts and it is formulated in terms of the partial molar properties of the oxide components. The model predicts the density of volatile-bearing liquids to within 42 kg/m3 in the calibration interval and the model extrapolations up to 3000 K and 100 GPa are in good agreement with results from ab initio calculations. The density model has been applied to examine the mineral-melt buoyancy relations at depth and the implications of these results for the dynamics of magma chambers, crystal settling and the stability and mobility of magmas in the upper mantle will be discussed.

Xe incorporation in crust and upper mantle minerals: new experimental and theoretical evidences

NASA Astrophysics Data System (ADS)

Celine, C.; Sanloup, C.; Blanchard, M.; Lazzeri, M.; Balan, E.; Hudspeth, J.

2017-12-01

Storage of Xe in silicate minerals has been proposed to explain the `Missing Xenon' issue, i.e. the low Xe abundance in the Earth's and Mars' atmospheres compared to other noble gases [1]. However, data about Xe incorporation in minerals remain scarce due to high Xe volatility preventing studies at ambient conditions. Xe incorporations in olivine [2] and quartz [3] have been proposed based on experimental evidences at high pressures and temperatures. Nevertheless, Xe incorporation mechanisms remained so far only hypothetical. We present here new in situ X-ray diffraction data in diamond-anvil cell showing Xe incorporation in widespread silicate minerals of the continental crust (feldspars and quartz) and of the upper mantle (olivine) at relevant pressure and temperature conditions. Significant variations in cell parameters are retrieved in Xe-rich minerals as well as new peaks, implying change in the crystal structures linked to Xe incorporation. Theoretical calculations have been performed (using the density functional theory) to propose Xe incorporation sites able to reproduce experimental observations. In olivine, a Xe for Si substitutions is proposed, with up to 0.4 at% Xe potentially stored in olivine at depth. These new constraints on Xe incorporation at depths in silicate minerals, often neglected, could be crucial in the `Missing Xenon' issue. [1] Anders and Owen (1977) Science 198, 453-465, [2] Sanloup et al. (2011) Geochim. Cosmochim. Acta 75, 6271-6284, [3] Sanloup et al., (2005) Science, 310, 1174-1177

Depletion of potassium and sodium in mantles of Mars, Moon and Vesta by core formation.

PubMed

Steenstra, E S; Agmon, N; Berndt, J; Klemme, S; Matveev, S; van Westrenen, W

2018-05-04

The depletions of potassium (K) and sodium (Na) in samples from planetary interiors have long been considered as primary evidence for their volatile behavior during planetary formation processes. Here, we use high-pressure experiments combined with laser ablation analyses to measure the sulfide-silicate and metal-silicate partitioning of K and Na at high pressure (P) - temperature (T) and find that their partitioning into metal strongly increases with temperature. Results indicate that the observed Vestan and Martian mantle K and Na depletions can reflect sequestration into their sulfur-rich cores in addition to their volatility during formation of Mars and Vesta. This suggests that alkali depletions are not affected solely by incomplete condensation or partial volatilization during planetary formation and differentiation, but additionally or even primarily reflect the thermal and chemical conditions during core formation. Core sequestration is also significant for the Moon, but lunar mantle depletions of K and Na cannot be reconciled by core formation only. This supports the hypothesis that measured isotopic fractionations of K in lunar samples represent incomplete condensation or extensive volatile loss during the Moon-forming giant impact.

The solvation radius of silicate melts based on the solubility of noble gases and scaled particle theory.

PubMed

Ottonello, Giulio; Richet, Pascal

2014-01-28

The existing solubility data on noble gases in high-temperature silicate melts have been analyzed in terms of Scaling Particle Theory coupled with an ab initio assessment of the electronic, dispersive, and repulsive energy terms based on the Polarized Continuum Model (PCM). After a preliminary analysis of the role of the contracted Gaussian basis sets and theory level in reproducing appropriate static dipole polarizabilities in a vacuum, we have shown that the procedure returns Henry's law constants consistent with the values experimentally observed in water and benzene at T = 25 °C and P = 1 bar for the first four elements of the series. The static dielectric constant (ɛ) of the investigated silicate melts and its optical counterpart (ɛ(∞)) were then resolved through the application of a modified form of the Clausius-Mossotti relation. Argon has been adopted as a probe to depict its high-T solubility in melts through an appropriate choice of the solvent diameter σs, along the guidelines already used in the past for simple media such as water or benzene. The σs obtained was consistent with a simple functional form based on the molecular volume of the solvent. The solubility calculations were then extended to He, Ne, and Kr, whose dispersive and repulsive coefficients are available from theory and we have shown that their ab initio Henry's constants at high T reproduce the observed increase with the static polarizability of the series element with reasonable accuracy. At room temperature (T = 25 °C) the calculated Henry's constants of He, Ne, Ar, and Kr in the various silicate media predict higher solubilities than simple extrapolations (i.e., Arrhenius plots) based on high-T experiments and give rise to smooth trends not appreciably affected by the static polarizabilities of the solutes. The present investigation opens new perspectives on a wider application of PCM theory which can be extended to materials of great industrial interest at the core of metallurgical processes, ceramurgy, and the glass industry.

The influence of oxalate-promoted growth of saponite and talc crystals

USGS Publications Warehouse

Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D.; Sears, S. Kelly; Hesse, Reinhard; Vali, Hojatollah

2013-01-01

The intercalating growth of new silicate layers or metal hydroxide layers in the interlayer space of other clay minerals is known from various mixed-layer clay minerals such as illite-smectite (I-S), chlorite-vermiculite, and mica-vermiculite. In a recent study, the present authors proposed that smectite-group minerals can be synthesized from solution as new 2:1 silicate layers within the low-charge interlayers of rectorite. That study showed how oxalate catalyzes the crystallization of saponite from a silicate gel at low temperatures (60ºC) and ambient pressure. As an extension of this work the aim of the present study was to test the claim that new 2:1 silicate layers can be synthesized as new intercalating layers in the low-charge interlayers of rectorite and whether oxalate could promote such an intercalation synthesis. Two experiments were conducted at 60ºC and atmospheric pressure. First, disodium oxalate solution was added to a suspension of rectorite in order to investigate the effects that oxalate anions have on the structure of rectorite. In a second experiment, silicate gel of saponitic composition (calculated interlayer charge −0.33 eq/O10(OH)2) was mixed with a suspension of rectorite and incubated in disodium oxalate solution. The synthesis products were extracted after 3 months and analyzed by X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The treatment of ultrathin sections with octadecylammonium (nC = 18) cations revealed the presence of 2:1 layer silicates with different interlayer charges that grew from the silicate gel. The oxalate-promoted nucleation of saponite and talc crystallites on the rectorite led to the alteration and ultimately to the destruction of the rectorite structure. The change was documented in HRTEM lattice-fringe images. The crystallization of new 2:1 layer silicates also occurred within the expandable interlayers of rectorite but not as new 2:1 silicate layers parallel to the previous 2:1 silicate layers. Instead, they grew independently of any orientation predetermined by the rectorite crystal substrate and their crystallization was responsible for the destruction of the rectorite structure.

Clouds on Hot Jupiters Illustration

NASA Image and Video Library

2016-10-18

Hot Jupiters are exoplanets that orbit their stars so tightly that their temperatures are extremely high, reaching over 2,400 degrees Fahrenheit (1600 Kelvin). They are also tidally locked, so one side of the planet always faces the sun and the other is in permanent darkness. Research suggests that the "dayside" is largely free of clouds, while the "nightside" is heavily clouded. This illustration represents how hot Jupiters of different temperatures and different cloud compositions might appear to a person flying over the dayside of these planets on a spaceship, based on computer modeling. Cooler planets are entirely cloudy, whereas hotter planets have morning clouds only. Clouds of different composition have different colors, whereas the clear sky is bluer than on Earth. For the hottest planets, the atmosphere is hot enough on the evening side to glow like a charcoal. Figure 1 shows an approximation of what various hot Jupiters might look like based on a combination of computer modeling and data from NASA's Kepler Space Telescope. From left to right it shows: sodium sulfide clouds (1000 to 1200 Kelvin), manganese sulfide clouds (1200 to 1600 Kelvin), magnesium silicate clouds (1600 to 1800 Kelvin), magnesium silicate and aluminum oxide clouds (1800 Kelvin) and clouds composed of magnesium silicate, aluminum oxide, iron and calcium titanate (1900 to 2200 Kelvin). http://photojournal.jpl.nasa.gov/catalog/PIA21074

Low-temperature MIR to submillimeter mass absorption coefficient of interstellar dust analogues. II. Mg and Fe-rich amorphous silicates

NASA Astrophysics Data System (ADS)

Demyk, K.; Meny, C.; Leroux, H.; Depecker, C.; Brubach, J.-B.; Roy, P.; Nayral, C.; Ojo, W.-S.; Delpech, F.

2017-10-01

Context. To model the cold dust emission observed in the diffuse interstellar medium, in dense molecular clouds or in cold clumps that could eventually form new stars, it is mandatory to know the physical and spectroscopic properties of this dust and to understand its emission. Aims: This work is a continuation of previous studies aiming at providing astronomers with spectroscopic data of realistic cosmic dust analogues for the interpretation of observations. The aim of the present work is to extend the range of studied analogues to iron-rich silicate dust analogues. Methods: Ferromagnesium amorphous silicate dust analogues were produced by a sol-gel method with a mean composition close to Mg1-xFexSiO3 with x = 0.1, 0.2, 0.3, 0.4. Part of each sample was annealed at 500 °C for two hours in a reducing atmosphere to modify the oxidation state of iron. We have measured the mass absorption coefficient (MAC) of these eight ferromagnesium amorphous silicate dust analogues in the spectral domain 30-1000 μm for grain temperature in the range 10-300 K and at room temperature in the 5-40 μm range. Results: The MAC of ferromagnesium samples behaves in the same way as the MAC of pure Mg-rich amorphous silicate samples. In the 30-300 K range, the MAC increases with increasing grain temperature whereas in the range 10-30 K, we do not see any change of the MAC. The MAC cannot be described by a single power law in λ- β. The MAC of the samples does not show any clear trend with the iron content. However the annealing process has, on average, an effect on the MAC that we explain by the evolution of the structure of the samples induced by the processing. The MAC of all the samples is much higher than the MAC calculated by dust models. Conclusions: The complex behavior of the MAC of amorphous silicates with wavelength and temperature is observed whatever the exact silicate composition (Mg vs. Fe amount). It is a universal characteristic of amorphous materials, and therefore of amorphous cosmic silicates, that should be taken into account in astronomical modeling. The enhanced MAC of the measured samples compared to the MAC calculated for cosmic dust model implies that dust masses are overestimated by the models. The tabulated mass absorption coefficients are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/606/A50

Laboratory simulation of infrared astrophysical features. [Terrestrial silicate, meteoritic and lunar soil 10-micron spectral comparisons with comets Bennet and Kohoutek

NASA Technical Reports Server (NTRS)

Rose, L. A.

1979-01-01

Laboratory infrared emission and absorption spectra have been taken of terrestrial silicates, meteorites, and lunar soils in the form of micrometer and submicrometer grains. The emission spectra were taken in a way that imitates telescopic observations. The purpose was to see which materials best simulate the 10-micron astrophysical feature. The emission spectra of dunite, fayalite, and Allende give a good fit to the 10-micron broadband emission feature of comets Bennett and Kohoutek. A study of the effect of grain size on the presence of the 10-micron emission feature of dunite shows that for particles larger than 37 microns no feature is seen. The emission spectrum of the Murray meteorite, a Type 2 carbonaceous chrondrite, is quite similar to the intermediate-resolution spectrum of comet Kohoutek in the 10-micron region. Hydrous silicates or amorphous magnesium silicates in combination with high-temperature condensates, such as olivine or anorthite, would yield spectra that match the intermediate-resolution spectrum of comet Kohoutek in the 10-micron region. Glassy olivine and glassy anorthite in approximately equal proportions would also give a spectrum that is a good fit to the cometary 10-micron feature.

Thermochemistry of Silicates

NASA Technical Reports Server (NTRS)

Costa, Gustavo; Jacobson, Nathan

2015-01-01

The thermodynamic properties of vapor and condensed phases of silicates are crucial in many fields of science. These quantities address fundamental questions on the formation, stability, transformation, and physical properties of silicate minerals and silicate coating compositions. Here the thermodynamic activities of silica and other species in solid solution have been measured by the analysis of the corresponding high temperature vapors using Knudsen Effusion Mass Spectrometry (KEMS). In first set of experiments KEMS has been used to examine the volatility sequence of species (Fe, SiO, Mg, O2 and O) present in the vapor phase during heating of fosterite-rich olivine (Fo93Fa7) up to 2400 C and to measure the Fe, SiO and Mg activities in its solid solution. The data of fosterite-rich olivine are essential for thermochemical equilibrium models to predict the atmospheric and surface composition of hot, rocky exoplanets (Lava Planets). In the second set of experiments the measured thermodynamic activities of the silica in Y2O3-SiO2 and Yb2O3-SiO2 systems are used to assess their reactivity and degradation recession as environmental barrier coatings (EBCs) in combustion environments (e.g. non-moveable parts of gas turbine engine).

Conductimetric determination of decomposition of silicate melts

NASA Technical Reports Server (NTRS)

Kroeger, C.; Lieck, K.

1986-01-01

A description of a procedure is given to detect decomposition of silicate systems in the liquid state by conductivity measurements. Onset of decomposition can be determined from the temperature curves of resistances measured on two pairs of electrodes, one above the other. Degree of decomposition can be estimated from temperature and concentration dependency of conductivity of phase boundaries. This procedure was tested with systems PbO-B2O3 and PbO-B2O3-SiO2.

Constraints on the subsurface structure of Europa

NASA Astrophysics Data System (ADS)

Golombek, M. P.; Banerdt, W. B.

1990-02-01

The wedge-shaped bands appearing near the anti-Jovian point on Europa are tension cracks which, after formation on an intact lithosphere, have facilitated the rotation of ice-lithosphere sections decoupled from the silicate interior. Such factors as fluid pressure, surface temperature, silicate impurities in the ice, and strain rates, would have affected the processes in question. A minimum degree of differentiation is required for Europa to mechanically decouple the rotated ice lithosphere from the underlying, predominantly silicate mantle.

Microbanded manganese formations; protoliths in the Franciscan Complex, California

USGS Publications Warehouse

Huebner, J. Stephen; Flohr, Marta J.

1990-01-01

The Buckeye manganese deposit, 93 km southeast of San Francisco in the California Coast Ranges, preserves a geologic history that provides clues to the origin of numerous lenses of manganese carbonate, oxides, and silicates that occur with interbedded radiolarian chert and metashale of the Franciscan Complex. Compositionally and mineralogically laminated Mn-rich protoliths were deformed and dismembered, in a manner that mimics in smaller scale the deformation of the host complex, and then were incipiently metamorphosed at blueschistfacies conditions. Eight phases occur as almost monomineralic protoliths and mixtures: rhodochrosite, caryopilite, chlorite, gageite, taneyamalite, braunite, hausmannite, and laminated chert (quartz). Braunite, gageite, and some chlorite and caryopilite layers were deposited as gel-like materials; rhodochrosite, most caryopilite, and at least some hausmannite layers as lutites; and the chert as turbidites of radiolarian sand. Some gel-like materials are now preserved as transparent, sensibly isotropic relics of materials that fractured or shattered when deformed, creating curved surfaces. In contrast, the micrites flowed between the fragments of gel-like materials. The orebody and most of its constituent minerals have unusually Mn-rich compositions that are described by the system MnO-SiO2-O2-CO2-H2O. High values of Mn/Fe and U/Th, and low concentrations of Co, Cu, and Ni, distinguish the Buckeye deposit from many high-temperature hydrothermal deposits and hydrogenous or diagenetic manganese and ferromanganese nodules and pavements. This chemical signature suggests that ore deposition was related to fluids from the sediment column and seawater. Tungsten is associated exclusively with gageite, in concentrations as high as 80 parts per million. The source of the manganese is unknown; because basalts do not occur near the deposit, it was probably manganese leached from the sediment column by reducing solutions. Low concentrations of calcium (CaO approximately 0.6 weight percent) suggest that the host sediments formed beneath the carbonate-compensation depth. The most probable cause of the microbanding is changing proportions of chemical fluxes supplied to the sediment-seawater interface. The principal fluxes were biogenic silica from the water column, carbon dioxide from organic matter in the sediment column, O2 and other seawater constituents, and Mn +2-bearing fluid. The presence of Al2O3 and TiO2 (supplied by a detrital flux) in the metashale but not the ore lens suggests rapid ore deposition. Material supply-rate changes were probably due to a complex combination of episodic variations in the hydrothermal flux and periodic flows of radiolarian sand (silica and CO2 fluxes) that may be related to climate variations. The processes that form recent marine hydrothermal mounds may be the same as processes that formed the Buckeye deposit. Features common to both include the presence of Mn-oxyhydroxide crusts (corresponding to the Buckeye orebody), a large Mn/Fe ratio, low abundances of most minor elements, and small size. The most important differences are the absence of rhodochrosite and manganese silicates, interlayered with oxide, and the absence of adjacent chert in the contemporary deposits. These differences may be due to an absence of the debris of siliceous pelagic organisms, which accumulated in the Buckeye paleoenvironment. Periodic turbidity flows of chert-forming radiolarian sand could provide the changes in the fluxes of silica and organic matter necessary to form manganese carbonate and silicates. Turbidity flows of graywacke indicate proximity to an environment with high relief. A possible paleodepositional environment is an oceanic spreading center approaching a continental margin at which subduction occurred.

High-pressure x-ray diffraction studies on the structure of liquid silicate using a Paris-Edinburgh type large volume press.

PubMed

Yamada, Akihiro; Wang, Yanbin; Inoue, Toru; Yang, Wenge; Park, Changyong; Yu, Tony; Shen, Guoyin

2011-01-01

An experimental setup for high-pressure liquid structure studies with synchrotron x-ray diffraction using the Paris-Edinburgh press has been installed at station 16-BM-B (HPCAT) of the Advanced Photon Source, Argonne National Laboratory. By collecting energy-dispersive data with a synchrotron white beam at various 2θ angles, the present device allows us to obtain the structure factor, S(Q), over a wide range of Q ( = 4πsinθ∕λ) owing to the excellent angular accessibility up to 37° in 2θ and high energy photons well beyond 100 keV. We have successfully collected XRD data on silicate (albite, NaAlSi(3)O(8)) liquids with Q up to ∼22 Å(-1) and pressure up to 5.3 GPa and temperature 1873 K, and obtained the radial distribution function, G(r), with a reasonable resolution. The T-O bond length (where T = Al, Si), which is a fundamental measure of local structure for aluminous silicate consisting of SiO(n) and AlO(n) polyhedra (tetrahedra at 1 atm condition), was found to be slightly shortened to 1.626 Å compared to that of glass at 1 atm. The T-O-T bound angle, which is the linkage of the above polyhedra, is the most responsible for densification. The T-O-T peak in G(r) splits into two peaks, suggesting a differentiation of the bond angle at high-pressure. The present technical development demonstrates that the Paris-Edinburgh press is suitable for studies of silicate liquids under high-pressure conditions.

On the Influence of North Pacific Sea Surface Temperature on the Arctic Winter Climate

NASA Technical Reports Server (NTRS)

Hurwitz, Margaret M.; Newman, P. A.; Garfinkel, C. I.

2012-01-01

Differences between two ensembles of Goddard Earth Observing System Chemistry-Climate Model simulations isolate the impact of North Pacific sea surface temperatures (SSTs) on the Arctic winter climate. One ensemble of extended winter season forecasts is forced by unusually high SSTs in the North Pacific, while in the second ensemble SSTs in the North Pacific are unusually low. High Low differences are consistent with a weakened Western Pacific atmospheric teleconnection pattern, and in particular, a weakening of the Aleutian low. This relative change in tropospheric circulation inhibits planetary wave propagation into the stratosphere, in turn reducing polar stratospheric temperature in mid- and late winter. The number of winters with sudden stratospheric warmings is approximately tripled in the Low ensemble as compared with the High ensemble. Enhanced North Pacific SSTs, and thus a more stable and persistent Arctic vortex, lead to a relative decrease in lower stratospheric ozone in late winter, affecting the April clear-sky UV index at Northern Hemisphere mid-latitudes.

Deep melting reveals liquid structural memory and anomalous ferromagnetism in bismuth.

PubMed

Shu, Yu; Yu, Dongli; Hu, Wentao; Wang, Yanbin; Shen, Guoyin; Kono, Yoshio; Xu, Bo; He, Julong; Liu, Zhongyuan; Tian, Yongjun

2017-03-28

As an archetypal semimetal with complex and anisotropic Fermi surface and unusual electric properties (e.g., high electrical resistance, large magnetoresistance, and giant Hall effect), bismuth (Bi) has played a critical role in metal physics. In general, Bi displays diamagnetism with a high volumetric susceptibility ([Formula: see text]10 -4 ). Here, we report unusual ferromagnetism in bulk Bi samples recovered from a molten state at pressures of 1.4-2.5 GPa and temperatures above [Formula: see text]1,250 K. The ferromagnetism is associated with a surprising structural memory effect in the molten state. On heating, low-temperature Bi liquid (L) transforms to a more randomly disordered high-temperature liquid (L') around 1,250 K. By cooling from above 1,250 K, certain structural characteristics of liquid L' are preserved in L. Bi clusters with characteristics of the liquid L' motifs are further preserved through solidification into the Bi-II phase across the pressure-independent melting curve, which may be responsible for the observed ferromagnetism.

Deep melting reveals liquid structural memory and anomalous ferromagnetism in bismuth

PubMed Central

Shu, Yu; Yu, Dongli; Hu, Wentao; Wang, Yanbin; Shen, Guoyin; Kono, Yoshio; Xu, Bo; He, Julong; Liu, Zhongyuan; Tian, Yongjun

2017-01-01

As an archetypal semimetal with complex and anisotropic Fermi surface and unusual electric properties (e.g., high electrical resistance, large magnetoresistance, and giant Hall effect), bismuth (Bi) has played a critical role in metal physics. In general, Bi displays diamagnetism with a high volumetric susceptibility (∼10−4). Here, we report unusual ferromagnetism in bulk Bi samples recovered from a molten state at pressures of 1.4–2.5 GPa and temperatures above ∼1,250 K. The ferromagnetism is associated with a surprising structural memory effect in the molten state. On heating, low-temperature Bi liquid (L) transforms to a more randomly disordered high-temperature liquid (L′) around 1,250 K. By cooling from above 1,250 K, certain structural characteristics of liquid L′ are preserved in L. Bi clusters with characteristics of the liquid L′ motifs are further preserved through solidification into the Bi-II phase across the pressure-independent melting curve, which may be responsible for the observed ferromagnetism. PMID:28289195

Distribution, microfabric, and geochemical characteristics of siliceous rocks in central orogenic belt, China: implications for a hydrothermal sedimentation model.

PubMed

Li, Hongzhong; Zhai, Mingguo; Zhang, Lianchang; Gao, Le; Yang, Zhijun; Zhou, Yongzhang; He, Junguo; Liang, Jin; Zhou, Liuyu; Voudouris, Panagiotis Ch

2014-01-01

Marine siliceous rocks are widely distributed in the central orogenic belt (COB) of China and have a close connection to the geological evolution and metallogenesis. They display periodic distributions from Mesoproterozoic to Jurassic with positive peaks in the Mesoproterozoic, Cambrian--Ordovician, and Carboniferous--Permian and their deposition is enhanced by the tensional geological settings. The compressional regimes during the Jinning, Caledonian, Hercynian, Indosinian, and Yanshanian orogenies resulted in sudden descent in their distribution. The siliceous rocks of the Bafangshan-Erlihe ore deposit include authigenic quartz, syn-depositional metal sulphides, and scattered carbonate minerals. Their SiO2 content (71.08-95.30%), Ba (42.45-503.0 ppm), and ΣREE (3.28-19.75 ppm) suggest a hydrothermal sedimentation origin. As evidenced by the Al/(Al + Fe + Mn), Sc/Th, (La/Yb) N, and (La/Ce) N ratios and δCe values, the studied siliceous rocks were deposited in a marginal sea basin of a limited ocean. We suggest that the Bafangshan-Erlihe area experienced high- and low-temperature stages of hydrothermal activities. The hydrothermal sediments of the former stage include metal sulphides and silica, while the latter was mainly composed of silica. Despite the hydrothermal sedimentation of the siliceous rocks, minor terrigenous input, magmatism, and biological activity partly contributed to geochemical features deviating from the typical hydrothermal characteristics.

Distribution, Microfabric, and Geochemical Characteristics of Siliceous Rocks in Central Orogenic Belt, China: Implications for a Hydrothermal Sedimentation Model

PubMed Central

Li, Hongzhong; Zhai, Mingguo; Zhang, Lianchang; Gao, Le; Yang, Zhijun; Zhou, Yongzhang; He, Junguo; Liang, Jin; Zhou, Liuyu; Voudouris, Panagiotis Ch.

2014-01-01

Marine siliceous rocks are widely distributed in the central orogenic belt (COB) of China and have a close connection to the geological evolution and metallogenesis. They display periodic distributions from Mesoproterozoic to Jurassic with positive peaks in the Mesoproterozoic, Cambrian—Ordovician, and Carboniferous—Permian and their deposition is enhanced by the tensional geological settings. The compressional regimes during the Jinning, Caledonian, Hercynian, Indosinian, and Yanshanian orogenies resulted in sudden descent in their distribution. The siliceous rocks of the Bafangshan-Erlihe ore deposit include authigenic quartz, syn-depositional metal sulphides, and scattered carbonate minerals. Their SiO2 content (71.08–95.30%), Ba (42.45–503.0 ppm), and ΣREE (3.28–19.75 ppm) suggest a hydrothermal sedimentation origin. As evidenced by the Al/(Al + Fe + Mn), Sc/Th, (La/Yb)N, and (La/Ce)N ratios and δCe values, the studied siliceous rocks were deposited in a marginal sea basin of a limited ocean. We suggest that the Bafangshan-Erlihe area experienced high- and low-temperature stages of hydrothermal activities. The hydrothermal sediments of the former stage include metal sulphides and silica, while the latter was mainly composed of silica. Despite the hydrothermal sedimentation of the siliceous rocks, minor terrigenous input, magmatism, and biological activity partly contributed to geochemical features deviating from the typical hydrothermal characteristics. PMID:25140349

From mean-field localized magnetism to itinerant spin fluctuations in the "nonmetallic metal" FeCrAs

NASA Astrophysics Data System (ADS)

Plumb, K. W.; Stock, C.; Rodriguez-Rivera, J. A.; Castellan, J.-P.; Taylor, J. W.; Lau, B.; Wu, W.; Julian, S. R.; Kim, Young-June

2018-05-01

FeCrAs displays an unusual electrical response that is neither metallic in character nor divergent at low temperatures, as expected for an insulating response, and therefore it has been termed a "nonmetal metal." The anomalous resistivity occurs for temperatures below ˜900 K. We have carried out neutron scattering experiments on powder and single crystal samples to study the magnetic dynamics and critical fluctuations in FeCrAs. Magnetic neutron diffraction measurements find Cr3 + magnetic order setting in at TN=115 K ˜10 meV with a mean-field critical exponent. Using neutron spectroscopy we observe gapless, high velocity, magnetic fluctuations emanating from magnetic positions with propagation wave vector q⃗0=(1/3 ,1/3 ) , which persists up to at least 80 meV ˜927 K, an energy scale much larger than TN. Despite the mean-field magnetic order at low temperatures, the magnetism in FeCrAs therefore displays a response which resembles that of itinerant magnets at high energy transfers. We suggest that the presence of stiff high-energy spin fluctuations extending up to a temperature scale of ˜900 K is the origin of the unusual temperature dependence of the resistivity.

Tuning of superconductivity by Ni substitution into noncentrosymmetric ThC o1 -xN ixC2

NASA Astrophysics Data System (ADS)

Grant, T. W.; Cigarroa, O. V.; Rosa, P. F. S.; Machado, A. J. S.; Fisk, Z.

2017-07-01

The recently discovered noncentrosymmetric superconductor ThCoC2 was observed to show unusual superconducting behavior with a critical temperature of Tc=2.65 K . Here we investigate the effect of nickel substitution on the superconducting state in ThC o1 -xN ixC2 . Magnetization, resistivity, and heat capacity measurements demonstrate Ni substitution has a dramatic effect with critical temperature increased up to Tc=12.1 K for x =0.4 Ni concentration, which is a rather high transition temperature for a noncentrosymmetric superconductor. In addition, the unusual superconducting characteristics observed in pure ThCoC2 appear to be suppressed or tuned with Ni substitution towards a more conventional fully gapped superconductor.

Ab Initio Predictions of K, He and Ar Partitioning Between Silicate Melt and Liquid Iron Under High Pressure

NASA Astrophysics Data System (ADS)

Xiong, Z.; Tsuchiya, T.

2017-12-01

Element partitioning is an important property in recording geochemical processes during the core-mantle differentiation. However, experimental measurements of element partitioning coefficients under extreme temperature and pressure condition are still challenging. Theoretical modeling is also not easy, because it requires estimation of high temperature Gibbs free energy, which is not directly accessible by the standard molecular dynamics method. We recently developed an original technique to simulate Gibbs free energy based on the thermodynamics integration method[1]. We apply it to element partitioning of geochemical intriguing trace elements between molten silicate and liquid iron such as potassium, helium and argon as starting examples. Radiogenic potassium in the core can provide energy for Earth's magnetic field, convection in the mantle and outer core[2]. However, its partitioning behavior between silicate and iron remains unclear under high pressure[3,4]. Our calculations suggest that a clear positive temperature dependence of the partitioning coefficient but an insignificant pressure effect. Unlike sulfur and silicon, oxygen dissolved in the metals considerably enhances potassium solubility. Calculated electronic structures reveal alkali-metallic feature of potassium in liquid iron, favoring oxygen with strong electron affinity. Our results suggest that 40K could serve as a potential radiogenic heat source in the outer core if oxygen is the major light element therein.­­ We now further extend our technique to partitioning behaviors of other elements, helium and argon, to get insides into the `helium paradox' and `missing argon' problems. References [1] T. Taniuchi, and T. Tsuchiya, Phys.Rev.B. In press [2] B.A. Buffett, H.E. Huppert, J.R. Lister, and A.W. Woods, Geophys.Res.Lett. 29 (1996) 7989-8006. [3] V.R. Murthy, W. Westrenen, and Y. Fei, Nature. 426 (2003) 163-165. [4] A. Corgne, S.Keshav, Y. Fei, and W.F. McDonough, Earth.Planet.Sci.Lett. 256 (2007) 567-576

Interpreting the 10 micron Astronomical Silicate Feature

NASA Astrophysics Data System (ADS)

Bowey, Janet E.

1998-11-01

10micron spectra of silicate dust in the diffuse medium towards Cyg OB2 no. 12 and towards field and embedded objects in the Taurus Molecular Cloud (TMC) were obtained with CGS3 at the United Kingdom Infrared Telescope (UKIRT). Cold molecular-cloud silicates are sampled in quiescent lines of sight towards the field stars Taurus-Elias 16 and Elias 13, whilst observations of the embedded young stellar objects HL Tau, Taurus-Elias 7 (Haro6-10) and Elias 18 also include emission from heated dust. To obtain the foreground silicate absorption profiles, featureless continua are estimated using smoothed astronomical and laboratory silicate emissivities. TMC field stars and Cyg OB2 no. 12 are modelled as photospheres reddened by foreground continuum and silicate extinction. Dust emission in the non-photospheric continua of HL Tau and Elias 7 (Haro6-10) is distinguished from foreground silicate absorption using a 10micron disk model, based on the IR-submm model of T Tauri stars by Adams, Lada & Shu (1988), with terms added to represent the foreground continuum and silicate extinction. The absorption profiles of HL Tau and Elias 7 are similar to that of the field star Elias 16. Fitted temperature indices of 0.43 (HL Tau) and 0.33 (Elias 7) agree with Boss' (1996) theoretical models of the 200-300K region, but are lower than those of IR-submm disks (0.5-0.61; Mannings & Emerson 1994); the modelled 10micron emission of HL Tau is optically thin, that of Elias 7 is optically thick. A preliminary arcsecond-resolution determination of the 10micron emissivity near θ1 Ori D in the Trapezium region of Orion and a range of emission temperatures (225-310K) are derived from observations by T. L. Hayward; this Ney-Allen emissivity is 0.6micron narrower than the Trapezium emissivity obtained by Forrest et al. (1975) with a large aperture. Published interstellar grain models, elemental abundances and laboratory studies of Solar System silicates (IDPs, GEMS and meteorites), the 10micron spectra of comets, interstellar silicates, synthetic silicates and terrestrial minerals, and the effects of laboratory processing on the 10micron spectra of crystalline and amorphous silicates are reviewed to provide insight into the mineralogy of interstellar silicate dust. The wavelengths of the peaks of the 10micron silicate profiles decrease between circumstellar, diffuse medium and molecular-cloud environments, indicating (after Gürtler & Henning 1986) that the amorphous pyroxene content of initially olivine-rich interstellar dust increases with time. This is accompanied by an increase in the FWHM of the features which indicates an increase in grain size and/or an increasing fraction of chemically-varied crystalline pyroxene. Fine structure in the Cyg OB2 no. 12, Elias 16, Elias 7, HL Tau profiles indicate that hydrated layer silicates similar to terrestrial serpentines, clays and talc may be a ubiquitous component of interstellar dust. At 10microns the narrow bands of mixed crystalline pyroxenes blend, making their identification difficult. Since no fine structure is observed near 11.2microns, the fraction of crystalline olivine is small. In geology direct olivine-plus-SiO2 to pyroxene reactions occur only at high pressure within the terrestrial mantle. Therefore the fraction of amorphous pyroxene is probably increased by the hydration of Mg-rich olivine to form a serpentine-like hydrated silicate, which is subsequently annealed to form a mixture of amorphous pyroxene and olivine. Terrestrial and laboratory olivine samples are readily converted to serpentine in the presence of water, and (after extended annealing) the first crystalline band to appear is the 11.2micron olivine feature frequently observed in cometary spectra.

Si and O partitioning between core metal and lower mantle minerals during core formation

NASA Astrophysics Data System (ADS)

Nakajima, Y.; Frost, D. J.; Rubie, D. C.

2010-12-01

In addition to Fe and Ni, the Earth’s core contains light alloying elements (e.g., H, C, O, Si, and/or S) in order to explain the 10% core density deficit (e.g., Birch, 1964, JGR). Experimental data on the partitioning behavior of siderophile elements such as Ni and Co between liquid Fe and mantle minerals indicate that equilibration between core-forming metal and a silicate magma ocean likely occurred at lower-mantle pressures (e.g., Li and Agee, 1996 Nature). If core-mantle differentiation has occurred under such conditions, significant quantities of O or Si could have entered the core. At these conditions the nature of the dominant light element in the core will depend strongly on the oxygen fugacity at which equilibration occurred. High pressure experiments were carried out at 25 GPa and 2400-2950 K using a Kawai-type multi-anvil apparatus in order to investigate the partitioning of Si and O between liquid Fe and (Mg,Fe)SiO3 perovskite (Pv), silicate melt, and (Mg,Fe)O ferropericlace (Fp). Starting materials consisting of metallic Fe (+-Si) and olivine (Fo70-95) were contained in single-crystal MgO capsules. Over the oxygen fugacity range IW-0.5 to -3, the Si molar partition coefficient D* (= [Si]metal /[Si]silicate) between metal and Pv increases linearly with decreasing oxygen fugacity at a fixed given temperature. The partition coefficient between metal and silicate melt is of a similar magnitude but is less dependent on the oxygen fugacity. The obtained oxygen distribution coefficient Kd (= [Fe]metal[O]metal /[FeO]Fp) is in agreement with that determined in the Fe-Fp binary system (Asahara et al., 2007 EPSL) below the silicate liquidus temperature. In contrast, a correlation between the O partitioning and Si concentration in Fe is observed above 2700 K where liquid metal coexists with silicate melt + Fp. With an increasing concentration of Si in the liquid metal, O partitioning into Fp is strongly enhanced. Five atomic% Si in the metal reduces the metal-silicate O partition coefficient by about 1 order magnitude. Near the base of a deep magma ocean where pressures exceed 20 GPa, liquid metal could have coexisted with silicate melt, Pv, and Fp. Our results show that Si would readily partitioned into core-forming metal from both perovskite and silicate liquid at a relevant oxygen fugacity (e.g., IW-2). Simultaneously, the Si solubility would hinder the dissolution of O in the liquid metal. This implies that the presence of Si in liquid metal must be included in models of O partitioning.

An effective utilization of the slag from acid leaching of coal-waste: preparation of water glass with a low-temperature co-melting reaction.

