MAS-NMR investigations of the crystallization behaviour of lithium aluminum silicate (LAS) glasses containing P 2O 5 and TiO 2 nucleants

NASA Astrophysics Data System (ADS)

Ananthanarayanan, A.; Kothiyal, G. P.; Montagne, L.; Revel, B.

2010-06-01

Lithium aluminum silicate (LAS) glass of composition (mol%) 20.4Li 2O-4.0Al 2O 3-68.6SiO 2-3.0K 2O-2.6B 2O 3-0.5P 2O 5-0.9TiO 2 was prepared by melt quenching. The glass was then nucleated and crystallized based on differential thermal analysis (DTA) data and was characterized by 29Si, 31P, 11B and 27Al MAS-NMR. XRD and 29Si NMR showed that lithium metasilicate (Li 2SiO 3) is the first phase to c form followed by cristobalite (SiO 2) and lithium disilicate (Li 2Si 2O 5). 29Si MAS-NMR revealed a change in the network structure already for the glasses nucleated at 550 °C. Since crystalline Li 3PO 4, as observed by 31P MAS-NMR, forms concurrently with the silicate phases, we conclude that crystalline Li 3PO 4 does not act as a nucleating agent for lithium silicate phases. Moreover, 31P NMR indicates the formation of M-PO 4 ( M=B, Al or Ti) complexes. The presence of BO 3 and BO 4 structural units in all the glass/glass-ceramic samples is revealed through 11B MAS-NMR. B remains in the residual glass and the crystallization of silicate phases causes a reduction in the number of alkali ions available for charge compensation. As a result, the number of trigonally coordinated B (BO 3) increases at the expense of tetrahedrally coordinated B (BO 4). The 27Al MAS-NMR spectra indicate the presence of tetrahedrally coordinated Al species, which are only slightly perturbed by the crystallization.

Digital evaluation of the fit of zirconia-reinforced lithium silicate crowns with a new three-dimensional approach.

PubMed

Zimmermann, Moritz; Valcanaia, Andre; Neiva, Gisele; Mehl, Albert; Fasbinder, Dennis

2017-11-30

Several methods for the evaluation of fit of computer-aided design/computer-assisted manufacture (CAD/CAM)-fabricated restorations have been described. In the study, digital models were recorded with an intraoral scanning device and were measured using a new three-dimensional (3D) computer technique to evaluate restoration internal fit. The aim of the study was to evaluate the internal adaptation and fit of chairside CAD/CAM-fabricated zirconia-reinforced lithium silicate ceramic crowns fabricated with different post-milling protocols. The null hypothesis was that different post-milling protocols did not influence the fitting accuracy of zirconia-reinforced lithium silicate restorations. A master all-ceramic crown preparation was completed on a maxillary right first molar on a typodont. Twenty zirconia-reinforced lithium silicate ceramic crowns (Celtra Duo, Dentsply Sirona) were designed and milled using a chairside CAD/CAM system (CEREC Omnicam, Dentsply Sirona). The 20 crowns were randomly divided into two groups based on post-milling protocols: no manipulation after milling (Group MI) and oven fired-glazing after milling (Group FG). A 3D computer method was used to evaluate the internal adaptation of the crowns. This was based on a subtractive analysis of a digital scan of the crown preparation and a digital scan of the thickness of the cement space over the crown preparation as recorded by a polyvinylsiloxane (PVS) impression material. The preparation scan and PVS scan were matched in 3D and a 3D difference analysis was performed with a software program (OraCheck, Cyfex). Three areas of internal adaptation and fit were selected for analysis: margin (MA), axial wall (AX), and occlusal surface (OC). Statistical analysis was performed using 80% percentile and one-way ANOVA with post-hoc Scheffé test (P = .05). The closest internal adaptation of the crowns was measured at the axial wall with 102.0 ± 11.7 µm for group MI-AX and 106.3 ± 29.3 µm for group FG

Making Earth's earliest continental crust - an analogue from voluminous Neogene silicic volcanism in NE-Iceland

NASA Astrophysics Data System (ADS)

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

2014-05-01

Borgarfjörður Eystri in NE-Iceland represents the second-most voluminous exposure of silicic eruptive rocks in Iceland and is a superb example of bimodal volcanism (Bunsen-Daly gap), which represents a long-standing controversy that touches on the problem of crustal growth in early Earth. The silicic rocks in NE-Iceland approach 25 % of the exposed rock mass in the region (Gústafsson et al., 1989), thus they significantly exceed the usual ≤ 12 % in Iceland as a whole (e.g. Walker, 1966; Jonasson, 2007). The origin, significance, and duration of the voluminous (> 300 km3) and dominantly explosive silicic activity in Borgarfjörður Eystri is not yet constrained (c.f. Gústafsson, 1992), leaving us unclear as to what causes silicic volcanism in otherwise basaltic provinces. Here we report SIMS zircon U-Pb ages and δ18O values from the region, which record the commencement of silicic igneous activity with rhyolite lavas at 13.5 to 12.8 Ma, closely followed by large caldera-forming ignimbrite eruptions from the Breiðavik and Dyrfjöll central volcanoes (12.4 Ma). Silicic activity ended abruptly with dacite lava at 12.1 Ma, defining a ≤ 1 Myr long window of silicic volcanism. Magma δ18O values estimated from zircon range from 3.1 to 5.5 (± 0.3; n = 170) and indicate up to 45 % assimilation of a low-δ18O component (e.g. typically δ18O = 0 ‰, Bindeman et al., 2012). A Neogene rift relocation (Martin et al., 2011) or the birth of an off-rift zone to the east of the mature rift associated with a thermal/chemical pulse in the Iceland plume (Óskarsson & Riishuus, 2013), likely brought mantle-derived magma into contact with fertile hydrothermally-altered basaltic crust. The resulting interaction triggered large-scale crustal melting and generated mixed-origin silicic melts. Such rapid formation of silicic magmas from sustained basaltic volcanism may serve as an analogue for generating continental crust in a subduction-free early Earth (e.g. ≥ 3 Ga, Kamber et

Chairside Fabrication of an All-Ceramic Partial Crown Using a Zirconia-Reinforced Lithium Silicate Ceramic

PubMed Central

Pabel, Anne-Kathrin; Rödiger, Matthias

2016-01-01

The chairside fabrication of a monolithic partial crown using a zirconia-reinforced lithium silicate (ZLS) ceramic is described. The fully digitized model-free workflow in a dental practice is possible due to the use of a powder-free intraoral scanner and the computer-aided design/computer-assisted manufacturing (CAD/CAM) of the restorations. The innovative ZLS material offers a singular combination of fracture strength (>370 Mpa), optimum polishing characteristics, and excellent optical properties. Therefore, this ceramic is an interesting alternative material for monolithic restorations produced in a digital workflow. PMID:27042362

CHEMISTRY OF SILICATE ATMOSPHERES OF EVAPORATING SUPER-EARTHS

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

Schaefer, Laura; Fegley, Bruce, E-mail: laura_s@levee.wustl.ed, E-mail: bfegley@levee.wustl.ed

2009-10-01

We model the formation of silicate atmospheres on hot volatile-free super-Earths. Our calculations assume that all volatile elements such as H, C, N, S, and Cl have been lost from the planet. We find that the atmospheres are composed primarily of Na, O{sub 2}, O, and SiO gas, in order of decreasing abundance. The atmospheric composition may be altered by fractional vaporization, cloud condensation, photoionization, and reaction with any residual volatile elements remaining in the atmosphere. Cloud condensation reduces the abundance of all elements in the atmosphere except Na and K. We speculate that large Na and K clouds suchmore » as those observed around Mercury and Io may surround hot super-Earths. These clouds would occult much larger fractions of the parent star than a closely bound atmosphere, and may be observable through currently available methods.« less

Open system models of isotopic evolution in Earth's silicate reservoirs: Implications for crustal growth and mantle heterogeneity

NASA Astrophysics Data System (ADS)

Kumari, Seema; Paul, Debajyoti; Stracke, Andreas

2016-12-01

An open system evolutionary model of the Earth, comprising continental crust (CC), upper and lower mantle (UM, LM), and an additional isolated reservoir (IR) has been developed to study the isotopic evolution of the silicate Earth. The model is solved numerically at 1 Myr time steps over 4.55 Gyr of Earth history to reproduce both the present-day concentrations and isotope ratios of key radioactive decay systems (Rb-Sr, Sm-Nd, and U-Th-Pb) in these terrestrial reservoirs. Various crustal growth scenarios - continuous versus episodic and early versus late crustal growth - and their effect on the evolution of Sr-Nd-Pb isotope systematics in the silicate reservoirs have been evaluated. Modeling results where the present-day UM is ∼60% of the total mantle mass and a lower mantle that is non-primitive reproduce the estimated geochemical composition and isotope ratios in Earth's silicate reservoirs. The isotopic evolution of the silicate Earth is strongly affected by the mode of crustal growth; only an exponential crustal growth pattern with crustal growth since the early Archean satisfactorily explains the chemical and isotopic evolution of the crust-mantle system and accounts for the so-called Pb paradoxes. Assuming that the OIB source is located in the deeper mantle, our model could, however, not reproduce its target ɛNd of +4.6 for the UM, which has been estimated from the average isotope ratios of 32 individual ocean island localities. Hence, either mantle plumes sample the LM in a non-representative way, or the simplified model set-up does not capture the full complexity of Earth's lower mantle (Nd isotope) evolution. Compared to the results obtained for a 4.55 Ga Earth, a model assuming a protracted U-Pb evolution of silicate Earth by ca. 100 Myr reproduces a slightly better fit for the Pb isotope ratios in Earth's silicate reservoirs. One notable feature of successful models is the early depletion of incompatible elements (as well as rapid decrease in Th/U) in

NREL, NASA, and UCL Team Up to Make Lithium-Ion Batteries Safer on Earth

Science.gov Websites

and in Space | News | NREL NREL, NASA, and UCL Team Up to Make Lithium-Ion Batteries Safer on Earth and in Space NREL, NASA, and UCL Team Up to Make Lithium-Ion Batteries Safer on Earth and in Space . NREL joined forces with NASA in finding new, more precise ways to trigger internal short circuits

Heterogeneous Delivery of Silicate and Metal to the Earth via Large Planetesimals

NASA Astrophysics Data System (ADS)

Marchi, S.; Canup, R. M.; Walker, R. J.

2017-12-01

Earth's mantle abundances of at least some highly siderophile elements, (HSE; Re, Os, Ir, Ru, Pt, Rh, Pd, and Au), are much higher than would result from metal-silicate equilibration during terrestrial core formation, and can be better explained as a result of late accretion of a minimum of 0.5% Earth's masses after core formation was complete. Traditional models assume that HSEs delivered by late projectiles completely mixed and chemically equilibrated with the Earth's mantle. This appears likely for undifferentiated, well-mixed projectiles, or for relatively small, differentiated projectiles. However several arguments suggest that late projectiles may have been large (> 1500 km in diameter) and differentiated, and in this case, portions of the projectile's core may merge with the Earth's core, rather than being mixed into the Earth's mantle. We investigate projectile mixing with a suite of SPH simulations of differentiated planetesimal colliding with the Earth. A range of outcomes emerge from our simulations suggesting that for large impactors (>1500 km), the delivery of HSE to the Earth's mantle may be disproportionate with the overall delivery of mass. For impacts with impact angles < 45° , between ˜ 20% to 80% of the impactor's core may merge directly with the Earth's core; while for impact angle > 60°, most of the impactor core escapes for moderate impact speeds. An implication is that the late accreted mass inferred from terrestrial HSE abundances may be a substantial underestimate, by a factor 2-5. In addition, partial mixing of projectiles result in an enrichment in mantle vs core material delivered to the bulk silicate Earth, implying substantial compositional variations in the accreted mass. Such variations could produce initially localized domains in Earth's mantle with distinct, mass independent isotopic signatures, given the isotopic variability resulting from nucleosynthetic heterogeneities among genetically diverse meteorites. In general we find

The neodymium stable isotope composition of the silicate Earth and chondrites

NASA Astrophysics Data System (ADS)

McCoy-West, Alex J.; Millet, Marc-Alban; Burton, Kevin W.

2017-12-01

The non-chondritic neodymium (Nd) 142Nd/144Nd ratio of the silicate Earth potentially provides a key constraint on the accretion and early evolution of the Earth. Yet, it is debated whether this offset is due to the Earth being formed from material enriched in s-process Nd isotopes or results from an early differentiation process such as the segregation of a late sulfide matte during core formation, collisional erosion or a some combination of these processes. Neodymium stable isotopes are potentially sensitive to early sulfide segregation into Earth's core, a process that cannot be resolved using their radiogenic counterparts. This study presents the first comprehensive Nd stable isotope data for chondritic meteorites and terrestrial rocks. Stable Nd measurements were made using a double spike technique coupled with thermal ionisation mass spectrometry. All three of the major classes of chondritic meteorites, carbonaceous, enstatite and ordinary chondrites have broadly similar isotopic compositions allowing calculation of a chondritic mean of δ146/144Nd = -0.025 ± 0.025‰ (±2 s.d.; n = 39). Enstatite chondrites yield the most uniform stable isotope composition (Δ146/144Nd = 26 ppm), with considerably more variability observed within ordinary (Δ146/144Nd = 72 ppm) and carbonaceous meteorites (Δ146/144Nd = 143 ppm). Terrestrial weathering, nucleosynthetic variations and parent body thermal metamorphism appear to have little measurable effect on δ146/144Nd in chondrites. The small variations observed between ordinary chondrite groups most likely reflect inherited compositional differences between parent bodies, with the larger variations observed in carbonaceous chondrites being linked to varying modal proportions of calcium-aluminium rich inclusions. The terrestrial samples analysed here include rocks ranging from basaltic to rhyolitic in composition, MORB glasses and residual mantle lithologies. All of these terrestrial rocks possess a broadly similar Nd

Iron-magnesium silicate bioweathering on Earth (and Mars?).

PubMed

Fisk, M R; Popa, R; Mason, O U; Storrie-Lombardi, M C; Vicenzi, E P

2006-02-01

We examined the common, iron-magnesium silicate minerals olivine and pyroxene in basalt and in mantle rocks to determine if they exhibit textures similar to bioweathering textures found in glass. Our results show that weathering in olivine may occur as long, narrow tunnels (1-3 microm in diameter and up to 100 microm long) and as larger irregular galleries, both of which have distinctive characteristics consistent with biological activity. These weathering textures are associated with clay mineral by-products and nucleic acids. We also examined olivine and pyroxene in martian meteorites, some of which experienced preterrestrial aqueous alteration. Some olivines and pyroxenes in the martian meteorite Nakhla were found to contain tunnels that are similar in size and shape to tunnels in terrestrial iron-magnesium silicates that contain nucleic acids. Though the tunnels found in Nakhla are similar to the biosignatures found in terrestrial minerals, their presence cannot be used to prove that the martian alteration features had a biogenic origin. The abundance and wide distribution of olivine and pyroxene on Earth and in the Solar System make bioweathering features in these minerals potentially important new biosignatures that may play a significant role in evaluating whether life ever existed on Mars.

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

Calcium Isotopic Composition of Bulk Silicate Earth

NASA Astrophysics Data System (ADS)

Kang, J.; Ionov, D. A.; Liu, F.; Zhang, C.; Zhang, Z.; Huang, F.

2016-12-01

Ca isotopes are used to study the accretion history of the Earth and terrestrial planets, but, Ca isotopic composition of the Bulk Silicate Earth (BSE) remains poorly constrained [1]. To better understand the Ca isotopic composition of BSE, we analyzed 22 well studied peridotite xenoliths from Tariat (Mongolia), Vitim (southern Siberia) and Udachnaya (Siberian Craton). These samples include both fertile and highly depleted garnet and spinel peridotites that show no or only minor post-melting metasomatism or alteration. Ca isotope measurements were done on a Triton-TIMS using double spike method at the Guangzhou Institute of Geochemistry, CAS. The data are reported as δ44/40Ca (relative to NIST SRM 915a). Results for geostandards are consistent with those from other laboratories. 2 standard deviations of SRM 915a analyses are 0.13‰ (n=48). δ44/40Ca of both and fertile and refractory peridotites range from 0.79 to 1.07‰ producing an average of 0.93±0.12‰ (2SD). This value defines the Ca isotopic composition of the BSE, which is consistent with the average δ44/40Ca of oceanic basalts ( 0.90‰)[2,3]. [1] Huang et al (2010) EPSL 292; [2] Valdes et al (2014) EPSL 394; [3]DePaolo (2004) RMG 55.

Experimental investigation of the partitioning of phosphorus between metal and silicate phases - Implications for the earth, moon and eucrite parent body

NASA Technical Reports Server (NTRS)

Newsom, H. E.; Drake, M. J.

1983-01-01

An experimental study is reported of the partitioning of Phosphorus between solid metal and basaltic silicate liquid as a function of temperature and oxygen fugacity and of the implications for the earth, moon and eucrite parent body (EPB). The relationship established between the partition coefficient and the fugacity is given at 1190 C by log D(P) = -1.12 log fO2 - 15.95 and by log D(P) = -1.53 log fO2 17.73 at 1300 C. The partition coefficient D(P) was determined, and it is found to be consistent with a valence state of 5 for P in the molten silicate. Using the determined coefficient the low P/La ratios of the earth, moon, and eucrites relative to C1 chondrites can be explained. The lowering of the P/La ratio in the eucrites relative to Cl chondrite by a factor of 40 can be explained by partitioning P into 20-25 wt% sulfur-bearing metallic liquid corresponding to 5-25% of the total metal plus silicate system. The low P/La and W/La ratios in the moon may be explained by the partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. These observations are consistent with independent formation of the moon and the earth.

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.

The Carbonate-Silicate Cycle on Earth-like Planets Near The End Of Their Habitable Lifetimes

NASA Astrophysics Data System (ADS)

Rushby, A. J.; Mills, B.; Johnson, M.; Claire, M.

2016-12-01

The terrestrial cycle of silicate weathering and metamorphic outgassing buffers atmospheric CO2 and global climate over geological time on Earth. To first order, the operation of this cycle is assumed to occur on Earth-like planets in the orbit of other main-sequence stars in the galaxy that exhibit similar continent/ocean configurations. This has important implications for studies of planetary habitability, atmospheric and climatic evolution, and our understanding of the potential distribution of life in the Universe. We present results from a simple biogeochemical carbon cycle model developed to investigate the operation of the carbonate-silicate cycle under conditions of differing planet mass and position within the radiative habitable zone. An active carbonate-silicate cycle does extend the length of a planet's habitable period through the regulation of the CO2 greenhouse. However, the breakdown of the negative feedback between temperature, pCO2, and weathering rates towards the end of a planet's habitable lifespan results in a transitory regime of `carbon starvation' that would inhibit the ability of oxygenic photoautotrophs to metabolize, and result in the collapse of any putative biosphere supported by these organisms, suggesting an earlier limit for the initiation of inhabitable conditions than when considering temperature alone. This conclusion stresses the importance of considering the full suite of planetary properties when determining potential habitability. A small sample of exoplanets was tested using this model, and the length of their habitable periods were found to be significantly longer than that of the Earth, primarily as a function of the differential rates of stellar evolution expected from their host stars. Furthermore, we carried out statistical analysis of a series of model input parameters, determining that both the mass of the planet and the sensitivity of seafloor weathering processes to dissolved CO2 exhibit significant controls on the

Silicate garnet studies at high pressures: A view into the Earth's mantle

NASA Astrophysics Data System (ADS)

Conrad, Pamela Gales

Silicate garnets are an abundant component in the Earth's upper mantle and transition zone. Therefore, an understanding of garnet behavior under the pressure and temperature conditions of the mantle is critical to the development of models for mantle mineralogy and dynamics. Work from three projects is presented in this report. Each investigation explores an aspect of silicate garnet behavior under high pressures. Moreover, each investigation was made possible by state-of-the-art methods that have previously been unavailable. Brillouin scattering was used to determine the elastic constants and aggregate elastic moduli of three end-member garnets at high pressures in a diamond anvil cell. These are the first high-pressure measurements of the elastic constants of end-member silicate garnets by direct measurement of acoustic velocities. The results indicate that the pressure dependence of silicate garnet elastic constants varies with composition. Therefore, extrapolation from measurements on mixed composition garnets is not possible. A new method of laser heating minerals in a diamond anvil cell has made possible the determination of the high-pressure and high-temperature stability of almandine garnet. This garnet does not transform to a silicate perovskite phase as does pyrope garnet, but it decomposes to its constituent oxides: FeO, Alsb2Osb3, and SiOsb2. These results disprove an earlier prediction that ferrous iron may expand the stability field of garnet to the lower mantle. The present results demonstrate that this is not the case. The third topic is a presentation of the results of a new technique for studying inclusions in mantle xenoliths with synchrotron X-ray microdiffraction. The results demonstrate the importance of obtaining structural as well as chemical information on inclusions within diamonds and other high-pressure minerals. An unusual phase with garnet composition is investigated and several other phases are identified from a suite of natural

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.

Surface protected lithium-metal-oxide electrodes

DOEpatents

Thackeray, Michael M.; Kang, Sun-Ho

2016-04-05

A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

Dispersion and thermal properties of lithium aluminum silicate glasses doped with Cr3+ ions

NASA Astrophysics Data System (ADS)

El-Diasty, Fouad; Abdel-Baki, Manal; Abdel Wahab, Fathy A.; Darwish, Hussein

2006-10-01

A series of new lithium aluminum silicate (LAS) glass systems doped with chromium ion is prepared. The reflectance and transmittance of the glass slabs are recorded. By means of an iteration procedure, the glass refractive index n and the extinction coefficient k and their dispersions are obtained. Across a wide spectral range of 0.2-1.6 μm, the dispersion curves are used to determine the atomic and quantum constants of the prepared glasses. These findings provide the average oscillator wavelength, the average oscillator strength, oscillator energy, dispersion energy, lattice energy, and material dispersion of the glass materials to be calculated. For optical waveguide applications, the wavelength for zero material dispersion is obtained. Dilatometric measurements are performed and the thermal expansion coefficient is calculated to throw some light on the thermo-optical properties of the present glasses correlating them with their structure and the presence of nonbridging oxygen ions.

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

Performance and Comparison of Lithium-Ion Batteries Under Low-Earth-Orbit Mission Profiles

NASA Technical Reports Server (NTRS)

Reid, Concha M.; Smart, Marshall C.; Bugga, Ratnakumar V.; Manzo, Michelle A.; Miller, Thomas B.; Gitzendanner, Rob

2007-01-01

The performance of two 28 V, 25 Ah lithium-ion batteries is being evaluated under low-Earth-orbit mission profiles for satellite and orbiter applications. The batteries are undergoing life testing and have achieved over 12,000 cycles to 40 percent depth-of-discharge.

A volatile topic: Parsing out the details of Earth's formation through experimental metal-silicate partitioning of volatile and moderately volatile elements

NASA Astrophysics Data System (ADS)

Mahan, B. M.; Siebert, J.; Blanchard, I.; Badro, J.; Sossi, P.; Moynier, F.

2017-12-01

Volatile and moderately volatile elements display different volatilities and siderophilities, as well as varying sensitivity to thermodynamic controls (X, P, T, fO2) during metal-silicate differentiation. The experimental determination of the metal-silicate partitioning of these elements permits us to evaluate processes controlling the distribution of these elements in Earth. In this work, we have combined metal-silicate partitioning data and results for S, Sn, Zn and Cu, and input these characterizations into Earth formation models. Model parameters such as source material, timing of volatile delivery, fO2 path, and degree of impactor equilibration were varied to encompass an array of possible formation scenarios. These models were then assessed to discern plausible sets of conditions that can produce current observed element-to-element ratios (e.g. S/Zn) in the Earth's present-day mantle, while also satisfying current estimates on the S content of the core, at no more than 2 wt%. The results of our models indicate two modes of accretion that can maintain chondritic element-to-element ratios for the bulk Earth and can arrive at present-day mantle abundances of these elements. The first mode requires the late addition of Earth's entire inventory of these elements (assuming a CI-chondritic composition) and late-stage accretion that is marked by partial equilibration of large impactors. The second, possibly more intuitive mode, requires that Earth accreted - at least initially - from volatile poor material preferentially depleted in S relative to Sn, Zn, and Cu. From a chemical standpoint, this source material is most similar to type I chondrule rich (and S poor) materials (Hewins and Herzberg, 1996; Mahan et al., 2017; Amsellem et al., 2017), such as the metal-bearing carbonaceous chondrites.

Metal-silicate Partitioning and Its Role in Core Formation and Composition on Super-Earths

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

Schaefer, Laura; Petaev, M. I.; Sasselov, Dimitar D.

We use a thermodynamic framework for silicate-metal partitioning to determine the possible compositions of metallic cores on super-Earths. We compare results using literature values of the partition coefficients of Si and Ni, as well as new partition coefficients calculated using results from laser shock-induced melting of powdered metal-dunite targets at pressures up to 276 GPa, which approaches those found within the deep mantles of super-Earths. We find that larger planets may have little to no light elements in their cores because the Si partition coefficient decreases at high pressures. The planet mass at which this occurs will depend on themore » metal-silicate equilibration depth. We also extrapolate the equations of state (EOS) of FeO and FeSi alloys to high pressures, and present mass–radius diagrams using self-consistent planet compositions assuming equilibrated mantles and cores. We confirm the results of previous studies that the distribution of elements between mantle and core will not be detectable from mass and radius measurements alone. While observations may be insensitive to interior structure, further modeling is sensitive to compositionally dependent properties, such as mantle viscosity and core freeze-out properties. We therefore emphasize the need for additional high pressure measurements of partitioning as well as EOSs, and highlight the utility of the Sandia Z-facilities for this type of work.« less

The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar

2016-06-01

The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate

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

Pulse energy dependence of refractive index change in lithium niobium silicate glass during femtosecond laser direct writing.

PubMed

Cao, Jing; Poumellec, Bertrand; Brisset, François; Lancry, Matthieu

2018-03-19

Femtosecond laser-induced refractive index changes in lithium niobium silicate glass were explored at high repetition rate (300 fs, 500 kHz) by polarized light microscopy, full-wave retardation plate, quantitative birefringence microscopy, and digital holographic microscopy. We found three regimes on energy increase. The first one corresponds to isotropic negative refractive index change (for pulse energy ranging 0.4-0.8 μJ/pulse, 0.6 NA, 5μm/s, 650μm focusing depth in the glass). The second one (0.8-1.2 μJ/pulse) corresponds to birefringence with well-defined slow axis orientation. The third one (above 1.2 μJ/pulse) is related to birefringence direction fluctuation. Interestingly, these regimes are consistent with crystallization ones. In addition, an asymmetric orientational writing effect has been detected on birefringence. These topics extend the possibility of controlling refractive index change in multi-component glasses.

MAS-NMR studies of lithium aluminum silicate (LAS) glasses and glass-ceramics having different Li 2O/Al 2O 3 ratio

NASA Astrophysics Data System (ADS)

Ananthanarayanan, A.; Kothiyal, G. P.; Montagne, L.; Revel, B.

2010-01-01

Emergence of phases in lithium aluminum silicate (LAS) glasses of composition (wt%) xLi 2O-71.7SiO 2-(17.7- x)Al 2O 3-4.9K 2O-3.2B 2O 3-2.5P 2O 5 (5.1≤ x≤12.6) upon heat treatment were studied. 29Si, 27Al, 31P and 11B MAS-NMR were employed for structural characterization of both LAS glasses and glass-ceramics. In glass samples, Al is found in tetrahedral coordination, while P exists mainly in the form of orthophosphate units. B exists as BO 3 and BO 4 units. 27Al NMR spectra show no change with crystallization, ruling out the presence of any Al containing phase. Contrary to X-ray diffraction studies carried out, 11B (high field 18.8 T) and 29Si NMR spectra clearly indicate the unexpected crystallization of a borosilicate phase (Li,K)BSi 2O 6, whose structure is similar to the aluminosilicate virgilite. Also, lithium disilicate (Li 2Si 2O 5), lithium metasilicate (Li 2SiO 3) and quartz (SiO 2) were identified in the 29Si NMR spectra of the glass-ceramics. 31P NMR spectra of the glass-ceramics revealed the presence of Li 3PO 4 and a mixed phase (Li,K) 3PO 4 at low alkali concentrations.

Silicate-catalyzed chemical grouting compositions

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

Not Available

1972-09-28

Chemical grouting compositions for stabilizing earth, sand, and other porous particulate formations or agglomerates of solids are described. The composition for producing a chemically grouting structure consists of an aqueous base solution of: (1) vegetative polyphenolic material consisting of condensed type tannins, and an aqueous catalyst solution of (2) a water-soluble alkali metal silicate. The polyphenolic material is present in an amount from 5% to 40% based on the weight of the base solution, and the water- soluble alkali metal silicate is present in an amount to provide from 1% to 15% SiOD2U in the silicate compound based on themore » weight of the polyphenolic material. These grouting compositions are completely safe to operating personnel and to surrounding environment, since the potassium or sodium silicate catalysts are nontoxic. (15 claims)« less

Copper Silicate Hydrate Hollow Spheres Constructed by Nanotubes Encapsulated in Reduced Graphene Oxide as Long-Life Lithium-Ion Battery Anode.