PubMed

Fang, Li; Duan, Xiaofang; Chen, Rongming; Cheng, Fangqin

2014-08-01

This paper presents an effective utilization of slag from acid leaching of coal-waste with a novel approach, namely low-temperature co-melting method, for preparation of sodium silicate (Na2O x nSiO2) using slag from acid leaching of coal-waste as feedstock. It is very interesting that the co-melting reaction temperature of the mixture of Na2CO3 and the feedstock (50-100 microm) was as low as 850 degrees C, which was significantly lower than the temperature used in traditional sodium silicate production (1400 degrees C). The optimum SiO2/Na2O ratio was identified as 7:3 according to the results of thermogravimetry-differential scanning calorimetry (TGA-DSC), ICP-AES, and X-ray diffraction (XRD) analyses. In this condition, the main product was sodium disilicate (Na2O x 2SiO2), with water solubility of 85.0%. More importantly, the impurities such as aluminum in the feedstock, which had adverse effect on subsequent treatment, were concentrated almost completely in the filter residue as insoluble sodium alumunosilicates, i.e., Na(Si2Al)O6 x H2O. The lower co-melting temperature of this process demonstrates a significant energy-saving opportunity and thus a promising approach for highly effective utilization of coal-waste. Implications: Recently, alumina extraction from coal-waste has been extensively investigated and industrial applied in China. However, the slag-containing silica generated from the acid leaching process of coal-waste led to a secondary pollution, which hindered large-scale production. The proposed low-temperature co-melting method for preparation of sodium silicate (Na2O x nSiO2) using slag from acid leaching of coal-waste as feedstock indicated that it is an efficient approach for the recovery of silica from the acid-leached slag of coal-waste with minimal environmental impact.

Interstellar and Solar Nebula Materials in Cometary Dust

NASA Technical Reports Server (NTRS)

Messenger, Scott; Nakamura-Messenger, Keiko; Keller, Lindsay; Nguyen, Ann; Clemett, Simon

2017-01-01

Laboratory studies of cometary dust collected in the stratosphere and returned from comet 81P/Wild 2 by the Stardust spacecraft have revealed ancient interstellar grains and molecular cloud organic matter that record a range of astrophysical processes and the first steps of planetary formation. Presolar materials are rarer meteorites owing to high temperature processing in the solar nebula and hydrothermal alteration on their asteroidal parent bodies. The greater preservation of presolar materials in comets is attributed to their low accretion temperatures and limited planetary processing. Yet, comets also contain a large complement of high temperature materials from the inner Solar System. Owing to the limited and biased sampling of comets to date, the proportions of interstellar and Solar System materials within them remains highly uncertain. Interstellar materials are identified by coordinated isotopic, mineralogical, and chemical measurements at the scale of individual grains. Chondritic porous interplanetary dust particles (CP IDPs) that likely derive from comets are made up of 0.1 - 10 micron-sized silicates, Fe-Ni-sulfides, oxides, and other phases bound by organic material. As much as 1% of the silicates are interstellar grains that have exotic isotopic compositions imparted by nucleosynthetic processes in their parent stars. Crystalline silicates in CP IDPs dominantly have normal isotopic compositions and probably formed in the Solar System. 81P samples include isotopically normal refractory minerals that resemble Ca-Al rich inclusions and chondrules common in meteorites. The origins of sub-micron amorphous silicates in IDPs are not certain, but at least a few % of them are interstellar grains. The remainder have isotopic compositions consistent with Solar System origins and elemental compositions that are inconsistent with interstellar grain properties, thus favoring formation in the solar nebula [4]. The organic component in comets and primitive meteorites has large enrichments in D/H and N-15/N-14 relative to terrestrial materials. These isotopic signatures are probably due to low temperature chemical processes in cold molecular clouds or the outermost reaches of the protoplanetary disk. The greatest isotopic anomalies are found in sub-micron organic nanoglobules that show chemical signatures of interstellar chemistry. The observation that cometary dust is mostly composed of isotopically normal minerals within isotopically anomalous organic matter is difficult to reconcile with the formation models of each component. The mineral component likely formed in high temperature processes in the inner Solar System, while the organic fraction shows isotopic and chemical signatures of formation near 10 K. Studying more primitive remnants of the Solar System starting materials would help in resolving this paradox. Comets formed across a vast expanse of the outer disk under differing thermal and collisional regimes, and some are likely to be better preserved than others. Finding truly pristine aggregates of presolar materials may require return of a pristine sample of comet nucleus material.

Nanoscale zinc silicate from phytoliths

NASA Astrophysics Data System (ADS)

Qadri, S. B.; Gorzkowski, E. P.; Rath, B. B.; Feng, C. R.; Amarasinghe, R.; Freitas, J. A.; Culbertson, J. C.; Wollmershauser, J. A.

2017-10-01

We report a faster, less expensive method of producing zinc silicate nanoparticles. Such particles are used in high volume to make phosphors and anti-corrosion coatings. The approach makes use of phytoliths (plant rocks), which are microscopic, amorphous, and largely silicate particles embedded in plants, that lend themselves to being easily broken down into nanoparticles. Nanoparticles of Zn2SiO4 were produced in a two stage process. In the refinement stage, plant residue, mixed with an appropriate amount of ZnO, was heated in an argon atmosphere to a temperature exceeding 1400 °C for four to six hours and then heated in air at 650 °C to remove excess carbon. TEM shows 50-100 nm nanoparticles. Raman scattering indicates that only the -Zn2SiO4 crystalline phase was present. X-ray analysis indicated pure rhombohedral R 3 bar phase results from using rice/wheat husks. Both samples luminesced predominantly at 523 nm when illuminated with X-rays or UV laser light.

Experimental determination of the partitioning of gallium between solid iron metal and synthetic basaltic melt Electron and ion microprobe study

NASA Technical Reports Server (NTRS)

Drake, M. J.; Newsom, H. E.; Reed, S. J. B.; Enright, M. C.

1984-01-01

The distribution of Ga between solid Fe metal and synthetic basaltic melt is investigated experimentally at temperatures of 1190 and 1330 C, and over a narrow range of oxygen fugacities. Metal-silicate reversal experiments were conducted, indicating a close approach to equilibrium. The analysis of the partitioned products was performed using electron and ion microprobes. At one bar total pressure, the solid metal/silicate melt partition coefficient D(Ga) is used to evaluate metal-silicate fractionation processes in the earth, moon, and Eucrite Parent Body (EPB). It is found that the depletion of Ga abundances in the EPB is due to the extraction of Ga into a metallic core. Likewise, the depletion of Ga in the lunar mantle is consistent with the extraction of Ga into a smaller lunar core if Ga was originally present in a subchondritic concentration. The relatively high Ga abundances in the earth's mantle are discussed, with reference to several theoretical models.

NASA's Advanced Environmental Barrier Coatings Development for SiC/SiC Ceramic Matrix Composites: Understanding Calcium Magnesium Alumino-Silicate (CMAS) Degradations and Resistance

NASA Technical Reports Server (NTRS)

Zhu, Dongming

2014-01-01

Environmental barrier coatings (EBCs) and SiCSiC ceramic matrix composites (CMCs) systems will play a crucial role in next generation turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures with improved efficiency, reduce engine weight and cooling requirements. The development of prime-reliant environmental barrier coatings is essential to the viability and reliability of the envisioned CMC engine component applications, ensuring integrated EBC-CMC system durability and designs are achievable for successful applications of the game-changing component technologies and lifing methodologies.This paper will emphasize recent NASA environmental barrier coating developments for SiCSiC turbine airfoil components, utilizing advanced coating compositions, state-of-the-art processing methods, and combined mechanical and environment testing and durability evaluations. The coating-CMC degradations in the engine fatigue-creep and operating environments are particularly complex; one of the important coating development aspects is to better understand engine environmental interactions and coating life debits, and we have particularly addressed the effect of Calcium-Magnesium-Alumino-Silicate (CMAS) from road sand or volcano-ash deposits on the durability of the environmental barrier coating systems, and how the temperature capability, stability and cyclic life of the candidate rare earth oxide and silicate coating systems will be impacted in the presence of the CMAS at high temperatures and under simulated heat flux conditions. Advanced environmental barrier coating systems, including HfO2-Si with rare earth dopant based bond coat systems, will be discussed for the performance improvements to achieve better temperature capability and CMAS resistance for future engine operating conditions.

Global climatology and variability of potential new production estimated from remote sensing of sea-surface temperature

NASA Technical Reports Server (NTRS)

Dugdale, Richard C.; Wilkerson, Frances P.

1995-01-01

During this project we have collected numerous shipboard data-bases of oceanic nitrate and silicate versus temperature for both equatorial and coastal upwelling regions. These cruises all have accompanying N-15 measurements of new production. The inverse relationships between nutrients and temperatures have been determined and are being used to obtain surface nutrient fields from sea surface temperatures measured remotely by satellite borne sensors- i.e. AVHRR data from NOAA satellites contained in the MCSST data set for the world ocean provided by the University of Miami. The images and data derived from space in this way show the strong seasonal fluctuations and interannual el Nino fluctuations of the nitrate field. the nitrate data has been used to make estimates of new production for the equatorial pacific which are compared with shipboard measurements when available. The importance of silicate as a nutrient driving new production and the ratio of nitrate to silicate has been discovered to be crucial to better understand the causes of new production variability, so we have added these parameters to our study and have begun to make estimates of these for the equatorial Pacific, derived from the weekly averaged sea surface temperatures (SSTs).

Recent Ship, Satellite and Autonomous Observations of Southern Ocean Eddies

NASA Astrophysics Data System (ADS)

Strutton, P. G.; Moreau, S.; Llort, J.; Phillips, H. E.; Patel, R.; Della Penna, A.; Langlais, C.; Lenton, A.; Matear, R.; Dawson, H.; Boyd, P. W.

2016-12-01

The Southern Ocean is the area of greatest uncertainty regarding the exchange of CO2 between the ocean and atmosphere. It is also a region of abundant energetic eddies that significantly impact circulation and biogeochemistry. In the Indian sector of the Southern Ocean, cyclonic eddies are unusual in that they are upwelling favorable, as for cyclonic eddies elsewhere, but during summer they are low in silicate and phytoplankton biomass. The reverse is true for anticyclonic eddies in that they have counter-intuitive positive chlorophyll anomalies in summer. Similar but less obvious patterns occur in the Pacific and Atlantic sectors. Using ship, satellite and autonomous observations in the region south of Australia, the physical and biogeochemical signatures of both types of eddies were documented in 2016. A cyclonic eddy that lived for seven weeks exhibited doming isopycnals indicative of upwelling. However, low surface silicate and chlorophyll concentrations appeared to be characteristic of surface waters to the south where the eddy formed. Higher chlorophyll was confined to filaments at the eddy edge. Surface nitrate and phosphate concentrations were more than sufficient for a bloom of non-siliceous phytoplankton to occur. Acoustic observations from a high resolution TRIAXUS transect through the eddy documented high zooplankton biomass in the upper 150m. It is hypothesized that a non-diatom bloom was prevented by grazing pressure, but light may have also been an important limiting resource in late summer (April). Two SOCCOM floats that were deployed in the eddy field continued to monitor the physics, nitrate and bio-optics through the transition to winter. These observations across complementary platforms have identified and then explained the reason for these unexpected biological anomalies in an energetic and globally important region of the global ocean. Understanding the role of eddies in this region will be critical to the representation of mesoscale processes in models used to simulate and project ocean biogeochemistry and carbon uptake.

Chemical composition of HAL, an isotopically-unusual Allende inclusion

NASA Astrophysics Data System (ADS)

Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

1982-09-01

Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

Chemical composition of HAL, an isotopically-unusual Allende inclusion

NASA Technical Reports Server (NTRS)

Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

1982-01-01

Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

What is really extraordinary in cuprate superconductors?

DOE PAGES

Bozovic, I.; Wu, J.; He, X.; ...

2018-03-07

Over the course of three decades of intense study, apart from the exceptionally high critical temperature, many unusual properties of cuprates have been discovered, notably including resistivity linear in temperature, electronic Raman continuum and optical absorption extending throughout the infrared region, pseudogap, hour-glass spin excitation spectrum, etc. However, each of these features have been also observed in other materials, including some that are not even superconducting at all. Here, we describe an extensive experiment in which over 2,000 films of the La 2-xSr xCuO 4 have been synthesized and studied in detail over the course of the last twelve years.more » We argue here that, uniquely, in the cuprates an unusual superconducting state, that defies the standard BCS description, develops from an unusual metallic state, in which the rotational symmetry of the electron fluid is spontaneously broken.« less

Redox dependent behaviour of molybdenum during magmatic processes in the terrestrial and lunar mantle: Implications for the Mo/W of the bulk silicate Moon

NASA Astrophysics Data System (ADS)

Leitzke, F. P.; Fonseca, R. O. C.; Sprung, P.; Mallmann, G.; Lagos, M.; Michely, L. T.; Münker, C.

2017-09-01

We present results of high-temperature olivine-melt, pyroxene-melt and plagioclase-melt partitioning experiments aimed at investigating the redox transition of Mo in silicate systems. Data for a series of other minor and trace elements (Sc, Ba, Sr, Cr, REE, Y, HFSE, U, Th and W) were also acquired to constrain the incorporation of Mo in silicate minerals. All experiments were carried out in vertical tube furnaces at 1 bar and temperatures ranging from ca. 1220 to 1300 °C. Oxygen fugacity was controlled via CO-CO2 gas mixtures and varied systematically from 5.5 log units below to 1.9 log units above the fayalite-magnetite-quartz (FMQ) redox buffer thereby covering the range in oxygen fugacities of terrestrial and lunar basalt genesis. Molybdenum is shown to be volatile at oxygen fugacities above FMQ and that its compatibility in pyroxene and olivine increases three orders of magnitude towards the more reducing conditions covered in this study. The partitioning results show that Mo is dominantly tetravalent at redox conditions below FMQ-4 and dominantly hexavalent at redox conditions above FMQ. Given the differences in oxidation states of the terrestrial (oxidized) and lunar (reduced) mantles, molybdenum will behave significantly differently during basalt genesis in the Earth (i.e. highly incompatible; average DMoperidotite/melt ∼ 0.008) and Moon (i.e. moderately incompatible/compatible; average DMoperidotite/melt ∼ 0.6). Thus, it is expected that Mo will strongly fractionate from W during partial melting in the lunar mantle, given that W is broadly incompatible at FMQ-5. Moreover, the depletion of Mo and the Mo/W range in lunar samples can be reproduced by simply assuming a primitive Earth-like Mo/W for the bulk silicate Moon. Such a lunar composition is in striking agreement with the Moon being derived from the primitive terrestrial mantle after core formation on Earth.

Direct measurement of the combined effects of lichen, rainfall, and temperature on silicate weathering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brady, P.V.; Dorn, R.I.; Brazel, A.J.

1999-10-01

A key uncertainty in models of the global carbonate-silicate cycle and long-term climate is the way that silicates weather under different climatologic conditions, and in the presence or absence of organic activity. Digital imaging of basalts in Hawaii resolves the coupling between temperature, rainfall, and weathering in the presence and absence of lichens. Activation energies for abiotic dissolution of plagioclase (23.1 {+-} 2.5 kcal/mol) and olivine (21.3 {+-} 2.7 kcal/mol) are similar to those measured in the laboratory, and are roughly double those measured from samples taken underneath lichen. Abiotic weathering rates appear to be proportional to rainfall. Dissolution ofmore » plagioclase and olivine underneath lichen is far more sensitive to rainfall.« less

A new nonlinear optical silicate carbonate K2Ca[Si2O5](CO3) with a hybrid structure of kalsilite and soda-like layered fragments

NASA Astrophysics Data System (ADS)

Belokoneva, Elena L.; Stefanovich, Sergey Yu.; Volkov, Anatoly S.; Dimitrova, Olga V.

2016-10-01

Single crystals of a new silicate carbonate, K2Ca[Si2O5](CO3), have been synthesized in a multi-components hydrothermal solution with a pH value close to neutral and a high concentration of a carbonate mineralizer. The new compound has an axial structure (s.g. P6322) with unit cell parameters a = 5.04789 (15), c = 17.8668 (6) Å. Pseudosymmetry of the structure corresponds to s.g. P63/mmc which is broken only by one oxygen position. The structure consists of two layered fragments: one of the type of the mineral kalsilite (KAlSiO4) and the other of the high-temperature soda-like α-Na2CO3, Ca substituting for Na. The electro-neutral layer K2[Si2O5] (denoted K) as well as the layer Ca(CO3) (denoted S) may separately correspond to individual structures. In K2Ca[Si2O5](CO3) the S-K layers are connected together via Ca-O interactions between Ca atoms from the carbonate layer and apical O atoms from the silicate one, and also via K-O interlayer interactions. A hypothetical acentric structure, sp.gr. P-62c, is predicted on the basis of the order-disorder theory. It presents another symmetrical option for the arrangement of K-layers relative to S-layers. The K,Ca-silicate-carbonate powder produces a moderate SHG signal that is two times larger that of the α-quartz powder standard and close to other silicates with acentric structures and low electronic polarizability.

Experimental determination of activities of FeO and Fe 2O 3 components in hydrous silicic melts under oxidizing conditions

NASA Astrophysics Data System (ADS)

Gaillard, Fabrice; Pichavant, Michel; Scaillet, Bruno

2003-11-01

The critical role of iron on crystal-silicate liquid relationships and melt differentiation is mainly controlled by the redox conditions prevailing in magmas, but the presently available database merely constrains the thermodynamic properties of iron-bearing components in strongly reduced and anhydrous molten silicate where iron is in the ferrous form. This paper provides new standard states for pure ferrous (FeOliq) and ferric (Fe2O3liq) molten iron oxides and extends the experimental database towards oxidizing and water-bearing domains. Iron-iridium, iron-platinum alloys, magnetite or hematite were equilibrated with synthetic silicic liquids at high temperature and high pressure under controlled oxygen fugacity (fO2) to determine activity-composition relationships for FeOliq and Fe2O3liq. Between 1000 and 1300°C, the fO2 ranges from that in air to 3-log units below that of the nickel-nickel oxide buffer (NNO). Experiments were performed on both anhydrous and hydrous melts containing up to 6-wt.% water. Incorporation of water under reducing conditions increases the activity coefficient of FeOliq but has an opposite effect on Fe2O3liq. As calcium is added to system, the effect of water becomes weaker and is inverted for Fe2O3liq. Under oxidizing conditions, water has a negligible effect on both activities of FeOliq and Fe2O3liq. In contrast, changes in redox conditions dominate the activity coefficients of both FeOliq and Fe2O3liq, which increase significantly with increasing fO2. The present results combined with the previous work provide a specific database on the energetics of iron in silicate melts that cover most of the condition prevailing in natural magmas.

Rapid high-silica magma generation in basalt-dominated rift settings

NASA Astrophysics Data System (ADS)

Berg, Sylvia E.; Troll, Valentin R.; Burchardt, Steffi; Deegan, Frances M.; Riishuus, Morten S.; Whitehouse, Martin J.; Harris, Chris; Freda, Carmela; Ellis, Ben S.; Krumbholz, Michael; Gústafsson, Ludvik E.

2015-04-01

The processes that drive large-scale silicic magmatism in basalt-dominated provinces have been widely debated for decades, with Iceland being at the centre of this discussion [1-5]. Iceland hosts large accumulations of silicic rocks in a largely basaltic oceanic setting that is considered by some workers to resemble the situation documented for the Hadean [6-7]. We have investigated the time scales and processes of silicic volcanism in the largest complete pulse of Neogene rift-related silicic magmatism preserved in Iceland (>450 km3), which is a potential analogue of initial continent nucleation in early Earth. Borgarfjörður Eystri in NE-Iceland hosts silicic rocks in excess of 20 vol.%, which exceeds the ≤12 vol% usual for Iceland [3,8]. New SIMS zircon ages document that the dominantly explosive silicic pulse was generated within a ≤2 Myr window (13.5 ± 0.2 to 12.2 ± 03 Ma), and sub-mantle zircon δ18O values (1.2 to 4.5 ± 0.2‰, n=337) indicate ≤33% assimilation of low-δ18O hydrothermally-altered crust (δ18O=0‰), with intense crustal melting at 12.5 Ma, followed by rapid termination of silicic magma production once crustal fertility declined [9]. This silicic outburst was likely caused by extensive rift flank volcanism due to a rift relocation and a flare of the Iceland plume [4,10] that triggered large-scale crustal melting and generated mixed-origin silicic melts. High-silica melt production from a basaltic parent was replicated in a set of new partial melting experiments of regional hydrated basalts, conducted at 800-900°C and 150 MPa, that produced silicic melt pockets up to 77 wt.% SiO2. Moreover, Ti-in-zircon thermometry from Borgarfjörður Eystri give a zircon crystallisation temperature ~713°C (Ti range from 2.4 to 22.1 ppm, average=7.7 ppm, n=142), which is lower than recorded elsewhere in Iceland [11], but closely overlaps with the zircon crystallisation temperatures documented for Hadean zircon populations [11-13], hinting at crustal recycling as a key process. Our results therefore provide a mechanism and a time-scale for rapid, voluminous silicic magma generation in modern and ancient basalt-dominated rift setting, such as Afar, Taupo, and potentially early Earth. The Neogene plume-related rift flank setting of NE-Iceland may thus constitute a plausible geodynamic and compositional analogue for generating silicic (continental) crust in the subduction-free setting of a young Earth (e.g. ≥3 Ga [14]). [1] Bunsen, R. 1851. Ann. Phys. Chem. 159, 197-272. [2] MacDonald R., et al., 1987. Mineral. Mag. 51, 183-202. [3] Jonasson, K., 2007. J. Geodyn. 43, 101-117. [4] Martin, E., et al., 2011. Earth Planet. Sci. Lett. 311, 28-38. [5] Charreteur, G., et al., 2013.Contrib. Mineral. Petr. 166, 471- 490. [6] Willbold, E., et al., 2009. Earth Planet. Sci. Lett. 279, 44-52. [7] Reimink, J.R., et al., 2014. Nat. Geosci. 7, 529-533. [8] Gústafsson, L.E., et al., 1989. Jökull 39, 75-89. [9] Meade, F.C., et al., 2014. Nat. comm. 5. [10] Óskarsson, B.V., Riishuus, M.S., 2013. J. Volcanol. Geoth. Res. 267, 92-118. [11] Carley, T.L., et al., 2014. Earth Planet. Sci. Lett. 405, 85-97. [12] Trail, D., et al., 2007. Geochem. Geophys. Geosyst.8, Q06014. [13] Harrison, T.M. et al., 2008. Earth Planet. Sci. Lett.268, 476-486. [14] Kamber, B. S., et al., 2005. Earth Planet. Sci. Lett. 240, 276-290.

The largest volcanic eruptions on Earth

NASA Astrophysics Data System (ADS)

Bryan, Scott E.; Peate, Ingrid Ukstins; Peate, David W.; Self, Stephen; Jerram, Dougal A.; Mawby, Michael R.; Marsh, J. S. (Goonie); Miller, Jodie A.

2010-10-01

Large igneous provinces (LIPs) are sites of the most frequently recurring, largest volume basaltic and silicic eruptions in Earth history. These large-volume (> 1000 km 3 dense rock equivalent) and large-magnitude (> M8) eruptions produce areally extensive (10 4-10 5 km 2) basaltic lava flow fields and silicic ignimbrites that are the main building blocks of LIPs. Available information on the largest eruptive units are primarily from the Columbia River and Deccan provinces for the dimensions of flood basalt eruptions, and the Paraná-Etendeka and Afro-Arabian provinces for the silicic ignimbrite eruptions. In addition, three large-volume (675-2000 km 3) silicic lava flows have also been mapped out in the Proterozoic Gawler Range province (Australia), an interpreted LIP remnant. Magma volumes of > 1000 km 3 have also been emplaced as high-level basaltic and rhyolitic sills in LIPs. The data sets indicate comparable eruption magnitudes between the basaltic and silicic eruptions, but due to considerable volumes residing as co-ignimbrite ash deposits, the current volume constraints for the silicic ignimbrite eruptions may be considerably underestimated. Magma composition thus appears to be no barrier to the volume of magma emitted during an individual eruption. Despite this general similarity in magnitude, flood basaltic and silicic eruptions are very different in terms of eruption style, duration, intensity, vent configuration, and emplacement style. Flood basaltic eruptions are dominantly effusive and Hawaiian-Strombolian in style, with magma discharge rates of ~ 10 6-10 8 kg s -1 and eruption durations estimated at years to tens of years that emplace dominantly compound pahoehoe lava flow fields. Effusive and fissural eruptions have also emplaced some large-volume silicic lavas, but discharge rates are unknown, and may be up to an order of magnitude greater than those of flood basalt lava eruptions for emplacement to be on realistic time scales (< 10 years). Most silicic eruptions, however, are moderately to highly explosive, producing co-current pyroclastic fountains (rarely Plinian) with discharge rates of 10 9-10 11 kg s -1 that emplace welded to rheomorphic ignimbrites. At present, durations for the large-magnitude silicic eruptions are unconstrained; at discharge rates of 10 9 kg s -1, equivalent to the peak of the 1991 Mt Pinatubo eruption, the largest silicic eruptions would take many months to evacuate > 5000 km 3 of magma. The generally simple deposit structure is more suggestive of short-duration (hours to days) and high intensity (~ 10 11 kg s -1) eruptions, perhaps with hiatuses in some cases. These extreme discharge rates would be facilitated by multiple point, fissure and/or ring fracture venting of magma. Eruption frequencies are much elevated for large-magnitude eruptions of both magma types during LIP-forming episodes. However, in basalt-dominated provinces (continental and ocean basin flood basalt provinces, oceanic plateaus, volcanic rifted margins), large magnitude (> M8) basaltic eruptions have much shorter recurrence intervals of 10 3-10 4 years, whereas similar magnitude silicic eruptions may have recurrence intervals of up to 10 5 years. The Paraná-Etendeka province was the site of at least nine > M8 silicic eruptions over an ~ 1 Myr period at ~ 132 Ma; a similar eruption frequency, although with a fewer number of silicic eruptions is also observed for the Afro-Arabian Province. The huge volumes of basaltic and silicic magma erupted in quick succession during LIP events raises several unresolved issues in terms of locus of magma generation and storage (if any) in the crust prior to eruption, and paths and rates of ascent from magma reservoirs to the surface. Available data indicate four end-member magma petrogenetic pathways in LIPs: 1) flood basalt magmas with primitive, mantle-dominated geochemical signatures (often high-Ti basalt magma types) that were either transferred directly from melting regions in the upper mantle to fissure vents at surface, or resided temporarily in reservoirs in the upper mantle or in mafic underplate thereby preventing extensive crustal contamination or crystallisation; 2) flood basalt magmas (often low-Ti types) that have undergone storage at lower ± upper crustal depths resulting in crustal assimilation, crystallisation, and degassing; 3) generation of high-temperature anhydrous, crystal-poor silicic magmas (e.g., Paraná-Etendeka quartz latites) by large-scale AFC processes involving lower crustal granulite melting and/or basaltic underplate remelting; and 4) rejuvenation of upper-crustal batholiths (mainly near-solidus crystal mush) by shallow intrusion and underplating by mafic magma providing thermal and volatile input to produce large volumes of crystal-rich (30-50%) dacitic to rhyolitic magma and for ignimbrite-producing eruptions, well-defined calderas up to 80 km diameter (e.g., Fish Canyon Tuff model), and which characterise of some silicic eruptions in silicic LIPs.

Lunar production of oxygen by electrolysis

NASA Technical Reports Server (NTRS)

Keller, Rudolf

1991-01-01

Two approaches to prepare oxygen from lunar resources by direct electrolysis are discussed. Silicates can be melted or dissolved in a fused salt and electrolyzed with oxygen evolved at the anode. Direct melting and electrolysis is potentially a very simple process, but high temperatures of 1400-1500 C are required, which aggravates materials problems. Operating temperatures can be lowered to about 1000 C by employing a molten salt flux. In this case, however, losses of electrolyte components must be avoided. Experimentation on both approaches is progressing.

Models of a partially hydrated Titan interior with a clathrate crust

NASA Astrophysics Data System (ADS)

Lunine, J. I.; Castillo-Rogez, J. C.; Choukroun, M.; Sotin, C.

2012-04-01

We present a model of the interior evolution of Titan over time, assuming the silicate core was hydrated early in Titan’s history and is dehydrating over time. The original model presented in Castillo-Rogez and Lunine (2010) was motivated by a Cassini-derived moment of inertia (Iess et al., 2010) for Titan too large to be accommodated by classical fully differentiated models in which an anhydrous silicate core was overlain by a water ice (with possible perched ocean) mantle. Our model consists of a silicate core still in the process of dehydrating today, a situation made possible by the leaching of radiogenic potassium from the silicates into the perched liquid water ocean. The most recent version of our model accounts for the likely presence of large amounts of methane in the upper crust invoked to explain methane’s persistence at present and through geologic time (Tobie et al. 2006). The methane-rich crust turns out to have essentially no bearing on the temperature of the silicate core and hence the timing of dehydration, but it profoundly affects the thickness of the high-pressure ice layer beneath the ocean. Indeed, the insulating effect of the methane clathrate crust could have delayed the formation of the high-pressure layer, resulting in the interaction of liquid water with the silicate core for extended periods of time. Although a high-pressure ice layer is likely in place today, it is thin enough that plumes of hot water from the dehydrating core probably breach that layer. The implications of such a deep hydrothermal system for the later stages of the evolution of Titan’s interior and surface will be discussed. Part of this work has been performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. Government sponsorship acknowledged. References: Castillo-Rogez, J., Lunine, J.: “Evolution of Titan’s rocky core constrained by Cassini observations”. GRL, Vol. 37, L20205, 2010. Iess, L., et al.: “Gravity field, shape, and moment of inertia of Titan”. Science, Vol. 327, 1367-1369. Tobie, G., et al.: “Episodic outgassing as the origin of atmospheric methane on Titan”. Nature 440: 61-64, 2006.

Application of soil block without burning process and calcium silicate panels as building wall in mountainous area

NASA Astrophysics Data System (ADS)

Noerwasito, Vincentius Totok; Nasution, Tanti Satriana Rosary

2017-11-01

Utilization of local building materials in a residential location in mountainous area is very important, considering local material as a low-energy building material because of low transport energy. The local building materials used in this study are walls made from soil blocks. The material was made by the surrounding community from compacted soil without burning process. To maximize the potential of soil block to the outdoor temperature in the mountains, it is necessary to add non-local building materials as an insulator from the influence of the outside air. The insulator was calcium silicate panel. The location of the research is Trawas sub-district, Mojokerto regency, which is a mountainous area. The research problem is on applying the composition of local materials and calcium silicate panels that it will be able to meet the requirements as a wall building material and finding to what extent the impact of the wall against indoor temperature. The result from this research was the application of soil block walls insulated by calcium silicate panels in a building model. Besides, because of the utilization of those materials, the building has a specific difference between indoor and outdoor temperature. Thus, this model can be applied in mountainous areas in Indonesia.

Unusual transformation from strong negative to positive thermal expansion in PbTiO3-BiFeO3 perovskite.

PubMed

Chen, Jun; Fan, Longlong; Ren, Yang; Pan, Zhao; Deng, Jinxia; Yu, Ranbo; Xing, Xianran

2013-03-15

Tetragonal PbTiO(3)-BiFeO(3) exhibits a strong negative thermal expansion in the PbTiO(3)-based ferroelectrics that consist of one branch in the family of negative thermal expansion materials. Its strong negative thermal expansion is much weakened, and then unusually transforms into positive thermal expansion as the particle size is slightly reduced. This transformation is a new phenomenon in the negative termal expansion materials. The detailed structure, temperature dependence of unit cell volume, and lattice dynamics of PbTiO(3)-BiFeO(3) samples were studied by means of high-energy synchrotron powder diffraction and Raman spectroscopy. Such unusual transformation from strong negative to positive thermal expansion is highly associated with ferroelectricity weakening. An interesting zero thermal expansion is achieved in a wide temperature range (30-500 °C) by adjusting particle size due to the negative-to-positive transformation character. The present study provides a useful method to control the negative thermal expansion not only for ferroelectrics but also for those functional materials such as magnetics and superconductors.

Synthesis of Fe3O4@nickel-silicate core-shell nanoparticles for His-tagged enzyme immobilizing agents

NASA Astrophysics Data System (ADS)

Shin, Moo-Kwang; Kang, Byunghoon; Yoon, Nam-Kyung; Kim, Myeong-Hoon; Ki, Jisun; Han, Seungmin; Ahn, Jung-Oh; Haam, Seungjoo

2016-12-01

Immobilizing enzymes on artificially fabricated carriers for their efficient use and easy removal from reactants has attracted enormous interest for decades. Specifically, binding platforms using inorganic nanoparticles have been widely explored because of the benefits of their large surface area, easy surface modification, and high stability in various pH and temperatures. Herein, we fabricated Fe3O4 encapsulated ‘sea-urchin’ shaped nickel-silicate nanoparticles with a facile synthetic route. The enzymes were then rapidly and easily immobilized with poly-histidine tags (His-tags) and nickel ion affinity. Porous nickel silicate covered nanoparticles achieved a high immobilization capacity (85 μg mg-1) of His-tagged tobacco etch virus (TEV) protease. To investigate immobilized TEV protease enzymatic activity, we analyzed the cleaved quantity of maltose binding protein-exendin-fused immunoglobulin fusion protein, which connected with the TEV protease-specific cleavage peptide sequence. Moreover, TEV protease immobilized nanocomplexes conveniently removed and recollected from the reactant by applying an external magnetic field, maintained their enzymatic activity after reuse. Therefore, our newly developed nanoplatform for His-tagged enzyme immobilization provides advantageous features for biotechnological industries including recombinant protein processing.

Recalescence during crystallization of stardust: Resolution of the amorphous interstellar medium paradox

NASA Astrophysics Data System (ADS)

Whittington, A. G.; Sehlke, A.; Speck, A. K.

2017-12-01

Dust that coalesces to form planetary systems originates around dying stars, before passing into the interstellar medium (ISM). Historically, observations of broad smooth features in the 10-µm region suggested that dust in circumstellar regions, and in the ISM, was mostly amorphous rather than crystalline. With improved space telescope capabilities, crystalline silicates were discovered in the circumstellar regions around both young and old stars, although they remain undetected in the ISM. Despite intensive study the precise conditions that lead to the formation of crystalline silicates are still unknown, and their absence in the ISM remains problematic. Here we show that recalescence (spontaneous reheating) of rapidly crystallizing dust can explain the formation and apparent disappearance of crystalline silicates in space. We have documented recalescence in rapidly crystallizing Mg-rich silicate melts, with local heating at the crystallization front exceeding 160˚C in some cases. In circumstellar dust shells, amorphous grains with similar compositions condense at temperatures near their glass transition, and if they crystallize, they will recalesce. The higher temperature (T) of newly crystallized dust allows crystalline spectral features to be seen, because flux emitted depends on T4. After cooling to ambient temperature, crystalline spectral features in the ISM are concealed by volumetrically dominant amorphous dust. Our results explain the existence of crystalline silicate pre-solar grains, which are older than the solar system, and have implications for radiative transfer modeling and hydrodynamics of dusty environments, which are sensitive to small variations in optical properties. Our observations of mm-scale temperature differences up to 100˚C in cooling lava suggest that thermal imaging of basaltic lava flows needs to be conducted with mm-scale spatial resolution (see figure; crucible is 5mm diameter). Temperatures recorded with low spatial resolution, which average cooler melt and hotter crystals in a single pixel, will systematically overestimate the temperature of the liquid phase. Only the surface of a lava flow is likely to cool quickly enough for recalescence to occur, but this is precisely the part of the lava that is monitored by thermal imaging.

A survey of IRAS data on 41 classical novae

NASA Astrophysics Data System (ADS)

Harrison, T. E.; Gehrz, R. D.

1988-09-01

The IRAS database has been searched for detections of 41 classical novae using coadditions of survey scans; 15 were detected. IRAS temporal observations of novae in outburst are discussed. The observed long-wavelength infrared distributions of DQ Her, and possibly HR Del, can be explained by emission from small (a of about 0.1 microns) dust grains heated by the central object. An alternative explanation for the energy distributions of DQ Her and HR Del is emission from fine-structure lines. FH Ser and LW Ser display energy distributions that have color temperatures much too hot to be due to heating of dust by the central source in any plausible scenario. Line emission is probably the best explanation of their observed energy distributions. The novae NQ Vul and LV Vul have energy distributions that may be contaminated by emission from galactic cirrus. The unusual object PL 1547.3-5612 exhibits an energy distribution that does not resemble those of planetary nebulae or other novae detected in this sample. An IRAS low-resolution spectrum of RR Tel shows the 10-micron silicate emission feature.

Experimentally determined sulfur isotope fractionation between metal and silicate and implications for planetary differentiation

NASA Astrophysics Data System (ADS)

Labidi, J.; Shahar, A.; Le Losq, C.; Hillgren, V. J.; Mysen, B. O.; Farquhar, J.

2016-02-01

The Earth's mantle displays a subchondritic 34S/32S ratio. Sulfur is a moderately siderophile element (i.e. iron-loving), and its partitioning into the Earth's core may have left such a distinctive isotope composition on the terrestrial mantle. In order to constrain the sulfur isotope fractionation occurring during core-mantle differentiation, high-pressure and temperature experiments were conducted with synthetic mixtures of metal and silicate melts. With the purpose to identify the mechanism(s) responsible for the S isotope fractionations, we performed our experiments in different capsules - namely, graphite and boron nitride capsules - and thus at different fO2, with varying major element chemistry of the silicate and metal fractions. The S isotope fractionations Δ34Smetal-silicate of equilibrated metal alloys versus silicate melts is +0.2 ± 0.1‰ in a boron-free and aluminum-poor system quenched at 1-1.5 GPa and 1650 °C. The isotope fractionation increases linearly with increasing boron and aluminum content, up to +1.4 ± 0.2‰, and is observed to be independent of the silicon abundance as well as of the fO2 over ∼3.5 log units of variations explored here. The isotope fractionations are also independent of the graphite or nitride saturation of the metal. Only the melt structural changes associated with aluminum and boron concentration in silicate melts have been observed to affect the strength of sulfur bonding. These results establish that the structure of silicate melts has a direct influence on the S2- average bonding strengths. These results can be interpreted in the context of planetary differentiation. Indeed, the structural environments of silicate evolve strongly with pressure. For example, the aluminum, iron or silicon coordination numbers increase under the effect of pressure. Consequently, based on our observations, the sulfur-bonding environment is likely to be affected. In this scheme, we tentatively hypothesize that S isotope fractionations between the silicate mantle and metallic core of terrestrial planetary bodies would depend on the average pressure at which their core-mantle differentiation occurred.

Genesis of IIICD Iron Meteorites: Evidence From Silicate Inclusions

NASA Astrophysics Data System (ADS)

McCoy, T. J.; Keil, K.; Scott, E. R. D.; Haack, H.

1992-07-01

The IAB and IIICD iron meteorite groups exhibit much larger ranges in siderophile concentrations than other groups and commonly contain silicate inclusions. Extensive studies of metal in both groups and silicates in IAB irons have led to a variety of ideas to explain the genesis of these groups. Wasson et al. (1980) envision each meteorite forming in a separate impact melt pool. Kracher (1982, 1985) suggested that the siderophile trends might result from fractional crystallization of both metal and troilite in a S-saturated magma. A role for oxidation-reduction in these groups has been proposed by Scott and Bild (1974). Similarities in siderophile elemental trends indicate that IIICD metal has a similar origin, although data on silicate inclusions in IIICD irons are scarce (Ramdohr, 1973; Scott and Bild, 1974; Kracher and Kurat, 1977; Prinz et al., 1982; Clayton et al., 1983). We report the first detailed study of silicate inclusions in IIICD iron meteorites in an attempt to elucidate their history. We have studied the only silicate-bearing IIICD irons - Carlton, Dayton, and the recently reported Maltahohe. Silicate-graphite-phosphate inclusions comprise at most a few percent of the bulk meteorite, and silicates comprise <25 vol% of the inclusion. Silicate mineralogy and chemistry vary systematically with increasing M content of the metal. Maltahohe (10.7 wt% Ni) and Carlton (13.0%) contain olivine, pyroxene, and plagioclase, whereas Dayton (17.0%) contains pyroxene, plagioclase, and SiO2. Pyroxene becomes more FeO-rich from Maltahohe (FS(sub)7.8) to Carlton (Fs(sub)9.7) to Dayton (Fs(sub)11.6). Inverse FeO zoning in silicates and lower Fa than Fs indicate reduction in all three meteorites. Plagioclase compositions in IIICD (An(sub)1.1-4.9) are lower than IAB (An(sub)9.2-2l.5) and uncorrelated with Ni content. The abundances of associated phases also vary. Graphite comprises ~25 vol% of Maltahohe silicate inclusions, but only a few percent in Carlton, and is absent in Dayton silicate inclusions. Phosphate mineralogy and modal abundance also vary, with phosphates absent in Maltahohe, chlorapatite comprising 0-70 vol% of inclusions in Carlton, and the unusual phosphates brianite and panethite, along with whitlockite, comprising up to 55 vol% of Dayton's inclusions. The small number of silicate-bearing IIICD irons require that any conclusions must be considered tentative. The precursor silicate assemblage was similar for IAB and IIICD, as suggested by the general similarity between Maltahohe and IAB silicate inclusions. With increasing Ni contents, however, IIICD and IAB silicate inclusions become dramatically different, as indicated by the mineralogical and chemical trends present in IIICD and absent in IAB silicate inclusions. Silicate inclusions in the Ni-rich IAB irons (e.g., San Cristobal, 25 wt% Ni) do not resemble the phosphate-rich, evolved-silicate assemblages observed in Dayton. It is clear that one or more processes were capable of producing changes in metal compositions and silicate inclusion mineralogy, which correlated with one another. None of the observed trends in silicate mineralogy are predicted by the impact-melt model, although impact might have played a role in mixing silicates into the metallic magma. Some trends are consistent with oxidation-reduction, but variations in some siderophiles (e.g., Ir, Cu) cannot be explained easily by this mechanism. We believe that solid silicates must have been mixed with an evolving metallic melt, with the metallic magma dramatically influencing the mineralogy and chemistry of the inclusion, similar to the fractional crystallization model of Kracher (1982,1985). However, many details of this process remain obscure, including the mechanism that concentrated a S-rich melt, the mixing of metal and silicates, and the fractionation of S. References: Clayton et al. (1983) EPSL 65, 229-232. Kracher (1982) GRL 9, 412-415. Kracher (1985) PLPSC 15, C689-C698. Kracher and Kurat (1977) Meteoritics 12, 282-283. Scott and Bild (1974) GCA 38, 1379-1391. Prinz et al. (1982) LPSC XIlI, 632-633. Ramdohr (1973) Elsevier Pub. Co. Wasson et al. (1980) Z. Naturforsch. 35a, 781-795.

Thermal Constraints from Siderophile Trace Elements in Acapulcoite-Lodranite Metals

NASA Technical Reports Server (NTRS)

Herrin, Jason S.; Mittlefehldt, D. W.; Humayun, M.

2006-01-01

A fundamental process in the formation of differentiated bodies is the segregation of metal-sulfide and silicate phases, leading to the formation of a metallic core. The only known direct record of this process is preserved in some primitive achondrites, such as the acapulcoite-lodranites. Meteorites of this clan are the products of thermal metamorphism of a chondritic parent. Most acapulcoites have experienced significant partial melting of the metal-sulfide system but not of silicates, while lodranites have experienced partial melting and melt extraction of both. The clan has experienced a continuum of temperatures relevant to the onset of metal mobility in asteroidal bodies and thus could yield insight into the earliest stages of core formation. Acapulcoite GRA 98028 contains relict chondrules, high modal sulfide/metal, has the lowest 2-pyroxene closure temperature, and represents the least metamorphosed state of the parent body among the samples examined. Comparison of the metal-sulfide component of other clan members to GRA 98028 can give an idea of the effects of metamorphism.

Partitioning of carbon between Fe-rich alloy melt and silicate melt in a magma ocean - Implications for the abundance and origin of volatiles in Earth, Mars, and the Moon

NASA Astrophysics Data System (ADS)

Chi, Han; Dasgupta, Rajdeep; Duncan, Megan S.; Shimizu, Nobumichi

2014-08-01

The budget and origin of carbon in Earth and other terrestrial planets are debated and one of the key unknowns is the fate of carbon during early planetary processes including accretion, core formation, and magma ocean (MO) crystallization. Here we determine, experimentally, the solubility of carbon in coexisting Fe-Ni alloy melt and basaltic silicate melt in shallow MO conditions, i.e., at 1-3 GPa, 1500-1800 °C. Oxygen fugacity of the experiments, estimated based on Fe (in metallic alloy melt)-FeO (in silicate melt) equilibrium, varied between ∼IW-0.4 and IW-1.0, where IW refers to the oxygen fugacity imposed by the coexistence of iron and wüstite. Four different starting mixes, each with 7:3 silicate:metal mass ratio and silicate melt NBO/T (estimated proportion of non-bridging oxygen with respect to tetrahedral cations; NBO/T=2×/total OT -4, where T = Si + Ti + Al + Cr + P) ranging from 0.81 to 1.54 were studied. Concentrations of carbon in the alloy melt were determined using electron microprobe whereas carbon contents of quenched basaltic glasses were determined using secondary ionization mass spectrometry (SIMS). Identification of carbon and hydrogen-bearing species in silicate glasses was performed using Raman and Fourier Transformed Infrared (FTIR) spectroscopy. Our results show that carbon in the metallic melt varies between 4.4 wt.% and 7.4 wt.% and increases with increasing temperature and modestly with increasing pressure but decreases with increasing Ni content of the alloy melt. Carbon concentration in the silicate melts, on the other hand, varies from 11 ± 1 ppm to 111 ± 7 ppm and is negatively correlated with pressure but positively correlated with temperature, the NBO/T, the oxygen fugacity and the water content of the silicate melts. Raman and FTIR results show that at our experimental conditions, carbon in silicate melt is dissolved both as hydrogenated species and CO32-. The calculated carbon partition coefficient DCmetal/silicate varies from 510 ± 53 to 5369 ± 217 and varies systematically as a function of P, T, fO2, water content, the composition of the silicate melt (expressed using NBO/T), and Ni content of alloy melt (XNi). The range of DCmetal/silicate measured in our study with carbonated and hydrogenated carbon species in silicate melt is similar to that reported in the literature for experiments where carbonyl complexes are the chief carbon species in silicate melts. A parameterization was derived using the data from this and existing studies such as lnDCmetal/silicate=a/T+b·P/T+c·ln(fO2)+d·(NBO/T)+e·ln(1-XNi)+f where a = -33,510, b = 1357, c = -0.596, d = -1.182, e = 4.15, f = 13.38, the temperature is in Kelvin, and the pressure is in gigapascal. Using this parameterization and the estimated conditions for the base of the MOs, the average DCmetal/silicate value for Earth, Mars, and the Moon can be predicted. The deep MO of Earth is predicted to cause the strongest depletion of its silicate carbon budget, closely followed by Mars with intermediate depth MO, and then the Moon with a shallow MO. We predict that the lunar mantle carbon budget, similar to that of the Earth’s present-day upper mantle, might have been set by equilibrium core-mantle fractionation in MO; whereas for Earth, later processes such as ingassing from a proto-atmosphere and late-stage accretion of volatile-rich material was necessary for delivery of carbon and other volatiles. Finally, the comparison of our measured and predicted value of DCmetal/silicate for terrestrial MO with similar constraints on DNmetal/silicate from the literature suggests that the apparent depletion of nitrogen relative to carbon for the bulk silicate Earth and the Earth’s upper mantle is unlikely to be caused by preferential partitioning of nitrogen to alloy melt during core formation.

Fe-Ti-oxide textures and microstructures in shear zones from oceanic gabbros at Atlantis Bank, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Till, Jessica; Morales, Luiz F. G.; Rybacki, Erik

2016-04-01

Ocean drilling expeditions at several oceanic core complexes formed at slow- and ultra-slow-spreading ridges have recovered cores containing numerous zones of oxide-rich gabbros containing ilmenite and magnetite. In these cores, high modal concentrations of Fe-Ti-oxides are systematically associated with high-temperature plastic deformation features in silicates. We present observations of Fe-Ti-oxide mineral structures and textural characteristics from a series of oxide-rich shear zones from Atlantis Bank (ODP Site 735B) on the Southwest Indian Ridge aimed at determining how oxide mineral abundances relate to strain localization. Fe-Ti-oxide minerals in undeformed oxide gabbros and in highly deformed samples from natural shear zones generally have morphologies characteristic of crystallized melt, including highly cuspate grains and low dihedral angles. Anisotropy of magnetic susceptibility in oxide-rich shear zones is very strong, with fabrics mainly characterized by strong magnetic foliations parallel to the macroscopic foliation. Crystallographic preferred orientations (CPO) in magnetite are generally weak, with occasionally well-defined textures. Ilmenite typically displays well-developed CPOs, however, the melt-like ilmenite grain shapes indicate that at least part of the crystallographic texture results from oriented ilmenite growth during post-deformation crystallization. The oxides are hypothesized to have initially been present as isolated pockets of trapped melt (intercumulus liquid) in a load-bearing silicate framework. Progressive plastic deformation of silicate phases at high-temperature mainly produced two features: (i) elongated melt pockets, which crystallized to form strings of opaque minerals and (ii), interconnected networks of melt regions. The latter lead to intense strain localization of the rock, which appears as oxide-rich mylonites in the samples. In some samples, abundant low-angle grain boundaries in both magnetite and ilmenite suggest that deformation may have continued after crystallization of the late melt, imposing a weak strain on the oxides. Recent experimental deformation results indicate that magnetite and ilmenite should be weaker than most mafic silicates under anhydrous conditions. However, melt-like oxide morphologies observed in Atlantis Bank shear zones indicate that the redistribution of Fe-Ti-oxide melts may have more influence on the strength and strain localization behavior of oceanic gabbros than their solid-state rheology.

The Origin of the Moon Within a Terrestrial Synestia

NASA Astrophysics Data System (ADS)

Lock, Simon J.; Stewart, Sarah T.; Petaev, Michail I.; Leinhardt, Zoë; Mace, Mia T.; Jacobsen, Stein B.; Cuk, Matija

2018-04-01

The giant impact hypothesis remains the leading theory for lunar origin. However, current models struggle to explain the Moon's composition and isotopic similarity with Earth. Here we present a new lunar origin model. High-energy, high-angular-momentum giant impacts can create a post-impact structure that exceeds the corotation limit, which defines the hottest thermal state and angular momentum possible for a corotating body. In a typical super-corotation-limit body, traditional definitions of mantle, atmosphere, and disk are not appropriate, and the body forms a new type of planetary structure, named a synestia. Using simulations of cooling synestias combined with dynamic, thermodynamic, and geochemical calculations, we show that satellite formation from a synestia can produce the main features of our Moon. We find that cooling drives mixing of the structure, and condensation generates moonlets that orbit within the synestia, surrounded by tens of bars of bulk silicate Earth vapor. The moonlets and growing moon are heated by the vapor until the first major element (Si) begins to vaporize and buffer the temperature. Moonlets equilibrate with bulk silicate Earth vapor at the temperature of silicate vaporization and the pressure of the structure, establishing the lunar isotopic composition and pattern of moderately volatile elements. Eventually, the cooling synestia recedes within the lunar orbit, terminating the main stage of lunar accretion. Our model shifts the paradigm for lunar origin from specifying a certain impact scenario to achieving a Moon-forming synestia. Giant impacts that produce potential Moon-forming synestias were common at the end of terrestrial planet formation.

RADIATION HYDRODYNAMICS MODELS OF THE INNER RIM IN PROTOPLANETARY DISKS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Flock, M.; Turner, N. J.; Fromang, S.

2016-08-20

Many stars host planets orbiting within a few astronomical units (AU). The occurrence rate and distributions of masses and orbits vary greatly with the host star’s mass. These close planets’ origins are a mystery that motivates investigating protoplanetary disks’ central regions. A key factor governing the conditions near the star is the silicate sublimation front, which largely determines where the starlight is absorbed, and which is often called the inner rim. We present the first radiation hydrodynamical modeling of the sublimation front in the disks around the young intermediate-mass stars called Herbig Ae stars. The models are axisymmetric and includemore » starlight heating; silicate grains sublimating and condensing to equilibrium at the local, time-dependent temperature and density; and accretion stresses parameterizing the results of MHD magnetorotational turbulence models. The results compare well with radiation hydrostatic solutions and prove to be dynamically stable. Passing the model disks into Monte Carlo radiative transfer calculations, we show that the models satisfy observational constraints on the inner rim’s location. A small optically thin halo of hot dust naturally arises between the inner rim and the star. The inner rim has a substantial radial extent, corresponding to several disk scale heights. While the front’s overall position varies with the stellar luminosity, its radial extent depends on the mass accretion rate. A pressure maximum develops near the location of thermal ionization at temperatures of about 1000 K. The pressure maximum is capable of halting solid pebbles’ radial drift and concentrating them in a zone where temperatures are sufficiently high for annealing to form crystalline silicates.« less

Evidence for a Late Reducing Event in IAB-Silicate Inclusions

NASA Astrophysics Data System (ADS)

Seckendorff, V. V.; O'Neill, H. St. C.; Zipfel, J.; Palme, H.

1992-07-01

Coexisting orthopyroxene (opx) and olivine (ol) in silicate inclusions of IAB-iron meteorites have different Fe/(Fe+Mg) ratios. Ferrosilite (fs) contents of opx are higher than fayalite contents (fa) of ol (e.g., Bunch and Keil 1970). Non-ideal solid solution of fs in opx and/or fa in ol is generally assumed. We reinvestigated the equilibrium Fe-Mg distribution between coexisting ol+opx in the system MgO-FeO-SiO2 (von Seckendorff and O'Neill 1992). Reversal experiments at high- Mg compositions were performed from 900 to 1600 degrees C at 16 and 20 kbar using a barium borosilicate flux. The data could be fitted to a simple thermodynamic model with ol and opx treated as regular solutions and this model was found to describe satisfactorily the literature data extending down to 700 degrees C. For Fe/(Fe+Mg) between 0.05 to 0.15 we find KD^ol-opx close to one from 1600 to 700 degrees C, virtually independent of pressure and temperature. Fig. 1 shows experimental results at the Mg-rich end. Error bars mark 1-sigma standard deviations. Ol is in all cases more Fe-rich than coexisting opx, except for a single run at 1000 degrees C that probably did not reach equilibrium because of slow reaction kinetics. Two calculated distribution curves (1300, 700 degrees C at 16 kbar) lie close together indicating the absence of any significant temperature dependence of the exchange reaction at the Mg- rich end of the system. IAB-silicate inclusions plot outside the range of experimental data (Fig. 1). Although some previous models for Fe-Mg exchange between ol and opx (e.g., Sack 1980) extrapolate to KD<1 at temperatures near 500 degrees C, such models reproduce the experimental data (700 to 1600 degrees C) less well, than our updated model. In addition, temperatures at 500 degrees C are probably too low to allow Fe diffusion in opx. Two pyroxene equilibration temperatures of IAB-silicate inclusions are around 900-1000 degrees C suggesting a similar closure temperature for Fe diffusion in opx. Because of this and because of the essentially temperature-independent Fe-Mg distribution between ol and opx from 1600 to 700 degrees C, we conclude that the Fe-Mg distribution between ol and opx in IAB-silicate inclusion does not reflect thermodynamic equilibrium. As Fe-diffusion in ol is faster than in opx, redistribution of Fe in ol should have occurred at a temperature below the closure temperature for Fe-diffusion in opx. We suggest that FeO in ol was reduced to Fe metal by some species such as C, P, S, etc. A lower limit for the temperature of the reducing event is provided by Ca-zoning in ol, which develops below 650 degrees C (Kohler et al. 1991). Since strong FeO zoning in ol is absent, reduction of FeO in ol should have occurred above 650 degrees C, assuming similar diffusion coefficients for Ca and Fe in ol. References: Bunch T.E. and Keil K. (1970) Contrib. Mineral. Petrol. 25, 297-340. Kohler T., Palme H. and Brey G. (1991) N. Jb. Miner. Mh. 9, 423-431. Sack R.O. (1980) Contrib. Mineral. Petrol. 71, 257-269. v. Seckendorff V. and O'Neill H.St.C. (1992) Contr. Min. Petrol. (submitted).

Petrologic evolution of divergent peralkaline magmas from the Silent Canyon caldera complex, southwestern Nevada volcanic field

USGS Publications Warehouse

Sawyer, D.A.; Sargent, K.A.

1989-01-01

The Silent Canyon volcanic center consists of a buried Miocene peralkaline caldera complex and outlying peralkaline lava domes. Two widespread ash flow sheets, the Tub Spring and overlying Grouse Canyon members of the Miocene Belted Range Tuff, were erupted from the caldera complex and have volumes of 60-100 km3 and 200 km3, respectively. Eruption of the ash flows was preceded by widespread extrusion of precaldera comendite domes and was followed by extrusion of postcollapse peralkaline lavas and tuffs within and outside the caldera complex. Lava flows and tuffs were also deposited between the two major ash flow sheets. Rocks of the Silent Canyon center vary significantly in silica content and peralkalinity. Weakly peralkaline silicic comendites (PI 1.0-1.1) are the most abundant precaldera lavas. Postcollapse lavas range from trachyte to silicic comendite; some have anomalous light rare earth element (LREE) enrichments. Silent Canyon rocks follow a common petrologic evolution from trachyte to low-silica comendite; above 73% SiO2, compositions of the moderately peralkaline comendites diverge from those of the weakly peralkaline silicic comendites. The development of divergent peralkaline magmas, toward both pantelleritic and weakly peralkaline compositions, is unusual in a single volcanic center. -from Authors

The Thermal States of Accreting Planets: From Mars-like Embryos to a MAD Earth

NASA Astrophysics Data System (ADS)

Stewart, S. T.; Lock, S. J.

2015-12-01

The thermal states of rocky planets can vary widely during the process of accretion. The thermal structure affects several major processes on the growing planet, including the mechanics of core formation, pressure-temperature conditions for metal-silicate equilibration, mixing, and atmospheric erosion. Because impact energy is distributed heterogeneously, accretional energy is preferentially deposited in the gravitationally re-equilibrated outer layers of the planet for both small and giant impacts. The resulting stably stratified structure inhibits complete mixing within the mantle. Initially, the specific energy of giant impacts between Mars-mass embryos leads to melting of the mantle. However, as planet formation progresses, the specific energies of giant impacts increase and can drive the mantle into a transient supercritical state. In the hottest regions of the planet, metal and silicates are miscible, and metal exsolution occurs as the structure cools. The cooling time of the supercritical structure is typically longer than the timescale for metal segregation to the core. Thus, these high temperature excursions during planet formation are significant for understanding metal-silicate equilibration. Furthermore, when a supercritical planet is also rapidly rotating, the mantle, atmosphere and disk (MAD) form a continuous dynamic and thermodynamic structure. Lunar origin by condensation from a MAD Earth can explain the major characteristics of the Moon (Lock et al., this meeting). One of the greatest uncertainties in understanding the thermal states of planets during accretion is the changing composition and mass of the atmosphere. After the dispersal of the solar nebula, the thermal boundary condition imposed by the atmosphere can vary between silicate vapor and condensed ices. The coupled problem of atmospheric origin and planetary accretion can be used to constrain the many uncertainties in the growth and divergence of the terrestrial planets in our solar system.

Diffusion of Oxygen Isotopes in Thermally Evolving Planetesimals and Size Ranges of Presolar Silicate Grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wakita, Shigeru; Nozawa, Takaya; Hasegawa, Yasuhiro, E-mail: shigeru@cfca.jp

Presolar grains are small particles found in meteorites through their isotopic compositions, which are considerably different from those of materials in the solar system. If some isotopes in presolar grains diffused out beyond their grain sizes when they were embedded in parent bodies of meteorites, their isotopic compositions could be washed out, and hence the grains could no longer be identified as presolar grains. We explore this possibility for the first time by self-consistently simulating the thermal evolution of planetesimals and the diffusion length of {sup 18}O in presolar silicate grains. Our results show that presolar silicate grains smaller thanmore » ∼0.03 μ m cannot keep their original isotopic compositions even if the host planetesimals experienced a maximum temperature as low as 600 °C. Since this temperature corresponds to that experienced by petrologic type 3 chondrites, isotopic diffusion can constrain the size of presolar silicate grains discovered in such chondrites to be larger than ∼0.03 μ m. We also find that the diffusion length of {sup 18}O reaches ∼0.3–2 μ m in planetesimals that were heated up to 700–800°C. This indicates that, if the original size of presolar grains spans a range from ∼0.001 μ m to ∼0.3 μ m like that in the interstellar medium, then the isotopic records of the presolar grains may be almost completely lost in such highly thermalized parent bodies. We propose that isotopic diffusion could be a key process to control the size distribution and abundance of presolar grains in some types of chondrites.« less

A SEM-ATEM and stable isotope study of carbonates from the Haughton impact crater, Canada

NASA Astrophysics Data System (ADS)

Martinez, Isabelle; Agrinier, Pierre; Schärer, Urs; Javoy, Marc

1994-02-01

Highly and intermediately shocked carbonate-rich fragments of the allochtonous polymict breccia from the Haughton impact crater (Canada) were studied by Scanning Electron Microscopy (SEM), Analytical Transmission Electron Microscopy (ATEM) and analyses of carbon and oxygen stable isotopes ( δ13C and δ18O). In areas subjected to severe shock conditions, carbonates represent only about 10 vol% of the shocked samples and they are located in holes and fractures within a matrix of SiO 2-rich glass. Shock features are absent in these crystals. High-temperature reactions have occurred between molten silicates and carbonates, producing Ca sbnd Mg-rich glasses, or crystalline phases such as augite and larnite (Ca 2SiO 4). The carbonates are dominated by calcite and they generally have significantly positive δ13C, ranging up to +9‰, with a weighted average value of +1.75‰. Their δ18O values range between +15‰ and +20‰ and they are about 5‰ lower than in unshocked reference sediments, a trend consistent with that resulting from silicate-carbonate reactions. The microstructures of the carbonates suggest that they did not undergo shock conditions but, instead, were produced by back-reactions between impact-released CO 2 and highly reactive residual oxides. Such a process would introduce isotope fractionations, which might explain the positive δ13C values observed. A simple kinetic fractionation model involving a Rayleigh distillation process is used to estimate the CO 2 fraction actually lost from the carbonates. It appears that this fraction is related to the amount of high-temperature carbonate-silicate reactions. Moderately shocked fragments from other areas of the polymict breccia consist of 40-81 vol% carbonates. Their δ13C values lie in the range of unshocked reference sediments between -2‰ and -4‰, whereas their δ18O values are by about 5‰ lower than in the unshocked equivalents. No evidence for important decarbonatization is observed from 13C, and 18O is again buffered by isotope exchange reactions between molten silicates and carbonate crystals producing Ca and Mg enriched SiO 2 glass and Ca sbnd Mg silicate crystals such as monoclinic pigeonite, which is indicative of fast cooling. This study indicates that significant evidence for outgassing is limited to a narrow zone in the centre of the crater, where peak shock pressures reached 50-60 GPa. Moreover, we suggest that, within this area, a large fraction of the shock-produced gas recombines with the highly reactive residual oxides and, in consequence, that such back-reactions might be a general mechanism for retaining impact-produced volatiles during impact events.

Characterization of Mason Gully (H5): The second recovered fall from the Desert Fireball Network

NASA Astrophysics Data System (ADS)

Dyl, Kathryn A.; Benedix, Gretchen K.; Bland, Phil A.; Friedrich, Jon M.; Spurný, Pavel; Towner, Martin C.; O'Keefe, Mary Claire; Howard, Kieren; Greenwood, Richard; Macke, Robert J.; Britt, Daniel T.; Halfpenny, Angela; Thostenson, James O.; Rudolph, Rebecca A.; Rivers, Mark L.; Bevan, Alex W. R.

2016-03-01

Mason Gully, the second meteorite recovered using the Desert Fireball Network (DFN), is characterized using petrography, mineralogy, oxygen isotopes, bulk chemistry, and physical properties. Geochemical data are consistent with its classification as an H5 ordinary chondrite. Several properties distinguish it from most other H chondrites. Its 10.7% porosity is predominantly macroscopic, present as intergranular void spaces rather than microscopic cracks. Modal mineralogy (determined via PS-XRD, element mapping via energy dispersive spectroscopy [EDS], and X-ray tomography [for sulfide, metal, and porosity volume fractions]) consistently gives an unusually low olivine/orthopyroxene ratio (0.67-0.76 for Mason Gully versus ~1.3 for typical H5 ordinary chondrites). Widespread "silicate darkening" is observed. In addition, it contains a bright green crystalline object at the surface of the recovered stone (diameter ≈ 1.5 mm), which has a tridymite core with minor α-quartz and a rim of both low- and high-Ca pyroxene. The mineralogy allows the calculation of the temperatures and ƒ(O2) characterizing thermal metamorphism on the parent body using both the two-pyroxene and the olivine-chromite geo-oxybarometers. These indicate that MG experienced a peak metamorphic temperature of ~900 °C and had a similar ƒ(O2) to Kernouvé (H6) that was buffered by the reaction between olivine, metal, and pyroxene. There is no evidence for shock, consistent with the observed porosity structure. Thus, while Mason Gully has some unique properties, its geochemistry indicates a similar thermal evolution to other H chondrites. The presence of tridymite, while rare, is seen in other OCs and likely exogenous; however, the green object itself may result from metamorphism.

Model for the formation of the earth's core

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCammon, C.A.; Ringwood, A.E.; Jackson, I.

1983-02-15

The recent discovery of a phase transformation in Fe/sub 0.94/O by Jeanloz and Ahrens has allowed a more detailed development of a model for core formation involving oxygen as the principal light alloying element in the core. It is predicted, based on calculations, that an increasing pressure in the system FeO-MgO will result in a gradual exsolution of an almost pure high-pressure phase FeO(hpp), leaving an iron-depleted (Fe,Mg)O rocksalt (B1) phase. We also predict that FeO(hhp) will form a low-melting point alloy with Fe at high temperature and high pressure. On the basis of our interpretations, we have constructed amore » model for core segregation. Assuming the earth to have accreted from the primordial solar nebula as a relatively homogeneous mixture of metallic iron and silicate-oxide phases, core segregation involving oxygen would commence at a depth where pressure is sufficiently high to cause exsolution of FeO(hpp) from the rocksalt phase, and temperature is sufficiently high to allow formation of an Fe-FeO(hpp) melt. A gravitational instability arises, leading to vertical differentiation of the earth as molten blobs of the metal sink downwards to form the core and the residual depleted silicate material coalesces to form large bodies which rise diapirically upwards to form the mantle.« less

A design of spectrophotometric microfluidic chip sensor for analyzing silicate in seawater

NASA Astrophysics Data System (ADS)

Cao, X.; Zhang, S. W.; Chu, D. Z.; Wu, N.; Ma, H. K.; Liu, Y.

2017-08-01

High quality and continuous in situ silicate data are required to investigate the mechanism of the biogeochemical cycles and the formation of red tide. There is an urgently growing need for autonomous in situ silicate instruments that perform determination on various platforms. However, due to the high reagents and power consumption, as well as high system complexity leading to low reliability and robustness, the performance of the commercially available silicate sensors is not satisfactory. With these problems, here we present a new generation of microfluidic continuous flow analysis silicate sensor with sufficient analytical performance and robustness, for in situ determination of soluble silicate in seawater. The reaction mechanism of this sensor is based on the reaction of silicate with ammonium molybdate to form a yellow silicomolybdate complex and further reduction to silicomoIybdenum blue by ascorbic acid. The minimum limit of detection was 45.1 nmol L-1, and the linear determination range of the sensor is 0-400 μmol L-1. The recovery rate of the actual water is between 98.1%-104.0%, and the analyzing cycle of the sensor is about 5 minutes. This sensor has the advantages of high accuracy, high integration, low water consumption, and strong anti-interference ability. It has been successfully applied to measuring the silicate in seawater in Jiaozhou Bay.

PMR-15/Layered Silicate Nanocomposites For Improved Thermal Stability And Mechanical Properties

NASA Technical Reports Server (NTRS)

Campbell, Sandi; Scheiman, Daniel; Faile, Michael; Papadopoulos, Demetrios; Gray, Hugh R. (Technical Monitor)

2002-01-01

Montmorillonite clay was organically modified by co-exchange of an aromatic diamine and a primary alkyl amine. The clay was dispersed into a PMR (Polymerization of Monomer Reactants)-15 matrix and the glass transition temperature and thermal oxidative stability of the resulting nanocomposites were evaluated. PMR-15/ silicate nanocomposites were also investigated as a matrix material for carbon fabric reinforced composites. Dispersion of the organically modified silicate into the PMR-15 matrix enhanced the thermal oxidative stability, the flexural strength, flexural modulus, and interlaminar shear strength of the polymer matrix composite.

The 8-13 micron spectra of comets and the composition of silicate grains

NASA Technical Reports Server (NTRS)

Hanner, Martha S.; Lynch, David K.; Russell, Ray W.

1994-01-01

We have analyzed the existing spectra of seven comets which show an emission feature at 7.8-13 micrometers. Most have been converted to a common calibration, taking into account the SiO feature in late-type standard stars. The spectra are compared with spectra of the Trapezium, interplanetary dust particles (IDPs), laboratory mineral samples, and small particle emission models. The emission spectra show a variety of shapes; there is no unique 'cometary silicate'. A peak at 11.20-11.25 micrometers, indicative of small crystalline olivine particles, is seen in only three comets of this sample, P/Halley, Bradfield 1987 XXIX, and Levy 1990 XX. The widths of the emission features range from 2.6 to 4.1 micrometers (FWHM). To explain the differing widths and the broad 9.8 micrometers maximum, glassy silicate particles, including both pyroxene and olivine compositions, are the most plausible candidates. Calculations of emission models confirm that small grains of glassy silicate well mixed with carbonaceous material are plausible cometary constituents. No single class of chondritic aggregate IDPs exhibits spectra closely matching the comet spectra. A mixture of IDP spectra, particularly the glass-rich aggregates, approximately matches the spectra of comets P/Halley, Levy, and Bradfield 1987 XXIX. Yet, if comets are simply a mix of IDP types, it is puzzling that the classes of IDPs are so distinct. None of the comet spectra match the spectrum of the Trapezium. Thus, the mineralogy of the cometary silicates is not the same as that of the interstellar medium. The presence of a component of crystalline silicates in comets may be evidence of mixing between high- and low-temperature regions in the solar nebula.

Study of the thermal-optics parameters of Nd3+-doped phosphate glass as a function of temperature

NASA Astrophysics Data System (ADS)

Filho, J. C.; Pilla, V.; Messias, D. N.; Lourenço, S. A.; Silva, A. C. A.; Dantas, N. O.; Andrade, A. A.

2017-02-01

The spectroscopic properties of rare earth ions in many different hosts have been investigated, including surveys of Nd3+ in silicate, phosphate, fluorophosphates and fluoride glasses. Some of the thermal-optical properties of materials are influenced by temperature change, such as thermal diffusivity, specific heat and luminescence quantum efficiency. In this work the luminescence quantum efficiency of PANK: Nd3+, as a function of temperature (80- 480 K), was investigated using the normalized lifetime thermal lens technique. This system presents high quantum efficiency at low Nd3+ concentration and at ambient temperature, 100%, which decrease as temperature increase. Below room temperature the effects are not in accord with the maximum value of η, which must be unity.

A high-temperature hydrothermal deposit on the seabed at a Gulf of California spreading center ( Guaymas Basin).

USGS Publications Warehouse

Lonsdale, P.F.; Bischoff, J.L.; Burns, V.M.; Kastner, M.; Sweeney, R.E.

1980-01-01

A submersible dive on a turbidite-covered spreading axis in Guaymas Basin photographed and sampled extensive terraces and ledges of talc. The rock contains siliceous microfossils, smectite, and euhedral pyrrhotite as well as rather pure iron-rich talc. S and O isotopes indicate precipitation around a hydrothermal vent, at about 2800C. - Authors

Microprobes aluminosilicate ceramic membranes

DOEpatents

Anderson, Marc A.; Sheng, Guangyao

1993-01-01

Methods have been developed to make mixed alumina-silicate and aluminosilicate particulate microporous ceramic membranes. One method involves the making of separate alumina and silica sols which are then mixed. Another method involves the creation of a combined sol with aluminosilicate particles. The resulting combined alumina and silica membranes have high surface area, a very small pore size, and a very good temperature stability.

Structural relaxation driven increase in elastic modulus for a bulk metallic glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arora, Harpreet Singh; Aditya, Ayyagari V.; Mukherjee, Sundeep, E-mail: sundeep.mukherjee@unt.edu

2015-01-07

The change in elastic modulus as a function of temperature was investigated for a zirconium-based bulk metallic glass. High temperature nano-indentation was done over a wide temperature range from room temperature to the glass-transition. At higher temperature, there was a transition from inhomogeneous to homogeneous deformation, with a decrease in serrated flow and an increase in creep displacement. Hardness was found to decrease, whereas elastic modulus was found to increase with temperature. The increase in elastic modulus for metallic glass at higher temperature was explained by diffusive rearrangement of atoms resulting in free volume annihilation. This is in contrast tomore » elastic modulus increase with temperature for silicate glasses due to compaction of its open three dimensional coordinated structure without any atomic diffusion.« less

The peculiar extinction of Herschel 36

NASA Technical Reports Server (NTRS)

Donn, B.; Hecht, J. H.; Helfer, H. L.; Wolf, J.; Pipher, J. L.

1982-01-01

The extinction of Herschel 36 was measured and found to be peculiar in the same sense as that observed in Orion. Following the treatment of Mathis and Wallenhorst, this can be explained by the presence of large silicate and graphite grains than are normally found in the interstellar medium. Correcting the stellar flux for foreground extinction results in a residual extinction curve for the associated dust cloud, with an unusually small normalized extinction (less than 1.0) at 1500 A. This low UV extinction may be due to the effects of scattering by the dust cloud material.

Exsolved silicate and oxide phases from clinopyroxenes in a single Hawaiian xenolith: Implications for oxidation state of the Hawaiian upper mantle

NASA Astrophysics Data System (ADS)

Sen, Gautam; Jones, Robert E.