PubMed

Wei, Xiujuan; Tang, Chunjuan; Wang, Xuanpeng; Zhou, Liang; Wei, Qiulong; Yan, Mengyu; Sheng, Jinzhi; Hu, Ping; Wang, Bolun; Mai, Liqiang

2015-12-09

Hierarchical copper silicate hydrate hollow spheres-reduced graphene oxide (RGO) composite is successfully fabricated by a facile hydrothermal method using silica as in situ sacrificing template. The electrochemical performance of the composite as lithium-ion battery anode was studied for the first time. Benefiting from the synergistic effect of the hierarchical hollow structure and conductive RGO matrix, the composite exhibits excellent long-life performance and rate capability. A capacity of 890 mAh/g is achieved after 200 cycles at 200 mA/g and a capacity of 429 mAh/g is retained after 800 cycles at 1000 mA/g. The results indicate that the strategy of combining hierarchical hollow structures with conductive RGO holds the potential in addressing the volume expansion issue of high capacity anode materials.

Optical band gap studies on lithium aluminum silicate glasses doped with Cr3+ ions

NASA Astrophysics Data System (ADS)

El-Diasty, Fouad; Abdel Wahab, Fathy A.; Abdel-Baki, Manal

2006-11-01

Lithium aluminum silicate glass system (LAS) implanted with chromium ions is prepared. The reflectance and transmittance measurements are used to determine the dispersion of absorption coefficient. The optical data are explained in terms of the different oxidation states adopted by the chromium ions into the glass network. It is found that the oxidation state of the chromium depends on its concentration. Across a wide spectral range, 0.2-1.6μm, analysis of the fundamental absorption edge provides values for the average energy band gaps for allowed direct and indirect transitions. The optical absorption coefficient just below the absorption edge varies exponentially with photon energy indicating the presence of Urbach's tail. Such tail is decreased with the increase of the chromium dopant. From the analysis of the optical absorption data, the absorption peak at ground state exciton energy, the absorption at band gap, and the free exciton binding energy are determined. The extinction coefficient data are used to determine the Fermi energy level of the studied glasses. The metallization criterion is obtained and discussed exploring the nature of the glasses. The measured IR spectra of the different glasses are used to throw some light on the optical properties of the present glasses correlating them with their structure and composition.

EPR of radiation defects in lithium-oxyfluoride glass ceramics

NASA Astrophysics Data System (ADS)

Fedotovs, A.; Rogulis, U.; Sarakovskis, A.; Dimitrocenko, L.

2010-11-01

We studied oxyfluoride composites based on lithium silicate glasses with yttrium fluorides and rare-earth dopants. The electron paramagnetic resonance (EPR) has been used to obtain information about radiation induced defects in these materials. Spectra have been measured before and after X-ray irradiation at room temperature and at liquid nitrogen temperature. Fluoride crystallites within samples were created by means of thermal treatment at specific temperatures. EPR spectra of radiation induced defects in oxyfluoride glass ceramics, in which crystallites have not been yet created, show no explicit hfs interaction of fluorine nuclei. However, in glass ceramics, which already contains fluoride crystallites, the hfs characteristic to fluorine nuclei appears in the EPR spectra. EPR hyperfine structure could be explained within a model of an F-type centre in YF3 crystalline phase.

Misfit and fracture load of implant-supported monolithic crowns in zirconia-reinforced lithium silicate

PubMed Central

GOMES, Rafael Soares; de SOUZA, Caroline Mathias Carvalho; BERGAMO, Edmara Tatiely Pedroso; BORDIN, Dimorvan; DEL BEL CURY, Altair Antoninha

2017-01-01

Abstract Zirconia-reinforced lithium silicate (ZLS) is a ceramic that promises to have better mechanical properties than other materials with the same indications as well as improved adaptation and fracture strength. Objective In this study, marginal and internal misfit and fracture load with and without thermal-mechanical aging (TMA) of monolithic ZLS and lithium disilicate (LDS) crowns were evaluated. Material and methods Crowns were milled using a computer-aided design/computer-aided manufacturing system. Marginal gaps (MGs), absolute marginal discrepancy (AMD), axial gaps, and occlusal gaps were measured by X-ray microtomography (n=8). For fracture load testing, crowns were cemented in a universal abutment, and divided into four groups: ZLS without TMA, ZLS with TMA, LDS without TMA, and LDS with TMA (n=10). TMA groups were subjected to 10,000 thermal cycles (5-55°C) and 1,000,000 mechanical cycles (200 N, 3.8 Hz). All groups were subjected to compressive strength testing in a universal testing machine at a crosshead speed of 1 mm/min until failure. Student’s t-test was used to examine misfit, two-way analysis of variance was used to analyze fracture load, and Pearson’s correlation coefficients for misfit and fracture load were calculated (α=0.05). The materials were analyzed according to Weibull distribution, with 95% confidence intervals. Results Average MG (p<0.001) and AMD (p=0.003) values were greater in ZLS than in LDS crowns. TMA did not affect the fracture load of either material. However, fracture loads of ZLS crowns were lower than those of LDS crowns (p<0.001). Fracture load was moderately correlated with MG (r=-0.553) and AMD (r=-0.497). ZLS with TMA was least reliable, according to Weibull probability. Conclusion Within the limitations of this study, ZLS crowns had lower fracture load values and greater marginal misfit than did LDS crowns, although these values were within acceptable limits. PMID:28678947

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.

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

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.

Thermodynamics and Kinetics of Silicate Vaporization

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Costa, Gustavo C. C.

2015-01-01

Silicates are a common class of materials that are often exposed to high temperatures. The behavior of these materials needs to be understood for applications as high temperature coatings in material science as well as the constituents of lava for geological considerations. The vaporization behavior of these materials is an important aspect of their high temperature behavior and it also provides fundamental thermodynamic data. The application of Knudsen effusion mass spectrometry (KEMS) to silicates is discussed. There are several special considerations for silicates. The first is selection of an appropriate cell material, which is either nearly inert or has well-understood interactions with the silicate. The second consideration is proper measurement of the low vapor pressures. This can be circumvented by using a reducing agent to boost the vapor pressure without changing the solid composition or by working at very high temperatures. The third consideration deals with kinetic barriers to vaporization. The measurement of these barriers, as encompassed in a vaporization coefficient, is discussed. Current measured data of rare earth silicates for high temperature coating applications are discussed. In addition, data on magnesium-iron-silicates (olivine) are presented and discussed.

Emergence of silicic continents as the lower crust peels off on a hot plate-tectonic Earth

NASA Astrophysics Data System (ADS)

Chowdhury, Priyadarshi; Gerya, Taras; Chakraborty, Sumit

2017-09-01

The rock record and geochemical evidence indicate that continental recycling has been occurring since the early history of the Earth. The stabilization of felsic continents in place of Earth's early mafic crust about 3.0 to 2.0 billion years ago, perhaps due to the initiation of plate tectonics, implies widespread destruction of mafic crust during this time interval. However, the physical mechanisms of such intense recycling on a hotter, (late) Archaean and presumably plate-tectonic Earth remain largely unknown. Here we use thermomechanical modelling to show that extensive recycling via lower crustal peeling-off (delamination but not eclogitic dripping) during continent-continent convergence was near ubiquitous during the late Archaean to early Proterozoic. We propose that such destruction of the early mafic crust, together with felsic magmatism, may have caused both the emergence of silicic continents and their subsequent isostatic rise, possibly above the sea level. Such changes in the continental character have been proposed to influence the Great Oxidation Event and, therefore, peeling-off plate tectonics could be the geodynamic trigger for this event. A transition to the slab break-off controlled syn-orogenic recycling occurred as the Earth aged and cooled, leading to reduced recycling and enhanced preservation of the continental crust of present-day composition.

The Obtaining of Nano Oxide Systems SiO2-REE with Alkoxide Technology

NASA Astrophysics Data System (ADS)

Amelina, Anna; Grinberg, Evgenii

A lot of oxides systems with REE as dopants are used in catalytic processes in organic synthesis. They are very perspectives as thermostable coating in aerospace technics. These systems are usually based on silicon or aluminium oxides and doped with rare-earth elements. This systems can be produced by different methods. One of the most perspective of them is “sol-gel”-method with silicium, aluminium and rare-earth alkoxides as a precursor of doped silica and alumina, or their derivatives. Thus the obtaining of composite SiO _{2} - REE oxide materials by the hydrolysis doped with rare-earth elements was suggested. Some of alcoholate derivatives such as El(OR)n were used in this processes. The SiO _{2}- REE oxides were precipitated during the sol-gel process, where tetraethoxysilane (TEOS) as used as SiO _{2} sources. Also it is known that alkoxides of alkali metals, including lithium alkoxides, are widely used in industry and synthetic chemistry, as well as a source of lithium in various mixed oxide compositions, such as lithium niobate, lithium tantalate or lithium silicate. Therefore, we attempted to obtain the lithium silicate, which is also doped with rare-earth elements. Lithium silicate was obtained by alkaline hydrolysis of tetraethoxysilane with lithium alkoxide. Lithium alkoxide were synthesized by dissolving at metal in the corresponding alcohol are examined. The dependence of the rate of dissolving of the metal on the method of mixing of the reaction mixture and the degree of metal dispersion was investigated. The mathematical model of the process was composed and also optimization of process was carried out. Some oxide SiO _{2}, Al _{2}O _{3} and rare-earth nanostructured systems were obtained by sol-gel-method. The size of particle was determined by electron and X-ray spectroscopy and was in the range of 5 - 15 nm. Purity of this oxide examples for contaminating of heavy metals consists n.(1E-4...1E-5) wt%. Sols obtained by this method may be used

Indirect zirconia-reinforced lithium silicate ceramic CAD/CAM restorations: Preliminary clinical results after 12 months.

PubMed

Zimmermann, Moritz; Koller, Christina; Mehl, Albert; Hickel, Reinhard

2017-01-01

No clinical data are available for the new computer-aided design/computer-assisted manufacture (CAD/CAM) material zirconia-reinforced lithium silicate (ZLS) ceramic. This study describes preliminary clinical results for indirect ZLS CAD/CAM restorations after 12 months. Indirect restorations were fabricated, using the CEREC method and intraoral scanning (CEREC Omnicam, CEREC MCXL). Sixty-seven restorations were seated adhesively (baseline). Sixty restorations were evaluated after 12 months (follow-up), using modified FDI criteria. Two groups were established, according to ZLS restorations' post-processing procedure prior to adhesive seating: group I (three-step polishing, n = 32) and group II (fire glazing, n = 28). Statistical analysis was performed with Mann-Whitney U test and Wilcoxon test (P < .05). The success rate of indirect ZLS CAD/CAM restorations after 12 months was 96.7%. Two restorations clinically failed as a result of bulk fracture (failure rate 3.3%). No statistically significant differences were found for baseline and follow-up criteria (Wilcoxon test, P > .05). Statistically significant differences were found for criteria surface gloss for group I and group II (Mann-Whitney U test, P < .05). This study demonstrates ZLS CAD/CAM restorations have a high clinical success rate after 12 months. A longer clinical evaluation period is necessary to draw further conclusions.

Optical band gap and spectroscopic study of lithium alumino silicate glass containing Y 3+ ions

NASA Astrophysics Data System (ADS)

Shakeri, M. S.; Rezvani, M.

2011-09-01

The effect of different amounts of Y 2O 3 dopant on lithium alumino silicate (LAS) glass has been studied in this work. Glasses having 14.8Li 2O-20Al 2O 3-65.2SiO 2 (wt%) composition accompanied with Y 2O 3 dopant were prepared by normal melting process. In order to calculate the absorption coefficient of samples, transmittance and reflectance spectra of polished samples were measured in the room temperature. Optical properties i.e. Fermi energy level, direct and indirect optical band gaps and Urbach energy were calculated using functionality of extinction coefficient from Fermi-Dirac distribution function, Tauc's plot and the exponential part of absorption coefficient diagram, respectively. It has been clarified that variation in mentioned optical parameters is associated with the changes in physical properties of samples i.e. density or molar mass. On the other hand, increasing of Y 3+ ions in the glassy microstructure of samples provides a semiconducting character to LAS glass by reducing the direct and indirect optical band gaps of glass samples from 1.97 to 1.67 and 3.46 to 2.1 (eV), respectively. These changes could be attributed to the role of Y 3+ ions as the network former in the track of SiO 4 tetrahedrals.

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.

Thermoluminescent properties of rare earth doped lithium strontium borate phosphors

NASA Astrophysics Data System (ADS)

Jakathamani, S.; Annalakshmi, O.; Jose, M. T.

2018-04-01

Thermoluminescence (TL) of borates is remarkable in the field of radiation dosimetry because they can detect both neutron and gamma radiations. Usually, the TL efficiency of pure borates is low and hence dopants have to be added to increase their TL output. Their sensitivity and thermal stability vary widely and depend strongly on the preparation method. In this study polycrystalline powders of different rare earth doped thermoluminescent phosphors of Lithium Strontium borate (LSB) were synthesized by solid state sintering technique. Among the different rare earth dopants, the phosphor doped with cerium was found to have a simple glow curve structure with a dosimetric peak at around 265°C for a heating rate of 5°C/s. In order to study the effect of dopant on the TL characteristics, LSB phosphor with different concentrations of Ce dopant was synthesized and the TL intensity was found to be maximum for a dopant concentration of 0.7 mol%. All other important dosimetric characteristics like dose response and fading were carried out for the LSB:Ce (0.7 mol%) phosphor. Kinetic parameters like trap depth and frequency factor were determined using Peak shape method from Chen's equation.

Preparation and physicochemical properties of surfactant-free emulsions using electrolytic-reduction ion water containing lithium magnesium sodium silicate.

PubMed

Okajima, Masahiro; Wada, Yuko; Hosoya, Takashi; Hino, Fumio; Kitahara, Yoshiyasu; Shimokawa, Ken-ichi; Ishii, Fumiyoshi

2013-04-01

Surfactant-free emulsions by adding jojoba oil, squalane, olive oil, or glyceryl trioctanoate (medium chain fatty acid triglycerides, MCT) to electrolytic-reduction ion water containing lithium magnesium sodium silicate (GE-100) were prepared, and their physiochemical properties (thixotropy, zeta potential, and mean particle diameter) were evaluated. At an oil concentration of 10%, the zeta potential was ‒22.3 ‒ ‒26.8 mV, showing no marked differences among the emulsions of various types of oil, but the mean particle diameters in the olive oil emulsion (327 nm) and MCT emulsion (295 nm) were smaller than those in the other oil emulsions (452-471 nm). In addition, measurement of the hysteresis loop area of each type of emulsion revealed extremely high thixotropy of the emulsion containing MCT at a low concentration and the olive emulsion. Based on these results, since surfactants and antiseptic agents markedly damage sensitive skin tissue such as that with atopic dermatitis, surfactant- and antiseptic-free emulsions are expected to be new bases for drugs for external use.

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.

Optical band gap and spectroscopic study of lithium alumino silicate glass containing Y3+ ions.

PubMed

Shakeri, M S; Rezvani, M

2011-09-01

The effect of different amounts of Y2O3 dopant on lithium alumino silicate (LAS) glass has been studied in this work. Glasses having 14.8Li2O-20Al2O3-65.2SiO2 (wt%) composition accompanied with Y2O3 dopant were prepared by normal melting process. In order to calculate the absorption coefficient of samples, transmittance and reflectance spectra of polished samples were measured in the room temperature. Optical properties i.e. Fermi energy level, direct and indirect optical band gaps and Urbach energy were calculated using functionality of extinction coefficient from Fermi-Dirac distribution function, Tauc's plot and the exponential part of absorption coefficient diagram, respectively. It has been clarified that variation in mentioned optical parameters is associated with the changes in physical properties of samples i.e. density or molar mass. On the other hand, increasing of Y3+ ions in the glassy microstructure of samples provides a semiconducting character to LAS glass by reducing the direct and indirect optical band gaps of glass samples from 1.97 to 1.67 and 3.46 to 2.1 (eV), respectively. These changes could be attributed to the role of Y3+ ions as the network former in the track of SiO4 tetrahedrals. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Interactions between tectonics, silicate weathering, and climate explored with carbon cycle modeling

NASA Astrophysics Data System (ADS)

Penman, D. E.; Caves Rugenstein, J. K.; Ibarra, D. E.; Winnick, M.

2017-12-01

Earth's long-term carbon cycle is thought to benefit from a stabilizing negative feedback in the form of CO2 consumption by the chemical weathering of silicate minerals: during periods of elevated atmospheric pCO2, chemical weathering rates increase, thus consuming more atmospheric CO2 and cooling global climate, whereas during periods of low pCO2, weathering rates decrease, allowing buildup of CO2 in the atmosphere and warming. At equilibrium, CO2 consumption by silicate weathering balances volcanic CO2 degassing at a specific atmospheric pCO2 dictated by the relationship between total silicate weathering rate and pCO2: Earth's "weathering curve." We use numerical carbon cycle modeling to demonstrate that the shape and slope of the weathering curve is crucial to understanding proposed tectonic controls on pCO2 and climate. First, the shape of the weathering curve dictates the equilibrium response of the carbon cycle to changes in the rate of background volcanic/solid Earth CO2 degassing, which has been suggested to vary significantly with plate tectonic reorganizations over geologic timescales. Second, we demonstrate that if tectonic events can significantly change the weathering curve, this can act as an effective driver of pCO2 and climate on tectonic timescales by changing the atmospheric pCO2 at which silicate weathering balances a constant volcanic/solid Earth degassing rate. Finally, we review the complex interplay of environmental factors that affect modern weathering rates in the field and highlight how the resulting uncertainty surrounding the shape of Earth's weathering curve significantly hampers our ability to quantitatively predict the response of pCO2 and climate to tectonic forcing, and thus represents a substantial knowledge gap in Earth science. We conclude with strategies for closing this knowledge gap by using precise paleoclimatic reconstructions of intervals with known tectonic forcings.

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.

Biological and Organic Chemical Decomposition of Silicates. Chapter 7.2

NASA Technical Reports Server (NTRS)

Silverman, M. P.

1979-01-01

The weathering of silicate rocks and minerals, an important concern of geologists and geochemists for many years, traditionally has been approached from strictly physical and chemical points of view. Biological effects were either unrecognized, ignored, or were mentioned in passing to account for such phenomena as the accumulation of organic matter in sediments or the generation of reducing environments. A major exception occurred in soil science where agricultural scientists, studying the factors important in the development of soils and their ability to nourish and sustain various crops, laid the foundation for much of what is known of the biological breakdown of silicate rocks and minerals. The advent of the space age accelerated the realization that many environmental problems and geo- chemical processes on Earth can only be understood in terms of ecosystems. This in turn, spurred renewed interest and activity among modem biologists, geologists and soil scientists attempting to unravel the intimate relations between biology and the weathering of silicate rocks and minerals of the earth surface.

Biological and Organic Chemical Decomposition of Silicates. Chapter 7.2

NASA Technical Reports Server (NTRS)

Sliverman, M. P.

1979-01-01

The weathering of silicate rocks and minerals, an important concern of geologists and geochemists for many years, traditionally has been approached from strictly physical and chemical points of view. Biological effects were either unrecognized, ignored, or were mentioned in passing to account for such phenomena as the accumulation of organic matter in sediments or the generation of reducing environments. A major exception occurred in soil science where agricultural scientists, studying the factors important in the development of soils and their ability to nourish and sustain various crops, laid the foundation for much of what is known of the biological breakdown of silicate rocks and minerals. The advent of the space age accelerated the realization that many environmental problems and geochemical processes on Earth can only be understood in terms of ecosystems. This in turn, spurred renewed interest and activity among modem biologists, geologists and soil scientists attempting to unravel the intimate relations between biology and the weathering of silicate rocks and minerals of the earth's surface.

Evolution of trees and mycorrhizal fungi intensifies silicate mineral weathering

PubMed Central

Quirk, Joe; Beerling, David J.; Banwart, Steve A.; Kakonyi, Gabriella; Romero-Gonzalez, Maria E.; Leake, Jonathan R.

2012-01-01

Forested ecosystems diversified more than 350 Ma to become major engines of continental silicate weathering, regulating the Earth's atmospheric carbon dioxide concentration by driving calcium export into ocean carbonates. Our field experiments with mature trees demonstrate intensification of this weathering engine as tree lineages diversified in concert with their symbiotic mycorrhizal fungi. Preferential hyphal colonization of the calcium silicate-bearing rock, basalt, progressively increased with advancement from arbuscular mycorrhizal (AM) to later, independently evolved ectomycorrhizal (EM) fungi, and from gymnosperm to angiosperm hosts with both fungal groups. This led to ‘trenching’ of silicate mineral surfaces by AM and EM fungi, with EM gymnosperms and angiosperms releasing calcium from basalt at twice the rate of AM gymnosperms. Our findings indicate mycorrhiza-driven weathering may have originated hundreds of millions of years earlier than previously recognized and subsequently intensified with the evolution of trees and mycorrhizas to affect the Earth's long-term CO2 and climate history. PMID:22859556

Evolution of trees and mycorrhizal fungi intensifies silicate mineral weathering.

PubMed

Quirk, Joe; Beerling, David J; Banwart, Steve A; Kakonyi, Gabriella; Romero-Gonzalez, Maria E; Leake, Jonathan R

2012-12-23

Forested ecosystems diversified more than 350 Ma to become major engines of continental silicate weathering, regulating the Earth's atmospheric carbon dioxide concentration by driving calcium export into ocean carbonates. Our field experiments with mature trees demonstrate intensification of this weathering engine as tree lineages diversified in concert with their symbiotic mycorrhizal fungi. Preferential hyphal colonization of the calcium silicate-bearing rock, basalt, progressively increased with advancement from arbuscular mycorrhizal (AM) to later, independently evolved ectomycorrhizal (EM) fungi, and from gymnosperm to angiosperm hosts with both fungal groups. This led to 'trenching' of silicate mineral surfaces by AM and EM fungi, with EM gymnosperms and angiosperms releasing calcium from basalt at twice the rate of AM gymnosperms. Our findings indicate mycorrhiza-driven weathering may have originated hundreds of millions of years earlier than previously recognized and subsequently intensified with the evolution of trees and mycorrhizas to affect the Earth's long-term CO(2) and climate history.

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

Ag-doped Lithium alumino silicate photostructurable glass for microdevice fabrication

NASA Astrophysics Data System (ADS)

Mishra, Richa; Goswami, Madhumita; Krishnan, Madangopal

2018-04-01

Ag-doped LAS glass of composition (wt.%):74SiO2-6Al2O3-15Li2O-5X (X=other additives) were prepared by melt-quench technique and characterized for thermal and optical properties using DTA and UV-Visible spectrometer. XRD technique was used for phase identification in the heat treated glasses. Glass samples were exposed to UV-light for conversion of Ce3+ to Ce4+ state and Ag+ into Ago metallic state. DTA shows a lower crystallization temperature (Tp) at around 605°C for exposed samples as compared to unexposed base glass which is at around 625°C. UV-Visible spectra shows a broad band at around 305nm which indicates Ce3+ in base glass whereas in case of UV-exposed sample the reduced peak intensity indicates conversion of Ce3+ to Ce4+ ions, which also confirm formation of Ago in glass samples. Ag agglomeration was also confirmed from the band position at 430nm in heat treated sample, found responsible for early growth of meta-silicate phase in exposed sample. The meta-silicate phase was selectively etched for fabrication of micro-devices.

Partitioning of Moderately Siderophile Elements Among Olivine, Silicate Melt, and Sulfide Melt: Constraints on Core Formation in the Earth and Mars

NASA Technical Reports Server (NTRS)

Gaetani, Glenn A.; Grove, Timothy L.

1997-01-01

This study investigates the effects of Variations in the fugacities of oxygen and sulfur on the partitioning of first series transition metals (V, Cr, Mn, Fe, Co, Ni. and Cu) and W among coexisting sulfide melt, silicate melt, and olivine. Experiments were performed at 1 atm pressure, 1350 C, with the fugacities of oxygen and sulfur controlled by mixing CO2, CO, and SO2 gases. Starting compositions consisted of a CaO-MgO-Al2O3-SiO2-FeO-Na2O analog for a barred olivine chondrule from an ordinary chondrite and a synthetic komatiite. The f(sub O2)/f(sub S2), conditions ranged from log of f(sub O2) = -7.9 to - 10.6, with log of f(sub S2) values ranging from - 1.0 to -2.5. Our experimental results demonstrate that the f(sub O2)/f(sub S2) dependencies of sulfide melt/silicate melt partition coefficients for the first series transition metals arc proportional to their valence states. The f(sub O2)/f(sub S2) dependencies for the partitioning of Fe, Co, Ni, and Cu are weaker than predicted on the basis of their valence states. Variations in conditions have no significant effect on olivine/melt partitioning other than those resulting from f(sub O2)-induced changes in the valence state of a given element. The strong f(sub O2)/f(sub S2) dependence for the olivine/silicate melt partitioning of V is attributable to a change of valence state, from 4+ to 3+, with decreasing f(sub O2). Our experimentally determined partition coefficients are used to develop models for the segregation of sulfide and metal from the silicate portion of the early Earth and the Shergottite parent body (Mars). We find that the influence of S is not sufficient to explain the overabundance of siderophile and chalcophile elements that remained in the mantle of the Earth following core formation. Important constraints on core formation in Mars are provided by our experimental determination of the partitioning of Cu between silicate and sulfide melts. When combined with existing estimates for siderophile

Silicates in Alien Asteroids

NASA Technical Reports Server (NTRS)

2009-01-01

This plot of data from NASA's Spitzer Space Telescopes shows that asteroid dust around a dead 'white dwarf' star contains silicates a common mineral on Earth. The data were taken primarily by Spitzer's infrared spectrograph, an instrument that breaks light apart into its basic constituents. The yellow dots show averaged data from the spectrograph, while the orange triangles show older data from Spitzer's infrared array camera. The white dwarf is called GD 40.

Characterization of iron-phosphate-silicate chemical garden structures.

PubMed

Barge, Laura M; Doloboff, Ivria J; White, Lauren M; Stucky, Galen D; Russell, Michael J; Kanik, Isik

2012-02-28

Chemical gardens form when ferrous chloride hydrate seed crystals are added or concentrated solutions are injected into solutions of sodium silicate and potassium phosphate. Various precipitation morphologies are observed depending on silicate and phosphate concentrations, including hollow plumes, bulbs, and tubes. The growth of precipitates is controlled by the internal osmotic pressure, fluid buoyancy, and membrane strength. Additionally, rapid bubble-led growth is observed when silicate concentrations are high. ESEM/EDX analysis confirms compositional gradients within the membranes, and voltage measurements across the membranes during growth show a final potential of around 150-200 mV, indicating that electrochemical gradients are maintained across the membranes as growth proceeds. The characterization of chemical gardens formed with iron, silicate, and phosphate, three important components of an early earth prebiotic hydrothermal system, can help us understand the properties of analogous structures that likely formed at submarine alkaline hydrothermal vents in the Hadean-structures offering themselves as the hatchery of life. © 2011 American Chemical Society

The adsorption kinetics of metal ions onto different microalgae and siliceous earth.

PubMed

Schmitt, D; Müller, A; Csögör, Z; Frimmel, F H; Posten, C

2001-03-01

In the present work the adsorption kinetics of the six metal ions aluminum, zinc, mercury, lead, copper, and cadmium onto living microalgae were measured. The freshwater green microalga Scenedesmus subspicatus, the brackish water diatom Cyclotella cryptica, the seawater diatom Phaeodactylum tricornutum, and the seawater red alga Porphyridium purpureum were the subject of investigation. In most cases the adsorption rate of the metals could be well described by using the equation of the Langmuir adsorption rate expression. Inverse parameter estimation allowed the determination of the rate constants of the adsorption process and the maximum metal content of the algae. The highest values for the rate constant were obtained for Porphyridium purpureum followed by Phaeodactylum tricornutum. High values for the maximum content were obtained for Cyclotella cryptica and Scenedesmus subspicatus. The maximum rate constant was 24.21 h-1 for the adsorption of Hg to Porphyridium purpureum whereas the maximum metal content (0.243 g g-1) was obtained for Zn on Cyclotella cryptica. A comparison of these values with those obtained for the mineral siliceous earth exhibiting low maximum content and high adsorption rates reveals that the mechanism of adsorption onto the algae is a mixture of adsorption and accumulation.

Partitioning of light lithophile elements during basalt eruptions on Earth and application to Martian shergottites

NASA Astrophysics Data System (ADS)

Edmonds, Marie

2015-02-01

An enigmatic record of light lithophile element (LLE) zoning in pyroxenes in basaltic shergottite meteorites, whereby LLE concentrations decrease dramatically from the cores to the rims, has been interpreted as being due to partitioning of LLE into a hydrous vapor during magma ascent to the surface on Mars. These trends are used as evidence that Martian basaltic melts are water-rich (McSween et al., 2001). Lithium and boron are light lithophile elements (LLE) that partition into volcanic minerals and into vapor from silicate melts, making them potential tracers of degassing processes during magma ascent to the surface of Earth and of other planets. While LLE degassing behavior is relatively well understood for silica-rich melts, where water and LLE concentrations are relatively high, very little data exists for LLE abundance, heterogeneity and degassing in basaltic melts. The lack of data hampers interpretation of the trends in the shergottite meteorites. Through a geochemical study of LLE, volatile and trace elements in olivine-hosted melt inclusions from Kilauea Volcano, Hawaii, it can be demonstrated that lithium behaves similarly to the light to middle rare Earth elements during melting, magma mixing and fractionation. Considerable heterogeneity in lithium and boron is inherited from mantle-derived primary melts, which is dominant over the fractionation and degassing signal. Lithium and boron are only very weakly volatile in basaltic melt erupted from Kilauea Volcano, with vapor-melt partition coefficients <0.1. Degassing of LLE is further inhibited at high temperatures. Pyroxene and associated melt inclusion LLE concentrations from a range of volcanoes are used to quantify lithium pyroxene-melt partition coefficients, which correlate negatively with melt H2O content, ranging from 0.13 at low water contents to <0.08 at H2O contents >4 wt%. The observed terrestrial LLE partitioning behavior is extrapolated to Martian primitive melts through modeling. The zoning

Lithium-aluminum-iron electrode composition

DOEpatents

Kaun, Thomas D.