1988-01-01

A single garnet-bearing clinopyroxenite xenolith from the Salt Lake crater on Oahu, Hawaii, contains two distinct types of clinopyroxene; one contains exsolved garnet, ilmenite, and magnetite, and the other contains exsolved hercynite-pleonaste spinel, orthopyroxene, and ilmenite. Application of mineral geothermometers, barometers, and oxygen barometers to this unusual combination of exsolved phases defines the following conditions of last mantle equilibration of this xenolith: P = 19 kbar, T =1153 °C, and log10fO2 = -9.7.

Spatial and Temporal Analysis of Bias HAST System Temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pfeifer, Kent B.; Furrer, III, Clint T; Sandoval, Paul Anthony

2017-03-01

High-reliability components for high-consequence systems require detailed testing of operation after having undergone highly accelerated stress testing (HAST) under unusual conditions of high-temperature and humidity. This paper describes the design and operation of a system called "Wormwood" that is a highly multiplexed temperature measurement system that is designed to operate under HAST conditions to allow measurement of the temperature as a function of time and position in a HAST chamber. HAST chambers have single-point temperature measurements that can be traceable to NIST standards. The objective of these "Wormwood" measurements is to verify the uniformity and stability of the remaining volumemore » of the HAST chamber with respect to the single traceable standard.« less

Molybdenum Valence in Basaltic Silicate Melts: Effects of Temperature and Pressure

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Choi, Y.; Pando, K.

2011-01-01

The metal-silicate partitioning behavior of molybdenum has been used as a test for equilibrium core formation hypotheses [for example, 1-6]. However, current models that apply experimental data to equilibrium core-mantle differentiation infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Molybdenum, a multi-valent element with a valence transition near the fO2 of interest for core formation (approx.IW-2) will be sensitive to changes in fO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo(6+) can be either octahedrally or tetrahedrally coordinated. Here we present X-ray absorption near edge structure (XANES) measurements of Mo valence in basaltic run products at a range of P, T, and fO2 and further quantify the valence transition of Mo.

Contribution of early impact events to metal-silicate separation, thermal annealing, and volatile redistribution: Evidence in the Pułtusk H chondrite

NASA Astrophysics Data System (ADS)

Krzesińska, Agata M.

2017-11-01

Three-dimensional X-ray tomographic reconstructions and petrologic studies reveal voluminous accumulations of metal in Pułtusk H chondrite. At the contact of these accumulations, the chondritic rock is enriched in troilite. The rock contains plagioclase-rich bands, with textures suggesting crystallization from melt. Unusually large phosphates are associated with the plagioclase and consist of assemblages of merrillite, and fluorapatite and chlorapatite. The metal accumulations were formed by impact melting, rapid segregation of metal-sulfide melt and the incorporation of this melt into the fractured crater basement. The impact most likely occurred in the early evolution of the H chondrite parent body, when post-impact heat overlapped with radiogenic heat. This enabled slow cooling and separation of the metallic melt into metal-rich and sulfide-rich fractions. This led to recrystallization of chondritic rock in contact with the metal accumulations and the crystallization of shock melts. Phosphorus was liberated from the metal and subsumed by the silicate shock melt, owing to oxidative conditions upon slow cooling. The melt was also a host for volatiles. Upon further cooling, phosphorus reacted with silicates leading to the formation of merrillite, while volatiles partitioned into the residual halogen-rich, dry fluid. In the late stages, the fluid altered merrillite to patchy Cl/F-apatite. The above sequence of alterations demonstrates that impact during the early evolution of chondritic parent bodies might have contributed to local metal segregation and silicate melting. In addition, postshock conditions supported secondary processes: compositional/textural equilibration, redistribution of volatiles, and fluid alterations.

The Development of HfO2-Rare Earth Based Oxide Materials and Barrier Coatings for Thermal Protection Systems

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Harder, Bryan James

2014-01-01

Advanced hafnia-rare earth oxides, rare earth aluminates and silicates have been developed for thermal environmental barrier systems for aerospace propulsion engine and thermal protection applications. The high temperature stability, low thermal conductivity, excellent oxidation resistance and mechanical properties of these oxide material systems make them attractive and potentially viable for thermal protection systems. This paper will focus on the development of the high performance and high temperature capable ZrO2HfO2-rare earth based alloy and compound oxide materials, processed as protective coating systems using state-or-the-art processing techniques. The emphasis has been in particular placed on assessing their temperature capability, stability and suitability for advanced space vehicle entry thermal protection systems. Fundamental thermophysical and thermomechanical properties of the material systems have been investigated at high temperatures. Laser high-heat-flux testing has also been developed to validate the material systems, and demonstrating durability under space entry high heat flux conditions.

Spitzer IRS Spectroscopy of the 10 Myr-Old EF Cha Debris Disk: Evidence for Phyllosilicate-Rich Dust in the Terrestrial Zone

NASA Technical Reports Server (NTRS)

Currie, Thayne; Lisse, Carey M.; Sicillia-Aguilar, Aurora; Rieke, George H.; Su, Kate Y. L.

2011-01-01

We describe Spitzer IRS spectroscopic observations of the approx. 10 Myr-old star, EF Chao Compositional modeling of the spectra from 5 micron to 35 micron confirms that it is surrounded by a luminous debris disk with L(sub D)/L(sub *) approx. 10(exp -3), containing dust with temperatures between 225 K and 430 K characteristic of the terrestrial zone. The EF Cha spectrum shows evidence for many solid-state features, unlike most cold, low-luminosity debris disks but like some other 10-20 Myr-old luminous, warm debris disks (e.g. HD 113766A). The EF Cha debris disk is unusually rich in a species or combination of species whose emissivities resemble that of finely-powdered, laboratory-measured phyllosilicate species (talc, saponite, and smectite), which are likely produced by aqueous alteration of primordial anhydrous rocky materials. The dust and, by inference, the parent bodies of the debris also contain abundant amorphous silicates and metal sulfides, and possibly water ice. The dust's total olivine to pyroxene ratio of approx. 2 also provides evidence of aqueous alteration. The large mass volume of grains with sizes comparable to or below the radiation blow-out limit implies that planetesimals may be colliding at a rate high enough to yield the emitting dust but not so high as to devolatize the planetesimals via impact processing. Because phyllosilicates are produced by the interactions between anhydrous rock and warm, reactive water, EF Cha's disk is a likely signpost for water delivery to the terrestrial zone of a young planetary system.

Evidence of Electron-Hole Imbalance in WTe2 from High-Resolution Angle-Resolved Photoemission Spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Chen-Lu; Zhang, Yan; Huang, Jian-Wei; Liu, Guo-Dong; Liang, Ai-Ji; Zhang, Yu-Xiao; Shen, Bing; Liu, Jing; Hu, Cheng; Ding, Ying; Liu, De-Fa; Hu, Yong; He, Shao-Long; Zhao, Lin; Yu, Li; Hu, Jin; Wei, Jiang; Mao, Zhi-Qiang; Shi, You-Guo; Jia, Xiao-Wen; Zhang, Feng-Feng; Zhang, Shen-Jin; Yang, Feng; Wang, Zhi-Min; Peng, Qin-Jun; Xu, Zu-Yan; Chen, Chuang-Tian; Zhou, Xing-Jiang

2017-08-01

WTe2 has attracted a great deal of attention because it exhibits extremely large and nonsaturating magnetoresistance. The underlying origin of such a giant magnetoresistance is still under debate. Utilizing laser-based angle-resolved photoemission spectroscopy with high energy and momentum resolutions, we reveal the complete electronic structure of WTe2. This makes it possible to determine accurately the electron and hole concentrations and their temperature dependence. We find that, with increasing the temperature, the overall electron concentration increases while the total hole concentration decreases. It indicates that the electron-hole compensation, if it exists, can only occur in a narrow temperature range, and in most of the temperature range there is an electron-hole imbalance. Our results are not consistent with the perfect electron-hole compensation picture that is commonly considered to be the cause of the unusual magnetoresistance in WTe2. We identified a flat band near the Brillouin zone center that is close to the Fermi level and exhibits a pronounced temperature dependence. Such a flat band can play an important role in dictating the transport properties of WTe2. Our results provide new insight on understanding the origin of the unusual magnetoresistance in WTe2.

Laboratory synthesis of silicate glass spherules: Application to impact ejecta

NASA Astrophysics Data System (ADS)

Stoddard, P. S.; Pahlevan, K.; Tumber, S.; Weber, R.; Lee, K. K.

2012-12-01

To investigate the process by which molten droplets of impact ejecta solidify into glassy spherule tektites, we employed laser levitation experiments to recreate the hot temperatures of falling molten rock. Following models for Earth composition based on enstatite chondrites, we levitated mixtures of oxide powders in a stream of gas and melted them with a laser, producing silicate glass beads. After quenching, we polished the ~1 mm diameter samples in cross-section and analyzed with electron probe microanalysis (EPMA). Fine and coarsely-spaced EPMA transects across each bead displayed diffusion profiles at their edges, particularly in their SiO2 and MgO content. Heating altered the beads' bulk composition as well; all of the glassy spherules were compositionally different from the initial combination of powders. By comparing these changes to the environmental factors acting on the bead (e.g., temperature, type of levitation gas, duration of heating and amount of rotation), we produced a model for how molten ejecta change chemically and physically as they solidify into a glass. We find that high temperatures likely generated on impact have a strong effect on the composition of tektites; therefore, attempts to correlate tektites to their parent rocks should correct for this effect.

Tribological properties of alumina-boria-silicate fabric from 25 to 850 C

NASA Technical Reports Server (NTRS)

Dellacorte, Christopher

1988-01-01

Demanding tribological properties are required of the materials used for the sliding seal between the sidewalls and the lower wall of the variable area hypersonic engine. Temperatures range from room temperature and below to operating temperatures of 1000 C in an environment of air, hydrogen, and water vapor. Candidate sealing materials for this application are an alumina-boria-silicate, ceramic, fabric rope sliding against the engine walls which may be made from copper- or nickel-based alloys. Using a pin-on-disk tribometer, the friction and wear properties of some of these potential materials and possible lubrication methods are evaluated. The ceramic fabric rope displayed unacceptably high friction coefficients (0.6 to 1.3) and, thus, requires lubrication. Sputtered thin films of gold, silver, and CaF2 reduced the friction by a factor of two. Sprayed coatings of boride nitride did not effectively lubricate the fabric. Static heat treatment tests at 950 C indicate that the fabric is chemically attacked by large quantities of silver, CaF2, and boron nitride. Sputtered films or powder impregnation of the fabric with gold may provide adequate lubrication up to 1000 C without showing any chemical attack.

Plagioclase-Hosted Magnetite Inclusions From the Bushveld Complex

NASA Astrophysics Data System (ADS)

Feinberg, J. M.; Scott, G. R.; Renne, P. R.; Wenk, H.

2004-12-01

Gabbros from the Main Zone of the 2.064 Ga Bushveld Complex have long been known to possess unusually stable magnetizations due to the presence of high coercivity, exsolved magnetite inclusions in plagioclase and clinopyroxene. The paleomagnetic pole for these rocks has been used to anchor apparent polar wander paths for the Kaapval craton during the Early-Mid Proterozoic. To better understand the rock magnetic properties of silicate-hosted magnetite inclusions, oriented paleomagnetic samples of gabbro were collected from quarries near Belfast and Rustenberg, South Africa, sampling the eastern and western limbs of the Complex, respectively. Plagioclase composition at both sites ranges from An55 (rims) to An65 (cores) based on optical and electron microprobe data. Four kinds of inclusions are present within the plagioclase: elongate magnetite needles, nanometer-scale magnetite particles (responsible for the "cloudy" appearance of some crystals), translucent brown hematite/ilmenite platelets, and colorless euhedral inclusions of pyroxene and/or feldspar. Magnetite inclusions are most abundant at the cores of the plagioclase crystals. Orientations of the needles and the platelets are crystallographically controlled by the silicate host. Although the elongation direction of the magnetite inclusions can occur in any of five possible orientations, only two or three of these directions dominates each plagioclase crystal. Alternating field demagnetization of bulk samples (NRM = 1.5 x 101 A m-1) shows univectorial remanence with average median destructive fields (MDF) of 115 mT (Belfast) and 90 mT (Rustenberg). AF demagnetization of single plagioclase crystals (NRM = 100 A m-1) also shows single component remanence with average MDFs >150 mT. The NRM coercivity spectra of single plagioclase crystals are indistinguishable from that of the bulk samples. When normalized to their abundance in bulk samples the magnetite-bearing plagioclase fully accounts for the NRM of Bushveld gabbros at both sites. Close examination of the inclusions' interiors using magnetic force microscopy shows no ulvöspinel exsolution as observed in other silicate exsolved titanomagnetites with comparably high coercivities. Consequently, we interpret the high coercivities of the inclusions to be a product of their small size and extreme shape anisotropy. Single crystals of plagioclase demonstrate a strong anisotropy of IRM acquisition (see Scott, et al. this conference). Additionally, electron backscatter diffraction (EBSD) orientation indexing shows a strongly preferred orientation for plagioclase and pyroxene (with (010)plag and (100)pyr parallel to subhorizontal layering) consistent with gravitational settling within a magma chamber. Thus, there are two anisotropies (silicate preferred orientation and magnetite inclusion remanence) to consider when describing the ancient magnetic field present during the emplacement of the Bushveld.

Silicic, high- to extremely high-grade ignimbrites and associated deposits from the Paraná Magmatic Province, southern Brazil

NASA Astrophysics Data System (ADS)

Luchetti, Ana Carolina F.; Nardy, Antonio J. R.; Madeira, José

2018-04-01

The Cretaceous trachydacites and dacites of Chapecó type (ATC) and dacites and rhyolites of Palmas type (ATP) make up 2.5% of the 800.000 km3 of volcanic pile in the Paraná Magmatic Province (PMP), emplaced at the onset of Gondwana breakup. Together they cover extensive areas in southern Brazil, overlapping volcanic sequences of tholeiitic basalts and andesites; occasional mafic units are also found within the silicic sequence. In the central region of the PMP silicic volcanism comprises porphyritic ATC-type, trachydacite high-grade ignimbrites (strongly welded) overlying aphyric ATP-type, rhyolite high- to extremely high-grade ignimbrites (strongly welded to lava-like). In the southwestern region strongly welded to lava-like high-grade ignimbrites overlie ATP lava domes, while in the southeast lava domes are found intercalated within the ignimbrite sequence. Characteristics of these ignimbrites are: widespread sheet-like deposits (tens to hundreds of km across); absence of basal breccias and basal fallout layers; ubiquitous horizontal to sub-horizontal sheet jointing; massive, structureless to horizontally banded-laminated rock bodies locally presenting flow folding; thoroughly homogeneous vitrophyres or with flow banding-lamination; phenocryst abundance presenting upward and lateral decrease; welded glass blobs in an 'eutaxitic'-like texture; negligible phenocryst breakage; vitroclastic texture locally preserved; scarcity of lithic fragments. These features, combined with high eruption temperatures (≥ 1000 °C), low water content (≤ 2%) and low viscosities (104-7 Pa s) suggest that the eruptions were characterized by low fountaining, little heat loss during collapse, and high mass fluxes producing extensive deposits.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kasuga, Toshihiro; Usui, Fumihiko; Hasegawa, Sunao

Primitive, outer-belt asteroids are generally of low albedo, reflecting carbonaceous compositions like those of CI and CM meteorites. However, a few outer-belt asteroids having high albedos are known, suggesting the presence of unusually reflective surface minerals or, conceivably, even exposed water ice. Here, we present near-infrared (1.1-2.5 {mu}m) spectra of four outer-belt C-complex asteroids with albedos {>=}0.1. We find no absorption features characteristic of water ice (near 1.5 and 2.0 {mu}m) in the objects. Intimate mixture models set limits to the water ice by weight {<=}2%. Asteroids (723) Hammonia and (936) Kunigunde are featureless and have (60%-95%) amorphous Mg pyroxenesmore » that might explain the high albedos. Asteroid (1276) Ucclia also shows a featureless reflection spectrum with (50%-60%) amorphous Mg pyroxenes. Asteroid (1576) Fabiola shows a possible weak, broad absorption band (1.5-2.1 {mu}m). The feature can be reproduced by (80%) amorphous Mg pyroxenes or orthopyroxene (crystalline silicate), either of which is likely to cause its high albedo. We discuss the origin of high-albedo components in primitive asteroids.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kasuga, Toshihiro; Shirahata, Mai; Usui, Fumihiko

Most outer main-belt asteroids have low albedos because of their carbonaceouslike bodies. However, infrared satellite surveys have revealed that some asteroids have high albedos, which may suggest the presence of unusual surface minerals for those primitive objects. We present new near-infrared (1.1–2.5 μm) spectra of four outer main-belt asteroids with albedos ≥ 0.1. The C-complex asteroids (555) Norma and (2542) Calpurnia are featureless and have (50%–60%) amorphous Mg pyroxenes that might explain the high albedos. Asteroids (701) Oriola (which is a C-complex asteroid) and (2670) Chuvashia (a D/T-type or M-type asteroid) show possible broad absorption bands (1.5–2.1 μm). The featuremore » can be reproduced by either Mg-rich amorphous pyroxene (with 50%–60% and 80%–95% Mg, respectively) or orthopyroxene (crystalline silicate), which might be responsible for the high albedos. No absorption features of water ice (near 1.5 and 2.0 μm) are detected in the objects. We discuss the origin of high albedo components in the outer main-belt asteroids and their physical relations to comets.« less

The role of liquid-liquid immiscibility and crystal fractionation in the genesis of carbonatite magmas: insights from Kerimasi melt inclusions

NASA Astrophysics Data System (ADS)

Guzmics, Tibor; Zajacz, Zoltán; Mitchell, Roger H.; Szabó, Csaba; Wälle, Markus

2015-02-01

We have reconstructed the compositional evolution of the silicate and carbonate melt, and various crystalline phases in the subvolcanic reservoir of Kerimasi Volcano in the East African Rift. Trace element concentrations of silicate and carbonate melt inclusions trapped in nepheline, apatite and magnetite from plutonic afrikandite (clinopyroxene-nepheline-perovskite-magnetite-melilite rock) and calciocarbonatite (calcite-apatite-magnetite-perovskite-monticellite-phlogopite rock) show that liquid immiscibility occurred during the generation of carbonatite magmas from a CO2-rich melilite-nephelinite magma formed at relatively high temperatures (1,100 °C). This carbonatite magma is notably more calcic and less alkaline than that occurring at Oldoinyo Lengai. The CaO-rich (32-41 wt%) nature and alkali-"poor" (at least 7-10 wt% Na2O + K2O) nature of these high-temperature (>1,000 °C) carbonate melts result from strong partitioning of Ca (relative to Mg, Fe and Mn) in the immiscible carbonate and the CaO-rich nature (12-17 wt%) of its silicate parent (e.g., melilite-nephelinite). Evolution of the Kerimasi carbonate magma can result in the formation of natrocarbonatite melts with similar composition to those of Oldoinyo Lengai, but with pronounced depletion in REE and HFSE elements. We suggest that this compositional difference results from the different initial parental magmas, e.g., melilite-nephelinite at Kerimasi and a nephelinite at Oldoinyo Lengai. The difference in parental magma composition led to a significant difference in the fractionating mineral phase assemblage and the element partitioning systematics upon silicate-carbonate melt immiscibility. LA-ICP-MS analysis of coeval silicate and carbonate melt inclusions provides an opportunity to infer carbonate melt/silicate melt partition coefficients for a wide range of elements. These data show that Li, Na, Pb, Ca, Sr, Ba, B, all REE (except Sc), U, V, Nb, Ta, P, Mo, W and S are partitioned into the carbonate melt, whereas Mg, Mn, Fe, Co, Cu, Zn, Al, Sc, Ti, Hf and Zr are partitioned into the silicate melt. Potassium and Rb show no preferential partitioning. Kerimasi melt inclusions show that the immiscible calcic carbonate melt is strongly enriched in Sr, Ba, Pb, LREE, P, W, Mo and S relative to other trace elements. Comparison of our data with experimental results indicates that preferential partitioning of oxidized sulfur (as SO4 2-), Ca and P (as PO4 3-) into the carbonate melt may promote the partitioning of Nb, Ta, Pb and all REE, excluding Sc, into this phase. Therefore, it is suggested that P and S enrichment in calcic carbonate magmas promotes the genesis of REE-rich carbonatites by liquid immiscibility. Our study shows that changes in the partition coefficients of elements between minerals and the coexisting melts along the liquid line of descent are rather significant at Kerimasi. This is why, in addition to the REE, Nb, Ta and Zr are also enriched in Kerimasi calciocarbonatites. We consider significant amounts of apatite and perovskite precipitated from melilite-nephelinite-derived carbonate melt as igneous minerals can have high LREE, Nb and Zr contents relative to other carbonatite minerals.

Pressure-induced nano-crystallization of silicate garnets from glass

PubMed Central

Irifune, T.; Kawakami, K.; Arimoto, T.; Ohfuji, H.; Kunimoto, T.; Shinmei, T.

2016-01-01

Transparent ceramics are important for scientific and industrial applications because of the superior optical and mechanical properties. It has been suggested that optical transparency and mechanical strength are substantially enhanced if transparent ceramics with nano-crystals are available. However, synthesis of the highly transparent nano-crystalline ceramics has been difficult using conventional sintering techniques at relatively low pressures. Here we show direct conversion from bulk glass starting material in mutianvil high-pressure apparatus leads to pore-free nano-polycrystalline silicate garnet at pressures above ∼10 GPa in a limited temperature range around 1,400 °C. The synthesized nano-polycrystalline garnet is optically as transparent as the single crystal for almost the entire visible light range and harder than the single crystal by ∼30%. The ultrahigh-pressure conversion technique should provide novel functional ceramics having various crystal structures, including those of high-pressure phases, as well as ideal specimens for some mineral physics applications. PMID:27924866

Planar edge Schottky barrier-tunneling transistors using epitaxial graphene/SiC junctions.

PubMed

Kunc, Jan; Hu, Yike; Palmer, James; Guo, Zelei; Hankinson, John; Gamal, Salah H; Berger, Claire; de Heer, Walt A

2014-09-10

A purely planar graphene/SiC field effect transistor is presented here. The horizontal current flow over one-dimensional tunneling barrier between planar graphene contact and coplanar two-dimensional SiC channel exhibits superior on/off ratio compared to conventional transistors employing vertical electron transport. Multilayer epitaxial graphene (MEG) grown on SiC(0001̅) was adopted as the transistor source and drain. The channel is formed by the accumulation layer at the interface of semi-insulating SiC and a surface silicate that forms after high vacuum high temperature annealing. Electronic bands between the graphene edge and SiC accumulation layer form a thin Schottky barrier, which is dominated by tunneling at low temperatures. A thermionic emission prevails over tunneling at high temperatures. We show that neglecting tunneling effectively causes the temperature dependence of the Schottky barrier height. The channel can support current densities up to 35 A/m.

Implications for Core Formation of the Earth from High Pressure-Temperature Au Partitioning Experiments

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Sharp, T. G.; Hervig, R. L.

2005-01-01

Siderophile elements in the Earth.s mantle are depleted relative to chondrites. This is most pronounced for the highly siderophile elements (HSEs), which are approximately 400x lower than chondrites. Also remarkable is the relative chondritic abundances of the HSEs. This signature has been interpreted as representing their sequestration into an iron-rich core during the separation of metal from silicate liquids early in the Earth's history, followed by a late addition of chondritic material. Alternative efforts to explain this trace element signature have centered on element partitioning experiments at varying pressures, temperatures, and compositions (P-T-X). However, first results from experiments conducted at 1 bar did not match the observed mantle abundances, which motivated the model described above, a "late veneer" of chondritic material deposited on the earth and mixed into the upper mantle. Alternatively, the mantle trace element signature could be the result of equilibrium partitioning between metal and silicate in the deep mantle, under P-T-X conditions which are not yet completely identified. An earlier model determined that equilibrium between metal and silicate liquids could occur at a depth of approximately 700 km, 27(plus or minus 6) GPa and approximately 2000 (plus or minus 200) C, based on an extrapolation of partitioning data for a variety of moderately siderophile elements obtained at lower pressures and temperatures. Based on Ni-Co partitioning, the magma ocean may have been as deep as 1450 km. At present, only a small range of possible P-T-X trace element partitioning conditions has been explored, necessitating large extrapolations from experimental to mantle conditions for tests of equilibrium models. Our primary objective was to reduce or remove the additional uncertainty introduced by extrapolation by testing the equilibrium core formation hypothesis at P-T-X conditions appropriate to the mantle.

Partitioning of Pd Between Fe-S-C and Mantle Liquids at High Pressure and Temperature: Implications for Core Formation

NASA Technical Reports Server (NTRS)

Righter, K.; Humayun, M.; Danielson, L.

2007-01-01

One of the most elusive geochemical aspects of the early Earth has been explaining the near chondritic relative abundances of the highly siderophile elements (HSE; Au, Re and the platinum group elements) in Earth's primitive upper mantle (PUM). Perhaps they were delivered to the Earth after core formation, by late addition of carbonaceous chondrite material. However, the recognition that many moderately siderophile elements can be explained by high pressure and temperature (PT) metal-silicate equilibrium, leads to the question whether high PT equilibrium can also explain the HSE concentrations. Answers to this question have been slowed by experimental difficulties (nugget effect and very low solubilities). But two different perspectives have emerged from recent studies. One perspective is that D(M/S) for HSE at high PT are not low enough to explain terrestrial mantle depletions of these elements (for Pd and Pt). A second perspective is D(M/S) are reduced substantially at high PT and even low enough to explain terrestrial mantle depletions (for Au and Pt). Issues complicating interpretation of all experiments include use of MgO- and FeO-free silicate melts, and S-free and FeNi metal-free systems. In addition, conclusions for Pt rest on an interpretation that the tiny metallic nuggets plaguing many such experiments, were formed upon quench. There is not agreement on this issue, and the general question of HSE solubility at high PT remains unresolved

High quality interlayer dielectric for 4H SiC DMOSFETs

NASA Astrophysics Data System (ADS)

Okayama, T.; Arthur, S. D.; Waldrab, P.; Rao, Mulpuri V.

2007-11-01

In this work useful weight percentages of boron and phosphorus in boro-phospho-silicate-glass (BPSG) interlayer dielectric (ILD) films to getter mobile ions effectively in 4H-SiC DMOSFET structures are developed, considering the limitations, such as the required low glass flow temperature, and the possible hygroscopic nature of the films and formation of crystalline BPO4 particles, which may occur for high B and P weight percentages. The B and P weight percentage viscous flow temperature contours and empirical inequalities representing the above-mentioned limitations are developed and discussed. Results of this work are useful for both silicon and compound semiconductor device technologies.

Impact crater morphology and the Central Pit/Dome of Occator: Ceres as an Ice-rich Body

NASA Astrophysics Data System (ADS)

Schenk, P.; Marchi, S.; O'Brien, D. P.; Platz, T.; Bland, M. T.; Buczkowski, D.; Scully, J. E. C.; Ammannito, E.; Raymond, C. A.; Russell, C. T.

2016-12-01

Pristine crater morphologies on Ceres (at D <40 km) are astonishingly similar to those on midsize icy bodies (e.g., moons of Saturn) but very different from those on silicate-rich Vesta. All these bodies have similar gravity and broadly similar impact velocities, and these patterns reveal that the upper 10s of km of Ceres are much weaker than on silicate-rich Vesta. This stands in contrast to the lack of viscous relaxation (Bland et al., 2016), which implies an upper layer on Ceres capable of resisting flow despite the relatively high surface temperatures. This can be explained as distinct responses of an outer layer partially composed of weak ices and strong silicates that fail during high-strain impact processes (which are apparently controlled by the weak phase) but does not flow under low-strain creep (which is apparently controlled more by the strong phase). Furthermore, comparison with Martian craters indicates that, in contrast to Ceres, the amount of water ice in the crust of Mars results in hybrid morphologies only midway between silicate and ice worlds, indicating that the upper layers of Ceres must have more ice than does Mars. The presence of apparent impact melt deposits and central pits in larger craters (D>40 km and D>75 km, respectively) on Ceres implies either warmer conditions than at Saturn, or the presence of a deeper layer enriched in (weaker) ice at comparable depths, also consistent with partial relaxation in larger craters. The formation of a fractured dome 3-km-wide and 0.75-km-high within recently formed Occator crater may be due to refreezing of a water zone melted after impact, or mobilization of carbonates or ice in the crater center, possibly from such deeper layers.

Brillouin-scattering studies of a sodium silicate glass in solid and melt conditions at temperatures up to 1000 °C

NASA Astrophysics Data System (ADS)

Xu, Ji-An; Manghnani, Murli H.

1992-01-01

By using the sapphire-glass-sapphire sandwich-glass-assemblage Brillouin-scattering technique, the velocities of shear and longitudinal modes of a sodium silicate glass have been measured as a function of temperature up to 1000 °C. A turning point was found at the strain point (494 °C) but not at the softening point (720 °C). Combined with the results of the 90°- and 180°-scattering-geometry measurements, the refractive index (n) of the glass as a function of temperature was also determined. As a result, independent criteria for both the strain and softening points are suggested.

The composition of Earth's core from equations of state, metal-silicate partitioning, and core formation modeling

NASA Astrophysics Data System (ADS)

Fischer, Rebecca; Campbell, Andrew; Ciesla, Fred

2016-04-01

The Earth accreted in a series of increasingly large and violent collisions. Simultaneously, the metallic core segregated from the silicate mantle, acquiring its modern composition through high pressure (P), high temperature (T) partitioning reactions. Here we present a model that couples these aspects of early planetary evolution, building on recent accretion simulations and metal-silicate partitioning experiments, constrained by density measurements of Fe-rich alloys. Previously, the equations of state of FeO, Fe-9Si, Fe-16Si, and FeSi were measured to megabar pressures and several thousand K using a laser-heated diamond anvil cell. With these equations of state, we determined that the core's density can be reproduced through the addition of 11.3 +/- 0.6 wt% silicon or 8.1 +/- 1.1 wt% oxygen to an Fe-Ni alloy (Fischer et al., 2011, 2014). Metal-silicate partitioning experiments of Ni, Co, V, Cr, Si, and O have been performed in a diamond anvil cell to 100 GPa and 5700 K, allowing the effects of P, T, and composition on the partitioning behaviors of these elements to be parameterized (Fischer et al., 2015; Siebert et al., 2012). Here we apply those experimental results to model Earth's core formation, using N-body simulations to describe the delivery, masses, and original locations of planetary building blocks (Fischer and Ciesla, 2014). As planets accrete, their core and mantle compositions are modified by high P-T reactions with each collision (Rubie et al., 2011). For partial equilibration of the mantle at 55% of the evolving core-mantle boundary pressure and the liquidus temperature, we find that the core contains 5.4 wt% Si and 1.9 wt% O. This composition is consistent with the seismologically-inferred density of Earth's core, based on comparisons to our equations of state, and indicate that the core cannot contain more than ~2 wt% S or C. Earth analogues experience 1.2 +/- 0.2 log units of oxidation during accretion, due to both the effects of high P-T partitioning and the temporal evolution of the Earth's feeding zone. This modeling can reveal the relative importance of various accretion and differentiation processes to core composition, highlighting targets for future experimental and numerical studies.

Environmental Barrier Coatings for Turbine Engines: A Design and Performance Perspective

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Fox, Dennis S.; Ghosn, Louis; Smialek, James L.; Miller, Robert A.

2009-01-01

Ceramic thermal and environmental barrier coatings (TEBC) for SiC-based ceramics will play an increasingly important role in future gas turbine engines because of their ability to effectively protect the engine components and further raise engine temperatures. However, the coating long-term durability remains a major concern with the ever-increasing temperature, strength and stability requirements in engine high heat-flux combustion environments, especially for highly-loaded rotating turbine components. Advanced TEBC systems, including nano-composite based HfO2-aluminosilicate and rare earth silicate coatings are being developed and tested for higher temperature capable SiC/SiC ceramic matrix composite (CMC) turbine blade applications. This paper will emphasize coating composite and multilayer design approach and the resulting performance and durability in simulated engine high heat-flux, high stress and high pressure combustion environments. The advances in the environmental barrier coating development showed promise for future rotating CMC blade applications.

An Iron-Rain Model for Core Formation on Asteroid 4 Vesta

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Mittlefehldt, David W.

2016-01-01

Asteroid 4 Vesta is differentiated into a crust, mantle, and core, as demonstrated by studies of the eucrite and diogenite meteorites and by data from NASA's Dawn spacecraft. Most models for the differentiation and thermal evolution of Vesta assume that the metal phase completely melts within 20 degrees of the eutectic temperature, well before the onset of silicate melting. In such a model, core formation initially happens by Darcy flow, but this is an inefficient process for liquid metal and solid silicate. However, the likely chemical composition of Vesta, similar to H chondrites with perhaps some CM or CV chondrite, has 13-16 weight percent S. For such compositions, metal-sulfide melting will not be complete until a temperature of at least 1350 degrees Centigrade. The silicate solidus for Vesta's composition is between 1100 and 1150 degrees Centigrade, and thus metal and silicate melting must have substantially overlapped in time on Vesta. In this chemically and physically more likely view of Vesta's evolution, metal sulfide drops will sink by Stokes flow through the partially molten silicate magma ocean in a process that can be envisioned as "iron rain". Measurements of eucrites show that moderately siderophile elements such as Ni, Mo, and W reached chemical equilibrium between the metal and silicate phases, which is an important test for any Vesta differentiation model. The equilibration time is a function of the initial metal grain size, which we take to be 25-45 microns based on recent measurements of H6 chondrites. For these sizes and reasonable silicate magma viscosities, equilibration occurs after a fall distance of just a few meters through the magma ocean. Although metal drops may grow in size by merger with other drops, which increases their settling velocities and decreases the total core formation time, the short equilibration distance ensures that the moderately siderophile elements will reach chemical equilibrium between metal and silicate before metal drop merger becomes important. In this model, there must be at least 30 percent melting of the silicate phase when metal melting is complete, corresponding to a crust thickness of at least 30 kilometers on Vesta, consistent with Dawn gravity observations. Greater degrees of silicate melting and a correspondingly thicker crust are possible if Vesta accreted sufficiently rapidly.

Unusual Thermal Hall Effect in a Kitaev Spin Liquid Candidate α -RuCl3

NASA Astrophysics Data System (ADS)

Kasahara, Y.; Sugii, K.; Ohnishi, T.; Shimozawa, M.; Yamashita, M.; Kurita, N.; Tanaka, H.; Nasu, J.; Motome, Y.; Shibauchi, T.; Matsuda, Y.

2018-05-01

The Kitaev quantum spin liquid displays the fractionalization of quantum spins into Majorana fermions. The emergent Majorana edge current is predicted to manifest itself in the form of a finite thermal Hall effect, a feature commonly discussed in topological superconductors. Here we report on thermal Hall conductivity κx y measurements in α -RuCl3 , a candidate Kitaev magnet with the two-dimensional honeycomb lattice. In a spin-liquid (Kitaev paramagnetic) state below the temperature characterized by the Kitaev interaction JK/kB˜80 K , positive κx y develops gradually upon cooling, demonstrating the presence of highly unusual itinerant excitations. Although the zero-temperature property is masked by the magnetic ordering at TN=7 K , the sign, magnitude, and T dependence of κx y/T at intermediate temperatures follows the predicted trend of the itinerant Majorana excitations.

Radiation-induced amorphization of Ce-doped Mg2Y8(SiO4)6O2 silicate apatite

NASA Astrophysics Data System (ADS)

Zhou, Jianren; Yao, Tiankai; Lian, Jie; Shen, Yiqiang; Dong, Zhili; Lu, Fengyuan

2016-07-01

Ce-doped Mg2Y8(SiO4)6O2 silicate apatite (Ce = 0.05 and 0.5) were irradiated with 1 MeV Kr2+ ion beam irradiation at different temperatures and their radiation response and the cation composition dependence of the radiation-induced amorphization were studied by in situ TEM. The two Ce-doped Mg2Y8(SiO4)6O2 silicate apatites are sensitive to ion beam induced amorphization with a low critical dose (0.096 dpa) at room temperature, and exhibits significantly different radiation tolerance at elevated temperatures. Ce concentration at the apatite AI site plays a critical role in determining the radiation response of this silicate apatite, in which the Ce3+ rich Mg2Y7.5Ce0.5(SiO4)6O2 displays lower amorphization susceptibility than Mg2Y7.95Ce0.05(SiO4)6O2 with a lower Ce3+ occupancy at the AI sites. The critical temperature (Tc) and activation energy (Ea) change from 667.5 ± 33 K and 0.162 eV of Mg2Y7.5Ce0.5(SiO4)6O2 to 963.6 ± 64 K and 0.206 eV of Mg2Y7.95Ce0.05(SiO4)6O2. We demonstrate that the radiation tolerance can be controlled by varying the chemical composition, and enhanced radiation tolerance is achieved by increasing the Ce concentration at the AI site.

Evaporation and Accompanying Isotopic Fractionation of Sulfur from FE-S Melt During Shock Wave Heating

NASA Technical Reports Server (NTRS)

Tachibana, S.; Huss, G. R.; Miura, H.; Nakamoto, T.