1979-01-01

A negative electrode composition is presented for use in a secondary electrochemical cell. The cell also includes an electrolyte with lithium ions such as a molten salt of alkali metal halides or alkaline earth metal halides that can be used in high-temperature cells. The cell's positive electrode contains a a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent in an alloy of aluminum-iron. Various binary and ternary intermetallic phases of lithium, aluminum and iron are formed. The lithium within the intermetallic phase of Al.sub.5 Fe.sub.2 exhibits increased activity over that of lithium within a lithium-aluminum alloy to provide an increased cell potential of up to about 0.25 volt.

Equation of state of silicate liquids

NASA Astrophysics Data System (ADS)

Jing, Zhicheng

Equation of state of silicate liquids is crucial to our understanding of melting processes such as the generation and differentiation of silicate melts in Earth and hence to explore the geophysical and geochemical consequences of melting. A comparison of compressional properties reveals fundamental differences in compressional mechanisms between silicate liquids and solids. Due to a liquid's ability to change structures, the compression of liquids is largely controlled by the entropic contribution to the free energy in addition to the internal energy contribution that is available to solids. In order to account for the entropic contribution, a new equation of state of silicate liquids is proposed based on the theory of hard-sphere mixtures. The equation of state is calibrated for SiO2-Al 2O3-FeO-MgO-CaO liquids and other systems. The new equation of state provides a unified explanation for the experimental observations on compressional properties of liquids including the bulk moduli of silicate liquids as well as the pressure dependence of Gruneisen parameter. The effect of chemical composition on melt density can be studied by the equation of state. Results show that FeO and H2O are the most important components in melts that control the melt density at high pressure due to their very different mean atomic masses from other melt components. Adding SiO2 can make a melt more compressible at high pressure due to its continuous change of coordination from 4-fold to 6-fold. The effect of 1-120 on melt density is further investigated by high-pressure experiments at the conditions of 9 to 15 GPa (corresponding to the depths of 300-500 km in the Earth) and 1900 °C to 2200 °C. The density of three dry melts and four hydrous melts with 2-7 wt% H2O was determined. Density data are analyzed by both the Birch-Mumaghan equation of state and the hard sphere equation of state. The partial molar volume of H2O is determined to be 8.8 cm3/mol at 14 GPa and 2173 K. The hypothesis

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

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

NASA Astrophysics Data System (ADS)

Singletary, S.; Drake, M. J.

2004-12-01

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 (Drake and Righter, 2002; Jones and Drake, 1986; Righter et al. 1997). The partitioning of siderophile elements is controlled by temperature, pressure, oxygen fugacity, and by the compositions of the metal and silicate phases. In this work, we investigate the role of silicate melt composition on the partitioning of the siderophile elements W, Ge, Ga and Ni between metallic and silicate liquid. Experiments were performed in the Experimental Geochemistry Laboratory at the University of Arizona utilizing a non-end loaded piston cylinder apparatus with a barium carbonate pressure medium. Starting materials were created by combining the mafic and silicic compositions of Jaeger and Drake (2000) with Fe powder (~25 wt% of the total mixture) to achieve metal saturation. Small amounts of W, Ge, Ga2O3 and NiO powder (less than 2 wt% each) were also added to the starting compositions. The experiments were contained in a graphite capsule and performed with temperature and pressure fixed at 1400ºC and 1.5 GPa. Experimental run products were analyzed with the University of Arizona Cameca SX50 electron microprobe with four wavelength dispersive spectrometers and a PAP ZAF correction program. All experiments in our set are saturated with metal and silicate liquid, indicating that oxygen fugacity is below IW. Several of the runs also contain a gallium-rich spinel as an additional saturating phase. Quench phases are also present in the silicate liquid in all runs. The experimentally produced liquids have nbo/t values (calculated using the method of Mills, 1993) that range from 1.10 to 2.97. These values are higher than those calculated for the liquids in the Jaeger and Drake (2000) study. The higher nbo/t values are due to uptake of Fe by the melt. The initial silicate

Natural Weathering Rates of Silicate Minerals

NASA Astrophysics Data System (ADS)

White, A. F.

2003-12-01

Silicates constitute more than 90% of the rocks exposed at Earth's land surface (Garrels and Mackenzie, 1971). Most primary minerals comprising these rocks are thermodynamically unstable at surface pressure/temperature conditions and are therefore susceptible to chemical weathering. Such weathering has long been of interest in the natural sciences. Hartt (1853) correctly attributed chemical weathering to "the efficacy of water containing carbonic acid in promoting the decomposition of igneous rocks." Antecedent to the recent interest in the role of vegetation on chemical weathering, Belt (1874) observed that the most intense weathering of rocks in tropical Nicaragua was confined to forested regions. He attributed this effect to "the percolation through rocks of rain water charged with a little acid from decomposing vegetation." Chamberlin (1899) proposed that the enhanced rates of chemical weathering associated with major mountain building episodes in Earth's history resulted in a drawdown of atmospheric CO2 that led to periods of global cooling. Many of the major characteristics of chemical weathering had been described when Merrill (1906) published the groundbreaking volume Rocks, Rock Weathering, and Soils.The major advances since that time, particularly during the last several decades, have centered on understanding the fundamental chemical, hydrologic, and biologic processes that control weathering and in establishing quantitative weathering rates. This research has been driven by the importance of chemical weathering to a number environmentally and economically important issues. Undoubtedly, the most significant aspect of chemical weathering is the breakdown of rocks to form soils, a process that makes life possible on the surface of the Earth. The availability of many soil macronutrients such as magnesium, calcium, potassium, and PO4 is directly related to the rate at which primary minerals weather. Often such nutrient balances are upset by anthropogenic

Effect of H2O on metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe: Implications for the oxidation state of the Earth and Mars

NASA Astrophysics Data System (ADS)

Clesi, V.; Bouhifd, M. A.; Bolfan-Casanova, N.; Manthilake, G.; Fabbrizio, A.; Andrault, D.

2016-11-01

This study investigates the metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe during core mantle differentiation of terrestrial planets under hydrous conditions. For this, we equilibrated a molten hydrous CI chondrite model composition with various Fe-rich alloys in the system Fe-C-Ni-Co-Si-S in a multi-anvil over a range of P, T, fO2 and water content (5-20 GPa, 2073-2500 K, from 1 to 5 log units below the iron-wüstite (IW) buffer and for XH2O varying from 500 ppm to 1.5 wt%). By comparing the present experiments with the available data sets on dry systems, we observes that the effect of water on the partition coefficients of moderately siderophile elements is only moderate. For example, for iron we observed a decrease in the partition coefficient of Fe (Dmet/silFe) from 9.5 to 4.3, with increasing water content of the silicate melt, from 0 to 1.44 wt%, respectively. The evolution of metal-silicate partition coefficients of Ni, Co, V, Cr, Mn and Fe are modelled based on sets of empirical parameters. These empirical models are then used to refine the process of core segregation during accretion of Mars and the Earth. It appears that the likely presence of 3.5 wt% water on Mars during the core-mantle segregation could account for ∼74% of the FeO content of the Martian mantle. In contrast, water does not play such an important role for the Earth; only 4-6% of the FeO content of its mantle could be due to the water-induced Fe-oxidation, for a likely initial water concentration of 1.8 wt%. Thus, in order to reproduce the present-day FeO content of 8 wt% in the mantle, the Earth could initially have been accreted from a large fraction (between 85% and 90%) of reducing bodies (similar to EH chondrites), with 10-15% of the Earth's mass likely made of more oxidized components that introduced the major part of water and FeO to the Earth. This high proportion of enstatite chondrites in the original constitution of the Earth is consistent with the 17O,48Ca,50Ti,62Ni

Influence of accretion on lead in the Earth

NASA Astrophysics Data System (ADS)

Galer, Stephen J. G.; Goldstein, Steven L.

The Pb abundance and isotope composition of the Earth is fundamentally altered from bulk solar system values by the processes occurring during accretion. The most important of the possible processes are volatile element loss and core formation, or some form of inhomogeneous accretion/condensation. The final result is an Earth highly impoverished in 204Pb and other Pb isotopes in primordial abundance. Depending on the exact timing, some radiogenic Pb is also lost either to space or to the core; the degree of loss occurs in the same order as the parent decay constants, namely 207Pb > 206Pb > 208Pb. In this contribution, we explore the likely effects accretion had on the Pb isotope composition of the present day bulk silicate Earth and its secular isotope evolution. This is used to address a number of questions: (1) What can be learned about accretion from the Pb isotope composition of the bulk silicate Earth? (2) Can effects of accretion reconcile the classical "Pb paradox" of a 206Pb-rich bulk silicate Earth? (3) What exactly is the meaning of the "age of the Earth" within the context of Pb isotopes? By consideration of a number of accretion scenarios it is demonstrated that Pb isotopes yield information only on the following two coupled quantities: Firstly, the accretion interval Δ T, the time between initial condensation of the solar nebula (at 4.566Ga) and when accretion-produced U/Pb fractionation (whether loss of Pb to the core or to space) in the silicate Earth ceased. Secondly, the mean 238U/204 Pb ratio μ during accretion—no details of changes in μ during the accretion interval can be resolved. The effects of accretion are thus adequately considered in terms of a simple two-stage model described by μ over ΔT followed by a postaccretion μ. The systematics of μ and ΔT are then examined for the cases of present day terrestrial reservoirs and Archean leads. These estimates of μ and ΔT for the present and past silicate Earth are not compatible with �

PROCESS FOR SEPARATING AMERICIUM AND CURIUM FROM RARE EARTH ELEMENTS

DOEpatents

Baybarz, R.D.; Lloyd, M.H.

1963-02-26

This invention relates to methods of separating americium and curium values from rare earth values. In accordance with the invention americium, curium, and rare earth values are sorbed on an anion exchange resin. A major portion of the rare earth values are selectively stripped from the resin with a concentrated aqueous solution of lithium chloride, and americium, curium, and a minor portion of rare earth values are then stripped from the resin with a dilute aqueous solution of lithium chloride. The americium and curium values are further purified by increasing the concentration of lithium chloride in the solution to at least 8 molar and selectively extracting rare earth values from the resulting solution with a monoalkylphosphoric acid. (AEC)

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.

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

PubMed

Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

2018-02-19

The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

Geochemical Constraints on Core Formation in the Earth

NASA Technical Reports Server (NTRS)

Jones, John H.; Drake, Michael J.

1986-01-01

New experimental data on the partitioning of siderophile and chalcophile elements among metallic and silicate phases may be used to constrain hypotheses of core formation in the Earth. Three current hypotheses can explain gross features of mantle geochemistry, but none predicts siderophile and chalcophile element abundances to within a factor of two of observed values. Either our understanding of metal-silicate interactions and/or our understanding of the early Earth requires revision.

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.

Thermoluminescence response of rare earth activated zinc lithium borate glass

NASA Astrophysics Data System (ADS)

Saidu, A.; Wagiran, H.; Saeed, M. A.; Obayes, H. K.; Bala, A.; Usman, F.

2018-03-01

New glasses of zinc lithium borate doped with terbium oxide were synthesized by high temperature solid-state reaction. The amorphous nature of the glasses was confirmed using x-ray diffraction analysis (XRD). Thermoluminescence (TL) response of pure zinc lithium borate (ZLB) and zinc lithium borate doped with terbium (ZLB: Tb) exposed to gamma radiation was measured and compared. There is significant enhancement in the TL yields of ZLB: Tb compared to that of pure ZLB. Effect of varying concentration of dopant (Tb4O7) on the TL response of zinc lithium borate was investigated. 0.3 mol% concentration of Tb exhibited strongest TL intensity. Thermoluminescence curve of the phosphor consist of single isolated peak. The TL response of the new materials to the exposed radiation is linear within 0.5-100 Gy range of dose with sublinearity at the lower region of the curve. High sensitivity was exhibited by the new amorphous materials. Reproducibility, thermal fading and energy response of the proposed TLD were investigated and shows remarkable result that made the phosphor suitable for radiation dosimetry.

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.

Lithium-aluminum-magnesium electrode composition

DOEpatents

Melendres, Carlos A.; Siegel, Stanley

1978-01-01

A negative electrode composition is presented for use in a secondary, high-temperature electrochemical cell. The cell also includes a molten salt electrolyte of alkali metal halides or alkaline earth metal halides and a positive electrode including a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent and a magnesium-aluminum alloy as a structural matrix. Various binary and ternary intermetallic phases of lithium, magnesium, and aluminum are formed but the electrode composition in both its charged and discharged state remains substantially free of the alpha lithium-aluminum phase and exhibits good structural integrity.

Scenario of Growing Crops on Silicates in Lunar Gargens

NASA Astrophysics Data System (ADS)

Kozyrovska, N.; Kovalchuk, M.; Negutska, V.; Lar, O.; Korniichuk, O.; Alpatov, A.; Rogutskiy, I.; Kordyum, V.; Foing, B.

Self-perpetuating gardens will be a practical necessity for humans, living in permanently manned lunar bases. A lunar garden has to supplement less appetizing packaged food brought from the Earth, and the ornamental plants have to serve as valuable means for emotional relaxation of crews in a hostile lunar environment. The plants are less prone to the inevitable pests and diseases when they are in optimum condition, however, in lunar greenhouses there is a threat for plants to be hosts for pests and predators. Although the lunar rocks are microorganism free, there will be a problem with the acquired infection (pathogens brought from the Earth) in the substrate used for the plant growing. On the Moon pests can be removed by total fumigation, including seed fumigation. However, such a treatment is not required when probiotics (biocontrol bacteria) for seed inoculation are used. A consortium of bacteria, controlling plant diseases, provides the production of an acceptable harvest under growth limiting factors and a threatening infection. To model lunar conditions we have used terrestrial alumino-silicate mineral anorthosite (Malyn, Ukraine) which served us as a lunar mineral analog for a substrate composition. With the idea to provide a plant with some essential growth elements siliceous bacterium Paenibacillus sp. has been isolated from alumino-silicate mineral, and a mineral leaching has been simulated in laboratory condition. The combination of mineral anorthosite and siliceous bacteria, on one hand, and a consortium of beneficial bacteria for biocontrol of plant diseases, on the other hand, are currently used in model experiments to examine the wheat and potato growth and production in cultivating chambers under controlled conditions.

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

Thermal Cycling and High-Temperature Corrosion Tests of Rare Earth Silicate Environmental Barrier Coatings

NASA Astrophysics Data System (ADS)

Darthout, Émilien; Gitzhofer, François

2017-12-01

Lutetium and yttrium silicates, enriched with an additional secondary zirconia phase, environmental barrier coatings were synthesized by the solution precursor plasma spraying process on silicon carbide substrates. A custom-made oven was designed for thermal cycling and water vapor corrosion testing. The oven can test four specimens simultaneously and allows to evaluate environmental barrier performances under similar corrosion kinetics compared to turbine engines. Coatings structural evolution has been observed by SEM on the polished cross sections, and phase composition has been analyzed by XRD. All coatings have been thermally cycled between 1300 °C and the ambient temperature, without spallation, due to their porosity and the presence of additional secondary phase which increases the thermal cycling resistance. During water vapor exposure at 1200 °C, rare earth disilicates showed a good stability, which is contradictory with the literature, due to impurities—such as Si- and Al-hydroxides—in the water vapor jets. The presence of vertical cracks allowed the water vapor to reach the substrate and then to corrode it. It has been observed that thin vertical cracks induced some spallation after 24 h of corrosion.

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

Textural constraints on effusive silicic volcanism - Beyond the permeable foam model

NASA Technical Reports Server (NTRS)

Fink, Jonathan H.; Anderson, Steven W.; Manley, Curtis R.

1992-01-01

The paper reports textural observations and presents isotopic evidence from active and recent silicic lava flows which show that at least some vesiculation occurs during surface advance of extrusions, after magma has reached the earth's surface. This view is in contrast to the widely promoted 'permeable foam' model, which states that all volatiles escape during ascent of the magma, and that all dense glassy material in lava flows forms from the collapse of pumiceous lava, i.e., that silicic lavas emerge as highly inflated foam flows. The permeable foam model also implies the unlikely requirement that explosive-to-effusive transitions be associated with an increase in the eruption rate. A more comprehensive model for the emplacement of silicic extrusions that allows for early gas loss during ascent, as well as late-stage vesiculation, is presented. The way in which the redistribution of volatiles during surface flow can increase explosive hazards from silicic lavas days, weeks, or months after the lava emerges from the event is discussed.

Comparison of light harmonic generation in Al and Ge consisted silicate materials

NASA Astrophysics Data System (ADS)

Smirnov, Vitaly A.; Vostrikova, Liubov I.

2018-04-01

The silicate materials are perspective for different areas of laser physics and photonics. In this paper the comparison of the nonlinear conversion with the generation of the light harmonic in Al- and Ge-containing silicate materials is presented. The peculiarities of the processes of the light harmonic generation in dependence on the concentrations of the chemical components are discussed and the influences of the additional small inclusion of the elements of fifth group and the rare-earth elements are estimated.

Mg-perovskite/silicate melt and magnesiowuestite/silicate melt partition coefficients for KLB-1 at 250 Kbars

NASA Technical Reports Server (NTRS)

Drake, Michael J.; Rubie, David C.; Mcfarlane, Elisabeth A.

1992-01-01

The partitioning of elements amongst lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements was reported previously, and these results as well as interpretations based on them have generated controversy. Here we report what are to our knowledge only the second set of directly measured trace element partition coefficients for a natural system (KLB-1).

An Update on the Lithium-Ion Cell Low-Earth-Orbit Verification Test Program

NASA Technical Reports Server (NTRS)

Reid, Concha M.; Manzo, Michelle A.; Miller, Thomas B.; McKissock, Barbara I.; Bennett, William

2007-01-01

A Lithium-Ion Cell Low-Earth-Orbit Verification Test Program is being conducted by NASA Glenn Research Center to assess the performance of lithium-ion (Li-ion) cells over a wide range of low-Earth-orbit (LEO) conditions. The data generated will be used to build an empirical model for Li-ion batteries. The goal of the modeling will be to develop a tool to predict the performance and cycle life of Li-ion batteries operating at a specified set of mission conditions. Using this tool, mission planners will be able to design operation points of the battery system while factoring in mission requirements and the expected life and performance of the batteries. Test conditions for the program were selected via a statistical design of experiments to span a range of feasible operational conditions for LEO aerospace applications. The variables under evaluation are temperature, depth-of-discharge (DOD), and end-of-charge voltage (EOCV). The baseline matrix was formed by generating combinations from a set of three values for each variable. Temperature values are 10 C, 20 C and 30 C. Depth-of-discharge values are 20%, 30% and 40%. EOCV values are 3.85 V, 3.95 V, and 4.05 V. Test conditions for individual cells may vary slightly from the baseline test matrix depending upon the cell manufacturer s recommended operating conditions. Cells from each vendor are being evaluated at each of ten sets of test conditions. Cells from four cell manufacturers are undergoing life cycle tests. Life cycling on the first sets of cells began in September 2004. These cells consist of Saft 40 ampere-hour (Ah) cells and Lith ion 30 Ah cells. These cells have achieved over 10,000 cycles each, equivalent to about 20 months in LEO. In the past year, the test program has expanded to include the evaluation of Mine Safety Appliances (MSA) 50 Ah cells and ABSL battery modules. The MSA cells will begin life cycling in October 2006. The ABSL battery modules consist of commercial Sony hard carbon 18650 lithium

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.

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.

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

Experimental constraints on Earth's core formation

NASA Astrophysics Data System (ADS)

Bouhifd, Mohamed Ali

2017-04-01

The Earth contains a Fe-rich metallic core that segregated from the primitive silicate mantle very early in its 4.5 billion year history. One major consequence of this segregation is the depletion of the Earth's mantle from the siderophile elements "high core affinity" relative to primitive solar system abundances. The way in which siderophile elements partition between metal and silicate depends strongly on pressure (P), temperature (T), oxygen fugacity (fO2) and chemical compositions of both metal and silicate phases. In the present presentation, I will discuss the experimental results of metal-silicate partitioning of Ni and Co that show a marked change with increasing pressure (e.g. Bouhifd and Jephcoat, 2011; Siebert et al., 2012; Fischer et al., 2015 for the most recent studies). This behavior coincides with a change in the coordination of silicon (in a basaltic melt composition) from 4-fold coordination under ambient conditions to 6-fold coordination at about 35 GPa, indicating that melt compressibility may controls siderophile-element partitioning (Sanloup et al., 2013). I will also discuss the impact of Earth's core formation on "lithophile" elements such as Sm, Nd, Ta and Nb (e.g. Bouhifd et al. 2015; Cartier et al., 2014), as well as the impact of sulphur on the behavior of various elements during core formation (e.g. Boujibar et al., 2014; Wohlers and Wood, 2015). By combining the metal-silicate partitioning data from siderophile, lithophile and chalcophile elements I will present and discuss the most plausible conditions for Earth's core formation. References Bouhifd and Jephcoat (2011) EPSL, 307, 341-348. Bouhifd et al. (2015) EPSL 413, 158-166. Boujibar et al. (2014) EPSL 391, 42-54. Cartier et al. (2014) Nature Geoscience, 7, 573-576. Fischer et al. (2015) GCA 167, 177-194. Sanloup et al. (2013) Nature, 503, 104-107. Siebert et al. (2012) EPSL 321-322, 189-197. Wohlers and Wood (2015) Nature 520, 337-340.

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.

Earth After the Moon Forming Impact

NASA Technical Reports Server (NTRS)

Zahnle, Kevin

2006-01-01

The Hadean Earth is widely and enduringly pictured as a world of exuberant volcanism, exploding meteors, huge craters, infernal heat, and billowing sulfurous steams; i.e., a world of fire and brimstone punctuated with blows to the head. In the background the Moon looms gigantic in the sky. The popular image has given it a name that celebrates our mythic roots. A hot early Earth is an inevitable consequence of accretion. The Moon-forming impact ensured that Earth as we know it emerged from a fog of silicate vapor. The impact separated the volatiles from the silicates. It took -100 years to condense and rain out the bulk of the vaporized silicates, although relatively volatile elements may have remained present in the atmosphere throughout the magma ocena stage. The magma ocean lasted approx. 2 Myr, its lifetime prolonged by tidal heating and thermal blanketing by a thick (CO2-rich steam atmosphere. Water oceans condensed quickly after the mantle solidified, but for some 10-100 Myr the surface would have stayed warm (approx. 500 K) until the CO2 was removed into the mantle. Thereafter the faint young Sun suggests that a lifeless Earth would always have been evolving toward a bitterly cold ice world, but the cooling trend was frequently interrupted by volcanic or impact induced thaws.

Simultaneous alloy-silicate fractionation of carbon, nitrogen, and sulfur at high pressures and temperatures: Implications for establishing the volatile budget of the Earth

NASA Astrophysics Data System (ADS)

Grewal, D. S.; Dasgupta, R.; Sun, C.; Tsuno, K.

2017-12-01

Constraining the origin, distribution and evolution of volatiles such as carbon (C), nitrogen (N) and sulfur (S) in terrestrial planets is essential to understand planetary differentiation, habitability and comparative planetology [1]. C/N ratio of Bulk Silicate Earth (BSE) is superchondritic (40 ± 8), while C/S ratio is nearly chondritic (0.49 ± 0.14) [2]. Accretion, core formation, and magma ocean (MO) crystallization are the key processes that could have set the relative budgets of C, N and S in different planetary reservoirs [3]. However, experiments using either C-N or C-S-bearing systems have shown that C is more siderophile than N and S, consequently core formation would have left behind subchondritic C/N and C/S ratios in BSE [4-6]. Accretion of extremely C-rich bodies during core formation or/and as a late veneer along with an early atmospheric blow-off are amongst the scenarios that have been suggested to explain C/N ratio while the addition of a differentiated body with a C-rich mantle has been suggested to explain C/S ratio in BSE [4-6]. However, no internally consistent explanations exist on the origin of all the volatile elements. We performed piston cylinder and multi-anvil experiments, using Fe-Ni-N-C±S alloy with variable amounts of S and mafic-ultramafic silicate mixtures in graphite saturated conditions at 1-7 GPa, 1600-1800 °C, and fO2 ranging from ΔIW of -1.1 to -0.3. EPMA and SIMS were used to determine major elements and volatile abundances in the coexisting alloy and silicate melt phases, while the speciation of the volatiles was determined using Raman spectroscopy. Our experimental data reveals that C becomes less siderophile in the presence of N and S during core-mantle differentiation involving an S-rich alloy. Using a set of inverse Monte-Carlo simulations, we propose that a disequilibrium merger of a Mars-sized planetary embryo with a C-saturated, S-rich core to a volatile-depleted proto-Earth during the main stage of accretion

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.

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.

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

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.

Climate stability of habitable Earth-like planets

NASA Astrophysics Data System (ADS)

Menou, Kristen

2015-11-01

The carbon-silicate cycle regulates the atmospheric CO2 content of terrestrial planets on geological timescales through a balance between the rates of CO2 volcanic outgassing and planetary intake from rock weathering. It is thought to act as an efficient climatic thermostat on Earth and, by extension, on other habitable planets. If, however, the weathering rate increases with the atmospheric CO2 content, as expected on planets lacking land vascular plants, the carbon-silicate cycle feedback can become severely limited. Here we show that Earth-like planets receiving less sunlight than current Earth may no longer possess a stable warm climate but instead repeatedly cycle between unstable glaciated and deglaciated climatic states. This has implications for the search for life on exoplanets in the habitable zone of nearby stars.

Ultrasonic Monitoring of the Interaction between Cement Matrix and Alkaline Silicate Solution in Self-Healing Systems.

PubMed

Ait Ouarabi, Mohand; Antonaci, Paola; Boubenider, Fouad; Gliozzi, Antonio S; Scalerandi, Marco

2017-01-07

Alkaline solutions, such as sodium, potassium or lithium silicates, appear to be very promising as healing agents for the development of encapsulated self-healing concretes. However, the evolution of their mechanical and acoustic properties in time has not yet been completely clarified, especially regarding their behavior and related kinetics when they are used in the form of a thin layer in contact with a hardened cement matrix. This study aims to monitor, using linear and nonlinear ultrasonic methods, the evolution of a sodium silicate solution interacting with a cement matrix in the presence of localized cracks. The ultrasonic inspection via linear methods revealed that an almost complete recovery of the elastic and acoustic properties occurred within a few days of healing. The nonlinear ultrasonic measurements contributed to provide further insight into the kinetics of the recovery due to the presence of the healing agent. A good regain of mechanical performance was ascertained through flexural tests at the end of the healing process, confirming the suitability of sodium silicate as a healing agent for self-healing cementitious systems.

The effects of lithium hydroxide solution on alkali silica reaction gels created with opal

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

Mitchell, Lyndon D.; Beaudoin, James J.; Grattan-Bellew, Patrick

The reaction of Nevada opal with calcium hydroxide, potassium hydroxide and lithium hydroxide solutions was investigated. In addition, opal was exposed to a combined solution of these three hydroxides. The progress of the three reactions was followed using X-ray diffraction (XRD), {sup 29}Si nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). The XRD results indicated the presence of a low-angle peak exclusive to the lithium-based reactions. The NMR results suggested a change in the silicate structure in the presence of lithium. These techniques indicated that the reaction of the alkali with the opal starting material is inhibited and perhapsmore » stopped in the presence of lithium hydroxide. SEM revealed that the morphology of the reaction products on the surface of the reacted opal grains is markedly different invariably. It was concluded that evidence to support the theory of a protective layer exists and that the nature of the layer varies with ion type.« less

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.

Detrital zircons and Earth system evolution

NASA Astrophysics Data System (ADS)

McKenzie, R.

2016-12-01

Zircon is a mineral commonly produced in silicic magmatism. Therefore, due to its resilience and exceedingly long residence times in the continental crust, detrital zircon records can be used to track processes associated with silicic magmatism throughout Earth history. In this contribution I will address the potential role of preservational biases in zircon record, and further discuss how zircon datasets can be used to help better understand the relationship between lithospheric and Earth system evolution. I will use large compilations of zircon data to trace the composition and weatherability of the continental crust, to evaluate temporal rates of crustal recycling, and finally to track spatiotemporal variation in continental arc magmatism and volcanic CO2 outgassing throughout Earth history. These records demonstrate that secular changes in plate tectonic regimes played a prominent role in modulating conditions of the ocean+atmosphere system and long-term climate state for the last 3 billion years.

Enamel and Dentin Surface Finishing Influence on the Roughness and Microshear Bond Strength of a Lithium Silicate Glass-Ceramic for Laminate Veneers.