2004-01-01

Chondrules probably formed by melting and subsequent cooling of solid precursors. Evaporation during chondrule melting may have resulted in depletion of volatile elements in chondrules. It is known that kinetic evaporation, especially evaporation from a melt, often leads to enrichment of heavy isotopes in an evaporation residue. However, no evidence for a large degree of heavy-isotope enrichment has been reported in chondrules for K, Mg, Si, and Fe (as FeO). The lack of isotopic fractionation has also been found for sulfur in troilites (FeS) within Bishunpur (LL3.1) and Semarkona (LL3.0) chondrules by an ion microprobe study. The largest fractionation, found in only one grain, was 2.7 +/- 1.4 %/amu, while all other troilite grains showed isotopic fractionations of <1 %/amu. The suppressed isotopic fractionation has been interpreted as results of (i) rapid heating of precursors at temperatures below the silicate solidus and (ii) diffusion-controlled evaporation through a surrounding silicate melt at temperatures above the silicate solidus. The kinetic evaporation model suggests that a rapid heating rate of >10(exp 4)-10(exp 6) K/h for a temperature range of 1000-1300 C is required to explain observed isotopic fractionations. Such a rapid heating rate seems to be difficult to be achieved in the X-wind model, but can be achieved in shock wave heating models. In this study, we have applied the sulfur evaporation model to the shock wave heating conditions of to evaluate evaporation of sulfur and accompanying isotopic fractionation during shock wave heating at temperatures below the silicate solidus.

Sealing glass-ceramics with near linear thermal strain, Part II: Sequence of crystallization and phase stability

DOE PAGES

Dai, Steve Xunhu; Rodriguez, Mark A.; Griego, James M.

2016-06-01

Here, the sequence of crystallization in a re-crystallizable lithium silicate sealing glass-ceramic Li 2O-SiO 2-Al 2O 3-K 2O-B 2O 3-P 2O 5-ZnO was analyzed by in situ high temperature X-ray diffraction (HTXRD). Glass-ceramic specimens have been subjected to a 2-stage heat treatment schedule, including rapid cooling from sealing temperature to a 1st hold temperature 650 °C, following by heating to a 2nd hold temperature of 810 °C. Notable growth and saturation of Quartz was observed at 650 °C (1st hold).

Extra-terrestrial igneous granites and related rocks: A review of their occurrence and petrogenesis

NASA Astrophysics Data System (ADS)

Bonin, Bernard

2012-11-01

The telluric planets and the asteroid belt display the same internal structure with a metallic inner core and a silicate outer shell. Experimental data and petrological evidence in silicate systems show that granite can be produced by extreme igneous differentiation through various types of igneous processes. On Moon, 4.4-3.9 Ga granite clasts display dry mineral assemblages. They correspond to at least 8 discrete intrusive events. Large K/Ca enrichment and low REE abundances in granite relative to KREEP are consistent with silicate liquid immiscibility, a process observed in melt inclusions within olivine of lunar basalts and in lunar meteorites. Steep-sided domes identified by remote sensing can represent intrusive or extrusive felsic formations. On Mars, black-and-white rhythmic layers observed on the Tharsis rise along the flanks of the peripheral scarps of the Tharsis Montes giant volcanoes suggest the possible eruption of felsic pyroclastites. Though no true granites were found so far in the Martian SNC meteorites, felsic glasses and mesostases were identified and a component close to terrestrial continental (granitic) crust is inferred from trace element and isotope systematics. Venus has suffered extensive volcanic resurfacing, whereas folded and faulted areas resemble terrestrial continents. Near large shield volcanoes, with dominant basaltic compositions, steep-sided domes have been interpreted as non-degassed silicic extrusions. The hypothesis of a granitic component is "tantalising". Extra-terrestrial granite is frequently found as clasts and mesostases in asteroidal meteorites. Porphyritic textures, with alkali feldspar crystals up to several centimetres in size, were observed in silicate enclaves within iron meteorites. In the chondrite clan, polymict breccias can contain granitic clasts, whose provenance is debated. One clast from the Adzhi-Bogdo meteorite yields a 4.53 ± 0.03 Ga Pb-Pb age, making it the oldest known granite in the solar system. The vast majority of granitic materials recognised so far in the extra-terrestrial record are characterised by ferroan A-type compositions, characterised by high to very high K2O and medium CaO contents, sodic varieties being exceedingly rare. Textural evidence of graphic quartz-alkali feldspar intergrowths within crystallised products suggests that they are igneous in origin and crystallised quickly from a liquid. In water-depleted to water-free environments, fluorine and chlorine can play significant roles, as their effects on liquidus temperatures and crystallising assemblages are nearly identical to those of water. The distribution of alkalis and alkaline earths cannot be related only to extensive crystal fractionation, but is likely induced by supplementary silicate liquid immiscibility. Medium-temperature silicate liquid immiscibility is well known as a mode of differentiation in experimental petrology studies at very low pressures on systems dominated by Fe, Ti, K, and P as major elements. The ultimate question is, therefore, not whether granite (s.l.) occurs in any given planetary body, but if sufficient volumes of granitic materials could have been produced to constitute stable continental nuclei.

Fluid Sources at the Panasqueira Tungsten-Vein Deposit

NASA Astrophysics Data System (ADS)

Lecumberri-Sanchez, P.; Heinrich, C. A.; Wälle, M.; Codeço, M.; Weis, P.; Pinto, F.; Vieira, R.

2017-12-01

Panasqueira is a world-class tungsten-vein deposit. Several paragenetic stages have been proposed (Polya et al., 2000) including two pre-ore stages (crack-seal quartz-seam, and muscovite selvages) and four ore stages (main oxide-silicate stage, main sulfide stage, pyrrhotite alteration stage, and late carbonate stage). In this study, compositions of the mineralizing fluids at Panasqueira have been determined by a combination of detailed petrography, microthermometric measurements and LA-ICPMS analyses. We have characterized the fluids related to several mineralizing stages and determined the information they provide about the fluid sources in this system. Three fluid generations recorded in pseudosecondary to secondary fluid inclusions have been identified at Panasqueira. The first fluid generation identified consists of CO2-bearing fluid inclusions with homogenization temperatures ranging between 260 and 320 °C and salinities between 5 and 8 eq wt % NaCl. Petrographic constraints indicate that this first generation (1) is paragenetically related to the main oxide-silicate stage. Two lower-temperature CO2-absent fluid generations (2a and 2b) have been identified and are represented by secondary fluid inclusions postdating the main oxide-silicate stage. This stage was likely trapped under high pressures and lithostatic conditions (Jacques and Pascal, 2017). Generation (2a) consists of high-salinity (20-30 eq wt % NaCl) fluids with homogenization temperatures ranging between 180°C and 250°C. Generation (2b) consists of low-salinity (<2 wt %) low homogenization temperature (100-150°C) fluid inclusions. Conclusive petrographic evidence of the relationship between these two late-stage fluid generations and specific late mineral stages are scarce. However, fluid compositions suggests that generation (2a) is related to the main sulfide stage and generation (2b) is related to the late carbonate stage. The PTX evolution of fluids at Panasqueira indicate a transition from magmatic dominated fluids to a likely influx of non-magmatic fluids at least in the latest stages of mineralization (main sulfide stage and late carbonate stage) which is in good agreement with recent results from isotopic studies (Codeço et al., 2017).

Reprobing the mechanism of negative thermal expansion in siliceous faujasite

DOE PAGES

Attfield, Martin P.; Feygenson, Mikhail; Neuefeind, Joerg C.; ...

2016-02-11

A combination of Rietveld refinement and PDF analysis of total neutron scattering data are used to provide further insight into the negative thermal expansion mechanism of siliceous faujasite. The negative thermal expansion mechanism of siliceous faujasite is attributed to the transverse vibrations of bridging oxygen atoms resulting in the coupled librations of the SiO 4 tetrahedra. The constituent SiO 4 tetrahedra are revealed to expand in size with temperature which is a behaviour that has not been determined directly previously and they are also shown to undergo some distortion as temperature is increased. However, these distortions are not distinct enoughmore » in any geometric manner for the average behaviour of the SiO 4 tetrahedra not to be considered as that of a rigid units. The work further displays the benefits of using total scattering experiments to unveil the finer details of dynamic thermomechanical processes within crystalline materials.« less

High-pressure, high-temperature Raman spectroscopy of Ca 2GeO 4 (olivine form): some insights on anharmonicity

NASA Astrophysics Data System (ADS)

Gillet, Philippe; Guyot, Francois; Malezieux, Jean-Marie

1989-12-01

High pressure (up to 2.7 GPa) and high temperature (up to 1000 K) Raman spectra of Ca 2GeO 4 (olivine form) have been recorded. Measurements of the pressure- and temperature-induced frequency shifts of 14 modes have been performed. The classical mode Gruneisen parameter and a corresponding parameter related to temperature variation are calculated. For the high frequency modes (GeO stretching) we calculate these parameters with local tetrahedral elastic parameters. From these parameters anharmonic parameters are calculated for each Raman active mode. The effect of anharmonicity on the specific heat is calculated and compared with calorimetric data. Taking anharmonicity into account leads to a departure from the Dulong and Petit limit of the order of 2% at 1000 K and more than 6% at 2000 K, in good accord with experimental data. We propose that, eventually, such effects might be significant in the calculations of thermodynamic properties of mantle silicates like forsterite and its polymorphs.

Weird planets and odd relations: Atmospheric Circulation on Hot Jupiters

NASA Astrophysics Data System (ADS)

Zhang, Michael; Knutson, Heather; Kataria, Tiffany; Burrows, Adam; Fortney, Jonathan

2018-01-01

We extract phase curves from Spitzer photometry for the highly irradiated hot Jupiter WASP-33b and the unusually dense Saturn-mass planet HD 149026b. To do so, we develop a new variant of Pixel Level Decorrelation that is effective at removing intrapixel sensitivity variations for long observations (> 10 hours) where the position of the star can vary by a significant fraction of a pixel. Using this algorithm, we derive eclipse depths, phase amplitudes, and phase offsets for both planets at 3.6 um and 4.5 um. We use a simple toy model to show that WASP-33b's phase offset, albedo, and heat recirculation efficiency are largely similar to those of other hot Jupiters despite its very high irradiation. On the other hand, our fits for HD 149026b prefer a very high albedo and an unusually high recirculation efficiency. We also compare our results to predictions from GCM models, and find that while neither provide a good match to the data, the discrepancies for HD 149026b are unusually large. We speculate that this may be related to its high bulk metallicity, which could lead to enhanced atmospheric opacities and the formation of reflective cloud layers in localized regions of the atmosphere. We then place these two planets in a broader context by exploring relationships between the temperatures, albedos, efficiencies, and phase offsets of all planets with published thermal phase curves. We find a striking relationship between phase offset and irradiation temperature--the former dips with temperature until around 3300 K, and rises thereafter. Although some aspects of this trend are mirrored in GCM models, there are notable differences that provide important clues for future modeling efforts.

Solubility of K in Fe-S liquid, silicate-K/Fe-S/liq equilibria, and their planetary implications

NASA Technical Reports Server (NTRS)

Gangully, J.; Kennedy, G. C.

1977-01-01

Potassium has been found to have extremely limited absolute solubility in Fe-S liquid in the pressure-temperature range of 18 to 40 kbars, 1050 to 1150 C, and fO2 within the field of metallic iron. It also partitioned into a certain silicate phase highly in preference to Fe-S liquid at 30 kbar and 1100 C. The dependence of the partitioning of K between solid silicate and Fe-S liquid on fO2 and compositions of mineral solid solutions have been analyzed. These experimental data, along with those of others, limit the amount of K that could fractionate in Fe-S liquid layers or a core in the early history of the moon and, thus, act as localized heat sources in its thermal history models; the data also seem to argue against a chondritic abundance of potassium for earth. The question of fractionation of enough K-40 in an Fe-S liquid outer core of earth to provide the necesary thermal energy for the geomagnetic dynamo remains unresolved.

Molar volume, excess enthalpy, and Prigogine-Defay ratio of some silicate glasses with different (P,T) histories.

PubMed

Wondraczek, Lothar; Behrens, Harald

2007-10-21

Structural relaxation in silicate glasses with different (p,T) histories was experimentally examined by differential scanning calorimetry and measurements of molar volume under ambient pressure. Temperature and pressure-dependent rates of changes in molar volume and generation of excess enthalpy were determined for sodium trisilicate, soda lime silicate, and sodium borosilicate (NBS) compositions. From the derived data, Prigogine-Defay ratios are calculated and discussed. Changes of excess enthalpy are governed mainly by changes in short-range structure, as is shown for NBS where boron coordination is highly sensitive to pressure. For all three glasses, it is shown how the relaxation functions that underlie volume, enthalpy, and structural relaxation decouple for changes in cooling rates and pressure of freezing, respectively. The magnitude of the divergence between enthalpy and volume may be related to differences in structural sensitivity to changes in the (p,V,T,t) space on different length scales. The findings suggest that the Prigogine-Defay ratio is related to the magnitude of the discussed decoupling effect.

Modelling the Thermal History of Asteroid 4 Vesta

NASA Technical Reports Server (NTRS)

Solano, James M.; Kiefer, W. S.; Mittlefehldt, D. W.

2012-01-01

The asteroid 4 Vesta is widely thought to be the source of the HED (Howardite, Eucrite and Diogenite) meteorites, with this link supported by spectroscopic and dynamical studies. The availability of the HED meteorites for study and the new data being gained from the Dawn mission provides an excellent opportunity to investigate Vesta s history. In this study, modelling of Vesta has been undertaken to investigate its evolution from an unconsolidated chondritic body to a differentiated body with an iron core. In contrast to previous modelling, both heat and mass transfer are considered as coupled processes. This work draws on models of melt segregation in terrestrial environments to inform the evolution of Vesta into the differentiated body observed today. In order for a core to form in this body, a separation of the metallic iron from the silicates must take place. Temperatures in excess of the solidus temperatures for the Fe-FeS system and the silicates are therefore required. Thermal modelling has shown accretion before 2Myr leads to temperatures in excess of the silicate solidus.

On the 10 μm Silicate Feature in Active Galactic Nuclei

NASA Astrophysics Data System (ADS)

Nikutta, Robert; Elitzur, Moshe; Lacy, Mark

2009-12-01

The 10 μm silicate feature observed with Spitzer in active galactic nuclei (AGNs) reveals some puzzling behavior. It (1) has been detected in emission in type 2 sources, (2) shows broad, flat-topped emission peaks shifted toward long wavelengths in several type 1 sources, and (3) is not seen in deep absorption in any source observed so far. We solve all three puzzles with our clumpy dust radiative transfer formalism. Addressing (1), we present the spectral energy distribution (SED) of SST1721+6012, the first type 2 quasar observed to show a clear 10 μm silicate feature in emission. Such emission arises in models of the AGN torus easily when its clumpy nature is taken into account. We constructed a large database of clumpy torus models and performed extensive fitting of the observed SED. We find that the cloud radial distribution varies as r -1.5 and the torus contains 2-4 clouds along radial equatorial rays, each with optical depth at visual ~60-80. The source bolometric luminosity is ~3 × 1012 Lsun. Our modeling suggests that lsim35% of objects with tori sharing these characteristics and geometry would have their central engines obscured. This relatively low obscuration probability can explain the clear appearance of the 10 μm emission feature in SST1721+6012 together with its rarity among other QSO2. Investigating (2), we also fitted the SED of PG1211+143, one of the first type 1 QSOs with a 10 μm silicate feature detected in emission. Together with other similar sources, this QSO appears to display an unusually broadened feature whose peak is shifted toward longer wavelengths. Although this led to suggestions of non-standard dust chemistry in these sources, our analysis fits such SEDs with standard galactic dust; the apparent peak shifts arise from simple radiative transfer effects. Regarding (3), we find additionally that the distribution of silicate feature strengths among clumpy torus models closely resembles the observed distribution, and the feature never occurs deeply absorbed. Comparing such distributions in several AGN samples we also show that the silicate emission feature becomes stronger in the transition from Seyfert to quasar luminosities.

Investigations on Heat Treatment of a High-Speed Steel Roll

NASA Astrophysics Data System (ADS)

Fu, Hanguang; Qu, Yinhu; Xing, Jiandong; Zhi, Xiaohui; Jiang, Zhiqiang; Li, Mingwei; Zhang, Yi

2008-08-01

High-carbon high-speed steels (HSS) are very abrasion-resistant materials primarily due to their high hardness MC-type carbide and high hardness martensitic matrix. The effects of quenching and tempering treatment on the microstructure, mechanical properties, and abrasion resistance of centrifugal casting high-carbon HSS roll were studied. Different microstructures and mechanical properties were obtained after the quenching and tempering temperatures of HSS roll were changed. With air-cooling and sodium silicate solution cooling, when the austenitizing temperature reaches 1273 K, the metallic matrix all transforms into the martensite. Afterwards, the eutectic carbides dissolve into the metallic matrix and their continuous network distribution changes into the broken network. The second hardening temperature of high-carbon HSS roll is around 793 K. No significant changes in tensile strength and elongation percentage are observed unless the tempering temperature is beyond 753 K. The tensile strength increases obviously and the elongation percentage decreases slightly beyond 753 K. However, the tensile strength decreases and the elongation percentage increases when the tempering temperature exceeds 813 K. When the tempering temperature excels 773 K, the impact toughness has a slight decrease. Tempering at 793-813 K, high-carbon HSS roll presents excellent abrasion resistance.

Dust in the Solar System - Properties and Origins

NASA Technical Reports Server (NTRS)

Messenger, Scott; Keller, Lindsay; Nakamura-Messenger, Keiko

2013-01-01

Interplanetary dust pervades the inner Solar System, giving rise to a prominent glow above the horizon at sunrise and sunset known as the zodiacal light. This dust derives from the disintegration of comets as they approach the Sun and from collisions among main-belt asteroids. The Earth accretes roughly 4x10(exp 6) kg/year of 1 - 1,000 micron dust particles as they spiral into the Sun under the influence of Poynting-Robertson drag and solar wind drag. Samples of these grains have been collected from deep sea sediments, Antarctic ice and by high-altitude aircraft and balloon flights. Interplanetary dust particles (IDPs) collected in the stratosphere have been classified by their IR spectra into olivine, pyroxene, and hydrated silicate-dominated classes. Most IDPs have bulk major and minor element abundances that are similar to carbonaceous chondrite meteorites. Hydrated silicate-rich IDPs are thought to derive from asteroids based on their mineralogy and low atmospheric entry velocities estimated from peak temperatures reached during atmospheric entry. Anhydrous IDPs are typically aggregates of 0.1 - approx. 1 micron Mg-rich olivine and pyroxene, amorphous silicates (GEMS), Fe, Nisulfides and rare spinel and oxides bound together by carbonaceous material. These IDPs are often argued to derive from comets based on compositional similarities and high atmospheric entry velocities that imply high eccentricity orbits. Infrared spectra obtained from anhydrous IDPs closely match remote IR spectra obtained from comets. The most primitive (anhydrous) IDPs appear to have escaped the parent-body thermal and aqueous alteration that has affected meteorites. These samples thus consist entirely of grains that formed in the ancient solar nebula and pre-solar interstellar and circumstellar environments. Isotopic studies of IDPs have identified silicate stardust grains that formed in the outflows of red giant and asymptotic giant branch stars and supernovae]. These stardust grains include both amorphous and crystalline silicates. The organic matter in these samples also exhibits highly anomalous H, C, and N isotopic compositions that are consistent with formation in low temperature environments at the outermost regions of the solar nebula or presolar cold molecular cloud. The scientific frontiers for these samples include working toward a better understanding of the origins of the solar system amorphous and crystalline grains in IDPs and the very challenging task of determining the chemical composition of sub-micron organic grains. Laboratory studies of ancient and present-day dust in the Solar System thus reveal in exquisite detail the chemistry, mineralogy and isotopic properties of materials that derive from a range of astrophysical environments. These studies are an important complement to astronomical observations that help to place the laboratory observations into broader context.

Rice husks as a sustainable silica source for hierarchical flower-like metal silicate architectures assembled into ultrathin nanosheets for adsorption and catalysis.

PubMed

Zhang, Shouwei; Gao, Huihui; Li, Jiaxing; Huang, Yongshun; Alsaedi, Ahmed; Hayat, Tasawar; Xu, Xijin; Wang, Xiangke

2017-01-05

Metal silicates have attracted extensive interests due to their unique structure and promising properties in adsorption and catalysis. However, their applications were hampered by the complex and expensive synthesis. In this paper, three-dimensional (3D) hierarchical flower-like metal silicate, including magnesium silicate, zinc silicate, nickel silicate and cobalt silicate, were for the first time prepared by using rice husks as a sustainable silicon source. The flower-like morphology, interconnected ultrathin nanosheets structure and high specific surface area endowed them with versatile applications. Magnesium silicate was used as an adsorbent with the maximum adsorption capacities of 557.9, 381.3, and 482.8mg/g for Pb 2+ , tetracycline (TC), and UO 2 2+ , respectively. Ni nanoparticles/silica (Ni NPs/SiO 2 ) exhibited high catalytic activity and good stability for 4-nitrophenol (4-NP) reduction within only ∼160s, which can be attributed to the ultra-small particle size (∼6.8nm), good dispersion and high loading capacity of Ni NPs. Considering the abundance and renewability of rice husks, metal silicate with complex architecture can be easily produced at a large scale and become a sustainable and reliable resource for multifunctional applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Calcium silicate-based drug delivery systems.

PubMed

Zhu, Ying-Jie; Guo, Xiao-Xuan; Sham, Tsun-Kong

2017-02-01

Compared with other inorganic materials such as silica, metal oxides, noble metals and carbon, calcium silicate-based materials, especially nanostructured calcium silicate materials, have high biocompatibility, bioactivity and biodegradability, high specific surface area, nanoporous/hollow structure, high drug-loading capacity, pH-responsive drug release behavior and desirable drug release properties, and thus they are promising for the application in drug delivery. Calcium silicate-based drug delivery systems have a long drug-release time, which can significantly prolong the therapeutic effect of drugs. Another advantage of calcium silicate-based drug delivery systems is their pH-responsive drug release property, which can act as an ideal platform for targeted drug delivery. Areas covered: In recent years, studies have been carried out on calcium silicate-based drug delivery systems, and important results and insights have been documented. This article is not intended to offer a comprehensive review on the research on calcium silicate-based drug delivery systems, but presents some examples reported in the literature, and includes new insights obtained by tracking the interactions between drug molecules and calcium silicate carriers on the molecular level using the synchrotron-based X-ray spectroscopy. Expert opinion: Finally, our opinions on calcium silicate-based drug delivery systems are provided, and several research directions for the future studies are proposed.

ACFER 182/207/214 A Metal-rich, Volatile-poor Chondritic Meteorite, Similar to ALH85085

NASA Astrophysics Data System (ADS)

Palme, H.; Spettel, B.

1992-07-01

The unique Antarctic meteorite ALH85085 was the first chondritic meteorite to contain a significant excess of metallic Fe and associated siderophile elements (e.g., Grossman et al. 1988, Wasson and Kallemeyn 1990). Recently three Sahara meteorites, Acfer 182/207/214, apparently belonging to the same fall, were shown to be chemically and mineralogically very similar to ALHA85085, although minor textural differences appear to exclude a common origin with ALH85085. A mineralogical description and chemical composition of Acfer182/207/214 (henceforth ACFER182) are given in Bischoff et al. (1992). These authors suggested designating ALH85085 and ACFER182 as HH-chondrites reflecting high total Fe and high metal. The Fe/Mg-ratio of ACFER182 is 1.7 times that of CI-chondrites. All metals more refractory than Fe have similar enrichment factors, i.e., non-volatile metals occur in chondritic proportions, except for a slightly lower W enrichment. Metals more volatile than Fe are strongly depleted, with the depletion sequence closely following decreasing condensation temperatures. CI-normalized abundances are: Fe(1.92), Au(1.33), As(1.04), Cu(0.62), Ga(0.38), and the chalcophile Se(0.17). Lithophiles, more refractory than Mg, but including Mg and Cr, also occur in CI-abundance ratios (e.g., Sc/Mg in ACFER182 is 1.05xCI), although their absolute abundances are lower than those of metals. More volatile lithophile elements (Mn, Zn, etc.) decrease in abundance with decreasing condensation temperatures, just as the metals. The parallel (metal and silicate) decrease in moderately volatile element abundances with condensation temperatures suggests a similar nebular history for metal and silicate and is readily understood in a model where nebular gas is continually removed during condensation (Wasson and Chou 1974). Actual mixing of silicate and metal, i.e., agglomeration of silicate and metal grains in non-chondritic proportions (with 70% metal excess) could have occurred at relatively low temperatures, after the chondrule-forming process had transformed silicate grains into chondrules and fine metal grains into coarser metal. Partial loss of volatiles during chondrule formation or reheating of a metal-silicate assemblage with high volatile element abundances are very unlikely to produce the observed depletion sequence as argued by Grossman et al. (1988) for ALH85085. In addition, experiments on artificially heated meteorites produce losses of volatiles that are strongly dependent on fO(sub)2 and are incompatible with the patterns observed in ACFER182 (Wulf and Palme 1991). For example, the observed depletion of Mn in Acfer182 is 0.35 (i.e., 65 % are not condensed). However, Mn loss was never observed in the heating experiments, while large losses of Ga, Se, and Zn were found at temperatures up to 1300 degrees C. At temperatures required for Mn-volatilisation most other moderately volatiles would be quantitatively removed. However, the delicate pattern of moderate volatiles excludes ACFER182 as being a simple mixture of volatile-rich and volatile-poor material. Chemically, ACFER182 and ALHA85085 are related to CR-chondrites. These meteorites follow a trend of increasingly lower contents of volatile elements (e.g., Se, Zn) with decreasing contents of refractory element contents (e.g., Sc), opposite to the major trend in carbonaceous chondrites (from CI to CV). The ACFER182 and ALH85085 meteorites with their low Zn and Se contents and their low Sc abundances appear to form an endmember of this trend. Additional similarities with CR-meteorites in texture, mineralogy, and O, C, and N isotopic compositions (Bischoff et al. 1992; Prinz and Weisberg 1992 and references therein) may indicate that these meteorites are not as unique as originally thought. References: Bischoff A., Palme H., Schultz L., Weber D., Weber H.W. and Spettel B. (submitted to Geochim. Cosmochim. Acta 1992). Grossman J.N., Rubin A.E., MacPherson G.J. (1988) Earth Planet. Sci. Lett. 91, 33-54. Prinz M. and Weisberg M.K. (1992) Lunar. Planet. Sci. (abstract) 23, 1109. Wasson J.T. and Chou C.L. (1974) Meteoritics 9, 69-84. Wasson J.T. and Kallemeyn G.W. (1990) Earth Planet. Sci. Lett. 101, 148-161. Wulf A.-V. and Palme H.(1991) Lunar. Planet. Sci. (abstract) 22, 1527.

Metal/silicate partitioning of Pt and the origin of the "late veneer"

NASA Astrophysics Data System (ADS)

Ertel, W.; Walter, M. J.; Drake, M. J.; Sylvester, P. J.

2002-12-01

Highly siderophile elements (HSEs) are perfect tools for investigating core forming processes in planetary bodies due to their Fe-loving (siderophile) geochemical behavior. Tremendous scientific effort was invested into this field during the past 10 years - mostly in 1 atm experiments. However, little is known about their high-pressure geochemistry and partitioning behavior between core and mantle forming phases. This knowledge is essential to distinguish between equilibrium (Magma Ocean) and non-equilibrium (heterogeneous accretion, late veneer) models for the accretion history for the early Earth. We therefore chose to investigate the partitioning behavior of Pt up to pressures of 140 kbar (14 GPa) and temperatures of 1950°C. The used melt composition - identical to melt systems used in 1 atm experiments - is the eutectic composition of Anorthite-Diopside (AnDi), a pseudo-basalt. A series of runs were performed which were internaly buffered by the piston cylinder apparatus, and were followed by duplicate experiments buffered in the AnDi-C-CO2 system. These experiments constitute reversals since they approach equilibrium from an initially higher and lower Pt solubility (8 ppm in the non-buffered runs, and essentially Pt free in the buffered runs). Experimental charges were encapsulated in Pt capsules which served as source for Pt. Experiments up to 20 kbar were performed in a Quickpress piston cylinder apparatus, while experiments at higher pressures were performed in a Walker-type (Tucson, AZ) and a Kawai-type (Misasa, Japan) multi anvil apparatus. Time series experiments were performed in piston-cylinder runs to determine minimum run durations for the achievement of equilibrium, and to guarantee high-quality partitioning data. 6 hours was found to be sufficient to obtain equilibrium. In practice, all experiments exceeded 12 hours to assure equilibrium. In a second set of runs the temperature dependence of the partitioning behavior of Pt was investigated between the melting point of the 1 atm, AnDi system and the melting point of the Pt capsule material. Over 150 piston cylinder and 12 multi anvil experiments have been performed. Pt solubility is only slightly dependent on temperature, decreasing between 1800 and 1400°C by less than an order of magnitude. In consequence, the partitioning behavior of Pt is mostly determined by its oxygen fugacity dependence, which has only been determined in 1 atm experiments. At 10 kbar, metal/silicate partition coefficients (D's) decrease by about 3 orders of magnitude. The reason for this is not understood, but might be attributed to a first order phase transition as found for, e.g., SiO2 or H2O. Above 10 kbar any increase in pressure does not lead to any further significant decrease in partition coefficients. Solubilities stay roughly constant up to 140 kbar. Abundances of moderately siderophile elements were possibly established by metal/silicate equilibrium in a magma ocean. These results for Pt suggest that the abundances of HSEs were most probably established by the accretion of a chondritic veneer following core formation, as metal/silicate partition coefficients are too high to be consistent with metal/silicate equilibrium in a magma ocean.

Method for fluorination of uranium oxide

DOEpatents

Petit, George S.

1987-01-01

Highly pure uranium hexafluoride is made from uranium oxide and fluorine. The uranium oxide, which includes UO.sub.3, UO.sub.2, U.sub.3 O.sub.8 and mixtures thereof, is introduced together with a small amount of a fluorine-reactive substance, selected from alkali chlorides, silicon dioxide, silicic acid, ferric oxide, and bromine, into a constant volume reaction zone. Sufficient fluorine is charged into the zone at a temperature below approximately 0.degree. C. to provide an initial pressure of at least approximately 600 lbs/sq. in. at the ambient atmospheric temperature. The temperature is then allowed to rise in the reaction zone until reaction occurs.

Silicate Crystal Formation in the Disk of an Erupting Star Artist Concept

NASA Image and Video Library

2009-05-13

This artist's concept illustrates how silicate crystals like those found in comets can be created by an outburst from a growing star. The image shows a young sun-like star encircled by its planet-forming disk of gas and dust. The silicate that makes up most of the dust would have begun as non-crystallized, amorphous particles. Streams of material are seen spiraling from the disk onto the star increasing its mass and causing the star to brighten and heat up dramatically. The outburst causes temperatures to rise in the star's surrounding disk. The animation (figure 1) zooms into the disk to show close-ups of silicate particles. When the disk warms from the star's outburst, the amorphous particles of silicate melt. As they cool off, they transform into forsterite (figure 2), a type of silicate crystal often found in comets in our solar system. In April 2008, NASA's Spitzer Space Telescope detected evidence of this process taking place on the disk of a young sun-like star called EX Lupi. http://photojournal.jpl.nasa.gov/catalog/PIA12008

Q-Speciation and Network Structure Evolution in Invert Calcium Silicate Glasses.

PubMed

Kaseman, Derrick C; Retsinas, A; Kalampounias, A G; Papatheodorou, G N; Sen, S

2015-07-02

Binary silicate glasses in the system CaO-SiO2 are synthesized over an extended composition range (42 mol % ≤ CaO ≤ 61 mol %), using container-less aerodynamic levitation techniques and CO2-laser heating. The compositional evolution of Q speciation in these glasses is quantified using (29)Si and (17)O magic angle spinning nuclear magnetic resonance spectroscopy. The results indicate progressive depolymerization of the silicate network upon addition of CaO and significant deviation of the Q speciation from the binary model. The equilibrium constants for the various Q species disproportionation reactions for these glasses are found to be similar to (much smaller than) those characteristic of Li (Mg)-silicate glasses, consistent with the corresponding trends in the field strengths of these modifier cations. Increasing CaO concentration results in an increase in the packing density and structural rigidity of these glasses and consequently in their glass transition temperature Tg. This apparent role reversal of conventional network-modifying cations in invert alkaline-earth silicate glasses are compared and contrasted with that in their alkali silicate counterparts.

Spin-polarized Molecular Dynamics simulations of liquid iron silicate at high pressures.

NASA Astrophysics Data System (ADS)

Munoz Ramo, David; Stixrude, Lars

2010-05-01

Liquid iron silicate (Fe2SiO4) is an important component of natural silicate liquids appearing in Earth's interior. The effect of iron in the properties of these melts is a crucial issue, as it displays a high-spin to low-spin transition at high pressures which is accompanied by volume reduction and changes in the optical absorption spectrum. This phenomenon has a major influence on properties like the buoyancy or the thermal conductivity of the melt, and ultimately on the chemical and thermal evolution of our planet. Computer simulations using ab initio methods have proven to be a powerful approach to the study of liquid silicate systems[1,2], although not yet including Fe. In this paper, we report ab initio molecular dynamics studies of liquid iron silicate at high pressure (up to 400 GPa) and high temperatures (from 3000K to 6000K) that allow us to predict different properties of the system. We use the spin-polarized formalism and the GGA+U density functional for a better treatment of the iron magnetic moments in the system. Previous studies in the solid phase have shown that GGA predicts fayalite as a metal, while the introduction of U leads to a correct description of the band gap and the magnetic ordering of the system. We extend this analysis to the liquid phase. By means of these simulations we predict the liquid structure and thermodynamic properties of the liquid. We compute the theoretical Hugoniot for the system and find good agreement with values obtained from shock experiments [3]. Our calculations show large differences in the magnitude and orientation of the magnetic moments depending on the choice of functional; the GGA+U functional consistently provides larger values of the individual moments (about 1 unit larger) and of the total magnetization of the system. The high-spin to low-spin transition is predicted to take place at pressures from around 260GPa at 3000K to around 280GPa at 6000K in this iron-rich system. [1] N. P. de Koker, L. Stixrude, B. B. Karki, Geochim Cosmochim Acta 2008, 72, 1427. [2] B. B. Karki, D. Bhattarai, L. Stixrude, Phys. Rev. B 2007, 76, 104205. [3] G. Q. Chen, T. J. Ahrens, E. M. Stolper, Phys. Earth Planet. Inter. 2002, 134, 35.

Planetary Protection Considerations in EVA System Design

NASA Technical Reports Server (NTRS)

Eppler, Dean B.; Kosmo, Joseph J.

2011-01-01

To better constrain their origin, we have performed systematic studies of the siderophile element distribution in metal from Enstatite achondrites and iron-rich meteorites linked to Enstatite achondrites. Humayun (2010) reported 20 siderophile elements in the metal of Horse Creek, Mt. Egerton and Tucson, three iron meteorites known for their high Si content in their metal. The Horse Creek and Mt. Egerton irons have elemental patterns identical to metallic solids derived from partially molten enstatite chondrites. Tucson has an unusual siderophile element pattern that is reminiscent of IVA irons, except for the most volatile siderophiles with condensation temperatures below that of Cu (Sb, Ge, Sn) which are more depleted. The origin of Tucson metal is likely linked to an impact involving a reduced chondritic body that provided the silicates, and IVA iron. In a related study, van Acken et al. (2010) reported siderophile element abundances in metal and sulfides from aubrites, chondritic inclusions in aubrites, and other enstatite achondrites (including a separate section of Mt. Egerton). They found that aubrite metal was linked to metal in enstatite chondrites by low degree partial melting forming sulfur-rich metallic liquids. A restite origin of aubrites is not consistent with these metal compositions. The link between the metal compositions and cumulate silicates is not simple. The metal must have been incorporated from enstatite chondritic material that was assimilated by the aubrite magma. A manuscript is in preparation (van Acken et al., 2010). In a related study, van Acken et al. (2010, submitted) reported new precise Os isotope ratios and highly siderophile element abundances in Enstatite chondrites, Enstatite achondrites, Rumurutite chondrites to explore the range of nucleosynthetic variation in s-process Os. They observed nucleosynthetic anomalies, deficiencies of s-process Os, in most primitive enstatite chondrites, but showed the Rumurutite chondrites have very little expression of these anomalies. hardware from the human-occupied area may limit (although not likely eliminate) external materials in the human habitat. Definition of design-to requirements is critical to understanding technical feasibility and costs. The definition of Planetary Protection needs in relation to EVA mission and system element development cost impacts should be considered and interpreted in terms of Plausible Protection criteria. Since EVA operations will have the most direct physical interaction with the Martian surface, PP needs should be considered in the terms of mitigating hardware and operations impacts and costs.

Targeted Control of Permeability Using Carbonate Dissolution/Precipitation Reactions

NASA Astrophysics Data System (ADS)

Clarens, A. F.; Tao, Z.; Plattenberger, D.