PubMed

Gonzaga, Carla Castiglia; Bravo, Ruth Peggy; Pavelski, Thiago Vinícius; Garcia, Paula Pontes; Correr, Gisele Maria; Leonardi, Denise Piotto; da Cunha, Leonardo Fernandes; Furuse, Adilson Yoshio

2015-01-01

Objectives. This study evaluated the influence of cavity surface finishing with diamond burs of different grit mounted on high-speed turbine and ultrasound on the roughness and microshear bond strength (MBS) of a lithium silicate glass-ceramic to enamel and dentin. Methods. Enamel and dentin specimens were divided into seven groups, according to the type of surface finishing: 1200-grit sandpaper (control), two different brands of medium-grit and fine-grit diamond burs in a high-speed turbine; medium-grit and fine-grit CVD (chemical vapor deposition) tips in an ultrasonic device. Roughness parameters (n = 5) and MSBS to a glass-ceramic (n = 10) were determined. Data were analyzed using ANOVA and Tukey's test (α = 5%). Results. Control group showed lower mean roughness readings and groups that used medium-grit diamond burs showed the highest mean roughness values. Regarding MSBS, there was no statistical difference when comparing the groups gritted with the same brand of medium- and fine-grit burs and tips. Conclusions. Cavity surface finishing influenced the roughness parameters and MSBS of a glass-ceramic to enamel and dentin. Medium-grit diamond burs in high-speed turbine showed the highest mean roughness values. Fine-grit CVD tips in ultrasound presented the highest MSBS values for both enamel and dentin.

Enamel and Dentin Surface Finishing Influence on the Roughness and Microshear Bond Strength of a Lithium Silicate Glass-Ceramic for Laminate Veneers

PubMed Central

Gonzaga, Carla Castiglia; Bravo, Ruth Peggy; Pavelski, Thiago Vinícius; Garcia, Paula Pontes; Correr, Gisele Maria; Leonardi, Denise Piotto; da Cunha, Leonardo Fernandes; Furuse, Adilson Yoshio

2015-01-01

Objectives. This study evaluated the influence of cavity surface finishing with diamond burs of different grit mounted on high-speed turbine and ultrasound on the roughness and microshear bond strength (MBS) of a lithium silicate glass-ceramic to enamel and dentin. Methods. Enamel and dentin specimens were divided into seven groups, according to the type of surface finishing: 1200-grit sandpaper (control), two different brands of medium-grit and fine-grit diamond burs in a high-speed turbine; medium-grit and fine-grit CVD (chemical vapor deposition) tips in an ultrasonic device. Roughness parameters (n = 5) and MSBS to a glass-ceramic (n = 10) were determined. Data were analyzed using ANOVA and Tukey's test (α = 5%). Results. Control group showed lower mean roughness readings and groups that used medium-grit diamond burs showed the highest mean roughness values. Regarding MSBS, there was no statistical difference when comparing the groups gritted with the same brand of medium- and fine-grit burs and tips. Conclusions. Cavity surface finishing influenced the roughness parameters and MSBS of a glass-ceramic to enamel and dentin. Medium-grit diamond burs in high-speed turbine showed the highest mean roughness values. Fine-grit CVD tips in ultrasound presented the highest MSBS values for both enamel and dentin. PMID:27347507

The Earth's Mantle.

ERIC Educational Resources Information Center

McKenzie, D. P.

1983-01-01

The nature and dynamics of the earth's mantle is discussed. Research indicates that the silicate mantle is heated by the decay of radioactive isotopes and that the heat energizes massive convention currents in the upper 700 kilometers of the ductile rock. These currents and their consequences are considered. (JN)

Lithium-Ion Batteries Being Evaluated for Low-Earth-Orbit Applications

NASA Technical Reports Server (NTRS)

McKissock, Barbara I.

2005-01-01

The performance characteristics and long-term cycle life of aerospace lithium-ion (Li-ion) batteries in low-Earth-orbit applications are being investigated. A statistically designed test using Li-ion cells from various manufacturers began in September 2004 to study the effects of temperature, end-of-charge voltage, and depth-of-discharge operating conditions on the cycle life and performance of these cells. Performance degradation with cycling is being evaluated, and performance characteristics and failure modes are being modeled statistically. As technology improvements are incorporated into aerospace Li-ion cells, these new designs can be added to the test to evaluate the effect of the design changes on performance and life. Cells from Lithion and Saft have achieved over 2000 cycles under 10 different test condition combinations and are being evaluated. Cells from Mine Safety Appliances (MSA) and modules made up of commercial-off-the-shelf 18650 Li-ion cells connected in series/parallel combinations are scheduled to be added in the summer of 2005. The test conditions include temperatures of 10, 20, and 30 C, end-of-charge voltages of 3.85, 3.95, and 4.05 V, and depth-of-discharges from 20 to 40 percent. The low-Earth-orbit regime consists of a 55 min charge, at a constant-current rate that is 110 percent of the current required to fully recharge the cells in 55 min until the charge voltage limit is reached, and then at a constant voltage for the remaining charge time. Cells are discharged for 35 min at the current required for their particular depth-of-discharge condition. Cells are being evaluated in four-cell series strings with charge voltage limits being applied to individual cells by the use of charge-control units designed and produced at the NASA Glenn Research Center. These charge-control units clamp the individual cell voltages as each cell reaches its end-of-charge voltage limit, and they bypass the excess current from that cell, while allowing the full

Fatigue failure load of two resin-bonded zirconia-reinforced lithium silicate glass-ceramics: Effect of ceramic thickness.

PubMed

Monteiro, Jaiane Bandoli; Riquieri, Hilton; Prochnow, Catina; Guilardi, Luís Felipe; Pereira, Gabriel Kalil Rocha; Borges, Alexandre Luiz Souto; de Melo, Renata Marques; Valandro, Luiz Felipe

2018-06-01

To evaluate the effect of ceramic thickness on the fatigue failure load of two zirconia-reinforced lithium silicate (ZLS) glass-ceramics, adhesively cemented to a dentin analogue material. Disc-shaped specimens were allocated into 8 groups (n=25) considering two study factors: ZLS ceramic type (Vita Suprinity - VS; and Celtra Duo - CD), and ceramic thickness (1.0; 1.5; 2.0; and 2.5mm). A trilayer assembly (ϕ=10mm; thickness=3.5mm) was designed to mimic a bonded monolithic restoration. The ceramic discs were etched, silanized and luted (Variolink N) into a dentin analogue material. Fatigue failure load was determined using the Staircase method (100,000 cycles at 20Hz; initial fatigue load ∼60% of the mean monotonic load-to-failure; step size ∼5% of the initial fatigue load). A stainless-steel piston (ϕ=40mm) applied the load into the center of the specimens submerged in water. Fractographic analysis and Finite Element Analysis (FEA) were also performed. The ceramic thickness influenced the fatigue failure load for both ZLS materials: Suprinity (716N up to 1119N); Celtra (404N up to 1126N). FEA showed that decreasing ceramic thickness led to higher stress concentration on the cementing interface. Different ZLS glass-ceramic thicknesses influenced the fatigue failure load of the bonded system (i.e. the thicker the glass ceramic is, the higher the fatigue failure load will be). Different microstructures of the ZLS glass-ceramics might affect the fatigue behavior. FEA showed that the thicker the glass ceramic is, the lower the stress concentration at the tensile surface will be. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

Recent Progress in Advanced Materials for Lithium Ion Batteries

PubMed Central

Chen, Jiajun

2013-01-01

The development and commercialization of lithium ion batteries is rooted in material discovery. Promising new materials with high energy density are required for achieving the goal toward alternative forms of transportation. Over the past decade, significant progress and effort has been made in developing the new generation of Li-ion battery materials. In the review, I will focus on the recent advance of tin- and silicon-based anode materials. Additionally, new polyoxyanion cathodes, such as phosphates and silicates as cathode materials, will also be discussed. PMID:28809300

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.

Earth after the Moon-forming Impact

NASA Technical Reports Server (NTRS)

Zahnle, K. J.

2006-01-01

The Hadean Earth is widely and enduringly pictured as a world of exuberant volcanism, exploding meteors, huge craters, infernal heat, and billowing sulfurous steams; i.e., a world of fire and brimstone punctuated with blows to the head. In the background the Moon looms gigantic in the sky. The popular image has given it a name that celebrates our mythic roots. A hot early Earth is an inevitable consequence of accretion. The Moon-forming impact ensured that Earth as we know it emerged from a fog of silicate vapor. The impact separated the volatiles from the silicates. It took approx. 100 years to condense and rain out the bulk of the vaporized silicates, although relatively volatile elements may have remained present in the atmosphere throughout the magma ocena stage. The magma ocean lasted approx. 2 Myr, its lifetime prolonged by tidal heating and thermal blanketing by a thick CO2-rich steam atmosphere. Water oceans condensed quickly after the mantle solidified, but for some 10-100 Myr the surface would have stayed warm (approx. 500 K) until the CO2 was removed into the mantle. Thereafter the faint young Sun suggests that a lifeless Earth would always have been evolving toward a bitterly cold ice world, but the cooling trend was fiequently interrupted by volcanic or impact induced thaws. A cartoon history of water, temperature, and carbon dioxide in the aftermath of the moon-formining-impact is shown. How long it stays hot depends on how long it takes to scrub the C02 out of the atmosphere.

Li2C2, a High-Capacity Cathode Material for Lithium Ion Batteries.

PubMed

Tian, Na; Gao, Yurui; Li, Yurong; Wang, Zhaoxiang; Song, Xiaoyan; Chen, Liquan

2016-01-11

As a typical alkaline earth metal carbide, lithium carbide (Li2C2) has the highest theoretical specific capacity (1400 mA h g(-1)) among all the reported lithium-containing cathode materials for lithium ion batteries. Herein, the feasibility of using Li2C2 as a cathode material was studied. The results show that at least half of the lithium can be extracted from Li2C2 and the reversible specific capacity reaches 700 mA h g(-1). The C≡C bond tends to rotate to form C4 (C≡C⋅⋅⋅C≡C) chains during lithium extraction, as indicated with the first-principles molecular dynamics (FPMD) simulation. The low electronic and ionic conductivity are believed to be responsible for the potential gap between charge and discharge, as is supported with density functional theory (DFT) calculations and Arrhenius fitting results. These findings illustrate the feasibility to use the alkali and alkaline earth metal carbides as high-capacity electrode materials for secondary batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lithium isotopes as indicators of meteorite parent body alteration

NASA Astrophysics Data System (ADS)

Sephton, Mark A.; James, Rachael H.; Fehr, Manuela A.; Bland, Philip A.; Gounelle, Matthieu

2013-05-01

Hydrothermal processing on planetesimals in the early solar system produced new mineral phases, including those generated by the transformation of anhydrous silicates into their hydrated counterparts. Carbonaceous chondrites represent tangible remnants of such alteration products. Lithium isotopes are known to be responsive to aqueous alteration, yet previously recognized variability within whole rock samples from the same meteorite appears to complicate the use of these isotopes as indicators of processing by water. We demonstrate a new way to use lithium isotopes that reflects aqueous alteration in carbonaceous chondrites. Temperature appears to exert a control on the production of acetic acid-soluble phases, such as carbonates and poorly crystalline Fe-oxyhydroxides. Temperature and degree of water-rock interaction determines the amount of lithium isotope fractionation expressed as the difference between whole rock and acetic acid-leachable fractions. Using these features, the type 1 chondrite Orgueil (δ7Li(whole rock) = 4.3‰; Δ7Li(acetic-whole) = 1.2‰) can be distinguished from the type 2 chondrites Murchison (δ7Li(whole rock) = 3.8; Δ7Li(acetic-whole) = 8.8‰) and carbonate-poor Tagish Lake (δ7Li(whole rock) = 4.3; Δ7Li(acetic-whole) = 9.4‰). This initial study suggests that lithium isotopes have the potential to reveal the role of liquid water in the early solar system.

Early Earth differentiation [rapid communication

NASA Astrophysics Data System (ADS)

Walter, Michael J.; Trønnes, Reidar G.

2004-09-01

The birth and infancy of Earth was a time of profound differentiation involving massive internal reorganization into core, mantle and proto-crust, all within a few hundred million years of solar system formation ( t0). Physical and isotopic evidence indicate that the formation of iron-rich cores generally occurred very early in planetesimals, the building blocks of proto-Earth, within about 3 million years of t0. The final stages of terrestrial planetary accretion involved violent and tremendously energetic giant impacts among core-segregated Mercury- to Mars-sized objects and planetary embryos. As a consequence of impact heating, the early Earth was at times partially or wholly molten, increasing the likelihood for high-pressure and high-temperature equilibration among core- and mantle-forming materials. The Earth's silicate mantle harmoniously possesses abundance levels of the siderophile elements Ni and Co that can be reconciled by equilibration between iron alloy and silicate at conditions comparable to those expected for a deep magma ocean. Solidification of a deep magma ocean possibly involved crystal-melt segregation at high pressures, but subsequent convective stirring of the mantle could have largely erased nascent layering. However, primitive upper mantle rocks apparently have some nonchondritic major and trace element refractory lithophile element ratios that can be plausibly linked to early mantle differentiation of ultra-high-pressure mantle phases. The geochemical effects of crystal fractionation in a deep magma ocean are partly constrained by high-pressure experimentation. Comparison between compositional models for the primitive convecting mantle and bulk silicate Earth generally allows, and possibly favors, 10-15% total fractionation of a deep mantle assemblage comprised predominantly of Mg-perovskite and with minor but geochemically important amounts of Ca-perovskite and ferropericlase. Long-term isolation of such a crystal pile is generally

Zero-gravity growth of a sodium chloride-lithium fluoride eutectic mixture

NASA Technical Reports Server (NTRS)

Yue, A. S.; Yeh, C. W.; Yue, B. K.

1982-01-01

Continuous and discontinuous lithium fluoride fibers embedded in a sodium chloride matrix were produced in space and on Earth, respectively. The production of continuous fibers in a eutectic mixture was attributed to the absence of convective current in the liquid during solidification in space. Image transmission and optical transmittance measurements of transverse sections of the space-grown and Earth-grown ingots were made with a light microscope and a spectrometer. It was found that better optical properties were obtained from samples grown in space. This was attributed to a better alignment of lithium fluoride fibers along the growth direction.

How Deep and Hot was Earth's Magma Ocean? Combined Experimental Datasets for the Metal-silicate Partitioning of 11 Siderophile Elements - Ni, Co, Mo, W, P, Mn, V, Cr, Ga, Cu and Pd

NASA Technical Reports Server (NTRS)

Righter, Kevin

2008-01-01

Since approximately 1990 high pressure and temperature (PT) experiments on metal-silicate systems have showed that partition coefficients (D) for siderophile (iron-loving) elements are much different than those measured at low PT conditions. The high PT data have been used to argue for a magma ocean during growth of the early Earth. Initial conclusions were based on experiments and calculations for a small number of elements such as Ni and Co. However, for many elements only a limited number of experimental data were available then, and they only hinted at values of metal-silicate D's at high PT conditions. In the ensuing decades there have been hundreds of new experiments carried out and published on a wide range of siderophile elements. At the same time several different models have been advanced to explain the siderophile elements in the earth's mantle: a) intermediate depth magma ocean; 25-30 GPa, b) deep magma ocean; up to 50 GPa, and c) early reduced and later oxidized magma ocean. Some studies have drawn conclusions based on a small subset of siderophile elements, or a set of elements that provides little leverage on the big picture (like slightly siderophile elements), and no single study has attempted to quantitatively explain more than 5 elements at a time. The purpose of this abstract is to update the predictive expressions outlined by Righter et al. (1997) with new experimental data from the last decade, test the predictive ability of these expressions against independent datasets (there are more data now to do this properly), and to apply the resulting expressions to the siderophile element patterns in Earth's upper mantle. The predictive expressions have the form: lnD = alnfO2 + b/T + cP/T + d(1Xs) + e(1Xc) + SigmafiXi + g These expressions are guided by the thermodynamics of simple metal-oxide equilibria that control each element, include terms that mimic the activity coefficients of each element in the metal and silicate, and quantify the effect of

A nucleosynthetic origin for the Earth's anomalous (142)Nd composition.

PubMed

Burkhardt, C; Borg, L E; Brennecka, G A; Shollenberger, Q R; Dauphas, N; Kleine, T

2016-09-15

A long-standing paradigm assumes that the chemical and isotopic compositions of many elements in the bulk silicate Earth are the same as in chondrites. However, the accessible Earth has a greater (142)Nd/(144)Nd ratio than do chondrites. Because (142)Nd is the decay product of the now-extinct (146)Sm (which has a half-life of 103 million years), this (142)Nd difference seems to require a higher-than-chondritic Sm/Nd ratio for the accessible Earth. This must have been acquired during global silicate differentiation within the first 30 million years of Solar System formation and implies the formation of a complementary (142)Nd-depleted reservoir that either is hidden in the deep Earth, or lost to space by impact erosion. Whether this complementary reservoir existed, and whether or not it has been lost from Earth, is a matter of debate, and has implications for determining the bulk composition of Earth, its heat content and structure, as well as for constraining the modes and timescales of its geodynamical evolution. Here we show that, compared with chondrites, Earth's precursor bodies were enriched in neodymium that was produced by the slow neutron capture process (s-process) of nucleosynthesis. This s-process excess leads to higher (142)Nd/(144)Nd ratios; after correction for this effect, the (142)Nd/(144)Nd ratios of chondrites and the accessible Earth are indistinguishable within five parts per million. The (142)Nd offset between the accessible silicate Earth and chondrites therefore reflects a higher proportion of s-process neodymium in the Earth, and not early differentiation processes. As such, our results obviate the need for hidden-reservoir or super-chondritic Earth models and imply a chondritic Sm/Nd ratio for the bulk Earth. Although chondrites formed at greater heliocentric distances and contain a different mix of presolar components than Earth, they nevertheless are suitable proxies for Earth's bulk chemical composition.

An Earth-sized exoplanet with a Mercury-like composition

NASA Astrophysics Data System (ADS)

Santerne, A.; Brugger, B.; Armstrong, D. J.; Adibekyan, V.; Lillo-Box, J.; Gosselin, H.; Aguichine, A.; Almenara, J.-M.; Barrado, D.; Barros, S. C. C.; Bayliss, D.; Boisse, I.; Bonomo, A. S.; Bouchy, F.; Brown, D. J. A.; Deleuil, M.; Delgado Mena, E.; Demangeon, O.; Díaz, R. F.; Doyle, A.; Dumusque, X.; Faedi, F.; Faria, J. P.; Figueira, P.; Foxell, E.; Giles, H.; Hébrard, G.; Hojjatpanah, S.; Hobson, M.; Jackman, J.; King, G.; Kirk, J.; Lam, K. W. F.; Ligi, R.; Lovis, C.; Louden, T.; McCormac, J.; Mousis, O.; Neal, J. J.; Osborn, H. P.; Pepe, F.; Pollacco, D.; Santos, N. C.; Sousa, S. G.; Udry, S.; Vigan, A.

2018-05-01

Earth, Venus, Mars and some extrasolar terrestrial planets1 have a mass and radius that is consistent with a mass fraction of about 30% metallic core and 70% silicate mantle2. At the inner frontier of the Solar System, Mercury has a completely different composition, with a mass fraction of about 70% metallic core and 30% silicate mantle3. Several formation or evolution scenarios are proposed to explain this metal-rich composition, such as a giant impact4, mantle evaporation5 or the depletion of silicate at the inner edge of the protoplanetary disk6. These scenarios are still strongly debated. Here, we report the discovery of a multiple transiting planetary system (K2-229) in which the inner planet has a radius of 1.165 ± 0.066 Earth radii and a mass of 2.59 ± 0.43 Earth masses. This Earth-sized planet thus has a core-mass fraction that is compatible with that of Mercury, although it was expected to be similar to that of Earth based on host-star chemistry7. This larger Mercury analogue either formed with a very peculiar composition or has evolved, for example, by losing part of its mantle. Further characterization of Mercury-like exoplanets such as K2-229 b will help to put the detailed in situ observations of Mercury (with MESSENGER and BepiColombo8) into the global context of the formation and evolution of solar and extrasolar terrestrial planets.

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

Lithium isotope fractionation by diffusion in minerals Part 2: Olivine

NASA Astrophysics Data System (ADS)

Richter, Frank; Chaussidon, Marc; Bruce Watson, E.; Mendybaev, Ruslan; Homolova, Veronika

2017-12-01

Recent experiments have shown that lithium isotopes can be significantly fractionated by diffusion in silicate liquids and in augite. Here we report new laboratory experiments that document similarly large lithium isotopic fractionation by diffusion in olivine. Two types of experiments were used. A powder-source method where lithium from finely ground spodumene (LiAlSi2O6) diffused into oriented San Carlos olivine, and piston cylinder annealing experiments where Kunlun clinopyroxene (∼30 ppm lithium) and oriented San Carlos olivine (∼2 ppm lithium) were juxtaposed. The lithium concentration along traverses across the run products was measured using both laser ablation as a source for a Varian 820-MS quadrupole mass spectrometer and a CAMECA 1270 secondary ion mass spectrometer. The CAMECA 1270 was also used to measure the lithium isotopic fractionation across olivine grains recovered from the experiments. The lithium isotopes were found to be fractionationed by many tens of permil in the diffusion boundary layer at the grain edges as a result of 6Li diffusing significantly faster than 7Li. The lithium concentration and isotopic fractionation data across the olivine recovered from the different experiments were modeled using calculations in which lithium was assumed to be of two distinct types - one being fast diffusing interstitial lithium, the other much less mobile lithium on a metal site. The two-site diffusion model involves a large number of independent parameters and we found that different choices of the parameters can produce very comparable fits to the lithium concentration profiles and associated isotopic fractionation. Because of this nonuniqueness we are able to determine only a range for the relative diffusivity of 6Li compared to 7Li. When the mass dependence of lithium diffusion is parameterized as D6Li /D7Li =(7 / 6) β , the isotope fractionation for diffusion along the a and c crystallographic direction of olivine can be fit by β = 0.4 ± 0

Ground-based observation of near-Earth asteroids

NASA Technical Reports Server (NTRS)

Gaffey, Michael J.

1992-01-01

An increased ground-based observation program is an essential component of any serious attempt to assess the resource potential of near-Earth asteroids. A vigorous search and characterization program could lead to the discovery and description of about 400 to 500 near-Earth asteroids in the next 20 years. This program, in conjunction with meteorite studies, would provide the data base to ensure that the results of a small number of asteroid-rendezvous and sample-return missions could be extrapolated with confidence into a geological base map of the Aten, Apollo, and Amor asteroids. Ground-based spectral studies of nearly 30 members of the Aten/Apollo/Amor population provide good evidence that this class includes bodies composed of silicates, metal-silicates, and carbonaceous assemblages similar to those found in meteorites. The instruments that are being used or could be used to search for near-Earth asteroids are listed. Techniques useful in characterizing asteroids and the types of information obtainable using these techniques are listed.

Evidence against a chondritic Earth.

PubMed

Campbell, Ian H; O'Neill, Hugh St C

2012-03-28

The (142)Nd/(144)Nd ratio of the Earth is greater than the solar ratio as inferred from chondritic meteorites, which challenges a fundamental assumption of modern geochemistry--that the composition of the silicate Earth is 'chondritic', meaning that it has refractory element ratios identical to those found in chondrites. The popular explanation for this and other paradoxes of mantle geochemistry, a hidden layer deep in the mantle enriched in incompatible elements, is inconsistent with the heat flux carried by mantle plumes. Either the matter from which the Earth formed was not chondritic, or the Earth has lost matter by collisional erosion in the later stages of planet formation.

Lithium Iron Orthosilicate Cathode: Progress and Perspectives

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

Ni, Jiangfeng; Jiang, Yu; Bi, Xuanxuan

2017-07-18

The pursuit of cathodes with a high capacity is remarkably driven by the ever increasing demand of high-energy lithium ion batteries in electronics and transportation. In this regard, polyanionic lithium iron orthosilicate (Li2FeSiO4) offers a promising opportunity because it affords a high theoretical capacity of 331 mAh g–1. However, such a high theoretical capacity of Li2FeSiO4 has frequently been compromised in practice because of the extremely low electronic and ionic conductivity. To address this issue, material engineering strategies to boost the Li storage kinetics in Li2FeSiO4 have proven indispensable. In this Perspective, we will briefly present the structural characteristics, intrinsicmore » physicochemical properties, and electrochemical behavior of Li2FeSiO4. We particularly focus on recent materials engineering of silicates, which is implemented mainly through advanced synthetic techniques and elaborate controls. This Perspective highlights the importance of integrating theoretical analysis into experimental implementation to further advance the Li2FeSiO4 materials.« less

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.

Behaviour of Rare Earth Elements during the Earth's core formation

NASA Astrophysics Data System (ADS)

Faure, Pierre; Bouhifd, Mohamed Ali; Boyet, Maud; Hammouda, Tahar; Manthilake, Geeth

2017-04-01

Rare Earth Elements (REE) are classified in the refractory group, which means that they have a high temperature condensation and their volatility-controlled fractionation is limited to high-temperature processes. Anomalies have been measured for Eu, Yb and Sm, which are the REE with the lowest condensation temperatures in CAIs and chondrules (e.g. [1]). REE are particularly abundant in the sulfides of enstatite chondrites, 100 to 1000 times the CI value [e.g. 2,3], proving that these elements are not strictly lithophile under extremely reducing conditions. However by investigating experimentally the impact of Earth's core formation on the behavior of Sm and Nd, we have shown the absence of fractionation between Sm and Nd during the segregation of the metallic phase [4]. Recently, Wohlers and Wood [5] proposed that Nd and Sm could be fractionated in presence of a S-rich alloy phase. However, their results were obtained at pressure and temperature conditions below the plausible conditions of the Earth's core formation. Clearly, large pressure range needs to be covered before well-constrained model can be expected. Furthermore, our preliminary metal-silicate partitioning results show that Ce and Eu have higher metal/silicate partition coefficients than their neighboring elements, and that the presence of sulphur enhances the relative difference between partition coefficients. In this presentation, we will present and discuss new metal-silicate partition coefficients of all REE at a deep magma ocean at pressures ranging from those of the uppermost upper mantle ( 5 GPa) to a maximum pressure expected in the range of 20 GPa, temperatures ranging from 2500 to about 3000 K, and oxygen fugacities within IW-1 to IW-5 (1 to 5 orders of magnitude lower than the iron-wüstite buffer). We will discuss the effect of S, as well as the effect of H2O on the behaviour of REE during the Earth's core formation: recent models suggest that contrary to currently accepted beliefs, the

Hydrogen, lithium, and lithium hydride production

DOEpatents

Brown, Sam W.; Spencer, Larry S.; Phillips, Michael R.; Powell, G. Louis; Campbell, Peggy J.

2017-06-20

A method is provided for extracting hydrogen from lithium hydride. The method includes (a) heating lithium hydride to form liquid-phase lithium hydride; (b) extracting hydrogen from the liquid-phase lithium hydride, leaving residual liquid-phase lithium metal; (c) hydriding the residual liquid-phase lithium metal to form refined lithium hydride; and repeating steps (a) and (b) on the refined lithium hydride.

Time Evolution of Radiation-Induced Luminescence in Terbium-Doped Silicate Glass

NASA Technical Reports Server (NTRS)

West, Michael S.; Winfree, William P.

1996-01-01

A study was made on two commercially available terbium-doped silicate glasses. There is an increased interest in silicate glasses doped with rare-earth ions for use in high-energy particle detection and radiographic applications. These glasses are of interest due to the fact that they can be formed into small fiber sensors; a property that can be used to increase the spatial resolution of a detection system. Following absorption of radiation, the terbium ions become excited and then emit photons via 4f-4f electronic transitions as they relax back to the ground state. The lifetime of these transitions is on the order of milliseconds. A longer decay component lasting on the order of minutes has also been observed. While radiative transitions in the 4f shell of rare-earth ions are generally well understood by the Judd-Olfelt theory, the pr'esence of a longer luminescence decay component is not. Experimental evidence that the long decay component is due, in part, to the thermal release of trapped charge carriers will be presented. In addition, a theoretical model describing the time evolution of the radiation-induced luminescence will be presented.

Lithium conductivity in glasses of the Li2O-Al2O3-SiO2 system.

PubMed

Ross, Sebastian; Welsch, Anna-Maria; Behrens, Harald

2015-01-07

To improve the understanding of Li-dynamics in oxide glasses, i.e. the effect of [AlO4](-) tetrahedra and non-bridging oxygens on the potential landscape, electrical conductivity of seven fully polymerized and partly depolymerized lithium aluminosilicate glasses was investigated using impedance spectroscopy (IS). Lithium is the only mobile particle in these materials. Data derived from IS, i.e. activation energies, pre-exponential factors and diffusivities for lithium, are interpreted in light of Raman spectroscopic analyses of local structures in order to identify building units, which are crucial for lithium dynamics and migration. In polymerized glasses (compositional join LiAlSiO4-LiAlSi4O10) the direct current (DC) electrical conductivity continuously increases with increasing lithium content while lithium diffusivity is not affected by the Al/Si ratio in the glasses. Hence, the increase in electrical conductivity can be solely assigned to lithium concentration in the glasses. An excess of Li with respect to Al, i.e. the introduction of non-bridging oxygen into the network, causes a decrease in lithium mobility in the glasses. Activation energies in polymerized glasses (66 to 70 kJ mol(-1)) are significantly lower than those in depolymerized networks (76 to 78 kJ mol(-1)) while pre-exponential factors are nearly constant across all compositions. Comparison of the data with results for lithium silicates from the literature indicates a minimum in lithium diffusivity for glasses containing both aluminium tetrahedra and non-bridging oxygens. The findings allow a prediction of DC conductivity for a large variety of lithium aluminosilicate glass compositions.

Boson peak of alkali and alkaline earth silicate glasses: influence of the nature and size of the network-modifying cation.

PubMed

Richet, Nicolas F

2012-01-21

The influence of the size of the alkaline earth cation on the boson peak of binary metasilicate glasses, MSiO(3) (M = Mg, Ca, Sr, Ba), has been investigated from vibrational densities of states determined by inversion of low-temperature heat capacities. As given both by C(p)/T(3) and g(ω)/ω(2), the intensity of the boson peak undergoes a 7-fold increase from Mg to Ba, whereas its temperature and frequency correlatively decrease from 18 to 10 K and from 100 to 20 cm(-1), respectively. The boson peak results from a combination of librations of SiO(4) tetrahedra and localized vibrations of network-modifying cations with non-bridging oxygens whose contribution increases markedly with the ionic radius of the alkaline earth. As a function of ionic radii, the intensity for Sr and Ba varies in the same way as previously found for alkali metasilicate glasses. The localized vibrations involving alkali and heavy alkaline earth cations appear to be insensitive to the overall glass structure. Although the new data are coherent with an almost linear relationship between the temperature of the boson peak and transverse sound velocity, pure SiO(2) and SiO(2)-rich glasses make marked exceptions to this trend because of the weak transverse character of SiO(4) librations. Finally, the universality of the calorimetric boson peak is again borne out because all data for silicate glasses collapse on the same master curve when plotted in a reduced form (C(P)∕/T(3))/(C(P)/T(3))(b) vs. T/T(b). © 2012 American Institute of Physics

Final report on the safety assessment of potassium silicate, sodium metasilicate, and sodium silicate.

PubMed

Elmore, Amy R

2005-01-01

Potassium Silicate, Sodium Metasilicate, and Sodium Silicate combine metal cations with silica to form inorganic salts used as corrosion inhibitors in cosmetics. Sodium Metasilicate also functions as a chelating agent and Sodium Silicate as a buffering and pH adjuster. Sodium Metasilicate is currently used in 168 formulations at concentrations ranging from 13% to 18%. Sodium Silicate is currently used in 24 formulations at concentrations ranging from 0.3% to 55%. Potassium Silicate and Sodium Silicate have been reported as being used in industrial cleaners and detergents. Sodium Metasilicate is a GRAS (generally regarded as safe) food ingredient. Aqueous solutions of Sodium Silicate species are a part of a chemical continuum of silicates based on an equilibrium of alkali, water, and silica. pH determines the solubility of silica and, together with concentration, determines the degree of polymerization. Sodium Silicate administered orally is readily absorbed from the alimentary canal and excreted in the urine. The toxicity of these silicates has been related to the molar ratio of SiO2/Na2O and the concentration being used. The Sodium Metasilicate acute oral LD50 ranged from 847 mg/kg in male rats to 1349.3 mg/kg in female rats and from 770 mg/kg in female mice to 820 mg/kg in male mice. Gross lesions of variable severity were found in the oral cavity, pharynx, esophagus, stomach, larynx, lungs, and kidneys of dogs receiving 0.25 g/kg or more of a commercial detergent containing Sodium Metasilicate; similar lesions were also seen in pigs administered the same detergent and dose. Male rats orally administered 464 mg/kg of a 20% solution containing either 2.0 or 2.4 to 1.0 ratio of sodium oxide showed no signs of toxicity, whereas doses of 1000 and 2150 mg/kg produced gasping, dypsnea, and acute depression. Dogs fed 2.4 g/kg/day of Sodium Silicate for 4 weeks had gross renal lesions but no impairment of renal function. Dermal irritation of Potassium Silicate, Sodium

A case of the tail wagging the dog? Reverse weathering and Earth's CO2 thermostat.

NASA Astrophysics Data System (ADS)

Higgins, J. A.

2017-12-01

Feedbacks between climate, the global carbon cycle, and the chemistry of seawater stabilize Earth's surface temperature on geologic timescales and are likely responsible for its habitability over billions of years of Earth history. The most important component of the geologic carbon cycle is the precipitation and burial of carbonate sediments. The amount of carbonate sediment produced depends, in turn, on the alkalinity generated during silicate weathering less the amount consumed during the formation of secondary clay minerals both on the continents and in the ocean. In marine enviroments this process, often referred to as reverse weathering, consumes seawater alkalinity (and cations) via reaction with degraded Al-silicate minerals. Because these reactions constitute a sink of seawater alkalinity, changes in the amount of reverse weathering will lead to imbalances between alkalinity sources and sinks. The net effect is that on timescales greater than the timescale of carbonate compensation (< 10 kyr), changes in reverse weathering will lead to changes in the rate of continental silicate weathering through the dependence of continental silicate weathering on atmospheric CO2 and climate. This mechanism is capable of changing rates of continental silicate weathering without changing either the rate of volcanic outgassing or the rate constant for continental silicate weathering (i.e. through mountain-building or the exposure of different rock types) and as a result represents a unique way of modulating the global carbon cycle and Earth's climate on geologic timescales.

Nanosheets of earth-abundant jarosite as novel anodes for high-rate and long-life lithium-ion batteries.

PubMed

Ding, Yuan-Li; Wen, Yuren; Chen, Chia-Chin; van Aken, Peter A; Maier, Joachim; Yu, Yan

2015-05-20

Nanosheets of earth-abundant jarosite were fabricated via a facile template-engaged redox coprecipitation strategy at room temperature and employed as novel anode materials for lithium-ion batteries (LIBs) for the first time. These 2D materials exhibit high capacities, excellent rate capability, and prolonged cycling performance. As for KFe3(SO4)2(OH)6 jarosite nanosheets (KNSs), the reversible capacities of above 1300 mAh g(-1) at 100 mA g(-1) and 620 mAh g(-1) after 4000 cycles at a very high current density of 10 A g(-1) were achieved, respectively. Moreover, the resulting 2D nanomaterials retain good structural integrity upon cycling. These results reveal great potential of jarosite nanosheets as low-cost and high-performance anode materials for next-generation LIBs.

Constraints on cosmic silicates

NASA Astrophysics Data System (ADS)

Ossenkopf, V.; Henning, Th.; Mathis, J. S.

1992-08-01

Observational determinations of opacities of circumstellar silicates, relative to the peak value near 10 microns, are used to estimate the optical constants n and k, the real and imaginary parts of the index of refraction. Circumstellar dust is modified by processing within the interstellar medium. This leads to higher band strengths and a somewhat larger ratio of the opacities at the 18 and 10-micron peaks, compared with circumstellar silicates. By using an effective-medium theory, we calculate the effects of small spherical inclusions of various materials (various oxides, sulfides, carbides, amorphous carbon, and metallic iron) upon silicate opacities. Some of these can increase the absorption coefficient k in the 2-8 micron region appreciably, as is needed to reconcile laboratory silicate opacities with observations of both the interstellar medium and envelopes around late-type stars. We give tables of two sets of optical constants for warm oxygen-deficient and cool oxygen-rich silicates, representative for circumstellar and interstellar silicates. The required opacity in the 2-8 micron region is provided by iron and magnetite.

Hydrogen, lithium, and lithium hydride production

DOEpatents

Brown, Sam W; Spencer, Larry S; Phillips, Michael R; Powell, G. Louis; Campbell, Peggy J

2014-03-25

A method of producing high purity lithium metal is provided, where gaseous-phase lithium metal is extracted from lithium hydride and condensed to form solid high purity lithium metal. The high purity lithium metal may be hydrided to provide high purity lithium hydride.

The importance of the Maillard-metal complexes and their silicates in astrobiology

NASA Astrophysics Data System (ADS)

Liesch, Patrick J.; Kolb, Vera M.

2007-09-01

The Maillard reaction occurs when sugars and amino acids are mixed together in the solid state or in the aqueous solution. Since both amino acids and sugar-like compounds are found on meteorites, we hypothesized that they would also undergo the Maillard reaction. Our recent work supports this idea. We have shown previously that the water-insoluble Maillard products have substantial similarities with the insoluble organic materials from the meteorites. The Maillard organic materials are also part of the desert varnish on Earth, which is a dark, shiny, hard rock coating that contains iron and manganese and is glazed in silicate. Rocks that are similar in appearance to the desert varnish have been observed on the Martian surface. They may also contain the organic materials. We have undertaken study of the interactions between the Maillard products, iron and other metals, and silicates, to elucidate the role of the Maillard products in the chemistry of desert varnish and meteorites. Specifically, we have synthesized a series of the Maillard-metal complexes, and have tested their reactivity towards silicates. We have studied the properties of these Maillard-metal-silicate products by the IR spectroscopy. The astrobiological potential of the Maillard-metal complexes is assessed.

Measuring DAC metal-silicate partitioning experiments by electron microprobe: Thickness, fluorescence, and oxide spheres

NASA Astrophysics Data System (ADS)

Jennings, E. S.; Wade, J.; Laurenz, V.; Kearns, S.; Buse, B.; Rubie, D. C.

2017-12-01

The process by which the Earth's core segregated, and its resulting composition, can be inferred from the composition of the bulk silicate Earth if the partitioning of various elements into metal at relevant conditions is known. As such, partitioning experiments between liquid metal and liquid silicate over a wide range of pressures and temperatures are frequently performed to constrain the partitioning behaviour of many elements. The use of diamond anvil cell experiments to access more extreme conditions than those achievable by larger volume presses is becoming increasingly common. With a volume several orders of magnitude smaller than conventional samples, these experiments present unique analytical challenges. Typically, sample preparation is performed by FIB as a 2 mm thick slice, containing a small iron ball surrounded by a layer of silicate melt. This implies that analyses made by EPMA will be made near boundaries where fluoresced X-rays from the neighbouring phase may be significant. By measuring and simulating synthetic samples, we investigate thickness and fluorescence limitations. We find that for typical sample geometries, a thickness of 2 μm contains the entire analytical volume for standard 15kV analyses of metals. Fluoresced X-rays from light elements into the metal are below detection limits if there is no direct electron interaction with the silicate. Continuum fluorescence from higher atomic number elements from the metal into silicate poses significant difficulties [1]. This can cause metal-silicate partition coefficients of siderophile elements to be underestimated. Finally, we examine the origin and analytical consequences of oxide-rich exsolutions that are frequently found in the metal phase of such experiments. These are spherical with diameters of 100 nm and can be sparsely to densely packed. They appear to be carbon-rich and result in low analytical totals by violating the assumption of homogeneity in matrix corrections (e.g. φρz), which

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.

Chemistry of the subalkalic silicic obsidians

USGS Publications Warehouse

MacDonald, Ray; Smith, Robert L.; Thomas, John E.

1992-01-01

Nonhydrated obsidians are quenched magmatic liquids that record in their chemical compositions details of the tectonic environment of formation and of the differentiation mechanisms that affected their subsequent evolution. This study attempts to analyze, in terms of geologic processes, the compositional variations in the subalkalic silicic obsidians (Si02≥70 percent by weight, molecular (Na2O+K20)>Al2O3). New major- and trace-element determinations of 241 samples and a compilation of 130 published major-element analyses are reported and interpreted. Obsidians from five different tectonic settings are recognized: (1) primitive island arcs, (2) mature island arcs, (3) continental margins, (4) continental interiors, and (5) oceanic extensional zones. Tectonomagmatic discrimination between these groups is successfully made on Nb-Ta, Nb-FeOt and Th-Hf-Ta plots, and compositional ranges and averages for each group are presented. The chemical differences between groups are related to the type of crust in which magmas were generated. With increasingly sialic (continental type) crust, the obsidians show overall enrichment in F, Be, Li, Mo, Nb, Rb, Sn, Ta, U, W, Zn, and the rare-earth elements, and depletion in Mg, Ca, Ba, Co, Sc, Sr, and Zr. They become more potassic, have higher Fe/Mg and F/Cl ratios, and lower Zr/Hf, Nb/Ta, and Th/U ratios. Higher values of total rare-earth elements are accompanied by light rare-earth-element enrichment and pronounced negative Eu anomalies. An attempt is made to link obsidian chemistry to genetic mechanlism. Two broad groups of rocks are distinguished: one generated where crystal-liquid processes dominated (CLPD types), which are the products of crustal anatexis, possibly under conditions of low halogen fugacity, ± crystal fractionation ± magma mixing; and a second group represented by rocks formed in the upper parts of large magma chambers by interplays of crystal fractionation, volatile transfer, magma mixing, and possibly various

Metal-silicate partitioning of Co, Ni, V, Cr, Si, and O up to 100 GPa and 5500 K: Implications for core formation

NASA Astrophysics Data System (ADS)

Fischer, R. A.; Campbell, A. J.; Frost, D. J.; Harries, D.; Langenhorst, F.; Miyajima, N.; Pollok, K.; Rubie, D. C.

2013-12-01

During core formation, metal and silicate of accreted bodies equilibrated with the proto-Earth in a series of partitioning reactions, characterized by average (or time-intregrated) partition coefficients that can be calculated assuming a bulk Earth that is chondritic in nonvolatile elements [e.g. 1]. Comparisons to experimentally-measured partition coefficients allow constraints on the time-integrated conditions of core-mantle equilibration [e.g. 2-7], providing valuable input into more complex chemical models of Earth's evolution [8]. Partitioning has been studied extensively in the multi-anvil press [e.g. 3, 7], but very few studies extend to pressures above ~25 GPa [e.g. 2, 5-6]. In this study, we measure the metal-silicate partitioning of Co, Ni, V, Cr, Si, and O at higher pressures and temperatures. Thin foils of Fe-rich alloy doped with trace elements were loaded in a diamond anvil cell between layers of (Mg,Fe)2SiO4. Samples were laser-heated to melt the metal and silicate. After decompression, samples were cut parallel to the compression axis into sections ~100 nm thick with a focused ion beam (FIB). Chemical analyses of all elements except oxygen in the coexisting metal, silicate, and oxide were performed using energy dispersive X-ray spectroscopy (EDXS) in a transmission electron microscope (TEM). Later, samples were further thinned by FIB to ~60 nm and analyzed by electron energy loss spectroscopy (EELS) in a TEM to determine the Fe/O ratio of the metal. Analysis was performed on a suite of six experiments from pressures of 25, 31, 43, 57, 58, and 100 GPa and temperatures above the silicate liquidus, up to 5500 K. Our results are generally consistent with the recent findings of [5-6], although our log(KD) values for cobalt are ~0.1-0.2 log units lower. Some of our experiments contain carbon in the metal which may affect the partitioning of some elements. The metal in the experiment from 100 GPa and 5500 K contains 9 wt% silicon and an estimated 11 wt

Spectroscopy `outside the box': Towards wider application of NMR to minerals and glasses with abundant paramagnetic cations - Fe, Ni, Co, and Cu silicates

NASA Astrophysics Data System (ADS)

Stebbins, J. F.

2017-12-01

Since the early applications of solid-state NMR (Nuclear Magnetic Resonance) to silicates in the early 1980's, this powerful method has been widely applied to problems of short- to medium-range structure, particularly for materials in which order/disorder is critical, such as crystalline solid solutions, glasses, and even melts. However, almost all such work has been on materials with low (< a few %) contents of ions with unpaired electron spins. Such spins interact strongly with NMR-observed nuclear spins, and can cause severe line broadening and loss of information, in some cases making spectra nearly unobservable. Many groups of minerals with abundant, paramagnetic transition metals (notably Fe2+) and rare earth cations, as well as wide, petrologically important ranges of glass composition have thus been excluded. Inspired by in-depth NMR studies of 31P, 7Li, and other nuclides in lithium-transition metal oxide and phosphate battery materials (C. Grey and others), and with some serendipitous discovery plus persistence to look far outside of "normal" parameter space, we have recently shown that high resolution, structurally informative spectra can actually be obtained for silicate, oxide, and phosphate solid solutions with moderate (0.1 up to 10%) contents of paramagnetic cations such as Fe2+, Ni2+, Co2+ and REE3+. Very recently we have extended this to observe some of the first quantitative NMR spectra of silicate minerals in which a paramagnetic transition metal is the major cation, obtaining useful data for a series of Cu2+ silicates, fayalite (Fe2SiO4) and Ni- and Co- equivalents of diopside (CaMSi2O6). New data for glasses of the latter compositions may be the first such accurate results for any transition metal-rich glass. Although we are still far from a detailed theoretical understanding of these data, the spectra for the glasses are quite different from those of the crystals, suggesting the possibility of medium-range ordering and clustering of NiO and

XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

NASA Technical Reports Server (NTRS)

Fuss, T.; Mogus-Milankovic, A.; Ray, C. S.; Lesher, C. E.; Youngman, R.; Day, D. E.

2006-01-01

The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

Development of lithium doped radiation resistent solar cells

NASA Technical Reports Server (NTRS)

Berman, P. A.

1972-01-01

Lithium-doped solar cells have been fabricated with initial lot efficiencies averaging 11.9 percent in an air mass zero (AMO) solar simulator and a maximum observed efficiency of 12.8 percent. The best lithium-doped solar cells are approximately 15 percent higher in maximum power than state-of-the-art n-p cells after moderate to high fluences of 1-MeV electrons and after 6-7 months exposure to low flux irradiation by a Sr-90 beta source, which approximates the electron spectrum and flux associated with near Earth space. Furthermore, lithium-doped cells were found to degrade at a rate only one tenth that of state-of-the-art n-p cells under 28-MeV electron irradiation. Excellent progress has been made in quantitative predictions of post-irradiation current-voltage characteristics as a function of cell design by means of capacitance-voltage measurements, and this information has been used to achieve further improvements in lithium-doped cell design.

Carbonate-silicate liquid immiscibility upon impact melting, Ries Crater, Germany

NASA Astrophysics Data System (ADS)

Graup, Guenther

1999-05-01

The 24-km-diameter Ries impact crater in southern Germany is one of the most studied impact structures on Earth. The Ries impactor struck a Triassic to Upper Jurassic sedimentary sequence overlying Hercynian crystalline basement. At the time of impact (14.87 +/- 0.36 Ma; Storzer et al., 1995), the 350 m thick Malm limestone was present only to the S and E of the impact site. To the N and W, the Malm had been eroded away, exposing the underlying Dogger and Lias. The largest proportion of shocked target material is in the impact melt-bearing breccia suevite. The suevite had been believed to be derived entirely from the crystalline basement. Calcite in the suevite has been interpreted as a post-impact hydrothermal deposit. From optical inspection of 540 thin sections of suevite from 32 sites, I find that calcite in the suevite shows textural evidence of liquid immiscibility with the silicate impact melt. Textural evidence of liquid immiscibility between silicate and carbonate melt in the Ries suevite includes: carbonate globules within silicate glass, silicate globules embedded in carbonate, deformable and coalescing carbonate spheres within silicate glass, sharp menisci or cusps and budding between silicate and carbonate melt, fluidal textures and gas vesicles in carbonate schlieren, a quench crystallization sequence of the carbonate, spinifex textured quenched carbonate, separate carbonate spherules in the suevite mineral-fragment-matrix, and inclusions of mineral fragments suspended in carbonate blebs. Given this evidence of liquid immiscibility, the carbonate in the suevite has, therefore, like the silicate melt a primary origin by impact shock melting. Evidence of carbonate-silicate liquid immiscibility is abundant in the suevites to the SW to E of the Ries crater. The rarer suevites to the W to NE of the crater are nearly devoid of carbonate melts. This correspondence between the occurrence of outcropping limestones at the target surface and the formation of

The Effect of Core-Mantle Differentiation on V, Cr, and Mn: Experimental Metal/Silicate Partitioning Results

NASA Technical Reports Server (NTRS)

Chabot, N. L.; Agee, C. B.

2001-01-01

The abundances of V, Cr, and Mn are similarly depleted in the Earth and Moon. We present metal/silicate partitioning results which examine if the depletions can be explained by a core formation event. Additional information is contained in the original extended abstract.

A POSSIBLE CARBON-RICH INTERIOR IN SUPER-EARTH 55 Cancri e

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

Madhusudhan, Nikku; Lee, Kanani K. M.; Mousis, Olivier, E-mail: Nikku.Madhusudhan@yale.edu

Terrestrial planets in the solar system, such as the Earth, are oxygen-rich, with silicates and iron being the most common minerals in their interiors. However, the true chemical diversity of rocky planets orbiting other stars is yet unknown. Mass and radius measurements are used to constrain the interior compositions of super-Earths (exoplanets with masses of 1-10 M{sub Circled-Plus }), and are typically interpreted with planetary interior models that assume Earth-centric oxygen-rich compositions. Using such models, the super-Earth 55 Cancri e (mass 8 M{sub Circled-Plus }, radius 2 R{sub Circled-Plus }) has been suggested to bear an interior composition consisting ofmore » Fe, silicates, and an envelope ({approx}> 10% by mass) of supercritical water. We report that the mass and radius of 55 Cancri e can also be explained by a carbon-rich solid interior made of Fe, C, SiC, and/or silicates and without a volatile envelope. While the data allow Fe mass fractions of up to 40%, a wide range of C, SiC, and/or silicate mass fractions are possible. A carbon-rich 55 Cancri e is also plausible if its protoplanetary disk bore the same composition as its host star, which has been reported to be carbon-rich. However, more precise estimates of the stellar elemental abundances and observations of the planetary atmosphere are required to further constrain its interior composition. The possibility of a C-rich interior in 55 Cancri e opens a new regime of geochemistry and geophysics in extraterrestrial rocky planets, compared to terrestrial planets in the solar system.« less

Lithium isotope constraints on crust-mantle interactions and surface processes on Mars

NASA Astrophysics Data System (ADS)

Magna, Tomáš; Day, James M. D.; Mezger, Klaus; Fehr, Manuela A.; Dohmen, Ralf; Aoudjehane, Hasnaa Chennaoui; Agee, Carl B.

2015-08-01

Lithium abundances and isotope compositions are reported for a suite of martian meteorites that span the range of petrological and geochemical types recognized to date for Mars. Samples include twenty-one bulk-rock enriched, intermediate and depleted shergottites, six nakhlites, two chassignites, the orthopyroxenite Allan Hills (ALH) 84001 and the polymict breccia Northwest Africa (NWA) 7034. Shergottites unaffected by terrestrial weathering exhibit a range in δ7Li from 2.1 to 6.2‰, similar to that reported for pristine terrestrial peridotites and unaltered mid-ocean ridge and ocean island basalts. Two chassignites have δ7Li values (4.0‰) intermediate to the shergottite range, and combined, these meteorites provide the most robust current constraints on δ7Li of the martian mantle. The polymict breccia NWA 7034 has the lowest δ7Li (-0.2‰) of all terrestrially unaltered martian meteorites measured to date and may represent an isotopically light surface end-member. The new data for NWA 7034 imply that martian crustal surface materials had both a lighter Li isotope composition and elevated Li abundance compared with their associated mantle. These findings are supported by Li data for olivine-phyric shergotitte NWA 1068, a black glass phase isolated from the Tissint meteorite fall, and some nakhlites, which all show evidence for assimilation of a low-δ7Li crustal component. The range in δ7Li for nakhlites (1.8 to 5.2‰), and co-variations with chlorine abundance, suggests crustal contamination by Cl-rich brines. The differences in Li isotope composition and abundance between the martian mantle and estimated crust are not as large as the fractionations observed for terrestrial continental crust and mantle, suggesting a difference in the styles of alteration and weathering between water-dominated processes on Earth versus possibly Cl-S-rich brines on Mars. Using high-MgO shergottites (>15 wt.% MgO) it is possible to estimate the δ7Li of Bulk Silicate Mars

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.

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

Mantle convection and the distribution of geochemical reservoirs in the silicate shell of the Earth

NASA Astrophysics Data System (ADS)

Walzer, Uwe; Hendel, Roland

2010-05-01

We present a dynamic 3-D spherical-shell model of mantle convection and the evolution of the chemical reservoirs of the Earth`s silicate shell. Chemical differentiation, convection, stirring and thermal evolution constitute an inseparable dynamic system. Our model is based on the solution of the balance equations of mass, momentum, energy, angular momentum, and four sums of the number of atoms of the pairs 238U-206Pb, 235U-207Pb, 232Th-208Pb, and 40K-40Ar. Similar to the present model, the continental crust of the real Earth was not produced entirely at the start of the evolution but developed episodically in batches [1-7]. The details of the continental distribution of the model are largely stochastic, but the spectral properties are quite similar to the present real Earth. The calculated Figures reveal that the modeled present-day mantle has no chemical stratification but we find a marble-cake structure. If we compare the observational results of the present-day proportion of depleted MORB mantle with the model then we find a similar order of magnitude. The MORB source dominates under the lithosphere. In our model, there are nowhere pure unblended reservoirs in the mantle. It is, however, remarkable that, in spite of 4500 Ma of solid-state mantle convection, certain strong concentrations of distributed chemical reservoirs continue to persist in certain volumes, although without sharp abundance boundaries. We deal with the question of predictable and stochastic portions of the phenomena. Although the convective flow patterns and the chemical differentiation of oceanic plateaus are coupled, the evolution of time-dependent Rayleigh number, Rat , is relatively well predictable and the stochastic parts of the Rat(t)-curves are small. Regarding the juvenile growth rates of the total mass of the continents, predictions are possible only in the first epoch of the evolution. Later on, the distribution of the continental-growth episodes is increasingly stochastic

Physical and optical absorption studies of Fe{sup 3+} - ions doped lithium borate glasses containing certain alkaline earths

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

Bhogi, Ashok; Kumar, R. Vijaya; Kistaiah, P., E-mail: pkistaiah@yahoo.com

Iron ion doped lithium borate glasses with the composition 15RO-25Li{sub 2}O-59B{sub 2}O{sub 3}-1Fe{sub 2}O{sub 3} (where R= Ca, Sr and Ba) have been prepared by the conventional melt quenching technique and characterized to investigate the physical and optical properties using XRD, density, molar volume and UV-Visible spectroscopy. The optical absorption spectra exhibit a band at around 460 nm which is assigned to {sup 6}A{sub 1g}(S) → 4E{sub g} (G) of Fe{sup 3+} ions with distorted octahedral symmetry. From ultraviolet absorption edges, the optical band gap and Urbach energies have been evaluated. The effect of alkaline earths on these properties ismore » discussed.« less

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Calcium silicate. 172.410 Section 172.410 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely...

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium silicate. 172.410 Section 172.410 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely...

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Calcium silicate. 172.410 Section 172.410 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely...

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Calcium silicate. 172.410 Section 172.410 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely...

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Calcium silicate. 172.410 Section 172.410 Food and... PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Anticaking Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely used in food in accordance with the...

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.

Lithium

USGS Publications Warehouse

Jaskula, B.W.

2010-01-01

In 2009, lithium consumption in the United States was estimated to have been about 1.2 kt (1,300 st) of contained lithium, a 40-percent decrease from 2008. The United States was estimated to be the fourth largest consumer of lithium, and remained the leading importer of lithium carbonate and the leading producer of value-added lithium materials. Only one company, Chemetall Foote Corp. (a subsidiary of Chemetall GmbH of Germany), produced lithium compounds from domestic resources. In 2009, world lithium consumption was estimated to have been about 18.7 kt (20,600 st) of lithium contained in minerals and compounds.

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

Conditions for oceans on Earth-like planets orbiting within the habitable zone: importance of volcanic CO{sub 2} degassing

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

Kadoya, S.; Tajika, E., E-mail: kadoya@astrobio.k.u-tokyo.ac.jp, E-mail: tajika@astrobio.k.u-tokyo.ac.jp

2014-08-01

Earth-like planets in the habitable zone (HZ) have been considered to have warm climates and liquid water on their surfaces if the carbonate-silicate geochemical cycle is working as on Earth. However, it is known that even the present Earth may be globally ice-covered when the rate of CO{sub 2} degassing via volcanism becomes low. Here we discuss the climates of Earth-like planets in which the carbonate-silicate geochemical cycle is working, with focusing particularly on insolation and the CO{sub 2} degassing rate. The climate of Earth-like planets within the HZ can be classified into three climate modes (hot, warm, and snowballmore » climate modes). We found that the conditions for the existence of liquid water should be largely restricted even when the planet is orbiting within the HZ and the carbonate-silicate geochemical cycle is working. We show that these conditions should depend strongly on the rate of CO{sub 2} degassing via volcanism. It is, therefore, suggested that thermal evolution of the planetary interiors will be a controlling factor for Earth-like planets to have liquid water on their surface.« less

Lithium

USGS Publications Warehouse

Jaskula, B.W.

2011-01-01

In 2010, lithium consumption in the United States was estimated to have been about 1 kt (1,100 st) of contained lithium, a 23-percent decrease from 2009. The United States was estimated to be the fourth largest consumer of lithium. It remained the leading importer of lithium carbonate and the leading producer of value-added lithium materials. Only one company, Chemetall Foote Corp. (a subsidiary of Chemetall GmbH of Germany), produced lithium compounds from domestic resources. In 2010, world lithium consumption was estimated to have been about 21 kt (22,000 st) of lithium contained in minerals and compounds, a 12-percent increase from 2009.

The effect of melt composition on the partitioning of trace elements between titanite and silicate melt

NASA Astrophysics Data System (ADS)

Prowatke, S.; Klemme, S.