2016-12-01

Targeted mineral precipitation reactions are a promising approach for controlling fluid flow in the deep subsurface. Here we studied the potential to use calcium and magnesium bearing silicates as cation donors that would react with aqueous phase CO2 under reservoir conditions to form solid carbonate precipitates. Preliminary experiments in high pressure and temperature columns suggest that these reactions can effectively lower the permeability of a porous media. Wollastonite (CaSiO3) was used as the model silicate, injected as solid particles into the pore space of a packed column, which was then subsequently flooded with CO2(aq). The reactions occur spontaneously, leveraging the favorable kinetics that occur at the high temperature and pressure conditions characteristic of the deep subsurface, to form solid phase calcium carbonate (CaCO3) and amorphous silica (SiO2) within the pore space. Both x-ray tomography imaging of reacted columns and electron microscopy imaging of thin sections were used to characterize where dissolution/precipitation occurred within the porous media. The spatial distribution of the products was closely tied to the flow rate and the duration of the experiment. The SiO2 product precipitated in close spatial proximity to the CaSiO3 reactant. The CaCO3 product, which is sensitive to the low pH and high pCO2 brine, precipitated out of solution further down the column as Ca2+ ions moved with the brine. The permeability of the columns decreased by several orders of magnitude after injecting the CaSiO3 particles. Following carbonation, the permeability decreased even further as precipitates filled flow paths within the pore network. A pore network model was developed to help understand the interplay between precipitation kinetics and flow in altering the permeability of the porous media. The effect of particle concentration and size, pore size, reaction time, and pCO2, are explored on pore/fracture aperture and reaction extent. To provide better control of these dynamics and ultimately devise a mechanism to deliver carbonation seed particles into leakage pathways, we are exploring the potential to functionalize the silicate particles using temperature sensitive polymer coatings.

Shock-Induced Phase Transitions in the Martian Meteorite Tissint: Mechanisms and Constraints on Shock Pressure

NASA Astrophysics Data System (ADS)

Sharp, T. G.; Hu, J.; Walton, E. L.

2013-12-01

Martian meteorites are important samples for understanding the origin and age of the Martian crust. All of these samples have been shocked to some degree during their ejection from Mars or earlier. Tissint, a picritic shergottite, has many high-pressure phases that have been used to constrain shock conditions and suggest a deep crustal origin [1] and to argue for multiple impact events [2]. Here we investigate the products and mechanisms of various olivine transformation reactions. Olivine in and adjacent to shock-melt veins and pockets is transformed into high-pressure minerals. In the hottest parts of the sample, olivine dissociated into 50-nm crystals of magnesiowüstite intergrown with either a pyroxene-composition glass or with low-Ca clinopyroxene. In both cases, the olivine is inferred to have transformed to silicate perovskite + magnesiowüstite during shock with subsequent breakdown of the perovskite after pressure release. Olivine along the margins of shock veins transformed into ringwoodite. Polycrystalline ringwoodite formed at the olivine-melt interface wheras coherent ringwoodite lamellae formed farther from the melt. These ringwoodite lamellae have the same topotaxial relationship to olivine as seen in static high-pressure experiments [3] and shocked meteorites [4]: (100)Ol || {111}Rw and [011]Ol || <110>Rw. The various olivine reactions can be explained by a single shock to above 24 GPa where only the highest temperatures allowed the dissociation of olivine to silicate-perovskite plus magnesiowüstite. The silicate perovskite in the melt pocket transformed to pyroxene because the melt pocket remained very hot after pressure release. At lower temperatures, the kinetically easier polymorphic transformation of olivine to metastable ringwoodite occurred. At the lowest temperatures, this reaction was facilitated by nucleation of ringwoodite lamellae on stacking faults in olivine. The variation in assemblages that we see are consistent with a single shock and a relatively short shock pulse. References: [1] Baziotis1, I. P. et. al 2013 Nature Communications 4:1404, [2] El Goresey, A. et. al 2013 #1037. 44th LPSC. [3] Kerschhofer, L. et. al 1996 Science 274, 79-81. [4] Miyahara et. al, 2010 EPSL. 295, 321-327.

Water Vapor Corrosion in EBC Constituent Materials

NASA Technical Reports Server (NTRS)

Kowalski, Benjamin; Fox, Dennis; Jacobson, Nathan S.

2017-01-01

Environmental Barrier Coating (EBC) materials are sought after to protect ceramic matrix composites (CMC) in high temperature turbine engines. CMCs are particularly susceptible to degradation from oxidation, Ca-Al-Mg-Silicate (CMAS), and water vapor during high temperature operation which necessitates the use of EBCs. However, the work presented here focuses on water vapor induced recession in EBC constituent materials. For example, in the presence of water vapor, silica will react to form Si(OH)4 (g) which will eventually corrode the material away. To investigate the recession rate in EBC constituent materials under high temperature water vapor conditions, thermal gravimetric analysis (TGA) is employed. The degradation process can then be modeled through a simple boundary layer expression. Ultimately, comparisons are made between various single- and poly-crystalline materials (e.g. TiO2, SiO2) against those found in literature.

Coordinated Hard Sphere Mixture (CHaSM): A simplified model for oxide and silicate melts at mantle pressures and temperatures

NASA Astrophysics Data System (ADS)

Wolf, Aaron S.; Asimow, Paul D.; Stevenson, David J.

2015-08-01

We develop a new model to understand and predict the behavior of oxide and silicate melts at extreme temperatures and pressures, including deep mantle conditions like those in the early Earth magma ocean. The Coordinated Hard Sphere Mixture (CHaSM) is based on an extension of the hard sphere mixture model, accounting for the range of coordination states available to each cation in the liquid. By utilizing approximate analytic expressions for the hard sphere model, this method is capable of predicting complex liquid structure and thermodynamics while remaining computationally efficient, requiring only minutes of calculation time on standard desktop computers. This modeling framework is applied to the MgO system, where model parameters are trained on a collection of crystal polymorphs, producing realistic predictions of coordination evolution and the equation of state of MgO melt over a wide range of pressures and temperatures. We find that the typical coordination number of the Mg cation evolves continuously upward from 5.25 at 0 GPa to 8.5 at 250 GPa. The results produced by CHaSM are evaluated by comparison with predictions from published first-principles molecular dynamics calculations, indicating that CHaSM is accurately capturing the dominant physics controlling the behavior of oxide melts at high pressure. Finally, we present a simple quantitative model to explain the universality of the increasing Grüneisen parameter trend for liquids, which directly reflects their progressive evolution toward more compact solid-like structures upon compression. This general behavior is opposite that of solid materials, and produces steep adiabatic thermal profiles for silicate melts, thus playing a crucial role in magma ocean evolution.

Alkali-Activated Aluminium-Silicate Composites as Insulation Materials for Industrial Application

NASA Astrophysics Data System (ADS)

Dembovska, L.; Bajare, D.; Pundiene, I.; Bumanis, G.

2015-11-01

The article reports on the study of thermal stability of alkali-activated aluminium- silicate composites (ASC) at temperature 800-1100°C. ASC were prepared by using calcined kaolinite clay, aluminium scrap recycling waste, lead-silicate glass waste and quartz sand. As alkali activator, commercial sodium silicate solution modified with an addition of sodium hydroxide was used. The obtained alkali activation solution had silica modulus Ms=1.67. Components of aluminium scrap recycling waste (aluminium nitride (AlN) and iron sulphite (FeSO3)) react in the alkali media and create gases - ammonia and sulphur dioxide, which provide the porous structure of the material [1]. Changes in the chemical composition of ASC during heating were identified and quantitatively analysed by using DTA/TG, dimension changes during the heating process were determined by using HTOM, pore microstructure was examined by SEM, and mineralogical composition of ASC was determined by XRD. The density of ASC was measured in accordance with EN 1097-7. ASC with density around 560 kg/m3 and heat resistance up to 1100°C with shrinkage less than 5% were obtained. The intended use of this material is the application as an insulation material for industrial purposes at elevated temperatures.

Mid-Infrared Spectra of Comets P/Borrelly, P/Faye, and P/Schaumasse

NASA Technical Reports Server (NTRS)

Hanner, Martha S.; Lynch, David K.; Russell, Ray W.; Hackwell, John A.; Kellogg, Robert; Blaney, Diana

1996-01-01

A 10 micron silicate emission feature has been discovered in the spectra of comets P/BorrelIy and P/Faye at R approximately 1.5 AU. These are the first short period comets in which silicate emission has definitely been detected. The broad emission features are about 25% above the continuum. No emission feature was present in the spectrum of P/Schaumasse; it is possible that the nucleus of P/Schaumasse was directly detected. If all of the observed flux originated from the nucleus, then the effective radius is about 3 km; the observed color temperature is consistent with a rapidly rotating nucleus. We present models that show how the shape of the silicate feature can depend on the way in which silicate and absorbing material are mixed in the grains.

Structure and properties during aging of an ultra-high strength Al-Cu-Li-Ag-Mg alloy

NASA Technical Reports Server (NTRS)

Gayle, Frank W.; Heubaum, Frank H.; Pickens, Joseph R.

1990-01-01

The structure and properties of the strengthening phases formed during aging in an Al-Cu-Li-Ag-Mg alloy (Weldalite 049) were elulcidated, by following the development of the microstructure by means of TEM. The results of observations showed that the Weldalite 049 alloy has a series of unusual and technologically useful combinations of mechanical properties in different aging conditions, such as natural aging without prior cold work to produce high strengths, a reversion temper of lower yield strength and unusually high ductility, a room temperature reaging of the reversion temper eventually leading to the original T4 hardness, and ultrahigh-strength T6 properties.

Thermal diffusivity of electrical insulators at high temperatures: Evidence for diffusion of bulk phonon-polaritons at infrared frequencies augmenting phonon heat conduction

NASA Astrophysics Data System (ADS)

Hofmeister, Anne M.; Dong, Jianjun; Branlund, Joy M.

2014-04-01

We show that laser-flash analysis measurements of the temperature (T) dependence of thermal diffusivity (D) for diverse non-metallic (e.g., silicates) single-crystals is consistently represented by D(T) = FT-G + HT above 298 K, with G ranging from 0.3 to 2, depending on structure, and H being ˜10-4 K-1 for 51 single-crystals, 3 polycrystals, and two glasses unaffected by disorder or reconstructive phase transitions. Materials exhibiting this behavior include complex silicates with variable amounts of cation disorder, perovskite structured materials, and graphite. The high-temperature term HT becomes important by ˜1300 K, above which temperature its contribution to D(T) exceeds that of the FT-G term. The combination of the FT-G and HT terms produces the nearly temperature independent high-temperature region of D previously interpreted as the minimal phonon mean free path being limited by the finite interatomic spacing. Based on the simplicity of the fit and large number of materials it represents, this finding has repercussions for high-temperature models of heat transport. One explanation is that the two terms describing D(T) are associated with two distinct microscopic mechanisms; here, we explore the possibility that the thermal diffusivity of an electrical insulator could include both a contribution of lattice phonons (the FT-G term) and a contribution of diffusive bulk phonon-polaritons (BPP) at infrared (IR) frequencies (the HT term). The proposed BPP diffusion exists over length scales smaller than the laboratory sample sizes, and transfers mixed light and vibrational energy at a speed significantly smaller than the speed of light. Our diffusive IR-BPP hypothesis is consistent with other experimental observations such as polarization behavior, dependence of D on the number of IR peaks, and H = 0 for Ge and Si, which lack IR fundamentals. A simple quasi-particle thermal diffusion model is presented to begin understanding the contribution from bulk phonon-polaritons to overall heat conduction.

Composition of the core from gallium metal–silicate partitioning experiments

DOE PAGES

Blanchard, I.; Badro, J.; Siebert, J.; ...

2015-07-24

We present gallium concentration (normalized to CI chondrites) in the mantle is at the same level as that of lithophile elements with similar volatility, implying that there must be little to no gallium in Earth's core. Metal-silicate partitioning experiments, however, have shown that gallium is a moderately siderophile element and should be therefore depleted in the mantle by core formation. Moreover, gallium concentrations in the mantle (4 ppm) are too high to be only brought by the late veneer; and neither pressure, nor temperature, nor silicate composition has a large enough effect on gallium partitioning to make it lithophile. Wemore » therefore systematically investigated the effect of core composition (light element content) on the partitioning of gallium by carrying out metal–silicate partitioning experiments in a piston–cylinder press at 2 GPa between 1673 K and 2073 K. Four light elements (Si, O, S, C) were considered, and their effect was found to be sufficiently strong to make gallium lithophile. The partitioning of gallium was then modeled and parameterized as a function of pressure, temperature, redox and core composition. A continuous core formation model was used to track the evolution of gallium partitioning during core formation, for various magma ocean depths, geotherms, core light element contents, and magma ocean composition (redox) during accretion. The only model for which the final gallium concentration in the silicate Earth matched the observed value is the one involving a light-element rich core equilibrating in a FeO-rich deep magma ocean (>1300 km) with a final pressure of at least 50 GPa. More specifically, the incorporation of S and C in the core provided successful models only for concentrations that lie far beyond their allowable cosmochemical or geophysical limits, whereas realistic O and Si amounts (less than 5 wt.%) in the core provided successful models for magma oceans deeper that 1300 km. In conclusion, these results offer a strong argument for an O- and Si-rich core, formed in a deep terrestrial magma ocean, along with oxidizing conditions.« less

Experimental simulation of the alkali-carbonate metasomatism

NASA Astrophysics Data System (ADS)

Gorbachev, Nikolay; Kostyuk, Anastasia

2010-05-01

Close association of alkaline and ultrabasic rocks, carbonatites, apatitic and sulfidic mineralization, features of structure testify about mantle a source and the important role alcalic-carbonaceous fluids in genesis of these rocks. Formation alkaline silicate, carbonaceous and sulfidic melts, phase relationship, behaviour of the ti-tan, phosphorus, sulphur and zircon has been experimentally studied at pressure 3.9 GPa, temperature 1250°С in system peridotit-basalt (eclogite)-alcalic-carbonaceous fluid with additives in quality acces-sory minerals, apatite, nickel-containing pyrrhotite, ilmenite, zircon. Experiments were carried out using of apparatus high pressure (piston cilinder and anvil with hole) by a quenching technique. It was used two ampoules (platinum and peridotite, content basalt powder) method. Duration of experiments was 6-8 hours. Products of experiments were studied on electronic scanning microscope Tescan VEGA TS 5130MM with YAG detector of secondary and reflected elec-tron and energy-dispersive the x-ray microanalyzer with semi-conductor Si (Li) detector INCA Energy 350. The morphology, structure and relationship of glass, inclusions of carbonatic and sulfidic globules specify in existence in the conditions of experiment immiscibility silicate, carbonate and sulfidic melts. The composition of silicate melt answered phonolite, carbonaceous melts it is essential calciferous composition with an impurity of alkaline metals and silicate components. Solubility of zircon in silicate melts reached 0.8 wt.% ZrO2, in co-existing carbonaceous melt - 1.5 wt.%. Concentration TiO2 and Р2О5 in silicate melt reached 2 wt.%, in carbonaceous melt - 1.7 wt.% TiO2 and up to 14 wt.% Р2О5. Concentration of sulphur in these melts did not exceed 0.2 мас. %. From minerals of liqudus the main concentrators of the titan and phosphorus were the X-phase and phlogopite - up to 8 wt.% TiO2 and up to 3 wt.% Р2О5 in the X-phase, up to 6 wt. % TiO2 and to 2.5 wt. % Р2О5 in phlogopite. Absence ilmenite and apatite in experimental samples under the studied conditions is obviously caused by their high solubility in co-existing phases. The composition of X-phase is similar to composition of Cpx, but X-phase enrich in TiO2 and de-plete in SiO2 . The partition coefficient of oxides some elements between silicate and carbonaceous melts Dka/si increasing from SiO2 (D<1) to CaO (D>10). Reduction of solubility of apatite in alkaline silicate melt at pressure decline promotes silicate-phosphate stratification and formation of apatite mineralization at introduction of mantle magmas into the earth crust. Supported by grant RFBR № 09-05-01131, ONZ th. 2

The Role of Siliceous Hydrothermal Breccias in the Genesis of Volcanic Massive Sulphide Deposits - Ancient and Recent Systems

NASA Astrophysics Data System (ADS)

Costa, I. A.; Barriga, F. J.; Fouquet, Y.

2014-12-01

Siliceous hydrothermal breccias were sampled in two Mid-Atlantic Ridge active sites: Lucky Strike and Menez Gwen. These hydrothermal fields are located in the border of the Azorean plateau, southwest of the Azores islands where the alteration processes affecting basaltic rocks are prominent (Costa et al., 2003). The hydrothermal breccias are genetically related with the circulation of low temperature hydrothermal fluids in diffuse vents. The groundmass of these breccias precipitates from the fluid and consolidates the clastic fragments mostly composed of basalt. The main sources are the surrounding volcanic hills. Breccias are found near hydrothermal vents and may play an important role in the protection of subseafloor hydrothermal deposits forming an impermeable cap due to the high content in siliceous material. The amorphous silica tends to precipitate when the fluid is conductively cooled as proposed by Fouquet et al. (1998) after Fournier (1983). The process evolves gradually from an initial stage where we have just the fragments and circulating seawater. The ascending hydrothermal fluid mixes with seawater, which favours the precipitation of the sulphide components. Sealing of the initially loose fragments begins, the temperature rises below this crust, and the processes of mixing fluid circulation and conductive cooling are simultaneous. At this stage the fluid becomes oversaturated with respect to amorphous silica. This form of silica can precipitate in the open spaces of the porous sulphides and seal the system. Normally this can happen at low temperatures. At this stage the hydrothermal breccia is formed creating a progressively less permeable, eventually impermeable cap rock at the surface. Once the fluid is trapped under this impermeable layer, conductive cooling is enhanced and mixing with seawater is restricted, making the precipitation of amorphous silica more efficient. Since the first discovery and description of recent mineralized submarine hydrothermal deposits, comparison with ancient volcanic massive sulphide deposits is appropriate. The proposed model can explain some of the processes taking place in the early phase of formation of old deposits where equivalent siliceous material is found in the hanging wall of the ore bodies (e.g. Barriga and Fyfe, 1988).

On the Unusually High Temperature of the Cluster of Galaxies 1E 0657-56

NASA Technical Reports Server (NTRS)

Yaqoob, Tahir

1999-01-01

A recent X-ray observation of the cluster 1E 0657-56 (z = 0.296) with ASC,4 implied an unusually high temperature of approx. 17 keV. Such a high temperature would make it the hottest known cluster and severely constrain cosmological models since, in a Universe with critical density (Omega = 1) the probability of observing such a cluster is only approx. 4 x 10(exp -5). Here we test the robustness of this observational result since it has such important implications. We analysed the data using a variety of different data analysis methods and spectral analysis assumptions and find a temperature of approx. 11 - 12 keV in all cases, except for one class of spectral fits. These are fits in which the absorbing column density is fixed at the Galactic value. Using simulated data for a 12 keV cluster, we show that a high temperature of approx. 17 keV is artificially obtained if the true spectrum has a stronger low-energy cut-off than that for Galactic absorption only. The apparent extra absorption may be astrophysical in origin, (either intrinsic or line-of-sight), or it may be a problem with the low-energy CCD efficiency. Although significantly lower than previous measurements, this temperature of kT approx. 11 - 12 keV is still relatively high since only a few clusters have been found to have temperatures higher than 10 keV and the data therefore still present some difficulty for an Omega = 1 Universe. Our results will also be useful to anyone who wants to estimate the systematic errors involved in different methods of background subtraction of ASCA data for sources with similar signal-to-noise to that of the IE 0657-56 data reported here.

(Energetics of silicate melts from thermal diffusion studies)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1989-01-01

Research during the past year has been concentrated in four major areas. We are continuing work initiated during the first two years on modelling thermal diffusion on multicomponent silicate liquids. We have derived appropriate relations for ternary and quaternary systems and reanalyzed experimental thermal diffusion data for the ternary system fayalite-leucite-silica. In our manuscript entitled Thermal Diffusion in Petrology'', to be published in Adv. in Phy. Geochem., we show that these model results independently recover the compositional extent and temperature of liquid immiscibility in this system. Such retrieval provides a rigorous test of our theoretical predictions and simplified treatment ofmore » complex silicate liquids reported in Geochimica Cosmochimica Acta in 1986. The usefulness of our Soret research in providing mixing energies of silicate liquids has been recently confirmed by Ghiorso (1987, Cont. Min. Pet.). This demonstration provides a strategy for incorporating Soret data into the calibration of phase equilibrium-based solution models such as the one developed by Ghiorso. During the past year we also have resumed our studies of thermal diffusion in borosilicate glasses which also exhibit liquid immiscibility. Our objectives in studying these systems are (1) to further test of our multicomponent thermal diffusion model and (2) to provide quantitative constraints on the mixing properties of these glass-forming systems which are important for evaluating their suitability for storage of high-level nuclear waste. 16 refs.« less

A Novel Variable Wide Bandgap Material for High Power, High Frequency Devices

DTIC Science & Technology

2011-01-13

temperature above 1300 °C caused the back side of the Si substrates to soften and form molybdenum silicides with the holder or to simply sublime...copper while Figures 7b, 7d, and 7f show the measured impurity levels of aluminum and sodium in the 4H-SiC substrate, RF sputtered film, and DC... sodium which are completely absent in the 4H- SiC substrate. These impurities are also attributed to the aluminum silicate shell that is evidently

Silicate Dust in Active Galactic Nuclei

NASA Astrophysics Data System (ADS)

Xie, Yanxia; Li, Aigen; Hao, Lei

2017-01-01

The unification theory of active galactic nuclei (AGNs) hypothesizes that all AGNs are surrounded by an anisotropic dust torus and are essentially the same objects but viewed from different angles. However, little is known about the dust that plays a central role in the unification theory. There are suggestions that the AGN dust extinction law appreciably differs from that of the Galaxy. Also, the silicate emission features observed in type 1 AGNs appear anomalous (I.e., their peak wavelengths and widths differ considerably from that of the Galaxy). In this work, we explore the dust properties of 147 AGNs of various types at redshifts z≲ 0.5, with special attention paid to 93 AGNs that exhibit the 9.7 and 18 μm silicate emission features. We model their silicate emission spectra obtained with the Infrared Spectrograph aboard the Spitzer Space Telescope. We find that 60/93 of the observed spectra can be well explained with “astronomical silicate,” while the remaining sources favor amorphous olivine or pyroxene. Most notably, all sources require the dust to be micron-sized (with a typical size of ˜1.5 ± 0.1 μm), much larger than submicron-sized Galactic interstellar grains, implying a flat or “gray” extinction law for AGNs. We also find that, while the 9.7 μm emission feature arises predominantly from warm silicate dust of temperature T ˜ 270 K, the ˜5-8 μm continuum emission is mostly from carbon dust of T ˜ 640 K. Finally, the correlations between the dust properties (e.g., mass, temperature) and the AGN properties (e.g., luminosity, black hole mass) have also been investigated.

Identification of Gravity-Related Effects on Crystal Growth From Melts With an Immiscibility Gap

NASA Technical Reports Server (NTRS)

Kassemi, M.; Sayir, A.; Farmer, S.

1999-01-01

This work involves an experimental-numerical approach to study the effects of natural and Marangoni convections on solidification of single crystals from a silicate melt with a liquid-liquid immiscibility gap. Industrial use of crystals grown from silicate melts is becoming increasingly important in electronic, optical, and high temperature structural applications. Even the simplest silicate systems like Al203-SiO2 have had, and will continue to have, a significant role in the development of traditional and advanced ceramics. A unique feature of crystals grown from the silicate systems is their outstanding linear electro-optic properties. They also exhibit exceptionally high optical rotativity. As a result, these crystals are attractive materials for dielectric, optical, and microwave applications. Experimental work in our laboratory has indicated that directional solidification of a single crystal mullite appears to be preceded by liquid-liquid phase separation in the melt. Disruption of the immiscible state results in crystallization of a two phase structure. There is also evidence that mixing in the melt caused by density-driven convection can significantly affect the stability of the immiscible liquid layers and result in poly-crystalline growth. On earth, the immiscible state has only been observed for small diameter crystals grown in float zone systems where natural convection is almost negligible. Therefore, it is anticipated that growth of large single crystals from silicate melts would benefit from microgravity conditions because of the reduction of the natural convective mixing. The main objective of this research is to determine the effects of transport processes on the phase separation in the melt during growth of a single crystal while addressing the following issues: (1) When do the immiscible layers form and are they real?; (2) What are the main physical characteristics of the immiscible liquids?; and (3) How mixing by natural or Marangoni convection affects the stability of the phase separated melt.

Phase Equilibria in the System "FeO"-CaO-SiO2-Al2O3-MgO at Different CaO/SiO2 Ratios

NASA Astrophysics Data System (ADS)

Jang, Kyoung-oh; Ma, Xiaodong; Zhu, Jinming; Xu, Haifa; Wang, Geoff; Zhao, Baojun

2017-06-01

The "FeO"-containing slags play an important role in the operation of an ironmaking blast furnace (BF), in particular the primary slags such as the system "FeO"-CaO-SiO2-Al2O3-2 mass pct MgO with CaO/SiO2 weight ratios of 1.3, 1.5, and 1.8 saturated with metallic iron. To investigate the characteristics of such a slag system and its behavior in BF, the phase equilibria and liquidus temperatures in the slag system have been experimentally determined using the high-temperature equilibration and quenching technique followed by an electron probe X-ray microanalysis (EPMA). Isotherms between 1553 K and 1603 K (1280 °C and 1330 °C) were determined in the primary phase fields of dicalcium silicate, melilite, spinel, and monoxide [(Mg,Fe2+)O]. Pseudo-ternary phase diagrams of (CaO + SiO2)-Al2O3-"FeO" with a fixed MgO concentration at 2 mass pct and at CaO/SiO2 ratios of 1.3, 1.5, and 1.8 have been discussed, respectively, simplifying the complexity of the slag system for easy understanding and applying in BF operation. It was found that the liquidus temperatures increase in melilite and spinel primary phase fields, but decrease in dicalcium silicate and monoxide primary phase fields with increasing Al2O3/(CaO + SiO2) ratio. In addition, the liquidus temperatures decrease with increasing "FeO" concentration in dicalcium silicate and melilite primary phase fields, while showing an increasing trend in the spinel and monoxide primary phase fields. The data resulted from this study can be used to improve and optimize currently available database of thermodynamic models used in FactSage.

Iron K-edge X-ray absorption near-edge structure spectroscopy of aerodynamically levitated silicate melts and glasses

DOE PAGES

Alderman, O. L. G.; Wilding, M. C.; Tamalonis, A.; ...

2017-01-26

Here, the local structure about Fe(II) and Fe(III) in silicate melts was investigated in-situ using iron K-edge X-ray absorption near-edge structure (XANES) spectroscopy. An aerodynamic levitation and laser heating system was used to allow access to high temperatures without contamination, and was combined with a chamber and gas mixing system to allow the iron oxidation state, Fe 3+/ΣFe, to be varied by systematic control of the atmospheric oxygen fugacity. Eleven alkali-free, mostly iron-rich and depolymerized base compositions were chosen for the experiments, including pure oxide FeO, olivines (Fe,Mg) 2SiO 4, pyroxenes (Fe,Mg)SiO 3, calcic FeO-CaSiO 3, and a calcium aluminosilicatemore » composition, where total iron content is denoted by FeO for convenience. Melt temperatures varied between 1410 and 2160 K and oxygen fugacities between FMQ – 2.3(3) to FMQ + 9.1(3) log units (uncertainties in parentheses) relative to the fayalite-magnetite-β-quartz (FMQ) buffer.« less

Hot and cold gas toward young stellar objects

NASA Technical Reports Server (NTRS)

Mitchell, George F.; Maillard, Jean-Pierre; Allen, Mark; Beer, Reinhard; Belcourt, Kenneth

1990-01-01

High-resolution M band spectra are presented for the seven embedded IR sources W3 IRS 5, S140 IRS1, NGC 7538 IRS 1, NGC 7538 IRS 9, GL 2136, LkH-alpha 101, and MWC 349A, and the data are combined with previously published work for W33A and GL 2591. Cold CO is seen toward all nine sources, with temperatures from 11 K to 66 K. Column densities of cold CO are presented. Hot gas is seen toward eight of the nine objects with temperatures from 120 K to 1010 K. New lower limits to the hot gas density are obtained. The hot gas toward GL 2591, GL 2136, W3 IRS 5, and S140 IRS 1 is probably very near the central source and heated via gas-grain collisions. The optical depth in the silicate feature is strongly correlated with the (C-13)O column density, confirming that silicate optical depth is a useful measure of gas column density. The ratio of solid-to-gaseous CO is obtained for seven sources.

Quantitative and Qualitative Aspects of Gas-Metal-Oxide Mass Transfer in High-Temperature Confocal Scanning Laser Microscopy

NASA Astrophysics Data System (ADS)

Piva, Stephano P. T.; Pistorius, P. Chris; Webler, Bryan A.

2018-05-01

During high-temperature confocal scanning laser microscopy (HT-CSLM) of liquid steel samples, thermal Marangoni flow and rapid mass transfer between the sample and its surroundings occur due to the relatively small sample size (diameter around 5 mm) and large temperature gradients. The resulting evaporation and steel-slag reactions tend to change the chemical composition in the metal. Such mass transfer effects can change observed nonmetallic inclusions. This work quantifies oxide-metal-gas mass transfer of solutes during HT-CSLM experiments using computational simulations and experimental data for (1) dissolution of MgO inclusions in the presence and absence of slag and (2) Ca, Mg-silicate inclusion changes upon exposure of a Si-Mn-killed steel to an oxidizing gas atmosphere.

Enhancing Photovoltaic Performance Using Broadband Luminescent Down-Shifting by Combining Multiple Species of Eu-Doped Silicate Phosphors.

PubMed

Ho, Wen-Jeng; Shen, Yu-Tang; Liu, Jheng-Jie; You, Bang-Jin; Ho, Chun-Hung

2017-10-21

This paper demonstrates the application of a broadband luminescent downshifting (LDS) layer with multiple species of europium (Eu)-doped silicate phosphors using spin-on film technique to enhance the photovoltaic efficiency of crystalline silicon solar cells. The surface morphology of the deposited layer was examined using a scanning electron microscope (SEM). The chemical composition of the Eu-doped silicate phosphors was analyzed using energy-dispersive X-ray spectroscopy (EDS). The fluorescence emission of the Eu-doped silicate phosphors was characterized using photoluminescence (PL) measurements at room temperature. We also compared the optical reflectance and external quantum efficiency (EQE) response of cells with combinations of various Eu-doped phosphors species. The cell coated with two species of Eu-doped phosphors achieved a conversion efficiency enhancement (∆ η ) of 19.39%, far exceeding the ∆ η = 15.08% of the cell with one species of Eu-doped phosphors and the ∆ η = 8.51% of the reference cell with the same silicate layer without Eu-doped phosphors.

High performance aluminum–cerium alloys for high-temperature applications

DOE PAGES

Sims, Zachary C.; Rios, Orlando R.; Weiss, David; ...

2017-08-01

Light-weight high-temperature alloys are important to the transportation industry where weight, cost, and operating temperature are major factors in the design of energy efficient vehicles. Aluminum alloys fill this gap economically but lack high-temperature mechanical performance. Alloying aluminum with cerium creates a highly castable alloy, compatible with traditional aluminum alloy additions, that exhibits dramatically improved high-temperature performance. These compositions display a room temperature ultimate tensile strength of 400 MPa and yield strength of 320 MPa, with 80% mechanical property retention at 240 °C. A mechanism is identified that addresses the mechanical property stability of the Al-alloys to at least 300more » °C and their microstructural stability to above 500 °C which may enable applications without the need for heat treatment. Lastly, neutron diffraction under load provides insight into the unusual mechanisms driving the mechanical strength.« less

A framework for predicting global silicate weathering and CO2 drawdown rates over geologic time-scales.

PubMed

Hilley, George E; Porder, Stephen

2008-11-04

Global silicate weathering drives long-time-scale fluctuations in atmospheric CO(2). While tectonics, climate, and rock-type influence silicate weathering, it is unclear how these factors combine to drive global rates. Here, we explore whether local erosion rates, GCM-derived dust fluxes, temperature, and water balance can capture global variation in silicate weathering. Our spatially explicit approach predicts 1.9-4.6 x 10(13) mols of Si weathered globally per year, within a factor of 4-10 of estimates of global silicate fluxes derived from riverine measurements. Similarly, our watershed-based estimates are within a factor of 4-18 (mean of 5.3) of the silica fluxes measured in the world's ten largest rivers. Eighty percent of total global silicate weathering product traveling as dissolved load occurs within a narrow range (0.01-0.5 mm/year) of erosion rates. Assuming each mol of Mg or Ca reacts with 1 mol of CO(2), 1.5-3.3 x 10(8) tons/year of CO(2) is consumed by silicate weathering, consistent with previously published estimates. Approximately 50% of this drawdown occurs in the world's active mountain belts, emphasizing the importance of tectonic regulation of global climate over geologic timescales.

Thermal Conductivity and Thermal Gradient Cyclic Behavior of Refractory Silicate Coatings on SiC/SiC Ceramic Matrix Composites

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Lee, Kang N.; Miller, Robert A.

2001-01-01

Plasma-sprayed mullite and BSAS coatings have been developed to protect SiC/SiC ceramic matrix composites from high temperature environmental attack. In this study, thermal conductivity and thermal barrier functions of these coating systems are evaluated using a laser high-heat-flux test rig. The effects of water vapor on coating thermal conductivity and durability are studied by using alternating furnace and laser thermal gradient cyclic tests. The influence of laser high thermal-gradient cycling on coating failure modes is also investigated.

Thermal conductivity measurements on Mullite and Silica REI for the Space Shuttle - Complementary guarded hot plate and radical outflow measurements. [Reusable External Insulators

NASA Technical Reports Server (NTRS)

Brazel, J. P.; Kennedy, B. S.

1974-01-01

The materials studied are described along with the apparatus and the experimental techniques employed. The results of the measurements involving two REI Silica materials and a Mod 1 B REI Mullite are listed in a table. Measurements were conducted at unusually high temperature differences to detect 'shine-through' radiation transparency. Photographs are presented of the high-temperature guarded hot plate assembly.

Identification of an Extremely 180-Rich Presolar Silicate Grain in Acfer 094

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Messenger, S.

2009-01-01

Presolar silicate grains have been abundantly identified since their first discovery less than a decade ago [1,2,3]. The O isotopic compositions of both silicate and oxide stardust indicate the vast majority (>90%) condensed around Orich asymptotic giant branch (AGB) stars. Though both presolar phases have average sizes of 300 nm, grains larger than 1 m are extremely uncommon for presolar silicates. Thus, while numerous isotopic systems have been measured in presolar oxide grains [4], very few isotopic analyses for presolar silicates exist outside of O and Si [2,5]. And still, these measurements suffer from isotopic dilution with surrounding matrix material [6]. We conduct a search for presolar silicates in the primitive carbonaceous chondrite Acfer 094 and in some cases obtain high spatial resolution, high precision isotopic ratios.

Melting in super-earths.

PubMed

Stixrude, Lars

2014-04-28

We examine the possible extent of melting in rock-iron super-earths, focusing on those in the habitable zone. We consider the energetics of accretion and core formation, the timescale of cooling and its dependence on viscosity and partial melting, thermal regulation via the temperature dependence of viscosity, and the melting curves of rock and iron components at the ultra-high pressures characteristic of super-earths. We find that the efficiency of kinetic energy deposition during accretion increases with planetary mass; considering the likely role of giant impacts and core formation, we find that super-earths probably complete their accretionary phase in an entirely molten state. Considerations of thermal regulation lead us to propose model temperature profiles of super-earths that are controlled by silicate melting. We estimate melting curves of iron and rock components up to the extreme pressures characteristic of super-earth interiors based on existing experimental and ab initio results and scaling laws. We construct super-earth thermal models by solving the equations of mass conservation and hydrostatic equilibrium, together with equations of state of rock and iron components. We set the potential temperature at the core-mantle boundary and at the surface to the local silicate melting temperature. We find that ancient (∼4 Gyr) super-earths may be partially molten at the top and bottom of their mantles, and that mantle convection is sufficiently vigorous to sustain dynamo action over the whole range of super-earth masses.

Effect of aluminizing of Cr-containing ferritic alloys on the seal strength of a novel high-temperature solid oxide fuel cell sealing glass

NASA Astrophysics Data System (ADS)

Chou, Yeong-Shyung; Stevenson, Jeffry W.; Singh, Prabhakar

A novel high-temperature alkaline earth silicate sealing glass was developed for solid oxide fuel cell (SOFC) applications. The glass was used to join two metallic coupons of Cr-containing ferritic stainless steel for seal strength evaluation. In previous work, SrCrO 4 was found to form along the glass/steel interface, which led to severe strength degradation. In the present study, aluminization of the steel surface was investigated as a remedy to minimize or prevent the strontium chromate formation. Three different processes for aluminization were evaluated with Crofer22APU stainless steel: pack cementation, vapor-phase deposition, and aerosol spraying. It was found that pack cementation resulted in a rough surface with occasional cracks in the Al-diffused region. Vapor-phase deposition yielded a smoother surface, but the resulting high Al content increased the coefficient of thermal expansion (CTE), resulting in the failure of joined coupons. Aerosol spraying of an Al-containing salt resulted in the formation of a thin aluminum oxide layer without any surface damage. The room temperature seal strength was evaluated in the as-fired state and in environmentally aged conditions. In contrast to earlier results with uncoated Crofer22APU, the aluminized samples showed no strength degradation even for samples aged in air. Interfacial and chemical compatibility was also investigated. The results showed aluminization to be a viable candidate approach to minimize undesirable chromate formation between alkaline earth silicate sealing glass and Cr-containing interconnect alloys for SOFC applications.