2003-04-01

The aim of this study is to systematically investigate the influence of melt composition on the partitioning of trace elements between titanite and different silicate melts. Titanite was chosen because of its important role as an accessory mineral, particularly with regard to intermediate to silicic alkaline and calc-alkaline magmas [e.g. 1] and of its relative constant mineral composition over a wide range of bulk compositions. Experiments at atmospheric pressure were performed at temperatures between 1150°C and 1050°C. Bulk compositions were chosen to represent a basaltic andesite (SH3 - 53% SiO2), a dacite (SH2 - 65 SiO2) and a rhyolite (SH1 - 71% SiO2). Furthermore, two additional experimental series were conducted to investigate the effect of Al-Na and the Na-K ratio of melts on partitioning. Starting materials consisted of glasses that were doped with 23 trace elements including some selected rare earth elements (La, Ce, Pr, Sm, Gd, Lu), high field strength elements (Zr, Hf, Nb, Ta) and large ion lithophile elements (Cs, Rb, Ba) and Th and U. The experimental run products were analysed for trace elements using secondary ion mass spectrometry at Heidelberg University. Preliminary results indicate a strong effect of melt composition on trace element partition coefficients. Partition coefficients for rare-earth elements uniformly show a convex-upward shape [2, 3], since titanite accommodates the middle rare-earth elements more readily than the light rare-earth elements or the heavy rare-earth elements. Partition coefficients for the rare-earth elements follow a parabolic trend when plotted against ionic radius. The shape of the parabola is very similar for all studied bulk compositions, the position of the parabola, however, is strongly dependent on bulk composition. For example, isothermal rare-earth element partition coefficients (such as La) are incompatible (D<1) in alkali-rich silicate melts and strongly compatible (D>>1) in alkali-poor melt compositions

Lithium rich cathode/graphite anode combination for lithium ion cells with high tolerance to near zero volt storage

NASA Astrophysics Data System (ADS)

Crompton, K. R.; Staub, J. W.; Hladky, M. P.; Landi, B. J.

2017-03-01

Management of reversible lithium is an advantageous approach to design lithium ion cells that are tolerant to near zero volt (NZV) storage under fixed resistive load towards highly controllable, enhanced user-inactive safety. Presently, the first cycle loss from a high energy density Li-rich HE5050 cathode is used to provide excess reversible lithium when paired with an appropriately capacity matched mesocarbon microbead (MCMB) anode. Cells utilizing 1.2 M LiPF6 3:7 v/v ethylene carbonate:ethyl methyl carbonate electrolyte and a lithium reference were used for 3-electrode testing. After conditioning, a fixed resistive load was applied to 3-electrode cells for 72 or 168-h during which the anode potential and electrode asymptotic potential (EAP) remained less than the copper dissolution potential. After multiple storage cycles (room temperature or 40 °C), the NZV coulombic efficiency (cell reversibility) exceeded 97% and the discharge capacity retention was >98%. Conventional 2-electrode HE5050/MCMB pouch cells stored at NZV or open circuit for 3 days had nearly identical rate capability (up to 5C) and discharge performance stability (for 500 cycles under a 30% depth of discharge low-earth-orbit regime). Thus, lithium ion cells with appropriately capacity matched HE5050/MCMB electrodes have excellent tolerance to prolonged NZV storage, which can lead to enhanced user-inactive safety.

Thermal Ablation Modeling for Silicate Materials

NASA Technical Reports Server (NTRS)

Chen, Yih-Kanq

2016-01-01

A general thermal ablation model for silicates is proposed. The model includes the mass losses through the balance between evaporation and condensation, and through the moving molten layer driven by surface shear force and pressure gradient. This model can be applied in the ablation simulation of the meteoroid and the glassy ablator for spacecraft Thermal Protection Systems. Time-dependent axisymmetric computations are performed by coupling the fluid dynamics code, Data-Parallel Line Relaxation program, with the material response code, Two-dimensional Implicit Thermal Ablation simulation program, to predict the mass lost rates and shape change. The predicted mass loss rates will be compared with available data for model validation, and parametric studies will also be performed for meteoroid earth entry conditions.

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.

SILICATE COMPOSITION OF THE INTERSTELLAR MEDIUM

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

Fogerty, S.; Forrest, W.; Watson, D. M.

2016-10-20

The composition of silicate dust in the diffuse interstellar medium and in protoplanetary disks around young stars informs our understanding of the processing and evolution of the dust grains leading up to planet formation. An analysis of the well-known 9.7 μ m feature indicates that small amorphous silicate grains represent a significant fraction of interstellar dust and are also major components of protoplanetary disks. However, this feature is typically modeled assuming amorphous silicate dust of olivine and pyroxene stoichiometries. Here, we analyze interstellar dust with models of silicate dust that include non-stoichiometric amorphous silicate grains. Modeling the optical depth alongmore » lines of sight toward the extinguished objects Cyg OB2 No. 12 and ζ Ophiuchi, we find evidence for interstellar amorphous silicate dust with stoichiometry intermediate between olivine and pyroxene, which we simply refer to as “polivene.” Finally, we compare these results to models of silicate emission from the Trapezium and protoplanetary disks in Taurus.« less

Silicate-Promoted Phosphorylation of Glycerol in Non-Aqueous Solvents: A Prebiotically Plausible Route to Organophosphates

PubMed Central

Gull, Maheen; Cafferty, Brian J.; Hud, Nicholas V.; Pasek, Matthew A.

2017-01-01

Phosphorylation reactions of glycerol were studied using different inorganic phosphates such as sodium phosphate, trimetaphosphate (a condensed phosphate), and struvite. The reactions were carried out in two non-aqueous solvents: formamide and a eutectic solvent consisting of choline-chloride and glycerol in a ratio of 1:2.5. The glycerol reacted in formamide and in the eutectic solvent with phosphate to yield its phosphorylated derivatives in the presence of silicates such as quartz sand and kaolinite clay. The reactions were carried out by heating glycerol with a phosphate source at 85 °C for one week and were analyzed by 31P-nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS). The yield of the phosphorylated glycerol was improved by the presence of silicates, and reached 90% in some experiments. Our findings further support the proposal that non-aqueous solvents are advantageous for the prebiotic synthesis of biomolecules, and suggest that silicates may have aided in the formation of organophosphates on the prebiotic earth. PMID:28661422

Kinetics of lithium peroxide monohydrate thermal decomposition

NASA Astrophysics Data System (ADS)

Nefedov, Roman; Posternak, Nikolay; Ferapontov, Yuriy

2017-11-01

Topochemical dehydration of lithium peroxide was studied to determine kinetic parameters at the range of temperatures from 90°C to 147°C in non-isothermal conditions by derivatographic method. The study was conducted to select optimal conditions of lithium peroxide synthesis in dehydration reaction of triple LiOH-H2O2-H2O system in ultra-high frequency radiation field. Conditions of dehydration reaction were caused by the thermal conductivity of LiOH -H2O2-H2O system. It is determined that dehydration process runs close to the first order reaction (n=0.85±0.03). The activation energy and pre-exponential factor values were found as Eak = 86.0 ± 0.8 kJ/mol, k0 = (2.19 ± 0.16) .1011 min-1, correspondingly. It is supposed that there is a similarity between the dehydration mechanism of lithium peroxide monohydrate and peroxide hydrates of alkaline-earth metals (calcium, barium and strontium).

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

Dissolution of glass wool, rock wool and alkaline earth silicate wool: morphological and chemical changes in fibers.

PubMed

Campopiano, Antonella; Cannizzaro, Annapaola; Angelosanto, Federica; Astolfi, Maria Luisa; Ramires, Deborah; Olori, Angelo; Canepari, Silvia; Iavicoli, Sergio

2014-10-01

The behavior of alkaline earth silicate (AES) wool and of other biosoluble wools in saline solution simulating physiological fluids was compared with that of a traditional wool belonging to synthetic vitreous fibers. Morphological and size changes of fibers were studied by scanning electron microscopy (SEM). The elements extracted from fibers were analyzed by inductively coupled plasma atomic emission spectrometry. SEM analysis showed a larger reduction of length-weighted geometric mean fiber diameter at 4.5 pH than at 7.4 pH. At the 7.4 pH, AES wool showed a higher dissolution rate and a dissolution time less than a few days. Their dissolution was highly non-congruent with rapid leaching of calcium. Unlike rock wool, glass wool dissolved more rapidly at physiological pH than at acid pH. Dissolution of AES and biosoluble rock wool is accompanied by a noticeable change in morphology while by no change for glass wool. Biosoluble rock wool developed a leached surface with porous honeycomb structure. SEM analysis showed the dissolution for glass wool is mainly due to breakage transverse of fiber at pH 7.4. AES dissolution constant (Kdis) was the highest at pH 7.4, while at pH 4.5 only biosoluble rockwool 1 showed a higher Kdis. Copyright © 2014 Elsevier Inc. All rights reserved.

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

Nitrogen partitioning during Earth's accretion and core-mantle differentiation

NASA Astrophysics Data System (ADS)

Speelmanns, I. M.; Schmidt, M. W.; Liebske, C.

2017-12-01

On present day Earth, N is one of the key constituents of our atmosphere and forms the basis of life. However, the deep Earth geochemistry of N, i.e. its distribution and isotopic fractionation between Earth's deep reservoirs is not well constrained. This study investigates nitrogen partitioning between metal and silicate melts as relevant for core segregation during the accretion of planetesimals into the Earth. We have determined N-partitioning coefficients over a wide range of temperatures (1250-2000 °C), pressures (15-35 kbar) and oxygen fugacity's, the latter in the relevant range of core segregation (IW-5 to IW). Centrifuging piston cylinders were used to equilibrate and then gravitationally separate metal-silicate melt pairs. Separation of the two melts is necessary to avoid micro nugget contamination in the silicate melt at reducing conditions < IW-2.5. Complete segregation of the two melts was reached within 1 to 3 hours at 1000 g and 1600-1250 °C respectively, the interface showing a proper meniscus. The applied double capsule technique in all experiments, using an outer metallic (Pt) and inner non-metallic capsule (graphite or Al2O3), minimizes N-loss over the course of the experiments compared to single non-metallic capsules. The two quenched melts were cut apart mechanically, cleaned at the outside, their N concentrations were then analysed on bulk samples by an elemental analyser, the low abslute masses requiring careful development of analytical routines. Despite these difficulties, we were able to determine a DNmetal/silicate of 13±0.3 at IW-1 decreasing to 2.0±0.2 at IW-5.5, at 1250°C and 15 kbar, N partitioning into the core forming metal. Increasing temperature dramatically lowers the DNmetal/silicate to e.g. 0.5±0.15 at IW-4, during early core formation N was hence mildly incompatible in the metal. The results suggest that under magma ocean conditions (> 2000 oC and fO2 IW-2.5), N-partition coefficents were within a factor of 2 of unity

Lithium

USGS Publications Warehouse

Jaskula, B.W.

2012-01-01

In 2011, world lithium consumption was estimated to have been about 25 kt (25,000 st) of lithium contained in minerals and compounds, a 10-percent increase from 2010. U.S. consumption was estimated to have been about 2 kt (2,200 st) of contained lithium, a 100-percent increase from 2010. The United States was estimated to be the fourth-ranked consumer of lithium and remained the leading importer of lithium carbonate and the leading producer of value-added lithium materials. One company, Chemetall Foote Corp. (a subsidiary of Chemetall GmbH of Germany), produced lithium compounds from domestic brine resources near Silver Peak, NV.

Testing Urey's carbonate-silicate cycle using the calcium isotopic composition of sedimentary carbonates

NASA Astrophysics Data System (ADS)

Blättler, Clara L.; Higgins, John A.

2017-12-01

Carbonate minerals constitute a major component of the sedimentary geological record and an archive of a fraction of the carbon and calcium cycled through the Earth's surface reservoirs for over three billion years. For calcium, carbonate minerals constitute the ultimate sink for almost all calcium liberated during continental and submarine weathering of silicate minerals. This study presents >500 stable isotope ratios of calcium in Precambrian carbonate sediments, both limestones and dolomites, in an attempt to characterize the isotope mass balance of the sedimentary carbonate reservoir through time. The mean of the dataset is indistinguishable from estimates of the calcium isotope ratio of bulk silicate Earth, consistent with the Urey cycle being the dominant mechanism exchanging calcium among surface reservoirs. The variability in bulk sediment calcium isotope ratios within each geological unit does not reflect changes in the global calcium cycle, but rather highlights the importance of local mineralogical and/or diagenetic effects in the carbonate record. This dataset demonstrates the potential for calcium isotope ratios to help assess these local effects, such as the former presence of aragonite, even in rocks with a history of neomorphism and recrystallization. Additionally, 29 calcium isotope measurements are presented from ODP (Ocean Drilling Program) Site 801 that contribute to the characterization of altered oceanic crust as an additional sink for calcium, and whose distinct isotopic signature places a limit on the importance of this subduction flux over Earth history.

Core-Mantle Partitioning of Volatile Siderophile Elements and the Origin of Volatile Elements in the Earth

NASA Technical Reports Server (NTRS)

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

2012-01-01

There are currently several hypotheses on the origin of volatile siderophile elements in the Earth. One hypothesis is that they were added during Earth s accretion and core formation and mobilized into the metallic core [1], others claim multiple stage origin [2], while some hypothesize that volatiles were added after the core already formed [3]. Several volatile siderophile elements are depleted in Earth s mantle relative to the chondrites, something which continues to puzzle many scientists. This depletion is likely due to a combination of volatility and core formation. The Earth s core is composed of Fe and some lighter constituents, although the abundances of these lighter elements are unknown [4]. Si is one of these potential light elements [5] although few studies have analyzed the effect of Si on metal-silicate partitioning, in particular the volatile elements. As, In, Ge, and Sb are trace volatile siderophile elements which are depleted in the mantle but have yet to be extensively studied. The metal-silicate partition coefficients of these elements will be measured to determine the effect of Si. Partition coefficients depend on temperature, pressure, oxygen fugacity, and metal and silicate composition and can constrain the concentrations of volatile, siderophile elements found in the mantle. Reported here are the results from 13 experiments examining the partitioning of As, In, Ge, and Sb between metallic and silicate liquid. These experiments will examine the effect of temperature, and metal-composition (i.e., Si content) on these elements in or-der to gain a greater understanding of the core-mantle separation which occurred during the Earth s early stages. The data can then be applied to the origin of volatile elements in the Earth.

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.

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.

Polysilicate binding for silicate paints

NASA Astrophysics Data System (ADS)

Ivanovna, Loganina Valentina; Nikolaevna, Kislitsyna Svetlana; Bisengalievich, Mazhitov Yerkebulan

2018-06-01

It was suggested, that the polysilicate solutions obtained by mixing liquid glass and silicic acid sol as a binder in the manufacture of silicate paints. Information is provided on the structure and a property of the sodium polysilicate binder is presented. It has been found that the addition of silica powder to a liquid glass causes gelling in the course of time. It has been established that the introduction of the sol (increasing the silicate module) contributes to an increase in the fraction of high-polymer fractions of silicic anion, with the increase in the sol content of the polymer form of silica increasing. The research results the structure of sols and polysilicate solutions by the method of violation of total internal reflection. By the method of IR spectroscopy, the molybdate method established the presence of silica in the polysilicate binder polymeric varieties, which provides an increase in the stability of silicate coatings.

Lithium

USGS Publications Warehouse

Bradley, Dwight C.; Stillings, Lisa L.; Jaskula, Brian W.; Munk, LeeAnn; McCauley, Andrew D.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Lithium, the lightest of all metals, is used in air treatment, batteries, ceramics, glass, metallurgy, pharmaceuticals, and polymers. Rechargeable lithium-ion batteries are particularly important in efforts to reduce global warming because they make it possible to power cars and trucks from renewable sources of energy (for example, hydroelectric, solar, or wind) instead of by burning fossil fuels. Today, lithium is extracted from brines that are pumped from beneath arid sedimentary basins and extracted from granitic pegmatite ores. The leading producer of lithium from brine is Chile, and the leading producer of lithium from pegmatites is Australia. Other potential sources of lithium include clays, geothermal brines, oilfield brines, and zeolites. Worldwide resources of lithium are estimated to be more than 39 million metric tons, which is enough to meet projected demand to the year 2100. The United States is not a major producer at present but has significant lithium resources.

Lithium

USGS Publications Warehouse

Ober, J.A.

2006-01-01

In 2005, lithium consumption in the United States was at 2.5 kt of contained lithium, nearly 32% more than the estimate for 2004. World consumption was 14.1 kt of lithium contained in minerals and compounds in 2003. Exports from the US increased slightly compared with 2004. Due to strong demand for lithium compounds in 2005, both lithium carbonate plants in Chile were operating at or near capacity.

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.

21 CFR 582.2437 - Magnesium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Magnesium silicate. 582.2437 Section 582.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Magnesium silicate. (a) Product. Magnesium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions...

21 CFR 582.2437 - Magnesium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Magnesium silicate. 582.2437 Section 582.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Magnesium silicate. (a) Product. Magnesium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions...

21 CFR 582.2437 - Magnesium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Magnesium silicate. 582.2437 Section 582.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Magnesium silicate. (a) Product. Magnesium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions...

21 CFR 582.2437 - Magnesium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Magnesium silicate. 582.2437 Section 582.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Magnesium silicate. (a) Product. Magnesium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions...

21 CFR 582.2437 - Magnesium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Magnesium silicate. 582.2437 Section 582.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Magnesium silicate. (a) Product. Magnesium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions...

21 CFR 182.2437 - Magnesium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Magnesium silicate. 182.2437 Section 182.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Magnesium silicate. (a) Product. Magnesium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions...

21 CFR 182.2437 - Magnesium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Magnesium silicate. 182.2437 Section 182.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Magnesium silicate. (a) Product. Magnesium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions...

21 CFR 182.2437 - Magnesium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Magnesium silicate. 182.2437 Section 182.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Magnesium silicate. (a) Product. Magnesium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions...

21 CFR 182.2437 - Magnesium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Magnesium silicate. 182.2437 Section 182.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Magnesium silicate. (a) Product. Magnesium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2227 Calcium silicate. (a) Product. Calcium silicate...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

Conference on Deep Earth and Planetary Volatiles

NASA Technical Reports Server (NTRS)

1994-01-01

The following topics are covered in the presented papers: (1) rare gases systematics and mantle structure; (2) volatiles in the earth; (3) impact degassing of water and noble gases from silicates; (4) D/H ratios and H2O contents of mantle-derived amphibole megacrysts; (5) thermochemistry of dense hydrous magnesium silicates; (6) modeling of the effect of water on mantle rheology; (7) noble gas isotopes and halogens in volatile-rich inclusions in diamonds; (8) origin and loss of the volatiles of the terrestrial planets; (9) structure and the stability of hydrous minerals at high pressure; (10) recycling of volatiles at subduction zones and various other topics.

The Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses: Results from W L-Edge Xanes Measurements

NASA Technical Reports Server (NTRS)

Danielson, Lisa R.; Righter, K.; Sutton S.; Newville, M.; Le, L.

2007-01-01

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted approx. 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies (figure 1) are inconsistent on whether W occurs as W(4+) or W(6+).

Equilibrium lithium isotope fractionation in Li-rich minerals

NASA Astrophysics Data System (ADS)

Liu, S.; Li, Y.; Liu, J.

2017-12-01

Lithium is the lightest alkali metal, and only exhibits +1 valence state in minerals. It is widely distributed on the Earth, and usually substitutes for Mg in silicate minerals. Li has two stable isotopes, 6Li and 7Li, with the relative abundances of 7.52% and 92.48%, respectively. The large mass difference between 6Li and 7Li could induce significant isotope fractionation in minerals. Li isotopes can provide an important geochemical tracer for mantle processes. However, the fractionation factors for Li in most minerals remain poorly known, which makes the geochemical implications of Li isotope fractionations in minerals difficult to assess. Here, we try to use the vibrational frequencies obtained by the first-principles methods based on density-functional theory to calculate the Li isotope fractionation parameters for amblygonite (LiAlPO4F), bikitaite (LiSi2AlO7H2), eucryptite (LiAlSiO4), lithiophilite (LiMnPO4), lithiophosphate (Li3PO4), montebrasite (LiAlPO5H), and spodumene (LiAlSi2O6) in the temperature range of 0-1200 ºC. For forsterite (Mg2SiO4) and diopside (CaMgSi2O6) in which Li takes the place of Mg, the equilibrium Li isotope fractionation between them also be studied. Our preliminary calculations show that the coordination number of Li seems to play an important role in controlling Li isotope fractionation in these minerals, and concentration of Li in forsterite and diopside seems to have great effects on Li isotope fractionation factors of them.

Effect of Heat-Pressing Temperature and Holding Time on the Microstructure and Flexural Strength of Lithium Disilicate Glass-Ceramics

PubMed Central

Gao, Jing; Wang, Hui; Chen, Jihua

2015-01-01

The present study aimed to evaluate the influence of various heat-pressing procedures (different holding time and heat pressing temperature) on the microstructure and flexural strength of lithium disilicate glass ceramic. An experimental lithium silicate glass ceramic (ELDC) was prepared from the SiO2-Li2O-K2O-Al2O3-ZrO2-P2O5 system and heat-pressed following different procedures by varying temperature and holding time. The flexural strength was tested and microstructure was analyzed. The relationships between the microstructure, mechanical properties and heat-pressing procedures were discussed in-depth. Results verified the feasibility of the application of dental heat-pressing technique in processing the experimental lithium disilicate glass ceramic. Different heat-pressing procedures showed significant influence on microstructure and flexural strength. ELDC heat-pressed at 950℃ with holding time of 15 min achieved an almost pore-free microstructure and the highest flexural strength, which was suitable for dental restorative application. PMID:25985206

Inheritance of silicate differentiation during lunar origin by giant impact

NASA Technical Reports Server (NTRS)

Warren, Paul H.

1992-01-01

It is pointed out that the implication of the popular giant impact model of lunar origin (e.g., Hartmann and Davis, 1975; Cameron and Ward, 1976; Stevenson, 1987) is that any depth-related silicate differentiation within the impactor (and/or the earth) at the time of the impact must be partly inherited by the preferentially peripheral matter that forms the moon. This paper presents calculations of the magnitude of the net differentiation of the protolunar matter for a variety of elements and scenarios, with different assumptions regarding the geometries of the 'sampled' peripheral zones, the relative proportions of the earth-derived to impactor-derived matter in the final moon, and the degree to which the impactor mantle had crystallized prior to the giant impact. It is shown that these differention effects constrain the overall plausibility of the giant impact hypothesis.

Metal-silicate partitioning of U: Implications for the heat budget of the core and evidence for reduced U in the mantle

NASA Astrophysics Data System (ADS)

Chidester, Bethany A.; Rahman, Zia; Righter, Kevin; Campbell, Andrew J.

2017-02-01

Earth's core might require an internal heat source, such as radioactive decay, to explain the presence of the magnetic field through geologic time. To investigate whether U would be an important heat source in the core, we performed metal-silicate partitioning experiments of U at P-T (up to 67 GPa and 5400 K) conditions more relevant to a magma ocean scenario than has previously been reported. This study finds the partitioning of U to be strongly dependent on ƒO2, temperature, the S content of the metal and the SiO2 content of the silicate during core-mantle differentiation. Differentiation at mean conditions of 42-58 GPa and 3900-4200 K would put 1.4-3.5 ppb U (2-8 wt% S) in the core, amounting to a maximum of 1.4 (+1/-0.7) TW of heat 4.5 billion years ago. This is likely not enough heat to mitigate early widespread mantle melting. It was also found that U likely exists in the 2+ oxidation state in silicate melts in the deep Earth, a state which has not been previously observed in nature.

Lithium in Jack Hills zircons: Evidence for extensive weathering of Earth's earliest crust

NASA Astrophysics Data System (ADS)

Ushikubo, Takayuki; Kita, Noriko T.; Cavosie, Aaron J.; Wilde, Simon A.; Rudnick, Roberta L.; Valley, John W.

2008-08-01

In situ Li analyses of 4348 to 3362 Ma detrital zircons from the Jack Hills, Western Australia by SIMS reveal that the Li abundances (typically 10 to 60 ppm) are commonly over 10,000 times higher than in zircons crystallized from mantle-derived magmas and in mantle-derived zircon megacrysts (typically < 2 ppb). High Li concentrations in zircons (10 to 250 ppm) have also been found in igneous zircons from three continental parent rocks: granites, Li-rich pegmatites, and migmatites in pelitic metasediment. The substitution of trivalent cations (REEs and Y) in zircon correlates with Li + 1 and P + 5 , suggesting that an interstitial site for Li, as well as the xenotime substitution for P, provides charge balance for REEs. Li is thus fixed in the zircon structure by coupled substitutions, and diffusive changes in [Li] composition are rate-limited by slow diffusion of REEs. The Jack Hills zircons also have fractionated lithium isotope ratios ( δ7Li = - 19 to + 13‰) about five times more variable than those recorded in primitive ocean floor basalts (2 to 8‰), but similar to continental crust and its weathering products. Values of δ7Li below - 10‰ are found in zircons that formed as early as 4300 Ma. The high Li compositions indicate that primitive magmas were not the source of Jack Hills zircons and the fractionated values of δ7Li suggest that highly weathered regolith was sampled by these early Archean magmas. These new Li data provide evidence that the parent magmas of ancient zircons from Jack Hills incorporated materials from the surface of the Earth that interacted at low temperature with liquid water. These data support the hypothesis that continental-type crust and oceans existed by 4300 Ma, within 250 million years of the formation of Earth and the low values of δ7Li suggest that weathering was extensive in the early Archean.

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

The formation of cobalt-bearing ferromanganese crusts under fluid destruction of silicate matter

NASA Astrophysics Data System (ADS)

Maksimov, S. O.; Safronov, P. P.

2016-02-01

The processes of fluid destruction of various silicate rocks under diffusion of flows of compressed gases (mainly carbonaceous) were studied. The gas condensate nature was ascertained for the forming alumoslilicate and ore (cobalt-iron-manganese hydroxide) substances produced under this fluid destruction in the forms of microcrusts and microconcretions. The ore condensates contained in high concentrations the typomorphic elements of oceanic ferromanganese formations (Mn, Co, Ni, Cu, Pb, Ce, and Pt). The elemental composition of the ore oxide substance formed under the destruction of various silicate matrices exhibits a definite degree of endemism with prevalence of the Co-Mn association. The pronounced concentration of barium is related to the substantially carbonaceous composition of the fluid systems. A cerium paradox is revealed: Ce3+ is oxidized into Ce4+ and absorbed by ferromanganese hydrogel and the minimum of cerium appears in rare-earth phosphates.

Low Temperature Life-Cycle Testing of a Lithium-Ion Battery for Low-Earth-Orbiting Spacecraft

NASA Technical Reports Server (NTRS)

Reid, Concha

2006-01-01

A flight-qualified, lithium-ion (Li-ion) battery developed for the Mars Surveyor Program 2001 Landeris undergoing life-testing at low temperature under a low-Earth-orbit (LEO) profile to assess its capability to provide long term energy storage for aerospace missions. NASA has embarked upon an ambitious course to return humans to the moon by 2015-2020 in preparation for robotic and human exploration of Mars and robotic exploration of the moons of outer planets. Li-ion batteries are excellent candidates to provide power and energy storage for multiple aspects of these missions due to their high specific energy, high energy density, and excellent low temperature performance. Laboratory testing of Li-ion technology is necessary in order to assess lifetime, characterize multi-cell battery-level performance under aerospace conditions, and to gauge safety aspects of the technology. Life-cycle testing provides an opportunity to examine battery-level performance and the dynamics of individual cells in the stack over the entire life of the battery. Data generated through this testing will be critical to establish confidence in the technology for its widespread use in manned and unmanned missions.

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.

Siliceous Shrubs in Yellowstone's Hot Springs: Implications for Exobiological Investigations

NASA Technical Reports Server (NTRS)

Guidry, S. A.; Chafetz, H. S.

2003-01-01

Potential relict hot springs have been identified on Mars and, using the Earth as an analog, Martian hot springs are postulated to be an optimal locality for recognizing preserved evidence of extraterrestrial life. Distinctive organic and inorganic biomarkers are necessary to recognize preserved evidence of life in terrestrial and extraterrestrial hot spring accumulations. Hot springs in Yellowstone National Park, Wyoming, U.S.A., contain a wealth of information about primitive microbial life and associated biosignatures that may be useful for future exobiological investigations. Numerous siliceous hot springs in Yellowstone contain abundant, centimeter-scale, spinose precipitates of opaline silica (opal-A). Although areally extensive in siliceous hot spring discharge channel facies, these spinose forms have largely escaped attention. These precipitates referred to as shrubs, consist of porous aggregates of spinose opaline silica that superficially resemble miniature woody plants, i.e., the term shrubs. Shrubs in carbonate precipitating systems have received considerable attention, and represent naturally occurring biotically induced precipitates. As such, shrubs have great potential as hot spring environmental indicators and, more importantly, proxies for pre-existing microbial life.

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.

Engineering experimental program on the effects of near-space radiation on lithium doped solar cells

NASA Technical Reports Server (NTRS)

1971-01-01

The results of an experimental evaluation of the real-time degradation characteristics of lithium-diffused silicon solar cells are reported. A strontium-90 radioisotope was used for simulation of a typical earth-orbital electron environment. The experiment was performed in an ion pump vacuum chamber with samples maintained at -50, +20, +50, and +80 C. Samples were illuminated during the 6-month exposure run with solar cell 1-5 characteristics measured periodically in situ. This 6-month exposure corresponded to a 1 MeV equivalent fluence of approximately 10 to the 14th power electrons/sq cm. Several types of lithium cells were irradiatied and compared directly with conventional N/P cells. The best lithium cells compared favorably with N/P cells, particularly at the higher test temperatures. With a slight improvement of initial performance characteristics, lithium cells appear feasible for 5 to 10 year missions at synchronous altitude. Based on the reported results and those of other irradiation experiments, lithium cells would appear to be superior to N/P cells in proton-dominated earth-orbital environments. Another important conclusion of the effort was that illuminated/loaded cells degrade more rapidly than do dark/unloaded cells. The irradiation experiment provided data of high quality with a high degree of confidence because of the experimental and statistical analysis techniques utilized.

Lithium conductivity in an Li-bearing double-ring silicate mineral, sogdianite

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

Park, S.-H.; Hoelzel, M.; Forschungsneutronenquelle Heinz Maier-Leibnitz

The crystal structure of an Li-bearing double-ring silicate mineral, sogdianite ((Zr{sub 1.18}Fe{sup 3+} {sub 0.55}Ti{sub 0.24}Al{sub 0.03})(Y {sub 1.64},Na{sub 0.36})K{sub 0.85}[Li{sub 3}Si{sub 12}O{sub 30}], P6/mcc, a{approx}10.06 A, c{approx}14.30 A, Z=2), was investigated by neutron powder diffraction from 300 up to 1273 K. Rietveld refinements of displacement parameters revealed high anisotropic Li motions perpendicular to the crystallographic c-axis, indicating an exchange process between tetrahedral T2 and octahedral A sites. AC impedance spectra of a sogdianite single crystal (0.04x0.09x0.25 cm{sup 3}) show that the material is an ionic conductor with conductivity values of {sigma}=4.1x10{sup -5} S cm{sup -1} at 923 K andmore » 1.2x10{sup -3} S cm{sup -1} at 1219 K perpendicular to the c-axis, involving two relaxation processes with activation energies of 1.26(3) and 1.08(3) eV, respectively. - Graphical abstract: Structure of sogdianite with atomic displacement parameter (ADP) ellipsoids at 1273 K.« less

Metal-silicate partitioning and the light element in the core (Invited)

NASA Astrophysics Data System (ADS)

Wood, B. J.; Wade, J.; Tuff, J.

2009-12-01

Most attempts to constrain the concentrations of “light” elements in the Earth’s core rely either on cosmochemical arguments or on arguments based on the densities and equations of state of Fe-alloys containing the element of concern. Despite its utility, the latter approach yields a wide range of permissible compositions and hence weak constraints. The major problem with the cosmochemical approach is that the abundances in the bulk Earth of all the candidate “light” elements- H, C, O, Si and S are highly uncertain because of their volatile behavior during planetary accretion. In contrast, refractory elements appear to be in approximately CI chondritic relative abundances in the Earth. This leads to the potential for using the partitioning of refractory siderophile elements between the mantle and core to constrain the concentrations of light elements in the core. Recent experimental metal-silicate partitioning data, coupled with mantle abundances of refractory siderophile elements (e.g. Wade and Wood, EPSL v.236, 78—95,2005; Kegler et. al. EPSL v.268, 28-40,2008) have shown that the core segregated from the mantle under high pressure conditions (~40 GPa). If a wide range of elements, from very siderophile, (e.g. Mo) through moderately (Ni, Co, W) to weakly siderophile (V, Cr, Nb, Si) are considered, the Earth also appears to have become more oxidized during accretion. Metal-silicate partitioning of some elements is also sensitive to the light element content of the metal. For example, Nb and W partitioning depend strongly on carbon, Mo on silicon and Cr on sulfur. Given the measured mantle abundances of the refractory elements, these observations enable the Si and C contents of the core to be constrained at ~5% and <2% respectively while partitioning is consistent with a cosmochemically-estimated S content of ~2%.

International strategic minerals inventory summary report; lithium

USGS Publications Warehouse

Anstett, T.F.; Krauss, U.H.; Ober, J.A.; Schmidt, H.W.

1990-01-01

Major world resources of lithium are described in this summary report of information in the International Strategic Minerals Inventory (ISMI). ISMI is a cooperative data-collection effort of earth-science and mineral-resource agencies in Australia, Canada, the Federal Republic of Germany, the Republic of South Africa, the United Kingdom, and the United States of America. Part I of this report presents an overview of the resources and potential supply of lithium on the basis of inventory information; Part II contains tables of some of the geologic information and mineral-resource information and production data collected by ISMI participants. In terms of lithium-resource availability, present economically viable resources are more than sufficient to meet likely demand in the foreseeable future. In times of excess capacity such as currently exist, some pegmatite operations cannot compete with brine operations, which are less costly. A further production shift from pegmatites to brines will result in the concentration of supply in a few countries such as Chile and the United States. This shift would lead to the dependence of industrialized countries on deliveries from these sources.

Phospho-silicate and silicate layers modified by hydroxyapatite particles

NASA Astrophysics Data System (ADS)

Rokita, M.; Brożek, A.; Handke, M.

2005-06-01

Common used metal materials do not ensure good connection between an implant and biological neighbourhood. Covering implants by thin silicate or phosphate layers enable to improve biological properties of implants and create conditions for producing the non-concrete bonding between the implant and tissue. The project includes preparing silicate sols of different concentrations and proper (powder) fraction of synthetic as well as natural ox hydroxyapatite, depositing the sol mixed with hydroxyapatite onto the base material (metal, ceramic carbon) and heat treatment. Our work includes also preparation of phospho-silicate layers deposited onto different base materials using sol-gel method. Deposited sols were prepared regarding composition, concentration and layer heat treatment conditions. The prepared layers are examined to determine their phase composition (XRD, IR spectroscopy methods), density and continuity (scanning microscopy with EDX methods). Biological activity of layers was evaluated by means of estimation of their corrosive resistance in synthetic body fluids ('in vitro' method) and of bone cells growth on the layers surface. Introducing hydroxyapatite to the layer sol should improve connection between tissue and implant as well as limit the disadvantageous, corrosive influence of implant material (metal) on the tissue.

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.

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

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.

Exploring Iron Silicate Precursors of Ancient Iron Formations through Rock Record, Laboratory and Field Analogue Investigations

NASA Astrophysics Data System (ADS)

Johnson, J. E.; Rasmussen, B.; Muhling, J.; Benzerara, K.; Jezequel, D.; Cosmidis, J.; Templeton, A. S.

2016-12-01

crater lakes that are variably iron- and silica-rich. As we continue to probe the mechanism of Fe(II/III)-silicate formation, we can constrain the activity of silica, pH, and pO2 on early Earth and describe any potential influence of microbial activity on the precipitation of these phases.

Element Abundances in Meteorites and the Earth: Implication for the Accretion of Planetary Bodies

NASA Astrophysics Data System (ADS)

Mezger, K.; Vollstaedt, H.; Maltese, A.

2017-12-01

Essentially all known inner solar system materials show near chondritic relative abundances of refractory elements and depletion in volatile elements. To a first approximation volatile element depletion correlates with the respective condensation temperature (TC) of the elements. Possible mechanisms for this depletion are incomplete condensation and partial loss by evaporation caused by heating prior to or during the planetesimal accretion. The stable isotope compositions of almost all moderately volatile elements in different meteorite classes show only minor, or no evidence for a Rayleigh-type fractionation that could be attributed to partial condensation or evaporation. The different classes of meteorites also show that the degree of depletion in their parent bodies (i.e. mostly planetesimals) is quite variable, but nevertheless systematic. For primitive and least disturbed carbonaceous chondrites the element depletion pattern is a smooth function of TC. The accessible silicate Earth also shows this general depletion pattern, but in detail it is highly complex and requires differentiation processes that are not solely controlled by TC. If only highly lithophile elements are considered the depletion pattern of the silicate Earth reveals a step function that shows that moderately volatile lithophile elements have abundances that are ca. 0.1 times the chondritic value, irrespective of their TC. This element pattern observed for bulk silicate Earth can be modelled as a mixture of two distinct components: ca. 90% of a strongly reduced planetary body that is depleted in highly volatile elements and ca. 10% of a more volatile element rich and oxidized component. This mixture can account for the apparent Pb- paradox observed in melts derived from the silicate Earth and provides a time constraint for the mixing event, which is ca. 70 My after the beginning of the solar system. This event corresponds to the giant impact that also formed the Moon.

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

A review of bioactive silicate ceramics.

PubMed

Wu, Chengtie; Chang, Jiang

2013-06-01

Silicate bioceramics, as a new family of biomaterials, have received significant attention in their application to hard tissue regeneration. Some silicate bioceramics have shown excellent apatite mineralization in simulated body fluids and their ionic products have been shown to enhance the proliferation, osteogenic differentiation and gene expression of stem cells. In this paper, we review the advances in the research of silicate system bioceramics, including preparation methods, mechanical strength, apatite mineralization, dissolution and in vitro and in vivo biological properties. The biological properties and the corresponding mechanism have been highlighted. A look forward to the application of silicate bioceramics to bone regeneration is further suggested.

A volatile rich Earth's core?

NASA Astrophysics Data System (ADS)

Morard, G.; Antonangeli, D.; Andrault, D.; Nakajima, Y.

2017-12-01

The composition of the Earth's core is still an open question. Although mostly composed of iron, it contains impurities that lower its density and melting point with respect to pure Fe. Knowledge of the nature and abundance of light elements (O, S, Si, C or H) in the core has major implications for establishing the bulk composition of the Earth and for building the model of Earth's differentiation. Geochemical models of the Earth's formation point out that its building blocks were depleted in volatile elements compared to the chondritic abundance, therefore light elements such as S, H or C cannot be the major elements alloyed with iron in the Earth's core. However, such models should be compatible with the comparison of seismic properties of the Earth's core and physical properties of iron alloys under extreme conditions, such as sound velocity or density of solid and liquid. The present work will discuss the recent progress for compositional model issued from studies of phase diagrams and elastic properties of iron alloys under core conditions and highlight the compatibility of volatile elements with observed properties of the Earth's core, in potential contradiction with models derived from metal-silicate partitioning experiments.

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

Lithium Dinitramide as an Additive in Lithium Power Cells

NASA Technical Reports Server (NTRS)

Gorkovenko, Alexander A.

2007-01-01

Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with

Nanostructured silicon anodes for lithium ion rechargeable batteries.

PubMed

Teki, Ranganath; Datta, Moni K; Krishnan, Rahul; Parker, Thomas C; Lu, Toh-Ming; Kumta, Prashant N; Koratkar, Nikhil

2009-10-01

Rechargeable lithium ion batteries are integral to today's information-rich, mobile society. Currently they are one of the most popular types of battery used in portable electronics because of their high energy density and flexible design. Despite their increasing use at the present time, there is great continued commercial interest in developing new and improved electrode materials for lithium ion batteries that would lead to dramatically higher energy capacity and longer cycle life. Silicon is one of the most promising anode materials because it has the highest known theoretical charge capacity and is the second most abundant element on earth. However, silicon anodes have limited applications because of the huge volume change associated with the insertion and extraction of lithium. This causes cracking and pulverization of the anode, which leads to a loss of electrical contact and eventual fading of capacity. Nanostructured silicon anodes, as compared to the previously tested silicon film anodes, can help overcome the above issues. As arrays of silicon nanowires or nanorods, which help accommodate the volume changes, or as nanoscale compliant layers, which increase the stress resilience of silicon films, nanoengineered silicon anodes show potential to enable a new generation of lithium ion batteries with significantly higher reversible charge capacity and longer cycle life.

Trace element and isotope studies in oxide/phosphate/silicate inclusions of iron meteorites

NASA Technical Reports Server (NTRS)

Olsen, Edward J.

1996-01-01

Under the above grant research was funded in the following areas: 1. Pallasites: Rare earth element measurements in phosphates to determine if all pallasites fit into only two trace element groups. This work has been completed. 2. HIAB irons: To complete work on the only known silicate inclusion in a IIIAB iron meteorite. This work has been completed. 3. IIIAB irons: To continue the search for Cr-53 excesses in IIIAB iron meteorite phosphates. A part of this work has been completed 4. IIIAB irons: To complete the identification of the phosphate minerals in IIIAB iron meteorites and try to determine the phase relations and chemical history of trace element distributions during the core formation process. Work on this has been largely completed and preliminary results have been reported. The final work is being assessed prior to preparation of a manuscript for publication. 5. IIE irons: To complete work on the unique silicate assemblage in the IIE iron meteorite. Work on this was completed and a paper published. 6. Ungrouped irons: A partially devitrified silicate glass inclusion has been found in the ungrouped iron meteorite. Preliminary work on this has been reported. All the work on this has been now completed and a manuscript has been prepared and submitted for publication.

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Aluminum calcium silicate. 182.2122 Section 182...) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions, or explanation. This...

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

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Aluminum calcium silicate. 182.2122 Section 182.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Aluminum calcium silicate. 182.2122 Section 182.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Aluminum calcium silicate. 182.2122 Section 182.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Aluminum calcium silicate. 182.2122 Section 182.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

Grain Boundary Engineering of Lithium-Ion-Conducting Lithium Lanthanum Titanate for Lithium-Air Batteries

DTIC Science & Technology

2016-01-01

release; distribution is unlimited. 1 1. Introduction Lithium (Li)- ion batteries are currently one of the leading energy storage device technologies...ARL-TR-7584 ● JAN 2016 US Army Research Laboratory Grain Boundary Engineering of Lithium - Ion - Conducting Lithium Lanthanum...Titanate for Lithium -Air Batteries by Victoria L Blair, Claire V Weiss Brennan, and Joseph M Marsico Approved for public

Tableting properties of silica aerogel and other silicates.

PubMed

Hentzschel, C M; Alnaief, M; Smirnova, I; Sakmann, A; Leopold, C S

2012-04-01

In solid oral dosage forms silicates are commonly used as glidants in low concentration. However, due to their large specific surface area, silicates may also be used as carrier materials for drugs. Moreover, silicates allow amorphisation of drugs by co-grinding or processing with supercritical fluids. The aim of this study was to investigate the physical and the tableting properties of Silica Aerogel (special type of silica with an extremely large specific surface area), Neusilin(®) US2 (magnesium aluminometasilicate), Florite(®) (calcium silicate) and Aerosil(®) 200 (colloidal silica). Powder blends of Avicel(®) PH102 (microcrystalline cellulose) and different amounts of the respective silicate were compacted and analyzed for their tabletability (tensile strength vs. compaction pressure) as well as their Heckel plot. With Neusilin(®) the tabletability appeared to be independent of the silicate concentration, whereas with Florite(®) an increasing silicate concentration led to a higher tensile strength. In contrast, the addition of Silica Aerogel and Aerosil(®) resulted in a decrease of the tensile strength. With Aerosil(®) a maximum tolerable concentration of 20% [w/w] was determined. Plastic deformation of all powder blends decreased with increasing silicate concentration. This effect was most pronounced with Aerosil(®) and least with Florite(®). Tablets with acceptable tensile strength were obtained with all plain silicates except for Aerosil(®). Therefore, these silicates may be used in tablet formulations, e.g. as carrier materials for liquid or amorphous drugs.

Chemically bonded phospho-silicate ceramics

DOEpatents

Wagh, Arun S.; Jeong, Seung Y.; Lohan, Dirk; Elizabeth, Anne

2003-01-01

A chemically bonded phospho-silicate ceramic formed by chemically reacting a monovalent alkali metal phosphate (or ammonium hydrogen phosphate) and a sparsely soluble oxide, with a sparsely soluble silicate in an aqueous solution. The monovalent alkali metal phosphate (or ammonium hydrogen phosphate) and sparsely soluble oxide are both in powder form and combined in a stochiometric molar ratio range of (0.5-1.5):1 to form a binder powder. Similarly, the sparsely soluble silicate is also in powder form and mixed with the binder powder to form a mixture. Water is added to the mixture to form a slurry. The water comprises 50% by weight of the powder mixture in said slurry. The slurry is allowed to harden. The resulting chemically bonded phospho-silicate ceramic exhibits high flexural strength, high compression strength, low porosity and permeability to water, has a definable and bio-compatible chemical composition, and is readily and easily colored to almost any desired shade or hue.

Thermal Ablation Modeling for Silicate Materials

NASA Technical Reports Server (NTRS)

Chen, Yih-Kanq

2016-01-01

A thermal ablation model for silicates is proposed. The model includes the mass losses through the balance between evaporation and condensation, and through the moving molten layer driven by surface shear force and pressure gradient. This model can be applied in ablation simulations of the meteoroid or glassy Thermal Protection Systems for spacecraft. Time-dependent axi-symmetric computations are performed by coupling the fluid dynamics code, Data-Parallel Line Relaxation program, with the material response code, Two-dimensional Implicit Thermal Ablation simulation program, to predict the mass lost rates and shape change. For model validation, the surface recession of fused amorphous quartz rod is computed, and the recession predictions reasonably agree with available data. The present parametric studies for two groups of meteoroid earth entry conditions indicate that the mass loss through moving molten layer is negligibly small for heat-flux conditions at around 1 MW/cm(exp. 2).

Battery components employing a silicate binder

DOEpatents

Delnick, Frank M [Albuquerque, NM; Reinhardt, Frederick W [Albuquerque, NM; Odinek, Judy G [Rio Rancho, NM

2011-05-24

A battery component structure employing inorganic-silicate binders. In some embodiments, casting or coating of components may be performed using aqueous slurries of silicates and electrode materials or separator materials.

Lithium in 2012

USGS Publications Warehouse

Jaskula, B.W.

2013-01-01

In 2012, estimated world lithium consumption was about 28 kt (31,000 st) of lithium contained in minerals and compounds, an 8 percent increase from that of 2011. Estimated U.S. consumption was about 2 kt (2,200 st) of contained lithium, the same as that of 2011. The United States was thought to rank fourth in consumption of lithium and remained the leading importer of lithium carbonate and the leading producer of value-added lithium materials. One company, Rockwood Lithium Inc., produced lithium compounds from domestic brine resources near Silver Peak, NV.

Method of recycling lithium borate to lithium borohydride through diborane

DOEpatents

Filby, Evan E.

1976-01-01

This invention provides a method for the recycling of lithium borate to lithium borohydride which can be reacted with water to generate hydrogen for utilization as a fuel. The lithium borate by-product of the hydrogen generation reaction is reacted with hydrogen chloride and water to produce boric acid and lithium chloride. The boric acid and lithium chloride are converted to lithium borohydride through a diborane intermediate to complete the recycle scheme.

Microstructure of ultra high performance concrete containing lithium slag.

PubMed

He, Zhi-Hai; Du, Shi-Gui; Chen, Deng

2018-04-03

Lithium slag (LS) is discharged as a byproduct in the process of the lithium carbonate, and it is very urgent to explore an efficient way to recycle LS in order to protect the environments and save resources. Many available supplementary cementitious materials for partial replacement of cement and/or silica fume (SF) can be used to prepare ultra high performance concrete (UHPC). The effect of LS to replace SF partially by weight used as a supplementary cementitious material (0%, 5%, 10% and 15% of binder) on the compressive strengths and microstructure evolution of UHPC has experimentally been studied by multi-techniques including mercury intrusion porosimetry, scanning electron microscope and nanoindentation technique. The results show that the use of LS degrades the microstructure of UHPC at early ages, and however, the use of LS with the appropriate content improves microstructure of UHPC at later ages. The hydration products of UHPC are mainly dominated by ultra-high density calcium-silicate-hydrate (UHD C-S-H) and interfacial transition zone (ITZ) in UHPC has similar compact microstructure with the matrix. The use of LS improves the hydration degree of UHPC and increases the elastic modulus of ITZ in UHPC. LS is a promising substitute for SF for preparation UHPC. Copyright © 2018 Elsevier B.V. All rights reserved.

Suppression of dendritic lithium growth in lithium metal-based batteries.

PubMed

Li, Linlin; Li, Siyuan; Lu, Yingying

2018-06-19

Lithium metal-based batteries offer promising prospects as alternatives to today's lithium-ion batteries, due to their ultra-high energy density. Unfortunately, the application of lithium metal is full of challenges and has puzzled researchers for more than 40 years. In this feature article, we describe the history of the development of lithium metal batteries and their existing key challenges, which include non-uniform electrodeposition, volume expansion, high reactivity of the lithium metal/unstable solid electrolyte interphase (SEI), and the shuttling of active cathode materials. Then, we focus on the growth mechanisms of uneven lithium electrodeposition and extend the discussion to the approaches to inhibit lithium dendrites. Finally, we discuss future directions that are expected to drive progress in the development of lithium metal batteries.

Lithium Poisoning.

PubMed

Baird-Gunning, Jonathan; Lea-Henry, Tom; Hoegberg, Lotte C G; Gosselin, Sophie; Roberts, Darren M

2017-05-01

Lithium is a commonly prescribed treatment for bipolar affective disorder. However, treatment is complicated by lithium's narrow therapeutic index and the influence of kidney function, both of which increase the risk of toxicity. Therefore, careful attention to dosing, monitoring, and titration is required. The cause of lithium poisoning influences treatment and 3 patterns are described: acute, acute-on-chronic, and chronic. Chronic poisoning is the most common etiology, is usually unintentional, and results from lithium intake exceeding elimination. This is most commonly due to impaired kidney function caused by volume depletion from lithium-induced nephrogenic diabetes insipidus or intercurrent illnesses and is also drug-induced. Lithium poisoning can affect multiple organs; however, the primary site of toxicity is the central nervous system and clinical manifestations vary from asymptomatic supratherapeutic drug concentrations to clinical toxicity such as confusion, ataxia, or seizures. Lithium poisoning has a low mortality rate; however, chronic lithium poisoning can require a prolonged hospital length of stay from impaired mobility and cognition and associated nosocomial complications. Persistent neurological deficits, in particular cerebellar, are described and the incidence and risk factors for its development are poorly understood, but it appears to be uncommon in uncomplicated acute poisoning. Lithium is readily dialyzable, and rationale support extracorporeal treatments to reduce the risk or the duration of toxicity in high-risk exposures. There is disagreement in the literature regarding factors that define patients most likely to benefit from treatments that enhance lithium elimination, including specific plasma lithium concentration thresholds. In the case of extracorporeal treatments, there are observational data in its favor, without evidence from randomized controlled trials (none have been performed), which may lead to conservative practices and

Effects of Incorporating High-Volume Fly Ash into Tricalcium Silicate on the Degree of Silicate Polymerization and Aluminum Substitution for Silicon in Calcium Silicate Hydrate

DOE PAGES

Bae, Sungchul; Taylor, Rae; Kilcoyne, David; ...

2017-02-04

This study assesses the quantitative effects of incorporating high-volume fly ash (HVFA) into tricalcium silicate (C 3S) paste on the hydration, degree of silicate polymerization, and Al substitution for Si in calcium silicate hydrate (C–S–H). Thermogravimetric analysis and isothermal conduction calorimetry showed that, although the induction period of C 3S hydration was significantly extended, the degree of hydration of C 3S after the deceleration period increased due to HVFA incorporation. Synchrotron-sourced soft X-ray spectromicroscopy further showed that most of the C 3S in the C 3S-HVFA paste was fully hydrated after 28 days of hydration, while that in the puremore » C 3S paste was not. The chemical shifts of the Si K edge peaks in the near-edge X-ray fine structure of C–S–H in the C 3S-HVFA paste directly indicate that Al substitutes for Si in C–S–H and that the additional silicate provided by the HVFA induces an enhanced degree of silicate polymerization. This new spectromicroscopic approach, supplemented with 27Al and 29Si magic-angle spinning nuclear magnetic resonance spectroscopy and transmission electron microscopy, turned out to be a powerful characterization tool for studying a local atomic binding structure of C–S–H in C 3S-HVFA system and presented results consistent with previous literature.« less

Effects of Incorporating High-Volume Fly Ash into Tricalcium Silicate on the Degree of Silicate Polymerization and Aluminum Substitution for Silicon in Calcium Silicate Hydrate

PubMed Central

Bae, Sungchul; Taylor, Rae; Kilcoyne, David; Moon, Juhyuk; Monteiro, Paulo J. M.

2017-01-01

This study assesses the quantitative effects of incorporating high-volume fly ash (HVFA) into tricalcium silicate (C3S) paste on the hydration, degree of silicate polymerization, and Al substitution for Si in calcium silicate hydrate (C–S–H). Thermogravimetric analysis and isothermal conduction calorimetry showed that, although the induction period of C3S hydration was significantly extended, the degree of hydration of C3S after the deceleration period increased due to HVFA incorporation. Synchrotron-sourced soft X-ray spectromicroscopy further showed that most of the C3S in the C3S-HVFA paste was fully hydrated after 28 days of hydration, while that in the pure C3S paste was not. The chemical shifts of the Si K edge peaks in the near-edge X-ray fine structure of C–S–H in the C3S-HVFA paste directly indicate that Al substitutes for Si in C–S–H and that the additional silicate provided by the HVFA induces an enhanced degree of silicate polymerization. This new spectromicroscopic approach, supplemented with 27Al and 29Si magic-angle spinning nuclear magnetic resonance spectroscopy and transmission electron microscopy, turned out to be a powerful characterization tool for studying a local atomic binding structure of C–S–H in C3S-HVFA system and presented results consistent with previous literature. PMID:28772490

Effects of Incorporating High-Volume Fly Ash into Tricalcium Silicate on the Degree of Silicate Polymerization and Aluminum Substitution for Silicon in Calcium Silicate Hydrate

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

Bae, Sungchul; Taylor, Rae; Kilcoyne, David

This study assesses the quantitative effects of incorporating high-volume fly ash (HVFA) into tricalcium silicate (C 3S) paste on the hydration, degree of silicate polymerization, and Al substitution for Si in calcium silicate hydrate (C–S–H). Thermogravimetric analysis and isothermal conduction calorimetry showed that, although the induction period of C 3S hydration was significantly extended, the degree of hydration of C 3S after the deceleration period increased due to HVFA incorporation. Synchrotron-sourced soft X-ray spectromicroscopy further showed that most of the C 3S in the C 3S-HVFA paste was fully hydrated after 28 days of hydration, while that in the puremore » C 3S paste was not. The chemical shifts of the Si K edge peaks in the near-edge X-ray fine structure of C–S–H in the C 3S-HVFA paste directly indicate that Al substitutes for Si in C–S–H and that the additional silicate provided by the HVFA induces an enhanced degree of silicate polymerization. This new spectromicroscopic approach, supplemented with 27Al and 29Si magic-angle spinning nuclear magnetic resonance spectroscopy and transmission electron microscopy, turned out to be a powerful characterization tool for studying a local atomic binding structure of C–S–H in C 3S-HVFA system and presented results consistent with previous literature.« less

Commercial silicate phosphate sequestration and desorption leads to a gradual decline of aquatic systems.

PubMed

Svatos, Karl B W

2018-02-01

Laboratory desorption behaviour, function and elemental composition of commercially marketed silicate minerals used to sequester phosphorus pollution as well as Zeolite, Smectite, and Kaolinite were determined to see whether their use by environmental scientists and water managers in eutrophic waterways has the potential to contribute to longer-term environmental impacts. As expected, lower phosphorus concentrations were observed, following treatment. However, data relating to desorption, environmental fate and bioavailability of phospho-silicate complexes (especially those containing rare earth elements) appear to be underrepresented in product testing and trial publications. Analysis of desorption of phosphate (P) was > 5 μg[P]/L for all three non-commercial samples and 0 > μg[P]/L > 5 for all commercial silicates for a range of concentrations from 0 to 300 μg[P]/L. Based on a review of bioaccumulation data specific to the endangered Cherax tenuimanus (Hairy Marron) and other endemic species, this is significant considering anything > 20 μg[La]/L is potentially lethal to the hairy marron, other crustaceans and even other phyla. Where prokaryotic and eukaryotic effects are underreported, this represents a significant challenge. Especially where product protocols recommend continual reapplication, this is significant because both the forward and reverse reactions are equally important. The users of silicate minerals in water columns should accept the dynamic nature of the process and pay equal attention to both adsorption and desorption because desorption behaviour is an inherent trait. Even if broader desorption experimentation is difficult, expensive and time-consuming, it is a critical consideration nonetheless.

Phosphorus Equilibria Among Mafic Silicate Phases

NASA Technical Reports Server (NTRS)

Berlin, Jana; Xirouchakis, Dimitris

2002-01-01

Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The

Origin and mixing timescale of Earth's late veneer

NASA Astrophysics Data System (ADS)

Prescher, C.; Allu Peddinti, D.; Bell, E. A.; Bello, L.; Cernok, A.; Ghosh, N.; Tucker, J.; Wielicki, M. M.; Zahnle, K. J.

2012-12-01

Experimental studies on the partitioning behavior of highly siderophile elements (HSE) between silicate and metallic melts imply that the Earth's mantle should have been highly depleted in these elements by core formation in an early magma ocean. However, present HSE contents of the Earth's mantle are ~3 orders of magnitude higher than that expected by experiments. The apparent over-abundance of HSE has commonly been explained by the addition of meteoritic material in the "late veneer" which describes the exogenous mass addition following the moon forming impact and concluding with the late heavy bombardment at ~3.8-3.9 Ga. The strongest evidence for this theory is that the platinum group element (PGE) contents in today's mantle are present in chondritic relative abundances, as opposed to a fractionated pattern expected with metal-silicate partitioning. Archean komatiites indicate that the PGE content of the Earth's mantle increased from about half their present abundances at 3.5 Ga to their present abundances at 2.9 Ga. This secular increase in PGE content suggests a progressive mixing of the late veneer material into the Earth's mantle. However, this time scale also implies that the whole mantle was relatively well mixed by 2.9 Ga. We use a compilation of existing isotopic and trace element data in order to constrain the origin and composition of the late veneer. We use PGE abundances, W abundances and W isotopic compositions in chondritic meteorites and the primitive upper mantle to compute the amount of mass delivered during the late veneer and find the late veneer mass to be ~0.6 % the mass of the bulk silicate Earth (consistent with earlier estimates). We also use the 187Re-187Os and 190Pt-186Os systems to constrain the composition and timing of delivery of the impacting population. We model the efficiency of mantle mixing in this time frame by using 3-dimensional numerical geodynamical simulations and geochemical constraints. Initial parameters include the

A low-temperature electrolyte for lithium and lithium-ion batteries

NASA Astrophysics Data System (ADS)

Plichta, E. J.; Behl, W. K.