High-pressure Experimental Studies on Geo-liquids Using Synchrotron Radiation at the Advanced Photon Source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yanbin; Shen, Guoyin

2014-12-23

Here, we review recent progress in studying silicate, carbonate, and metallic liquids of geological and geophysical importance at high pressure and temperature, using the large-volume high-pressure devices at the third-generation synchrotron facility of the Advanced Photon Source, Argonne National Laboratory. These integrated high-pressure facilities now offer a unique combination of experimental techniques that allow researchers to investigate structure, density, elasticity, viscosity, and interfacial tension of geo-liquids under high pressure, in a coordinated and systematic fashion. Moreover, we describe experimental techniques, along with scientific highlights. Future developments are also discussed.

Process for the preparation of methane and/or ethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagstaff, N.

1981-09-22

According to Shell, methane and ethane can be produced from a C/sub 2/-C/sub 4/ paraffin feed stream (such as the by-product of mineral-oil production) by contacting the stream with certain crystalline silicates at temperatures of 800/sup 0/-1200/sup 0/F and 145 psi pressure. The crystalline silicates must be specially prepared to obtain the required characteristics.

Melt inclusions in veins: linking magmas and porphyry Cu deposits.

PubMed

Harris, Anthony C; Kamenetsky, Vadim S; White, Noel C; van Achterbergh, Esmé; Ryan, Chris G

2003-12-19

At a porphyry copper-gold deposit in Bajo de la Alumbrera, Argentina, silicate-melt inclusions coexist with hypersaline liquid- and vapor-rich inclusions in the earliest magmatic-hydrothermal quartz veins. Copper concentrations of the hypersaline liquid and vapor inclusions reached maxima of 10.0 weight % (wt %) and 4.5 wt %, respectively. These unusually copper-rich inclusions are considered to be the most primitive ore fluid found thus far. Their preservation with coexisting melt allows for the direct quantification of important oreforming processes, including determination of bulk partition coefficients of metals from magma into ore-forming magmatic volatile phases.

Investigation on the thermo-chemical reaction mechanism between yttria-stabilized zirconia (YSZ) and calcium-magnesium-alumino-silicate (CMAS)

NASA Astrophysics Data System (ADS)

Zhang, Dong-Bo; Wang, Bin-Yi; Cao, Jian; Song, Guan-Yu; Liu, Juan-Bo

2015-03-01

Thermal barrier coatings (TBCs) with Y2O3-stabilized ZrO2 (YSZ) top coat play a very important role in advanced turbine blades by considerably increasing the engine efficiency and improving the performance of highly loaded blades. However, at high temperatures, environment factors result in the failure of TBCs. The influence of calcium-magnesium-alumino-silicate (CMAS) is one of environment factors. Although thermo-physical effect is being paid attention to, the thermo-chemical reaction becomes the hot-spot in the research area of TBCs affected by CMAS. In this paper, traditional twolayered structured TBCs were prepared by electron beam physical vapor deposition (EBPVD) as the object of study. TBCs coated with CMAS were heated at 1240°C for 3 h. Additionally, 15 wt.% simulated molten CMAS powder and YSZ powder were mixed and heated at 1240°C or 1350°C for 48 h. SEM and EDS were adopted to detect morphology and elements distribution. According to XRD and TEM results, it was revealed that CMAS react with YSZ at high temperature and form ZrSiO4, Ca0.2Zr0.8O1.8 and Ca0.15Zr0.85O1.85 after reaction, as a result, leading to the failure of TBCs and decreasing the TBC lifetime.

The effects of sulfur on carbon partitioning and solubility in high pressure-temperature alloy-silicate systems: Implications for fractionation of carbon and sulfur during accretion and core formation of Earth and Mars

NASA Astrophysics Data System (ADS)

Tsuno, K.; Dasgupta, R.; Grewal, D. S.

2017-12-01

Constraining the carbon (C) fractionation between the silicate magma ocean (MO) and core-forming alloy liquid is required to determine the origin and evolution of C between reservoirs such as atmosphere, crust, mantle, and core of terrestrial planets. [1]. Alloy-silicate partitioning experiments of C have shown that preferential fractionation of C into the alloy liquid would have left the bulk silicate Earth (BSE) devoid of C [2-4]. Merger of a sulfur (S)-rich differentiated planetary embryo into the proto-Earth could have supplied almost the entire C budget of the present-day BSE [5], however, experimental data on the systematic effect of S on C solubility in Fe-Ni alloy liquid and its partitioning between the alloy liquid and silicate melt are lacking. We have performed multi anvil experiments with alloy-silicate±glassy carbon mixtures at 6-13 GPa and 1800-2000 °C, fO2 of ΔIW of -0.4 to -2.3, using graphite or MgO capsules and varying alloy S content from 10 to 36 wt.%. We find that C content of the alloy liquid decreases from 4.6 to 0.2 wt.% with increasing alloy S content of 10 to 36 wt.%. Temperature has a small positive effect and pressure has little effect on alloy C solubility. Alloy-silicate partition coefficient of C also decreases with increasing alloy S content at a given P-T-fO2. We used the data to quantify the distribution of C between the silicate MO and core-forming alloy liquid of an S-rich planetary embryo. The model calculations using our data suggest that the addition of a relatively oxidized, C-poor ( 0.3 wt.%) and S-rich ( 3 wt.%) large embryo (6-20% of the present-day Earth mass) to a volatile-poor growing Earth can establish the C and S contents [6, 7] and C/S ratio [8] in BSE. The resulting core composition after the accretion and core formation process is estimated to be C- and S-poor ( 0.05 wt.% and 0.6 wt.%, respectively). On the other hand, a single stage core formation on Mars that results in a core with 8-10 wt.% S can yield a mantle with terrestrial-mantle like carbon abundance if the bulk Mars contains 0.6 wt.% C and 1.5-1.7 wt.% S. [1] Dasgupta (2013) RiMG. [2] Dasgupta et al. (2013) GCA. [3] Chi et al. (2014) GCA. [4] Li et al. (2015) EPSL. [5] Li et al. (2016) Nat. Geo. [6] Dasgupta & Hirschmann (2010) EPSL. [7] Palme & O'Neill (2013), Treat. Geochem. [8] Hirschmann (2016) Am Min.

Crack healing in silicon nitride due to oxidation

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Tikare, Veena; Pawlik, Ralph

1991-01-01

The crack healing behavior of a commercial, MgO-containing, hot pressed Si3N4 was studied as a function of temperature in oxidizing and inert annealing environments. Crack healing occurred at a temperature 800 C or higher due to oxidation regardless of crack size, which ranged from 100 microns (indentation crack) to 1.7 mm (SEPB precrack). The resulting strength and apparent fracture toughness increased at crack healing temperature by 100 percent and 300 percent, respectively. The oxide layer present in the crack plane was found to be highly fatigue resistant, indicating that the oxide is not solely silicate glass, but a mixture of glass, enstatite, and/or cristobalite that was insensitive to fatigue in a room temperature water environment.

Glass viscosity calculation based on a global statistical modelling approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fluegel, Alex

2007-02-01

A global statistical glass viscosity model was developed for predicting the complete viscosity curve, based on more than 2200 composition-property data of silicate glasses from the scientific literature, including soda-lime-silica container and float glasses, TV panel glasses, borosilicate fiber wool and E type glasses, low expansion borosilicate glasses, glasses for nuclear waste vitrification, lead crystal glasses, binary alkali silicates, and various further compositions from over half a century. It is shown that within a measurement series from a specific laboratory the reported viscosity values are often over-estimated at higher temperatures due to alkali and boron oxide evaporation during the measurementmore » and glass preparation, including data by Lakatos et al. (1972) and the recently published High temperature glass melt property database for process modeling by Seward et al. (2005). Similarly, in the glass transition range many experimental data of borosilicate glasses are reported too high due to phase separation effects. The developed global model corrects those errors. The model standard error was 9-17°C, with R^2 = 0.985-0.989. The prediction 95% confidence interval for glass in mass production largely depends on the glass composition of interest, the composition uncertainty, and the viscosity level. New insights in the mixed-alkali effect are provided.« less

An early geodynamo driven by exsolution of mantle components from Earth’s core

PubMed Central

Badro, James; Siebert, Julien; Nimmo, Francis

2016-01-01

Terrestrial core formation occurred in the early molten Earth by gravitational segregation of immiscible metal and silicate melts, stripping iron-loving elements from the silicate mantle to the metallic core1–3, and leaving rock-loving components behind. Here we performed experiments showing that at high enough temperature, Earth’s major rock-loving component, magnesium oxide, can also dissolve in core-forming metallic melts. Our data clearly point to a dissolution reaction, and are in agreement with recent DFT calculations4. Using core formation models5, we further show that a high-temperature event during Earth’s accretion (such as the Moon-forming giant impact6) can contribute significant amounts of magnesium to the early core. As it subsequently cools, the ensuing exsolution7 of buoyant magnesium oxide generates a substantial amount of gravitational energy. This energy is comparable to if not significantly higher than that produced by inner core solidification8 — the primary driver of the Earth’s current magnetic field9–11. Since the inner core is too young12 to explain the existence of an ancient field prior to ~1 billion years, our results solve the conundrum posed by the recent paleomagnetic observation13 of an ancient field at least 3.45 Gyr old. PMID:27437583

Pressure effect on Fe3+/FeT in silicate melts and applications to magma redox, particularly in magma oceans

NASA Astrophysics Data System (ADS)

Zhang, H.; Hirschmann, M. M.

2014-12-01

The proportions of Fe3+ and Fe2+ in magmas reflect the redox conditions of their origin and influence the chemical and physical properties of natural silicate liquids, but the relationship between Fe3+/FeT and oxygen fugacity depends on pressure owing to different molar volumes and compressibilities of Fe3+ and Fe2+ in silicates. An important case where the effect of pressure effect may be important is in magma oceans, where well mixed (and therefore potentially uniform Fe3+/FeT) experiencses a wide range of pressures, and therefore can impart different ƒO2 at different depths, influencing magma ocean degassing and early atmospheres, as well as chemical gradients within magma oceans. To investigate the effect of pressure on magmatic Fe3+/FeT we conducted high pressure expeirments on ƒO2-buffered andestic liquids. Quenched glasses were analyzed by Mössbauer spectroscopy. To verify the accuracy of Mössbauer determinations of Fe3+/FeT in glasses, we also conducted low temperature Mössbauer studies to determine differences in the recoilless fraction (ƒ) of Fe2+ and Fe3. These indicate that room temperature Mössbauer determinations of on Fe3+/FeT glasses are systematically high by 4% compared to recoilless-fraction corrected ratios. Up to 7 GPa, pressure decreases Fe3+/FeT, at fixed ƒO2 relative to metal-oxide buffers, meaning that an isochemical magma will become more reduced with decreasing pressure. Consequently, for small planetary bodies such as the Moon or Mercury, atmospheres overlying their MO will be highly reducing, consisting chiefly of H2 and CO. The same may also be true for Mars. The trend may reverse at higher pressure, as is the case for solid peridotite, and so for Earth, Venus, and possibly Mars, more oxidized atmospheres above MO are possible. Diamond anvil experiments are underway to examine this hypothesis.

Oxygen and iron production by electrolytic smelting of lunar soil

NASA Technical Reports Server (NTRS)

Colson, R. O.; Haskin, L. A.

1991-01-01

Oxygen, present in abundance in nearly all lunar materials, can theoretically be extracted by molten silicate electrolysis from any known lunar rock. Derivation of oxygen by this method has been amply demonstrated experimentally in silicate melts of a variety of compositions. This work can be divided into three categories: (1) measurement of solubilities of metals (atomic) in silicate melts; (2) electrolysis experiments under various conditions of temperature, container material, electrode configuration, current density, melt composition, and sample mass (100 to 2000 mg) measuring energy required and character of resulting products; and (3) theoretical assessment of compositional requirements for steady state operations of an electrolysis cell.

Investigation of the stability of Co-doped apatite ionic conductors in NH 3

NASA Astrophysics Data System (ADS)

Headspith, D. A.; Orera, A.; Slater, P. R.; Young, N. A.; Francesconi, M. G.

2010-12-01

Hydrogen powered solid oxide fuel cells (SOFCs) are of enormous interest as devices for the efficient and clean production of electrical energy. However, a number of problems linked to hydrogen production, storage and transportation are slowing down the larger scale use of SOFCs. Identifying alternative fuel sources to act as intermediate during the transition to the full use of hydrogen is, therefore, of importance. One excellent alternative is ammonia, which is produced on a large scale, is relatively cheap and has the infrastructure for storage and transportation already in place. However, considering that SOFCs operate at temperatures higher than 500 °C, a potential problem is the interaction of gaseous ammonia with the materials in the cathode, anode and solid electrolyte. In this paper, we extend earlier work on high temperature reactions of apatite electrolytes with NH 3 to the transition metal (Co) doped systems, La 9.67Si 5CoO 26 and La 10(Si/Ge) 5CoO 26.5. A combination of PXRD, TGA and XAFS spectroscopy data showed a better structural stability for the silicate systems. Apatite silicates and germanates not containing transition metals tend to substitute nitride anions for their interstitial oxide anions, when reacted with NH 3 at high temperature and, consequentially, lower the interstitial oxide content. In La 9.67Si 5CoO 26 and La 10(Si/Ge) 5CoO 26.5 reduction of Co occurs as a competing process, favouring lower levels of nitride-oxide substitution.

A study of the trace sulfide mineral assemblages in the Stillwater Complex, Montana, USA

NASA Astrophysics Data System (ADS)

Aird, Hannah M.; Ferguson, Katherine M.; Lehrer, Malia L.; Boudreau, Alan E.

2017-03-01

The sulfide assemblages of the Stillwater Complex away from the well-studied ore zones are composed mainly of variable proportions of pyrrhotite, chalcopyrite, pentlandite, and ±pyrite. Excluding vein assemblages and those affected by greenschist and lower temperature alteration, the majority can be classified into two broad assemblages, defined here as pristine (multiphase, often globular in shape) or volatile-bearing (multiphase, high-temperature, volatile-rich minerals such as biotite, hornblende, or an unmixed calcite-dolomite assemblage). The volatile-bearing assemblages are mainly found within and below the J-M reef, where native copper and sphalerite are also locally present. Pristine sulfides are found throughout the stratigraphy. Both groups can be affected by apparent S loss in the form of pyrite being converted to magnetite and chalcopyrite to a Cu-Fe-oxide (delafossite), with little to no silicate alteration. An upward trend from pentlandite-rich to pyrrhotite-rich to pyrite-rich assemblages is observed in the footwall rocks in upper GN-I, and the same trend repeats from just below the reef and continues into the overlying N-II and GN-II. Modeling suggests that the sulfide Ni in the Peridotite Zone is largely controlled by silicate Ni. When taken together, observations are most readily explained by the remobilization of selected elements by a high-temperature fluid with the apparent loss of S > Cu > Ni. This could concentrate ore metals by vapor refining, eventually producing a platinum group element-enriched sulfide ore zone, such as the J-M reef.

Metastable Eutectic Equilibrium in Natural Environments: Recent Developments and Research Opportunities

NASA Technical Reports Server (NTRS)

Rietmeijer, Fans J. M.; Nuth, Joseph A., II; Jablonska, Mariola; Karner, James M.

2000-01-01

Chemical ordering at metastable eutectics was recognized in non-equilibrium gas-to- solid condensation experiments to constrain 'silicate' dust formation in O-rich circumstellar environments. The predictable metastable eutectic behavior successfully predicted the observed ferromagnesiosilica, compositions of circumstellar dust, presolar and solar nebula grains in the matrix of the collected aggregate IDPs. Many of the experimentally determined metastable eutectic solids match the fundamental building blocks of common rock-forming layer silicates: this could have implications for the origin of Life. The physical conditions conducive to metastable eutectic behavior, i.e. high temperature and (ultra)fast quenching, lead to unique amorphous, typically nano- to micrometer-sized, materials. The new paradigm of metastable eutectic behavior opens the door to new and exciting research opportunities in uncovering the many implications of these unique amorphous and typically nano- to micrometer-sized, metastable eutectic materials.

Ternary Phase-Separation Investigation of Sol-Gel Derived Silica from Ethyl Silicate 40

PubMed Central

Wang, Shengnan; Wang, David K.; Smart, Simon; Diniz da Costa, João C.

2015-01-01

A ternary phase-separation investigation of the ethyl silicate 40 (ES40) sol-gel process was conducted using ethanol and water as the solvent and hydrolysing agent, respectively. This oligomeric silica precursor underwent various degrees of phase separation behaviour in solution during the sol-gel reactions as a function of temperature and H2O/Si ratios. The solution composition within the immiscible region of the ES40 phase-separated system shows that the hydrolysis and condensation reactions decreased with decreasing reaction temperature. A mesoporous structure was obtained at low temperature due to weak drying forces from slow solvent evaporation on one hand and formation of unreacted ES40 cages in the other, which reduced network shrinkage and produced larger pores. This was attributed to the concentration of the reactive sites around the phase-separated interface, which enhanced the condensation and crosslinking. Contrary to dense silica structures obtained from sol-gel reactions in the miscible region, higher microporosity was produced via a phase-separated sol-gel system by using high H2O/Si ratios. This tailoring process facilitated further condensation reactions and crosslinking of silica chains, which coupled with stiffening of the network, made it more resistant to compression and densification. PMID:26411484

Legionella feeleii: an unusual organism associated with cutaneous infection in an immunocompromised patient.

PubMed

Verykiou, S; Goodhead, C; Parry, G; Meggitt, S

2018-04-01

We report a 23-year-old immunocompromised woman who, following cardiac transplantation, presented with an unusual cutaneous eruption. She developed a widespread pustular rash, systemic symptoms and a high temperature with raised inflammatory markers. The diagnosis was reached when a skin biopsy was cultured onto Legionella agar (buffered charcoal yeast extract) and Legionella feeleii was isolated. The patient was treated with 6 weeks of moxifloxacin and her cutaneous lesions gradually resolved. Cutaneous Legionella infections are uncommon and usually affect immunocompromised patients. © 2017 British Association of Dermatologists.

Development of aircraft brake materials. [evaluation of metal and ceramic materials in sliding tests simulation of aircraft braking

NASA Technical Reports Server (NTRS)

Ho, T. L.; Peterson, M. B.

1974-01-01

The requirements of brake materials were outlined and a survey made to select materials to meet the needs of high temperature brakes. A number of metals and ceramic materials were selected and evaluated in sliding tests which simulated aircraft braking. Nickel, molybdenum tungsten, Zr02, high temperature cements and carbons were tested. Additives were then incorporated into these materials to optimize their wear or strength behavior with particular emphasis on nickel and molybdenum base materials and a high temperature potassium silicate cement. Optimum materials were developed which improved wear behavior over conventional brake materials in the simulated test. The best materials are a nickel, aluminum oxide, lead tungstate composition containing graphite or molybdenum disulphite; a molybdenum base material containing LPA100 (an intermetallic compound of cobalt, molybdenum, and silicon); and a carbon material (P5).

Chlorite, Biotite, Illite, Muscovite, and Feldspar Dissolution Kinetics at Variable pH and Temperatures up to 280 C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carroll, S.; Smith, M.; Lammers, K.

2016-10-05

Summary Sheet silicates and clays are ubiquitous in geothermal environments. Their dissolution is of interest because this process contributes to scaling reactions along fluid pathways and alteration of fracture surfaces, which could affect reservoir permeability. In order to better predict the geochemical impacts on long-term performance of engineered geothermal systems, we have measured chlorite, biotite, illite, and muscovite dissolution and developed generalized kinetic rate laws that are applicable over an expanded range of solution pH and temperature for each mineral. This report summarizes the rate equations for layered silicates where data were lacking for geothermal systems.

Volatile Element Behavior During Melting and Vaporisation on Earth and Protoplanets.

NASA Astrophysics Data System (ADS)

Wood, B. J.; Norris, C. A.

2017-12-01

During accretion the Earth and many of the smaller bodies which were added to it, underwent periods of partial melting, vaporisation and re-condensation. This resulted in patterns of volatile element depletion relative to CI chondrite which are difficult to interpret. The behavior of moderately volatile elements (Pb, Cd, Zn,Cu, In,Tl etc) during these melting, vaporisation and condensation processes is usually approximated by the temperature of condensation from a gas of solar composition. Thus, Tl and In have low condensation temperatures and are regarded as the most volatile of this group. In order to test this volatility approximation we have studied the vaporisation behavior of 13 elements (Ag,Bi,Cd,Cr,Cu,Ga,Ge,In,Pb,Sb,Sn,Tl,Zn) from molten basalt at 1 atm pressure and oxygen fugacities between Ni-NiO and 2 log units below Fe-FeO. The relative volatilities of the elements turn out to be only weakly correlated with condensation temperature, indicating that the latter is a poor proxy for volatility on molten bodies. Cu, Zn and In for example all have similar volatility in the oxygen fugacity range of concern, despite the condensation temperature of Cu (1037K at 10-4bar) being 500K greater than that of In. The oxygen fugacity dependence of volatility indicates that the volatile species are, for all elements more reduced than the melt species. We addressed the differences between condensation temperature and relative volatility in 2 steps. Firstly we used metal-silicate partitioning experiments to estimate the activity coefficients of the trace element oxides in silicate melts. We then used available thermodynamic data to compute the vapor pressures of the stable species of these 13 elements over the silicate melt at oxygen fugacities ranging from Ni-NiO to about 6 log units below Fe-FeO, which approximates the solar gas. Thus we find that presence of Cl and S in the solar gas and the stable Cl and S species of In,Tl Ga Ge Cd and Sn are important contributing factors to volatility in the solar nebula. Our measured volatilities from silicate melt under reducing (S and Cl-absent) conditions are consistent with abundances in the silicate Earth, indicating that these moderately volatile elements were added to Earth in bodies which had undergone episodes of melting and vaporisation.

Major ion chemistry in the headwaters of the Yamuna river system:. Chemical weathering, its temperature dependence and CO 2 consumption in the Himalaya

NASA Astrophysics Data System (ADS)

Dalai, T. K.; Krishnaswami, S.; Sarin, M. M.

2002-10-01

The Yamuna river and its tributaries in the Himalaya constitute the Yamuna River System (YRS). The YRS basin has a drainage area and discharge comparable in magnitude to those of the Bhagirathi and the Alaknanda rivers, which merge to form the Ganga at the foothills of the Himalaya. A detailed geochemical study of the YRS was carried out to determine: (i) the relative significance of silicate, carbonate and evaporite weathering in contributing to its major ion composition; (ii) CO 2 consumption via silicate weathering; and (iii) the factors regulating chemical weathering of silicates in the basin. The results show that the YRS waters are mildly alkaline, with a wide range of TDS, ˜32 to ˜620 mg l-1. In these waters, the abundances of Ca, Mg and alkalinity, which account for most of TDS, are derived mainly from carbonates. Many of the tributaries in the lower reaches of the Yamuna basin are supersaturated with calcite. In addition to carbonic acid, sulphuric acid generated by oxidation of pyrites also seems to be supplying protons for chemical weathering. Silicate weathering in YRS basin contributes, on average, ˜25% (molar basis) of total cations on a basin wide scale. Silicate weathering, however, does not seem to be intense in the basin as evident from low Si/(Na*+K) in the waters, ˜1.2 and low values of chemical index of alteration (CIA) in bed sediments, ˜60. CO 2 drawdown resulting from silicate weathering in the YRS basin in the Himalaya during monsoon ranges between (4 to 7) × 10 5 moles km -2 y -1. This is higher than that estimated for the Ganga at Rishikesh for the same season. The CO 2 consumption rates in the Yamuna and the Ganga basins in the Himalaya are higher than the global average value, suggesting enhanced CO 2 drawdown in the southern slopes of the Himalaya. The impact of this enhanced drawdown on the global CO 2 budget may not be pronounced, as the drainage area of the YRS and the Ganga in the Himalaya is small. The CO 2 drawdown by silicates in the YRS basin is marginally higher than the reported values of CO 2 release from oxidation of organic rich sediments, estimated using Re as a proxy. This comparison shows the need to constrain CO 2 sources and sinks better to balance its budget in a regional scale. The results also show that silicate weathering rate in the YRS basin is ˜10 mm ky -1 and on the Ganga basin, it is ˜5 mm ky -1, which are several times lower than the carbonate weathering rates. The significantly higher silicate weathering rate observed in the YRS basin seems to be governed by rapid physical erosion in this region. The apparent activation energy for overall silicate weathering in the YRS basin, derived from Na* and Si concentrations and water temperature, ranges from ˜50 to 80 kJ mol -1. These values are comparable to those reported for granitoid weathering in natural watersheds and feldspar weathering in laboratory experiments. This study brings to light the sources contributing to major ions, enhanced chemical weathering rates in the Yamuna River Basin and interdependence of silicate weathering on physical erosion and temperature.

Recent and future warm extreme events and high-mountain slope stability.

PubMed

Huggel, C; Salzmann, N; Allen, S; Caplan-Auerbach, J; Fischer, L; Haeberli, W; Larsen, C; Schneider, D; Wessels, R

2010-05-28

The number of large slope failures in some high-mountain regions such as the European Alps has increased during the past two to three decades. There is concern that recent climate change is driving this increase in slope failures, thus possibly further exacerbating the hazard in the future. Although the effects of a gradual temperature rise on glaciers and permafrost have been extensively studied, the impacts of short-term, unusually warm temperature increases on slope stability in high mountains remain largely unexplored. We describe several large slope failures in rock and ice in recent years in Alaska, New Zealand and the European Alps, and analyse weather patterns in the days and weeks before the failures. Although we did not find one general temperature pattern, all the failures were preceded by unusually warm periods; some happened immediately after temperatures suddenly dropped to freezing. We assessed the frequency of warm extremes in the future by analysing eight regional climate models from the recently completed European Union programme ENSEMBLES for the central Swiss Alps. The models show an increase in the higher frequency of high-temperature events for the period 2001-2050 compared with a 1951-2000 reference period. Warm events lasting 5, 10 and 30 days are projected to increase by about 1.5-4 times by 2050 and in some models by up to 10 times. Warm extremes can trigger large landslides in temperature-sensitive high mountains by enhancing the production of water by melt of snow and ice, and by rapid thaw. Although these processes reduce slope strength, they must be considered within the local geological, glaciological and topographic context of a slope.

Measurements of the Activity of dissolved H2O in an Andesite Melt

NASA Astrophysics Data System (ADS)

Moore, G. M.; Touran, J. P.; Pu, X.; Kelley, K. A.; Cottrell, E.; Ghiorso, M. S.

2016-12-01

The large effect of dissolved H2O on the physical and chemical nature of silicate melts, and its role in driving volcanism, is well known and underscores the importance of this volatile component. A complete understanding of the chemical behavior of dissolved H2O in silicate melts requires the quantification of its thermodynamic activity as a function of pressure, temperature, and melt composition, particularly at low H2O contents (i.e. at under-saturated conditions). Knowledge of the activity of H2O in silicate melts at H2O-undersaturated conditions will improve our understanding of hydrous phase equilibria, as well as our models of physical melt properties. Measurement of the activity of any silicate melt component, much less that of a volatile component such as H2O, is a difficult experimental task however. By using a modified double capsule design (Matjuschkin et al, 2015) to control oxygen fugacity in piston cylinder experiments, along with high precision X-ray absorption techniques (XANES) to measure iron oxidation state in silicate glasses (Cottrell et al, 2009), we are able to constrain the H2O activity in silicate melts at under-saturated conditions. Preliminary results on an andesite melt with low H2O content (3 wt%) have been shown (Moore et al, 2016) to match predicted H2O activity values calculated using the H2O equation of state of Duan and Zhang (1996) and the H2O solubility model of Ghiorso and Gualda (2015). More recent results on the same andesite melt containing approximately 5 wt% H2O however show a large negative deviation from the predicted values. Reversal experiments involving an oxidized starting material are ongoing, as well as further characterization of the samples to detect the presence of possible contaminants that would induce reduction of the melt beyond that related to the H2O activity (e.g. graphite contamination).

Melting and vibrational properties of planetary materials under deep Earth conditions

NASA Astrophysics Data System (ADS)

Jackson, Jennifer

2013-06-01

The large chemical, density, and dynamical contrasts associated with the juxtaposition of a liquid iron-dominant alloy and silicates at Earth's core-mantle boundary (CMB) are associated with a rich range of complex seismological features. For example, seismic heterogeneity at this boundary includes small patches of anomalously low sound velocities, called ultralow-velocity zones. Their small size (5 to 40 km thick) and depth (about 2800 km) present unique challenges for seismic characterization and geochemical interpretation. In this contribution, we will present recent nuclear resonant inelastic x-ray scattering measurements on iron-bearing silicates, oxides, and metals, and their application towards our understanding of Earth's interior. Specifically, we will present measurements on silicates and oxide minerals that are important in Earth's upper and lower mantles, as well as iron to over 1 megabar in pressure. The nuclear resonant inelastic x-ray scattering method provides specific vibrational information, e.g., the phonon density of states, and in combination with compression data permits the determination of sound velocities and other vibrational information under high pressure and high temperature. For example, accurate determination of the sound velocities and density of chemically complex Earth materials is essential for understanding the distribution and behavior of minerals and iron-alloys with depth. The high statistical quality of the data in combination with high energy resolution and a small x-ray focus size permit accurate evaluation of the vibrational-related quantities of iron-bearing Earth materials as a function of pressure, such as the Grüneisen parameter, thermal pressure, sound velocities, and iron isotope fractionation quantities. Finally, we will present a novel method detecting the solid-liquid phase boundary of compressed iron at high temperatures using synchrotron Mössbauer spectroscopy. Our approach is unique because the dynamics of the iron atoms are monitored. This process is described by the Lamb-Mössbauer factor, which is related to the mean-square displacement of the iron atoms. We will discuss the implications of our results as they relate to Earth's core and core-mantle boundary regions.

An Exceptionally Narrow Band-Gap (∼4 eV) Silicate Predicted in the Cubic Perovskite Structure: BaSiO3.

PubMed

Hiramatsu, Hidenori; Yusa, Hitoshi; Igarashi, Ryo; Ohishi, Yasuo; Kamiya, Toshio; Hosono, Hideo

2017-09-05

The electronic structures of 35 A 2+ B 4+ O 3 ternary cubic perovskite oxides, including their hypothetical chemical compositions, were calculated by a hybrid functional method with the expectation that peculiar electronic structures and unique carrier transport properties suitable for semiconductor applications would be hidden in high-symmetry cubic perovskite oxides. We found unique electronic structures of Si-based oxides (A = Mg, Ca, Sr, and Ba, and B = Si). In particular, the unreported cubic BaSiO 3 has a very narrow band gap (4.1 eV) compared with conventional nontransition-metal silicates (e.g., ∼9 eV for SiO 2 and the calculated value of 7.3 eV for orthorhombic BaSiO 3 ) and a small electron effective mass (0.3m 0 , where m 0 is the free electron rest mass). The narrow band gap is ascribed to the nonbonding state of Si 3s and the weakened Madelung potential. The existence of the predicted cubic perovskite structure of BaSiO 3 was experimentally verified by applying a high pressure of 141 GPa. The present finding indicates that it could be possible to develop a new transparent oxide semiconductor of earth abundant silicates if the symmetry of its crystal structure is appropriately chosen. Cubic BaSiO 3 is a candidate for high-performance oxide semiconductors if this phase can be stabilized at room temperature and ambient pressure.

Slag of Greek provenance uses in materials science and geophysics: implications for a highly potential material in the service of the development of Greek economy

NASA Astrophysics Data System (ADS)

Leontakianakos, G.; Baziotis, I.; Sotiriadis, K.; Goulas, G.; Liakopoulos, S.; Karastathis, V.

2012-04-01

Ground granulated blast-furnace slag (GGBS) is a secondary raw material that can be used as an alternative low energy binder. Hydraulic properties can be occurred through its alkali activation. GGBS is characterized by the glassy to crystalline ratio and by its chemical and mineralogical composition. Acidic slag cannot easily get crystallized in oppose to the basic one. Crystalline phases show very low reactivity with Ca(OH)2, while amorphous phases can easily react in the presence of basic substances. The aim of the present study was to study the evolution of new advanced silicate materials presenting high durability at high temperature environments. Specimens were produced using two types of slag of Greek origin. The first type was a ferrous slag, while the second one was calcareous. Their maximum particle size was 4 mm and 0.07 mm respectively. Specimens were prepared using the above slag types and siliceous sand as an aggregate. Sand was divided according to European Standard EN 196-1 in three fractions: PG1 (1

Synthesis and re-investigation of the elastic properties of single-crystal magnesium silicate perovskite

NASA Astrophysics Data System (ADS)

Yeganeh-Haeri, Amir

1994-12-01

Single crystals of MgSiO3 in the perovskite structure have been grown at a peak pressure of 26 GPa and temperature of approximately 1600 K using a 2000 ton uniaxial split-sphere high-pressure apparatus (USSA-2000). The specimens were subsequently utilized to re-investigate the single-crystal elastic properties of this phase at ambient conditions using laser Brillouin spectroscopy. The nine adiabatic single-crystal elastic stiffness coefficients, in units of GPa, are: C11 = 482, C22 = 537, C33 = 485, C44 = 204, C55 = 186, C66 = 147, C12 = 144, C13 = 147, C23 = 146. The resulting estimated Voigt-Reuss-Hill (VRH) aggregate isotropic elastic moduli are: K=264.0 and mu = 177.3 GPa, respectively. The single-crystal elastic moduli of MgSiO3 perovskite display a pattern that is elastically somewhat anisotropic. The maximum shear and compressional velocities are 18% and 7% greater than the minimum. The (010) crystallographic direction contains both the fastest and the slowest shear wave velocities. If, under lower mantle conditions, magnesium silicate perovskite grains were to become preferentially oriented, a shear wave propagating in the Earth's lower mantle could become polarized with two distinct velocities. The observed density and seismic parameter of the lower mantle over the depth range of 1000-2700 km are compared with the calculated profiles for a model mantle consisting of pure perovskite (Mg(0.89)Fe(0.11))SiO3 and for a mixture composed of silicate perovskite and magnesiowuestite using our new elasticity results. At present, literature values of thermoelastic properties for silicate perovskite, in particular, the coefficient of thermal expansion and the temperature derivative of the isothermal bulk modulus, vary widely. Because of this disparity, we find that mantle models ranging from pure perovskite to 'pyrolitic'-type compositions provide acceptable fits to the seismically observed density and velocity profiles of the Earth's lower mantle.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blanchard, I.; Badro, J.; Siebert, J.

We present gallium concentration (normalized to CI chondrites) in the mantle is at the same level as that of lithophile elements with similar volatility, implying that there must be little to no gallium in Earth's core. Metal-silicate partitioning experiments, however, have shown that gallium is a moderately siderophile element and should be therefore depleted in the mantle by core formation. Moreover, gallium concentrations in the mantle (4 ppm) are too high to be only brought by the late veneer; and neither pressure, nor temperature, nor silicate composition has a large enough effect on gallium partitioning to make it lithophile. Wemore » therefore systematically investigated the effect of core composition (light element content) on the partitioning of gallium by carrying out metal–silicate partitioning experiments in a piston–cylinder press at 2 GPa between 1673 K and 2073 K. Four light elements (Si, O, S, C) were considered, and their effect was found to be sufficiently strong to make gallium lithophile. The partitioning of gallium was then modeled and parameterized as a function of pressure, temperature, redox and core composition. A continuous core formation model was used to track the evolution of gallium partitioning during core formation, for various magma ocean depths, geotherms, core light element contents, and magma ocean composition (redox) during accretion. The only model for which the final gallium concentration in the silicate Earth matched the observed value is the one involving a light-element rich core equilibrating in a FeO-rich deep magma ocean (>1300 km) with a final pressure of at least 50 GPa. More specifically, the incorporation of S and C in the core provided successful models only for concentrations that lie far beyond their allowable cosmochemical or geophysical limits, whereas realistic O and Si amounts (less than 5 wt.%) in the core provided successful models for magma oceans deeper that 1300 km. In conclusion, these results offer a strong argument for an O- and Si-rich core, formed in a deep terrestrial magma ocean, along with oxidizing conditions.« less

The Sm-Nd systematics of silicate inclusions in iron meteorites: Results from Caddo (IAB)

NASA Technical Reports Server (NTRS)

Stewart, Brian W.; Papanastassiou, D. A.; Wasserburg, G. J.

1993-01-01

The timing of events leading to the formation of silicate-rich and metal-rich regions in planetesimals remains an important problem in the study of planetary formation and differentiation in the early solar system. The IAB irons are especially important as they are considered to represent a magmatic differentiation series. Iron meteorites present a particular challenge for chronological studies, due to the relative paucity of phases serving as hosts for radioactive parent-daughter nuclides. Recent work using the Re-Os system, following on the pioneering work by Herr et al. and Luck and Allegre, appears promising, but investigators up to now have concentrated on whole rock isochrons. Silicate clasts enclosed within iron meteorites can provide information about the chronology and thermal history of irons. Extensive work on Rb-Sr, K-Ar, and I-Xe has been reported on silicate inclusions in iron meteorites. We report the initial results from our Sm-Nd study of an inclusion with the Caddo IAB iron, the first Sm-Nd isotopic study of a silicate clast embedded within an iron meteorite. Our results include measurements of the standard long-lived Sm-147/Nd-143 (tau = 152 AE) system, as well as the shorter-lived SM-146/Nd-142 (tau = 0.149 AE) system, which has been shown to be very useful in deciphering the history of the early solar system. The Caddo silicate clast was described by Palme et al., who kindly provided us with a major part of the inclusion. The inclusion is coarse-grained consisting predominantly of olivine, clinopyroxene, and plagioclase, with lesser amounts of orthopyroxene, Fe-Ni metal, sulfide, and phosphate. The relatively large grain size (up to 3 mm) and 120 degree grain boundaries suggest extensive metamorphism at high temperatures. Based on study of a thin section, there is evidence for metal invading along grain boundaries in some regions of the inclusion, suggesting that the Fe-Ni metal was molten when the silicate clast was incorporated. Metamorphic recrystallization may have occurred during this event.

Brillouin-scattering studies of K2Si4O9 glass and melt up to 1000 °C

NASA Astrophysics Data System (ADS)

Xu, Ji-An; Manghnani, Murli H.; Richet, Pascal

1992-10-01

The Brillouin-scattering technique has been used with glass plate samples and with glass sandwich assemblies to measure the acoustic velocities of K2Si4O9 glass as a function of temperature up to 1000 °C. Results differ from those of the sodium silicate glass reported earlier in that the turning points of the velocity versus temperature curves for the potassium silicate glass are found not only at the strain point (466 °C) but also at the softening point (720 °C). Combined with the results of the 90° platelet- and 180° back-scattering geometry measurements, the refractive index n and equation of state of the glass and melt as a function of temperature were also determined.

Magma Electrolysis: An update

NASA Technical Reports Server (NTRS)

Colson, Russell O.; Haskin, Larry A.

1991-01-01

Electrolytic extraction of O2 from molten lunar soil is conceptually simple and thus a candidate process for producing O2 on the Moon. Possible container and electrode materials are being tested for durability in corrosive high-temperature silicate melts and looking for complications that might increase energy requirements. Gaseous oxygen is being produced by electrolysis of 1-2 gram quantities of silicate melts in spinel (MgAl2O4) crucibles; in these melts, spinel is a stable phase. The concentration of FeO was kept low because FeO decrease O2 production efficiency. Platinum electrodes were placed about 0.5 cm apart in the melt. The spinel crucible was still intact after 40 minutes of electrolysis, when the experiment was halted for examination. The Pt anode was also intact; its Pt was maintained in a dynamci state in which the anode was continuously oxidized but quickly reduced again by the silicate melt, inhibiting migration of Pt away from the anode. In melts with low concentrations of Al2O3 + SiO2 (2 wt percent), the energy of resistance heating was only approximately equal to 10 to 20 percent of the theoretical amount required to produce O2. In melts substantially more concentrated in Al2O3 + SiO2, higher melt viscosity resulted in frothing that, in the worst case, caused high enough melt resistivities to raise the energy requirements to nearly 10 times theoretical. Both Fe and Si are produced at the cathode; in iron-rich melts, a- and c-iron and molten ferrosilicon were observed. Production was also observed at the cathode of a previously unrecognized gas; which is not yet identified. The solubility of metallic species was measured in silicate melts. They are too low to reduce significantly the efficiency of O2 production.

Spade: An H Chondrite Impact-melt Breccia that Experienced Post-shock Annealing

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Jones, Rhian H.

2006-01-01

The low modal abundances of relict chondrules (1.8 Vol%) and of coarse (i.e. >= 2200 micron-size) isolated mafic silicate grains (1.8 Vol%) in Spade relative to mean H6 chondrites (11.4 and 9.8 vol%, respectively) show Spade to be a rock that has experienced a significant degree of melting. Various petrographic features (e.g., chromite-plagioclase assemblages, chromite veinlets, silicate darkening) indicate that melting was caused by shock. Plagioclase was melted during the shock event and flowed so that it partially to completely surrounded nearby mafic silicate grains. During crystallization, plagioclase developed igneous zoning. Low-Ca pyroxene that crystallized from the melt (or equilibrated with the melt at high temperatures) acquired relatively high amounts of CaO. Metallic Fe-Ni cooled rapidly below the Fe-Ni solws and transformed into martensite. Subsequent reheating of the rock caused transformation of martensite into abundant duplex plessite. Ambiguities exist in the shock stage assignment of Spade. The extensive silicate darkening, the occurrence of chromite-plagioclase assemblages, and the impact-melted characteristics of Spade are consistent with shock stage S6. Low shock (stage S2) is indicated by the undulose extinction and lack of planar fractures in olivine. This suggests that Spade reached a maximum prior shock level equivalent to stage S6 and then experienced post-shock annealing (probably to stage Sl). These events were followed by a less intense impact that produced the undulose extinction in the olivine, characteristic of shock stage S2. Annealing could have occurred if Spade were emplaced near impact melts beneath the crater floor or deposited in close proximity to hot debris within an ejecta blanket. Spade firmly establishes the case for post-shock annealing. This may have been a common process on ordinary chondrites (OC) asteroids.

In situ insights to Se (S) partitioning between silicate and metallic melts at extreme conditions

NASA Astrophysics Data System (ADS)

Borchert, M.; Petitgirard, S.; Appel, K.; Watenphul, A.; Morgenroth, W.

2012-12-01

The Earth's core mainly consists of a metallic Fe-Ni mixture. However, seismic observations show that the density is about 5-10% lower than expected for an Fe-Ni alloy under similar pressure and temperature conditions (e.g., [1,2]). This discovery initiated numerous studies to identify and quantify light elements in the Earth0s core. Among others, sulphur has been suggested to be a promisingly candidate to alloy with the metallic core because of its depletion in the crust and the mantle relative to other volatile elements by several orders of magnitude (e.g., [3-5]). In the last decades, several experimental studies have aimed to quantify the sulphur content in the Earth's core and to determine its influence on the physical properties (e.g., [6]). However, experimental data on sulphur partitioning between silicate and metallic liquids at pressures and temperatures relevant for core-mantle boundary conditions are missing. This lack is due to pressure and temperature limitations of conventional experimental approaches (up to 25 GPa and 2200 K). New developments, like laser-heated diamond-anvil cells (LDAC), allow studies at core-mantle boundary conditions, but in-situ chemical analysis of sulphur in LDACs is impossible due to the high absorption of S fluorescence in the diamonds. Instead of sulphur, selenium can be used to model sulphur partitioning between silicate and metallic melts at elevated PT conditions. This is based on the fact that sulphur and selenium can be considered as geochemical twins ([7,8]). The main advantage of this approach is the much higher excitation energy of selenium compared to sulphur, which enables in-situ XRF analysis in LDACs. Here, we present preliminary data on Se partitioning between silicate and metallic melt at extreme conditions. The experiments have been performed in double-sided laser-heated LDACs at the high pressure beamlines P02.2 (DESY, Germany) and ID27 (ESRF, France) as described in [9]. Micro-XRF mappings are used to visualise changes of the Se distribution before and after laser heating. Micro-XRD is used to determine the experimental pressure, the onset of melting and also provides information on distribution of high-pressure / high temperature phases (XRD map). In order to fully apply the observed in-situ Se results to the S partitioning, the recovered samples will be additionally analysed ex-situ for Se and S by EMP, SEM and HRTEM. This will also set constraints on the effect of quenching. [1] Birch (1952) J. Geophys. Res. 57, 227-286. [2] McDonough (2003) Treatise on Geochemistry, Vol. 2, pp. 547-568. [3] Manson (1966) Nature 211, 616-618. [4] Rama Murthy and Hall (1970) Phys. Earth. Planet. Inter. 2, 276-282. [5] Dreibus and Palme (1996) Geochim. Cosmochim Acta. 60, 1125-1130. [6] Morard et al. (2008) Earth. Planet Sci Lett. 272, 620-626. [7] Jenner et al. (2009) Geostand. Geoanal. Res. 33, 309-317. [8] Wykes et al. (2010) Ontario Geological Survey, Miscellaneous Release-Data 269. [9] Petitgirard et al. (2012) Rev. Sci. Instrum. 83, 013904.

Scaling effects in sodium zirconium silicate phosphate (Na 1+ xZr 2Si xP 3- xO 12) ion-conducting thin films

DOE PAGES

Ihlefeld, Jon F.; Gurniak, Emily; Jones, Brad H.; ...

2016-05-04

Preparation of sodium zirconium silicate phosphate (NaSICon), Na 1+xZr 2Si xP 3–xO 12 (0.25 ≤ x ≤ 1.0), thin films has been investigated via a chemical solution approach on platinized silicon substrates. Increasing the silicon content resulted in a reduction in the crystallite size and a reduction in the measured ionic conductivity. Processing temperature was also found to affect microstructure and ionic conductivity with higher processing temperatures resulting in larger crystallite sizes and higher ionic conductivities. The highest room temperature sodium ion conductivity was measured for an x = 0.25 composition at 2.3 × 10 –5 S/cm. In conclusion, themore » decreasing ionic conductivity trends with increasing silicon content and decreasing processing temperature are consistent with grain boundary and defect scattering of conducting ions.« less

Water Solubility in the Proto-Lunar Disk

NASA Astrophysics Data System (ADS)

Hauri, E. H.; Nakajima, M.

2016-12-01

The giant impact model is the scenario most widely accepted for the origin of the Moon, yet no satisfactory version of this model exists to explain the Earth-like H2O content of primitive lunar magmas. Here we investigate the likelihood that H2O from the Earth was transferred to the Moon in the aftermath of the giant impact. Nearly all variants of the giant impact model produce an energetic impact-generated debris disk that eventually coalesces to form the Moon [1]. Here we investigate the behavior of H2O in disks of Bulk Silicate Earth (BSE) composition produced by three impact scenarios; (a) the standard model of a Mars-sized impactor striking the proto-Earth [2]; (b) impact into a fast-spinning Earth [3]; and (c) impact of two sub-earths each being half the mass of the current Earth [4]. All of these models have been shown to be sufficiently energetic that, at maximum entropy and hydrostatic equilibrium following the impact, most of the mass of the proto-lunar disk consists of silicate melt and vapor, with vapor mass fractions ranging from 20-100% and mid-plane temperatures of 3500-6000K [1]. From these models, we calculate the 2D axisymmetric pressure structure of the disk, and calculate the solubility of H2O in liquid droplets that condense from the vapor atmosphere. Assuming a high bulk Earth H2O content of 1000 ppm, at the Roche radius and close to the disk midplane where pressures are highest (1 to 1000 bars), the mass fraction of all H-bearing species in the vapor is calculated to be ≤0.001, and the maximum H2O solubility in silicate melt is predicted to be <50 ppm because most of the water is dissociated at these high temperatures, in agreement with [5]. As the disk cools past the condensation of silicate vapor, the remaining vapor is dominated by Na and similarly volatile elements, with H2O a minor component of the vapor phase from 2500-1000K. The calculated vapor pressures are low at the midplane with strong vertical gradients, and thus calculated H2O solubility ranges widely, from <10 to 100s of ppm. The water content of forming moonlets is thus sensitive to the disk temperature where the moonlets form as the disk cools. [1] Nakajima & Stevenson (2014) Icarus 233:259-267. [2] Canup (2008) Icarus 196:518-538. [3] Cuk & Stewart (2012) Science 338:1047-1052. [4] Canup (2012) Science 338:1052-1055. [5] Pahlevan (2016) EPSL 445:104-113.

Feb 2008 - Feb 2009 Progress Report and Final Report for NA26215: Experimental Studies of High-Energy Processing of Proto-Planetary and Planetary Materials in the Early Solar System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobsen, Stein B.

2009-05-28

The results of this project are the first experimental data on the behavior of metal-silicate mixtures under very high pressures and temperatures comparable to those of the putative Moon-forming impact experienced by Earth in its early history. Probably the most important outcome of this project was the discovery that metal-silicate interaction and equilibration during highly energetic transient events like impacts may be extremely fast and effective on relatively large scale that was not appreciated before. During the course of this project we have developed a technique for trapping supercritical melts produced in our experiments that allows studying chemical phenomena takingmore » place on a nanosecond timescales. Our results shed new light on the processes and conditions existed in the early Earth history, a subject of perennial interest of the humankind. The results of this project also provide important experimental constraints essential for development of the strategy and technology to mitigate imminent asteroid hazard.« less

Volcanic eruptions on Io: Heat flow, resurfacing, and lava composition

NASA Astrophysics Data System (ADS)

Blaney, Diana L.; Johnson, Torrence V.; Matson, Dennis L.; Veeder, Glenn J.

1995-01-01

We model an infrared outburst on Io as being due to a large, erupting lava flow which increased its area at a rate of 1.5 x 105/sq m and cooled from 1225 to 555 K over the 2.583-hr period of observation. The inferred effusion rate of 3 x 105 cu m/sec for this eruption is very high, but is not unprece- dented on the Earth and is similar to the high eruption rates suggested for early lunar volcanism. Eruptions occur approxi- mately 6% of the time on Io. These eruptions provide ample resurfacing to explain Io's lack of impact craters. We suggest that the large total radiometric heat flow, 1014 W, and the size and temperature distribution of the thermal anomalies (McEwen et al. 1992; Veeder et al. 1994) can be accounted for by a series of silicate lava flows in various stages of cooling. We propose that the whole suite of Io's currently observed thermal anomalies was produced by multiple, high-eruptive-rate silicate flows within the past century.

Volcanic eruptions on Io: Heat flow, resurfacing, and lava composition

NASA Technical Reports Server (NTRS)

Blaney, Diana L.; Johnson, Torrence V.; Matson, Dennis L.; Veeder, Glenn J.

1995-01-01

We model an infrared outburst on Io as being due to a large, erupting lava flow which increased its area at a rate of 1.5 x 10(exp 5)/sq m and cooled from 1225 to 555 K over the 2.583-hr period of observation. The inferred effusion rate of 3 x 10(exp 5) cu m/sec for this eruption is very high, but is not unprece- dented on the Earth and is similar to the high eruption rates suggested for early lunar volcanism. Eruptions occur approxi- mately 6% of the time on Io. These eruptions provide ample resurfacing to explain Io's lack of impact craters. We suggest that the large total radiometric heat flow, 10(exp 14) W, and the size and temperature distribution of the thermal anomalies (McEwen et al. 1992; Veeder et al. 1994) can be accounted for by a series of silicate lava flows in various stages of cooling. We propose that the whole suite of Io's currently observed thermal anomalies was produced by multiple, high-eruptive-rate silicate flows within the past century.

VOLATILECALC: A silicate melt-H2O-CO2 solution model written in Visual Basic for excel

USGS Publications Warehouse

Newman, S.; Lowenstern, J. B.

2002-01-01

We present solution models for the rhyolite-H2O-CO2 and basalt-H2O-CO2 systems at magmatic temperatures and pressures below ~ 5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within MicrosoftR Excel (Office'98 and 2000). The series of macros, entitled VOLATILECALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H2O and CO2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H2O and CO2 vapors at magmatic temperatures. The basalt-H2O-CO2 macros in VOLATILECALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar. ?? 2002 Elsevier Science Ltd. All rights reserved.

V OLATILEC ALC: a silicate melt-H 2O-CO 2 solution model written in Visual Basic for excel

NASA Astrophysics Data System (ADS)

Newman, Sally; Lowenstern, Jacob B.

2002-06-01

We present solution models for the rhyolite-H 2O-CO 2 and basalt-H 2O-CO 2 systems at magmatic temperatures and pressures below ˜5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within Microsoft ® Excel (Office'98 and 2000). The series of macros, entitled V OLATILEC ALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H 2O and CO 2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H 2O and CO 2 vapors at magmatic temperatures. The basalt-H 2O-CO 2 macros in V OLATILEC ALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar.

Nanohybrids of magnetic iron-oxide particles in hydrophobic organoclays for oil recovery.

PubMed

Hsu, Ru-Siou; Chang, Wen-Hsin; Lin, Jiang-Jen

2010-05-01

Nanohybrids with magnetic iron-oxide nanoparticles (FeNPs) embedded in the multilayered silicate clay were synthesized by in situ Fe(2+)/Fe(3+) coprecipitation. The natural clay, sodium montmorillonite (Na(+)-MMT), was first modified with hydrophobic poly(oxypropylene)amine salts (POP at 2000 and 4000 g/mol M(w)). The two POP-intercalated organoclays, with a silicate interlayer expansion from 1.2 to 5.2 and 9.2 nm, respectively, are suitable for embedding FeNPs. The presence of POP organics in layered structure created the space for intercalating with FeNPs of 2-4 nm in diameter, observed by transmission electronic microscope. The synthesized nanohybrids of POP4000/MMT-FeNP was composed of 17% iron oxide and 51 wt % POP within the silicate basal spacing of 5.0 nm. In contrast, the lower molecular weight of POP2000 intercalated MMT failed to encapsulate FeNPs in a significant amount, but resulting a "crowding-out effect" that caused the silicate interlayer space to shrink from 5.2 to 1.8 nm because of the replacement of the POP salt by Fe(2+)/Fe(3+) ions. The synthesis required the use of high molecular weight POP4000 and low temperatures (<4 degrees C) for a better dispersion in the reaction medium. The presence of POP in the layered silicate facilitated a homogeneous POP/MMT in water, associating with Fe(2+)/Fe(3+) ions and spatially accommodating for the subsequently generated FeNPs. The synthesized nanostructure consisting of POP and FeNP could be used as a pollutant remedy because of its ability to adsorbing crude oil and it is maneuverable under an applied magnetism.

Fe-Ti oxide geothermometry: thermodynamic formulation and the estimation of intensive variables in silicic magmas

NASA Astrophysics Data System (ADS)

Ghiorso, Mark S.; Sack, O.

1991-10-01

A new thermodynamic formulation of the Fe-Ti oxide geothermometer/oxygen barometer is developed. The method is based upon recently calibrated models for spinel solid solutions in the quinary system (Fe2+, Mg)(Al,Fe3+,Cr)2O4-(Fe2+, Mg)2TiO4 by Sack and Ghiorso, and rhombohedral oxides in the quaternary system (Fe2+,Mg,Mn)TiO3-Fe2O3 (this paper). The formulation is internally consistent with thermodynamic models for (Fe2+,Mg)-olivine and -orthopyroxene solid solutions and end-member thermodynamic properties tabulated by Berman. The constituent expressions account for compositional and temperature dependent cation ordering and reproduce miscibility gap features in all of the component binaries. The calibration does not account for the excess Gibbs energy resulting from compositional and temperature dependent magnetic ordering in either phase. This limits application of the method to assemblages that equilibrated at temperatures above 600° C. Practical implementation of the proposed geothermometer/oxygen barometer requires minimal use of projection algorthms in accommodating compositions of naturally occurring phases. The new formulation is applied to the estimation of temperature and oxygen fugacity in a wide variety of intermediate to silicic volcanic rocks. In combination with previous work on olivine and orthopyroxene thermodynamics, equilibration pressures are computed for a subset of these volcanics that contain the assemblage quartz, oxides and either ferromagnesian silicate. The calculated log10 f O 2- T relations are reflected in coexisting ferromagnesian mineral assemblages. Volcanics with the lowest relative oxygen fugacity (Δlog10 f O 2) are characterized by the assemblage olivine-quartz, those with slightly higher Δ log10 f O 2 s, by the assemblage orthopyroxene-quartz. The sequence proceeds with the necessary phases biotite-feldspar, then hornblende-quartz-clinopyroxene, and finally at the highest Δ log10 f O 2 s, sphene-quartz-clinopyroxene. Quantitative analysis of these trends, utilizing thermodynamic data for the constituent phases, establishes that, in most cases, the T-log10 f O 2value computed from the oxides is consistent with the compositions of coexisting silicate phases, indicating that phenocryst equilibrium was achieved prior to eruption. There is, however, considerable evidence of oxide-silicate disequilibrium in samples collected from more slowly cooled domes and obsidians. In addition, T-log10 f O 2trends from volcanic rocks that contain biotite and orthopyroxene are interpreted to imply a condition of Fe2+-Mg exchange disequilibrium between orthopyroxene and coexisting ferromagnesian silicates and melt. It is suspected that many biotite-feldspar-quartz-orthopyroxene bearing low temperature volcanic rocks inherit orthopyroxene xenocrysts which crystallized earlier in the cooling history of the magma body.

Elasticity of stishovite at high pressure

NASA Astrophysics Data System (ADS)

Li, Baosheng; Rigden, Sally M.; Liebermann, Robert C.

1996-08-01

The elastic-wave velocities of stishovite, the rutile-structured polymorph of SiO 2, were measured to 3 GPa at room temperature in a piston cylinder apparatus using ultrasonic interferometry on polycrystalline samples. These polycrystalline samples (2-3 mm in length and diameter) were hot-pressed at 14 GPa and 1050°C in a 2000 ton uniaxial split-sphere apparatus (USSA-2000) using fused silica rods as starting material. They were characterized as low porosity (less than 1%), single phase, fine grained, free of cracks and preferred orientation, and acoustically isotropic by using density measurement, X-ray diffraction, scanning electron microscopy, and bench-top velocity measurements. On the basis of subsequent in situ X-ray diffraction study at high P and T on peak broadening on similar specimens, it is evident that the single crystal grains within these polycrystalline aggregates are well equilibrated and that these specimens are free of residual strain. P- and S-wave velocities measured at 1 atm are within 1.5% of the Hashin-Shtrikman bounds calculated from single-crystal elastic moduli. Measured pressure derivatives of the bulk and shear moduli, K' 0 = 5.3 ± 0.1 and G' 0 = 1.8 ± 0.1, are not unusual compared with values measured for other transition zone phases such as silicate spinel and majorite garnet. Isothermal compression curves calculated with the measured values of K0 and K' 0 agree well with experimental P-V data to 16 GPa. The experimental value of dG /dP is in excellent agreement with predictions based on elasticity systematics. Theoretical models are not yet able to replicate the measured values of K' 0 and G' 0.

Carbon substitution for oxygen in silicates in planetary interiors

PubMed Central

Sen, Sabyasachi; Widgeon, Scarlett J.; Navrotsky, Alexandra; Mera, Gabriela; Tavakoli, Amir; Ionescu, Emanuel; Riedel, Ralf

2013-01-01

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiOxC4-x tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiOxC4-x tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10–100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle. PMID:24043830

Carbon substitution for oxygen in silicates in planetary interiors.

PubMed

Sen, Sabyasachi; Widgeon, Scarlett J; Navrotsky, Alexandra; Mera, Gabriela; Tavakoli, Amir; Ionescu, Emanuel; Riedel, Ralf

2013-10-01

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiO(x)C(4-x) tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiO(x)C(4-x) tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10-100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle.

Calcium titanium silicate based glass-ceramic for nuclear waste immobilisation

NASA Astrophysics Data System (ADS)

Sharma, K.; Srivastav, A. P.; Goswami, M.; Krishnan, Madangopal

2018-04-01

Titanate based ceramics (synroc) have been studied for immobilisation of nuclear wastes due to their high radiation and thermal stability. The aim of this study is to synthesis glass-ceramic with stable phases from alumino silicate glass composition and study the loading behavior of actinides in glass-ceramics. The effects of CaO and TiO2 addition on phase evolution and structural properties of alumino silicate based glasses with nominal composition x(10CaO-9TiO2)-y(10Na2O-5 Al2O3-56SiO2-10B2O3); where z = x/y = 1.4-1.8 are reported. The glasses are prepared by melt-quench technique and characterized for thermal and structural properties using DTA and Raman Spectroscopy. Glass transition and peak crystallization temperatures decrease with increase of CaO and TiO2 content, which implies the weakening of glass network and increased tendency of glasses towards crystallization. Sphene (CaTiSiO5) and perovskite (CaTiO3) crystalline phases are confirmed from XRD which are well known stable phase for conditioning of actinides. The microsturcture and elemental analysis indicate the presence of actinide in stable crystalline phases.

Does Comet WILD-2 contain Gems?

NASA Technical Reports Server (NTRS)

Chi, M.; Ishii, H.; Dai, Z. R.; Toppani, A.; Joswiak, D. J.; Leroux, H.; Zolensky, M.; Keller, L. P.; Browning, N. D.

2007-01-01

It is expected that Comet Wild-2 dust should resemble anhydrous carbon-rich, chondritic porous (CP) interplanetary dust particles (IDPs) collected in the stratosphere because some CP IDPs are suspected to be from comets. The rarity of carbonaceous grains and presolar silicates, as well as the presence of high-temperature inner solar nebula minerals in the Wild-2 sample (e.g. osbornite and melilite), appear incompatible with most CP IDPs. However, it is premature to draw firm conclusions about the mineralogy of comet Wild-2 because only approx. 1% of the sample has been examined. The most abundant silicates in CP IDPs are GEMS (glass with embedded metal and sulfides). Nonsolar O isotopic compositions confirm that at least some GEMS in IDPs are presolar amorphous silicates. The presence or absence of GEMS in the Wild-2 sample is important because it addresses, (a) the relationship between CP IDPs and comets, and (b) the hypothesis that other GEMS in IDPs formed in the solar nebula. Here we show that most of the GEMSlike materials so far identified in Stardust aerogel were likely impact generated during collection. At the nanometer scale, they are compositionally and crystallographically distinct from GEMS in IDPs.

Photoluminescence and cathodoluminescence of Mn doped zinc silicate nanophosphors for green and yellow field emissions displays

NASA Astrophysics Data System (ADS)

Omri, K.; Alyamani, A.; Mir, L. El

2018-02-01

Mn2+-doped Zn2SiO4 (ZSM2+) was synthesized by a facile sol-gel technique. The obtained samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, photoluminescence (PL) and cathodoluminescence (CL) techniques. Under UV excitation, spectra showed that the α-ZSM2+ phosphor exhibited a strong green emission around 525 nm and reached the highest luminescence intensity with the Mn doping concentration of 5 at.%. However, for the β-ZSM2+ phase, an interesting yellow emission band centered at 575 nm of Mn2+ at the Zn2+ tetrahedral sites was observed. In addition, an unusual red shift with increasing Mn2+ content was also found and attributed to an exchange interaction between Mn2+. Both PL and CL spectra exhibit an intense green and yellow emission centered at 525 and 573 nm, respectively, due to the 4T1 (4G)-6A1 (6S) transition of Mn2+. Furthermore, these results indicated that the Mn2+-doped zinc silicate phosphors may have potential applications in green and yellow emissions displays like field emission displays (FEDs).

Thermochemistry of dense hydrous magnesium silicates

NASA Technical Reports Server (NTRS)

Bose, Kunal; Burnley, Pamela; Navrotsky, Alexandra

1994-01-01

Recent experimental investigations under mantle conditions have identified a suite of dense hydrous magnesium silicate (DHMS) phases that could be conduits to transport water to at least the 660 km discontinuity via mature, relatively cold, subducting slabs. Water released from successive dehydration of these phases during subduction could be responsible for deep focus earthquakes, mantle metasomatism and a host of other physico-chemical processes central to our understanding of the earth's deep interior. In order to construct a thermodynamic data base that can delineate and predict the stability ranges for DHMS phases, reliable thermochemical and thermophysical data are required. One of the major obstacles in calorimetric studies of phases synthesized under high pressure conditions has been limitation due to the small (less than 5 mg) sample mass. Our refinement of calorimeter techniques now allow precise determination of enthalpies of solution of less than 5 mg samples of hydrous magnesium silicates. For example, high temperature solution calorimetry of natural talc (Mg(0.99) Fe(0.01)Si4O10(OH)2), periclase (MgO) and quartz (SiO2) yield enthalpies of drop solution at 1044 K to be 592.2 (2.2), 52.01 (0.12) and 45.76 (0.4) kJ/mol respectively. The corresponding enthalpy of formation from oxides at 298 K for talc is minus 5908.2 kJ/mol agreeing within 0.1 percent to literature values.

Transport properties of carbonated silicate melt at high pressure

PubMed Central

Ghosh, Dipta B.; Karki, Bijaya B.

2017-01-01

Carbon dioxide, generally considered as the second most abundant volatile component in silicate magmas, is expected to significantly influence various melt properties. In particular, our knowledge about its dynamical effects is lacking over most of Earth’s mantle pressure regime. Here, we report the first-principles molecular dynamics results on the transport properties of carbonated MgSiO3 liquid under conditions of mantle relevance. They show that dissolved CO2 systematically enhances the diffusion rates of all elements and lowers the melt viscosity on average by factors of 1.5 to 3 over the pressure range considered. It is remarkable that CO2 has very little or no influence on the electrical conductivity of the silicate melt under most conditions. Simulations also predict anomalous dynamical behavior, increasing diffusivity and conductivity and decreasing viscosity with compression in the low-pressure regime. This anomaly and the concomitant increase of pressure and temperature with depth together make these transport coefficients vary modestly over extended portions of the mantle regime. It is possible that the melt electrical conductivity under conditions corresponding to the 410- and 660-km seismic discontinuities is at a detectable level by electromagnetic sounding observation. In addition, the low melt viscosity values of 0.2 to 0.5 Pa⋅s at these depths and near the core-mantle boundary may imply high mobility of possible melts in these regions. PMID:29226244

Visible light induced green transformation of primary amines to imines using a silicate supported anatase photocatalyst.

PubMed

Zavahir, Sifani; Zhu, Huaiyong

2015-01-26

Catalytic oxidation of amine to imine is of intense present interest since imines are important intermediates for the synthesis of fine chemicals, pharmaceuticals, and agricultural chemicals. However, considerable efforts have been made to develop efficient methods for the oxidation of secondary amines to imines, while little attention has until recently been given to the oxidation of primary amines, presumably owing to the high reactivity of generated imines of primary amines that are easily dehydrogenated to nitriles. Herein, we report the oxidative coupling of a series of primary benzylic amines into corresponding imines with dioxygen as the benign oxidant over composite catalysts of TiO2 (anatase)-silicate under visible light irradiation of λ > 460 nm. Visible light response of this system is believed to be as a result of high population of defects and contacts between silicate and anatase crystals in the composite and the strong interaction between benzylic amine and the catalyst. It is found that tuning the intensity and wavelength of the light irradiation and the reaction temperature can remarkably enhance the reaction activity. Water can also act as a green medium for the reaction with an excellent selectivity. This report contributes to the use of readily synthesized, environmentally benign, TiO2 based composite photocatalyst and solar energy to realize the transformation of primary amines to imine compounds.

Shock recovery of a magnesium-silicate spinelloid

NASA Astrophysics Data System (ADS)

Tschauner, O. D.; Asimow, P. D.; Ahrens, T. J.; Kostandova, N.

2009-12-01

Previously it was believed that some high pressure polymorphs (e.g. of framework silicates) form under shock via growth from shock-induced precursor microscopic melt zones. Since diffusion in the melt was assumed to control crystallization rates, absence of shock recovery of any of those minerals was attributed to the short duration of laboratory shock (0.1 to 1 microsecond) experiments. In contrast to laboratory experiments, grains of high pressure polymorphs of 1 - 100 micrometer diameter have been found in melt veins of shocked meteorites and were widely believed to have formed via diffusion-controlled growth that occurred over seconds to minute time scales. Recently we reported formation of wadsleyite from a shock-generated melt in a laboratory shock experiment by analysis of the recovery products [1]. The growth rate of wadsleyite crystals at the experimental temperature of 2000 to 3000 K was estimated to be several m/s suggesting that diffusion was not the dominant factor in this ultra-rapid crystal growth. Consequently, S6 shock events in chondrites may not always be related to long shock duration and large impactors. Here we report formation of another high-pressure magnesium silicate polymorph in a shock experiment. The starting materials for this 30 GPa shot was single-crystal synthetic forsterite in a NIST 1157 tool-steel chamber. The recovered material was analyzed by micro-Raman spectroscopy and by synchrotron-based micro-X ray diffraction. Diffraction experiments were conducted in Gandolfi-geometry at station B2, CHESS, using a MAR345 image plate detector and a primary beam of 25 keV energy. Melted regions of the sample contained a spinelloid isotypic to a magnesium-gallium germanate spinelloid synthesized at ambient pressure [2]. As in the previous study [1] we observe oxidation of iron from melted metal of the recovery chamber wall entrained by the silicate melt while silicon is partially reduced. The new high-pressure silicate may have formed at less than the peak pressure experienced by the sample. [1]: O.Tschauner, P.D. Asimow, N. Kostandova,T.J. Ahrens, C. Ma, S. Sinogeikin, Z. Liu, S. Fakra, N. Tamura, Proc. Nat. Acad. Sci. USA 106, 13691-5 (2009) , [2]: Barbier, J., Hyde, B.G.,Acta Cryst. B 43, 34-40 (1987).

The Effect of Specific Surface Area of Chitin-Metal Silicate Coprocessed Excipient on the Chemical Decomposition of Cefotaxime Sodium.

PubMed

Al-Nimry, Suhair S; Alkhamis, Khouloud A; Alzarieni, Kawthar Z

2017-02-01

Chitin-metal silicates are multifunctional excipients used in tablets. Previously, a correlation between the surface acidity of chitin-calcium and chitin-magnesium silicate and the chemical decomposition of cefotaxime sodium was found but not with chitin-aluminum silicate. This lack of correlation could be due to the catalytic effect of silica alumina or the difference in surface area of the excipients. The objective of this study was to investigate the effect of the specific surface area of the excipient on the chemical decomposition of cefotaxime sodium in the solid state. Chitin was purified and coprocessed with different metal silicates to prepare the excipients. The specific surface area was determined using gas adsorption. The chemical decomposition was studied at constant temperature and relative humidity. Also, the degradation in solution was studied. A correlation was found between the degradation rate constant and the surface area of chitin-aluminum and chitin-calcium silicate but not with chitin-magnesium silicate. This was due to the small average pore diameter of this excipient. Also, the degradation in solution was slower than in solid state. In conclusion, the stability of cefotaxime sodium was dependent on the surface area of the excipient in contact with the drug. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Mid-infrared observations of sungrazing comet C/2012 S1 (ISON) with the Subaru Telescope

NASA Astrophysics Data System (ADS)

Ootsubo, T.; Usui, F.; Takita, S.; Watanabe, J.; Yanamandra-Fisher, P.; Honda, M.; Kawakita, H.; Furusho, R.

2014-07-01

Comets are the frozen reservoirs of the early solar nebula and are made of ice and dust. The determination of the properties for cometary dust provides us insight into both the early-solar-nebula environment and the formation process of the planetary system. A silicate feature is often observed in comet spectra in the mid-infrared region and may be used for probing the early history of the solar system. In most cases, the feature shows the existence of crystalline silicate (for example, 11.3 microns) together with amorphous silicate [1,2]. Since the crystallization of silicates from amorphous ones generally requires high-temperature annealing above 800 K (e.g., [3,4]), it is believed that the crystalline silicate grains produced at the inner part of the disk were transported to the outer cold regions where the comet nuclei formed. Comet C/2012 S1 (ISON) is a long-period Oort Cloud comet, discovered in September 2012. In particular, comet ISON is a sungrazing comet, which was predicted to pass close by the Sun and the Earth and becoming a bright object. Mid-infrared observations of this new comet and investigation of the 10-micron silicate feature help us understand the formation of crystalline silicate grains in the early solar nebula. We conducted observations of comet ISON in the mid-infrared wavelength region with the Cooled Mid-Infrared Camera and Spectrometer (COMICS) on the Subaru Telescope on Mauna Kea, Hawaii [5,6,7]. The observation of comet ISON was carried out on 2013 October 19 and 21 UT. Since the weather conditions were not so good when we observed, we carried out N-band imaging observations (8.8 and 12.4 microns) and N-band low-resolution spectroscopy. The spectrum of comet ISON can be fit with the 260--265-K blackbody spectrum when we use the regions of 7.8--8.2 and 12.4--13.0 microns as the continuum. The spectrum has only a weak silicate excess feature, which may be able to attribute to small amorphous olivine grains. We could not detect a clear crystalline silicate feature in the spectrum of our observations. We will compare the spectrum with other Oort Cloud comets, such as comets C/2011 L4 (PanSTARRS) and C/2013 R1 (Lovejoy), and discuss the dust properties and the birthplace of comet ISON.

The Design and Testing of a High-Temperature Graphite Dilatometer

DTIC Science & Technology

1992-06-24

characterization of its CTE is of little significance. Practical candidates are silica (fused quartz glass), Zerodur -type glass ceramics (5 x 10- 8 C-1 ), and...titanium silicates (< 5 x IO17 *C-1 ). Partially crystallized glasses, such as Zerodur , are limited to about 6006C. Silica can be subjected to almost...electronics, solid-state lasers , optical propagation and communications; cw and pulsed chemical laser development, optical resonators, beam control