An electrolyte consisting of 1 M solution of lithium hexafluorophosphate in 1:1:1 ethylene carbonate(EC)-dimethyl carbonate(DMC)-ethyl methyl carbonate(EMC) is proposed for low temperature applications of lithium and lithium-ion cells. The new electrolyte has good conductivity and electrochemical stability. Lithium and lithium-ion cells using the new electrolyte were found to be operable at temperatures down to -40°C. The paper also reports on the electrochemical stability of aluminum metal, which is used as a substrate for the positive electrodes in lithium-ion cells, in the new electrolyte.

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.

Determination of total tin in silicate rocks by graphite furnace atomic absorption spectrometry

USGS Publications Warehouse

Elsheimer, H.N.; Fries, T.L.

1990-01-01

A method is described for the determination of total tin in silicate rocks utilizing a graphite furnace atomic absorption spectrometer with a stabilized-temperature platform furnace and Zeeman-effect background correction. The sample is decomposed by lithium metaborate fusion (3 + 1) in graphite crucibles with the melt being dissolved in 7.5% hydrochloric acid. Tin extractions (4 + 1 or 8 + 1) are executed on portions of the acid solutions using a 4% solution of tricotylphosphine oxide in methyl isobutyl ketone (MIBK). Ascorbic acid is added as a reducing agent prior to extraction. A solution of diammonium hydrogenphosphate and magnesium nitrate is used as a matrix modifier in the graphite furnace determination. The limit of detection is > 10 pg, equivalent to > 1 ??g l-1 of tin in the MIBK solution or 0.2-0.3 ??g g-61 in the rock. The concentration range is linear between 2.5 and 500 ??g l-1 tin in solution. The precision, measured as relative standard deviation, is < 20% at the 2.5 ??g l-1 level and < 7% at the 10-30 ??g l-1 level of tin. Excellent agreement with recommended literature values was found when the method was applied to the international silicate rock standards BCR-1, PCC-1, GSP-1, AGV-1, STM-1, JGb-1 and Mica-Fe. Application was made to the determination of tin in geological core samples with total tin concentrations of the order of 1 ??g g-1 or less.

Multi-layered, chemically bonded lithium-ion and lithium/air batteries

DOEpatents

Narula, Chaitanya Kumar; Nanda, Jagjit; Bischoff, Brian L; Bhave, Ramesh R

2014-05-13

Disclosed are multilayer, porous, thin-layered lithium-ion batteries that include an inorganic separator as a thin layer that is chemically bonded to surfaces of positive and negative electrode layers. Thus, in such disclosed lithium-ion batteries, the electrodes and separator are made to form non-discrete (i.e., integral) thin layers. Also disclosed are methods of fabricating integrally connected, thin, multilayer lithium batteries including lithium-ion and lithium/air batteries.

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

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

Method of recycling lithium borate to lithium borohydride through methyl borate

DOEpatents

Filby, Evan E.

1977-01-01

This invention provides a method for the recycling of lithium borate to lithium borohydride which can be reacted with water to generate hydrogen for utilization as a fuel. The lithium borate by-product of the hydrogen generation reaction is reacted with hydrogen chloride and water to produce boric acid and lithium chloride. The boric acid and lithium chloride are converted to lithium borohydride through a methyl borate intermediate to complete the recycle scheme.

Deformation and seismic anisotropy of silicate post-perovskite in the Earth's lowermost mantle

NASA Astrophysics Data System (ADS)

wu, X.; Lin, J.; Mao, Z.; Liu, J.; Kaercher, P. M.; Wenk, H.; Prakapenka, V.; Zhuravlev, K. K.

2013-12-01

The D' layer in the Earth's lowermost mantle with an average thickness of 250 km right above the core-mantle boundary plays a significant role in the geophysics, geochemistry, and geodynamics of the planet's interior. Seismic observations of the region have shown a number of enigmatic features including shear wave discontinuity and seismic wave anisotropy. The seismic anisotropy, in which the horizontally-polarized shear wave (VSH) travels faster than the vertically-polarized shear wave (VSV) by 1%~3% in areas below the circum Pacific, has been proposed to be a result of the lattice-preferred orientation of silicate post-perovskite (PPv) that is to be the most abundant phase in the D' layer [1]. Therefore, understanding the elasticity and deformation of the PPv phase is critical under relevant P-T conditions of the region. However, experimental results on the textures and the elastic anisotropy of PPv remain largely limited and controversial. Specifically, a number of slip systems of PPv, such as (010), (100), (110) and (001), have been proposed based on experimental and theoretical results [2-4]. Here we have studied the textures and deformation mechanism of iron-bearing PPv ((Mg0.75,Fe0.25)SiO3) at relevant P-T conditions of the lowermost mantle using synchrotron radiation radial x-ray diffraction in a membrane-driven laser-heated diamond anvil cell. The diffraction patterns were recorded from the laser-heated PPv sample during further compression between 130 GPa and 150 GPa. Analyses of the diffraction patterns and simulation results from viscoplastic self-consistent polycrystal plasticity code (VPSC) show that the development of active slip systems can be strongly influenced by experimental pressure-temperature-time conditions. At relevant P-T conditions of the lowermost mantle, our results demonstrate that the dominant slip systems of PPv should be (001)[100] and (001)[010]. Combined these results with the elasticity of PPv, we provide more constrains on the

Silicate calculi, a rare cause of kidney stones in children.

PubMed

Taşdemir, Mehmet; Fuçucuoğlu, Dilara; Özman, Oktay; Sever, Lale; Önal, Bülent; Bilge, Ilmay

2017-02-01

Urinary silicate calculi in humans are extremely rare. Reported cases of silicate calculi are mostly documented in adults and are commonly related to an excessive intake of magnesium trisilicate in food or drugs. Published studies on the presence of silicate calculi in children are scarce. Three cases of silicate kidney stones without prior silicate intake are reported. Two patients underwent surgical treatment, and the third patient was treated using conservative methods. Urinalysis revealed no underlying metabolic abnormalities. Analyses revealed that silicate was the major component of the stones. Siliceous deposits in urinary stones may be more common than anticipated, and the underlying pathophysiology remains to be clarified.

Lithium-associated hyperthyroidism.

PubMed

Siyam, Fadi F; Deshmukh, Sanaa; Garcia-Touza, Mariana

2013-08-01

Goiters and hypothyroidism are well-known patient complications of the use of lithium for treatment of bipolar disease. However, the occurrence of lithium-induced hyperthyroidism is a more rare event. Many times, the condition can be confused with a flare of mania. Monitoring through serial biochemical measurement of thyroid function is critical in patients taking lithium. Hyperthyroidism induced by lithium is a condition that generally can be controlled medically without the patient having to discontinue lithium therapy, although in some circumstances, discontinuation of lithium therapy may be indicated. We report on a patient case of lithium-associated hyperthyroidism that resolved after discontinuation of the medication.

L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Sutton, S.; Newville, M.

2008-01-01

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2.

Lithium/water battery with lithium ion conducting glass-ceramics electrolyte

NASA Astrophysics Data System (ADS)

Katoh, Takashi; Inda, Yasushi; Nakajima, Kousuke; Ye, Rongbin; Baba, Mamoru

Lithium/water batteries have attracted considerable attention as high power supply devices because they use high energy density lithium metal as an anode and water as a cathode. In this study, we investigate the use of lithium/water batteries that use a glass-ceramics plate as an electrolyte. A lithium ion conducting glass-ceramics plate has no through-holes and does not exhibit moisture permeation. Such a plate has stable ionic conductivity in water. Lithium/water batteries that used a glass-ceramics plate as an electrolyte had a long and stable discharge for 50 days at room temperature when the lithium metal was prevented from coming into contact with water. Lithium/seawater batteries using a glass-ceramics plate as an electrolyte also operated well in the 10-70 °C temperature range.

Chemical evidence for differentiation, evaporation and recondensation from silicate clasts in Gujba

NASA Astrophysics Data System (ADS)

Oulton, Jonathan; Humayun, Munir; Fedkin, Alexei; Grossman, Lawrence

2016-03-01

The silicate and metal clasts in CB chondrites have been inferred to form as condensates from an impact-generated vapor plume between a metal-rich body and a silicate body. A detailed study of the condensation of impact-generated vapor plumes showed that the range of CB silicate clast compositions could not be successfully explained without invoking a chemically differentiated target. Here, we report the most comprehensive elemental study yet performed on CB silicates with 32 silicate clasts from nine slices of Gujba analyzed by laser ablation inductively coupled plasma mass spectrometry for 53 elements. Like in other studies of CBs, the silicate clasts are either barred olivine (BO) or cryptocrystalline (CC) in texture. In major elements, the Gujba silicate clasts ranged from chondritic to refractory enriched. Refractory element abundances ranged from 2 to 10 × CI, with notable anomalies in Ba, Ce, Eu, and U abundances. The two most refractory-enriched BO clasts exhibited negative Ce anomalies and were depleted in U relative to Th, characteristic of volatilization residues, while other BO clasts and the CC clasts exhibited positive Ce anomalies with excess U (1-3 × CI), and Ba (1-6 × CI) anomalies indicating re-condensation of ultra-refractory element depleted vapor. The Rare Earth Elements (REE) also exhibit light REE (LREE) enrichment or depletion in several clasts with a range of (La/Sm)CI of 0.9-1.8. This variation in the LREE is essentially impossible to accomplish by processes involving vapor-liquid or vapor-solid exchange of REE, and appears to have been inherited from a differentiated target. The most distinctive evidence for inherited chemical differentiation is observed in highly refractory element (Sc, Zr, Nb, Hf, Ta, Th) systematics. The Gujba clasts exhibit fractionations in Nb/Ta that correlate positively with Zr/Hf and span the range known from lunar and Martian basalts, and exceed the range in Zr/Hf variation known from eucrites. Variations of

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).

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

The problem of iron partition between Earth and Moon during simultaneous formation as a double planet system

NASA Technical Reports Server (NTRS)

Cassidy, W. A.

1984-01-01

A planetary model is described which requires fractional vapor/liquid condensation, planet accumulation during condensation, a late start for accumulation of the Moon, and volatile accretion to the surfaces of each planet only near the end of the accumulation process. In the model, initial accumulation of small objects is helped if the agglomerating particles are somewhat sticky. Assuming that growth proceeds through this range, agglomeration continues. If the reservoir of vapor is being preferentially depleted in iron by fractional condensation, an iron-rich planetary core forms. As the temperature decreases, condensing material becomes progressively richer in silicates and poorer in iron, forming the silicate-rich mantle of an already differentiated Earth. A second center of agglomeration successfully forms near the growing Earth after most of the iron in the reservoir has been used up. The bulk composition of the Moon then is similar to the outer mantle of the accumulating Earth.

Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method

DOEpatents

Bates, John B.

1994-01-01

A battery structure including a cathode, a lithium metal anode and an electrolyte disposed between the lithium anode and the cathode utilizes a thin-film layer of lithium phosphorus oxynitride overlying so as to coat the lithium anode and thereby separate the lithium anode from the electrolyte. If desired, a preliminary layer of lithium nitride may be coated upon the lithium anode before the lithium phosphorous oxynitride is, in turn, coated upon the lithium anode so that the separation of the anode and the electrolyte is further enhanced. By coating the lithium anode with this material lay-up, the life of the battery is lengthened and the performance of the battery is enhanced.

21 CFR 182.2437 - Magnesium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Magnesium silicate. 182.2437 Section 182.2437 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2437 Magnesium silicate. (a) Product. Magnesium...

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

About the Influence of the initial Atmosphere on the Earth's Temperature Distribution during it's Accumulation

NASA Astrophysics Data System (ADS)

Khachay, Y.; Anfilogov, V.; Antipin, A.

2012-04-01

We suggested a new model for accumulation of planets of the Earth's group [1], which is based on the contemporary results of geochemical analyses, which allow to obtain the concentrations of short living radioactive isotopes of 26Al in the matter of the pre planet cloud [2]. With use of that data new estimations of temperature distribution into the growing planetary pre planetary bodies into the Earth's nebular zone had been obtained. For the further Earth's temperature evolution, as it had been showed by the results of numerical modeling, the main role belongs to the temperature distribution in the forming Earth's core and the existence of a dense and transparent atmosphere. The shadow influence of the initial atmosphere had been researched in the paper [3]. We shall give the main consideration to these problems in that paper. It had been shown in [1], that on the earliest accumulation stage the heat release by the decay of 26Al it is sufficient for forming a central melted area and solid relatively thin mainly silicate upper envelope in the pre planetary body, with dimensions, larger than (50-100) km. The impact velocities on that stage are yet not large, therefore by the bodies impact with these or near dimensions liquid and mainly iron their parts merge, but the masses of the pre planetary bodies are not sufficient to gravitational keeping of silicate parts of the cold solid envelope. On that stage they remain into the nebular zone of the proto planet and the mechanism of matter differentiation for the future core and mantle reservoirs realizes. The process takes place yet in small bodies and is in time to finish during less than 10 million years. The next forming of the core and mantle structure continues according to all known estimations about 100 million years. Because of the merging of inner liquid parts of impacting bodies occur due to inelastic impact, the main part of potential energy transforms into heat. That continues up to that time when the iron

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

Fracture resistance of glazed, full-contour ZLS incisor crowns.

PubMed

Schwindling, Franz Sebastian; Rues, Stefan; Schmitter, Marc

2017-07-01

To compare the failure behaviour of zirconia-reinforced lithium silicate (Celtra Duo, DeguDent) with that of lithium disilicate (IPS e.max CAD, Ivoclar Vivadent) and feldspar (Mark II, VITA) ceramics. Three groups of sixteen glazed maxillary incisor crowns were produced. The inner surfaces of the crowns were etched, then luted to metal dies with self-adhesive cement. Single load-to-failure tests were performed before and after thermo-mechanical ageing. To simulate clinical conditions, the specimens were thermocycled (10,000 cycles between 6.5°C and 60°C) and underwent chewing simulation (1,200,000 cycles, F max =86N). Statistical analyses were performed by use of non-parametric Kruskal-Wallis and Mann-Whitney U-tests. Before ageing, all the monolithic incisor crowns fractured at test forces >285N. Mean fracture loads were highest for zirconia-reinforced lithium silicate (725N, SD 162N), slightly lower for lithium disilicate (701N, SD 276N), and lowest for feldspar (554N, SD 190N). The differences between the results were not statistically significant. After ageing, fracture resistance decreased for all materials except zirconia-reinforced lithium silicate. Mean fracture loads were highest for zirconia-reinforced lithium silicate (766N, SD 98N) and significantly lower for both lithium disilicate (485N, SD 64N) and feldspar (372N, SD 116N). Monolithic restorations fabricated from zirconia-reinforced lithium silicate retain high fracture resistance after extensive thermo-mechanical ageing. This preclinical study suggests that cohesive failures of monolithic anterior crowns produced of these ceramics will not be a major problem in dental practice. Copyright © 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Lithium in drinking water and suicide mortality: interplay with lithium prescriptions

PubMed Central

Helbich, Marco; Leitner, Michael; Kapusta, Nestor D.

2015-01-01

Background Little is known about the effects of lithium intake through drinking water on suicide. This intake originates either from natural rock and soil elution and/or accumulation of lithium-based pharmaceuticals in ground water. Aims To examine the interplay between natural lithium in drinking water, prescribed lithium-based pharmaceuticals and suicide in Austria. Method Spatial Bayesian regressions for males, females and pooled suicide mortality rates were estimated. Results Although the expected inverse association between lithium levels in drinking water and suicide mortality was confirmed for males and for total suicide rates, the relationship for females was not significant. The models do not indicate that lithium from prescriptions, assumed to accumulate in drinking water, is related to suicide risk patterns either as an individual effect or as a moderator of lithium levels in drinking water. Gender-specific differences in risk factors and local risk hot spots are confirmed. Conclusions The findings do not support the hypotheses that lithium prescriptions have measureable protective effects on suicide or that they interact with lithium in drinking water. PMID:25953888

Lithium in drinking water and suicide mortality: interplay with lithium prescriptions.

PubMed

Helbich, Marco; Leitner, Michael; Kapusta, Nestor D

2015-07-01

Little is known about the effects of lithium intake through drinking water on suicide. This intake originates either from natural rock and soil elution and/or accumulation of lithium-based pharmaceuticals in ground water. To examine the interplay between natural lithium in drinking water, prescribed lithium-based pharmaceuticals and suicide in Austria. Spatial Bayesian regressions for males, females and pooled suicide mortality rates were estimated. Although the expected inverse association between lithium levels in drinking water and suicide mortality was confirmed for males and for total suicide rates, the relationship for females was not significant. The models do not indicate that lithium from prescriptions, assumed to accumulate in drinking water, is related to suicide risk patterns either as an individual effect or as a moderator of lithium levels in drinking water. Gender-specific differences in risk factors and local risk hot spots are confirmed. The findings do not support the hypotheses that lithium prescriptions have measureable protective effects on suicide or that they interact with lithium in drinking water. © The Royal College of Psychiatrists 2015.

Development of lithium powder based anode with conductive carbon materials for lithium batteries

NASA Astrophysics Data System (ADS)

Park, Man Su

Current lithium ion battery with a graphite anode shows stable cycle performance and safety. However, the lithium ion battery still has the limitation of having a low energy density caused by the application of lithium intercalated cathode and anode with low energy density. The combination of high capacity non-lithiated cathode such as sulfur and carbon and lithium metal anode has been researched for a long time to maximize battery's energy density. However, this cell design also has a lot of technical challenges to be solved. Among the challenges, lithium anode's problem related to lithium dendrite growth causing internal short and low cycling efficiency is very serious. Thus, extensive research on lithium metal anode has been performed to solve the lithium dendrite problem and a major part of the research has been focused on the control of the interface between lithium and electrolyte. However, research on lithium anode design itself has not been much conducted. In this research, innovative lithium anode design for less dendrite growth and higher cycling efficiency was suggested. Literature review for the lithium dendrite growth mechanism was conducted in Chapter 2 to develop electrode design concept and the importance of the current density on lithium dendrite growth was also found in the literatures. The preliminary test was conducted to verify the developed electrode concept by using lithium powder based anode (LIP) with conductive carbon materials and the results showed that lithium dendrite growth could be suppressed in this electrode design due to its increased electrochemical surface area and lithium deposition sites during lithium deposition. The electrode design suggested in Chapter 2 was extensively studied in Chapter 3 in terms of lithium dendrite growth morphology, lithium cycling efficiency and full cell cycling performance. This electrode concept was further developed to maximize the electrode's performance and safety in Chapter 4. In this new

Silicate Inclusions in the Kodaikanal IIE Iron Meteorite

NASA Technical Reports Server (NTRS)

Kurat, G.; Varela, M. E.; Zinner, E.

2005-01-01

Silicate inclusions in iron meteorites display an astonishing chemical and mineralogical variety, ranging from chondritic to highly fractionated, silica- and alkali-rich assemblages. In spite of this, their origin is commonly considered to be a simple one: mixing of silicates, fractionated or unfractionated, with metal. The latter had to be liquid in order to accommodate the former in a pore-free way which all models accomplish by assuming shock melting. II-E iron meteorites are particularly interesting because they contain an exotic zoo of silicate inclusions, including some chemically strongly fractionated ones. They also pose a formidable conundrum: young silicates are enclosed by very old metal. This and many other incompatibilities between models and reality forced the formulation of an alternative genetic model for irons. Here we present preliminary findings in our study of Kodaikanal silicate inclusions.

Reagentless and calibrationless silicate measurement in oceanic waters.

PubMed

Giraud, William; Lesven, Ludovic; Jońca, Justyna; Barus, Carole; Gourdal, Margaux; Thouron, Danièle; Garçon, Véronique; Comtat, Maurice

2012-08-15

Determination of silicate concentration in seawater without addition of liquid reagents was the key prerequisite for developing an autonomous in situ electrochemical silicate sensor (Lacombe et al., 2007) [11]. The present challenge is to address the issue of calibrationless determination. To achieve such an objective, we chose chronoamperometry performed successively on planar microelectrode (ME) and ultramicroelectrode (UME) among the various possibilities. This analytical method allows estimating simultaneously the diffusion coefficient and the concentration of the studied species. Results obtained with ferrocyanide are in excellent agreement with values of the imposed concentration and diffusion coefficient found in the literature. For the silicate reagentless method, successive chronoamperometric measurements have been performed using a pair of gold disk electrodes for both UME and ME. Our calibrationless method was tested with different concentrations of silicate in artificial seawater from 55 to 140×10(-6) mol L(-1). The average value obtained for the diffusion coefficient of the silicomolybdic complex is 2.2±0.4×10(-6) cm(2) s(-1), consistent with diffusion coefficient values of molecules in liquid media. Good results were observed when comparing known concentration of silicate with experimentally derived ones. Further work is underway to explore silicate determination within the lower range of oceanic silicate concentration, down to 0.1×10(-6) mol L(-1). Copyright © 2012 Elsevier B.V. All rights reserved.

Tracing metal-silicate segregation and late veneer in the Earth and the ureilite parent body with palladium stable isotopes

NASA Astrophysics Data System (ADS)

Creech, J. B.; Moynier, F.; Bizzarro, M.

2017-11-01

Stable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal-silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd-110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = -0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal-silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = -0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation.

Stabilized Lithium-Metal Surface in a Polysulfide-Rich Environment of Lithium-Sulfur Batteries.

PubMed

Zu, Chenxi; Manthiram, Arumugam

2014-08-07

Lithium-metal anode degradation is one of the major challenges of lithium-sulfur (Li-S) batteries, hindering their practical utility as next-generation rechargeable battery chemistry. The polysulfide migration and shuttling associated with Li-S batteries can induce heterogeneities of the lithium-metal surface because it causes passivation by bulk insulating Li2S particles/electrolyte decomposition products on a lithium-metal surface. This promotes lithium dendrite formation and leads to poor lithium cycling efficiency with complicated lithium surface chemistry. Here, we show copper acetate as a surface stabilizer for lithium metal in a polysulfide-rich environment of Li-S batteries. The lithium surface is protected from parasitic reactions with the organic electrolyte and the migrating polysulfides by an in situ chemical formation of a passivation film consisting of mainly Li2S/Li2S2/CuS/Cu2S and electrolyte decomposition products. This passivation film also suppresses lithium dendrite formation by controlling the lithium deposition sites, leading to a stabilized lithium surface characterized by a dendrite-free morphology and improved surface chemistry.

The Earth's core formation: Constraints imposed by partitioning behaviour of Germanium and Copper.

NASA Astrophysics Data System (ADS)

Kegler, P.; Holzheid, A.; Palme, H.

2006-12-01

The abundances of the siderophile (metal-seeking) elements in the present Earth mantle are the result of the core formation in the early Earth. It is commonly assumed that the concentrations of the siderophile elements in the Earth mantle, especially of Ni and Co, can be explained by metal-silicate equilibrium at the base of a deep magma ocean during the core forming event [1,2], assuming values of Ni and Co metal-silicate partition coefficients at the bottom of a magma ocean that are identical to the Ni and Co core-mantle ratios (Ni:~39; pressure, where both partition coefficients have the same value, does exist within the Earth upper mantle [3,4]. In order to better constrain the origin of the siderophile elements in the upper mantle of the Earth we expanded our study and determined high pressure and high temperature metal/silicate partition coefficients of Ge and Cu (Dmet/sil = concentration of, e.g., Ge in metal / concentration of, e.g., Ge in silicate). The experiments were performed with Fe97Ge3 and Fe97Cu3 alloys. The metals were equilibrated with a synthetic basaltic melt (same composition as in [3,4]) within a pressure range from 0.5 to 2.5 GPa and at a temperature of 1450°C. The partition coefficients of both elements decrease within the investigated pressure range and at an oxygen fugacity of 1.4 log units more reduced than the Fe-FeO buffer (Dmet/sil at 0.5 GPa: Ge 5475, Cu 49; Dmet/sil at 2.5 GPa: Ge 4057, Cu 42). Although the pressure range covered by our experiments is narrow and extrapolations to pressures relevant to upper mantle conditions are therefore not very robust, it is still obvious that Dmet/sil of Ge and Cu at conditions at the bottom of a magma ocean would not be equal to their core/mantle ratios (Ge: 26; Cu: 6). These findings, in addition to the earlier results of Ni and Co, question the hypothesis of a simple single stage magma ocean. However, other models like inefficient core formation [5], heterogeneous accretion [6-7], or self

High Pressure Response of Siliceous Materials

DTIC Science & Technology

2013-02-01

iron-containing soda lime silicate glass, opal (a hydrated silicate glass), ROBAX glass ceramic, and others were single crystal (α-quartz) and...10 2.6. Opal (hydrated amorphous silica...Raman spectrum as a function of stress for opal (hydrated silica) glass. ................... 29 4.9. Raman spectrum as a function of stress for

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.

Lithium

MedlinePlus

Lithium is used to treat and prevent episodes of mania (frenzied, abnormally excited mood) in people with ... depression, episodes of mania, and other abnormal moods). Lithium is in a class of medications called antimanic ...

Biologically enhanced cathode design for improved capacity and cycle life for lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Oh, Dahyun; Qi, Jifa; Lu, Yi-Chun; Zhang, Yong; Shao-Horn, Yang; Belcher, Angela M.

2013-11-01

Lithium-oxygen batteries have a great potential to enhance the gravimetric energy density of fully packaged batteries by two to three times that of lithium ion cells. Recent studies have focused on finding stable electrolytes to address poor cycling capability and improve practical limitations of current lithium-oxygen batteries. In this study, the catalyst electrode, where discharge products are deposited and decomposed, was investigated as it has a critical role in the operation of rechargeable lithium-oxygen batteries. Here we report the electrode design principle to improve specific capacity and cycling performance of lithium-oxygen batteries by utilizing high-efficiency nanocatalysts assembled by M13 virus with earth-abundant elements such as manganese oxides. By incorporating only 3-5 wt% of palladium nanoparticles in the electrode, this hybrid nanocatalyst achieves 13,350 mAh g-1c (7,340 mAh g-1c+catalyst) of specific capacity at 0.4 A g-1c and a stable cycle life up to 50 cycles (4,000 mAh g-1c, 400 mAh g-1c+catalyst) at 1 A g-1c.

Incorporation of bitumen and calcium silicate in cement and lime stabilized soil blocks

NASA Astrophysics Data System (ADS)

Kwan, W. H.; Cheah, C. B.; Ramli, M.; Al-Sakkaf, Y. K.

2017-04-01

Providing affordable housing is the most critical problem in many of the developing countries. Using earth materials in building construction is one of the feasible methods to address this issue and it can be a way towards sustainable construction as well. However, the published information on the stabilized soil blocks is limited. Therefore, the present study is conducted to examine the characterization of the soils and engineering properties of the stabilized soil blocks. Four types of stabilizer were used in the study, namely; cement, slaked lime, bitumen emulsion and calcium silicate. Cement and slaked lime were added at different percentages in the range of 5% to 15%, with interval of 2.5%. The percentage was determined based on weight of soil. Meanwhile, bitumen emulsion and calcium silicate were incorporated at various percentages together with 10% of cement. Dosage of bitumen emulsion is in the range of 2% to 10% at interval of 2% while calcium silicate was incorporated at 0.50%, 0.75%, 1.00%, 1.25%, 1.50% and 2.00%. Results show that cement is the most viable stabilizer for the soil block among all stabilizers in this study. The bulk density, optimum moisture content and compressive strengths were increased with the increasing cement content. The most suitable cement content was 10% added at moisture content of 12%. Lime, bitumen and calcium contents were recommended at 5.0%, 6.0% and 1.25%, respectively.

Evidence of denser MgSiO3 glass above 133 gigapascal (GPa) and implications for remnants of ultradense silicate melt from a deep magma ocean.

PubMed

Murakami, Motohiko; Bass, Jay D

2011-10-18

Ultralow velocity zones are the largest seismic anomalies in the mantle, with 10-30% seismic velocity reduction observed in thin layers less than 20-40 km thick, just above the Earth's core-mantle boundary (CMB). The presence of silicate melts, possibly a remnant of a deep magma ocean in the early Earth, have been proposed to explain ultralow velocity zones. It is, however, still an open question as to whether such silicate melts are gravitationally stable at the pressure conditions above the CMB. Fe enrichment is usually invoked to explain why melts would remain at the CMB, but this has not been substantiated experimentally. Here we report in situ high-pressure acoustic velocity measurements that suggest a new transformation to a denser structure of MgSiO(3) glass at pressures close to those of the CMB. The result suggests that MgSiO(3) melt is likely to become denser than crystalline MgSiO(3) above the CMB. The presence of negatively buoyant and gravitationally stable silicate melts at the bottom of the mantle, would provide a mechanism for observed ultralow seismic velocities above the CMB without enrichment of Fe in the melt. An ultradense melt phase and its geochemical inventory would be isolated from overlying convective flow over geologic time.

Mechanical properties of silicate glasses exposed to a low-Earth orbit

NASA Technical Reports Server (NTRS)

Wiedlocher, David E.; Tucker, Dennis S.; Nichols, Ron; Kinser, Donald L.

1992-01-01

The effects of a 5.8 year exposure to low earth orbit environment upon the mechanical properties of commercial optical fused silica, low iron soda-lime-silica, Pyrex 7740, Vycor 7913, BK-7, and the glass ceramic Zerodur were examined. Mechanical testing employed the ASTM-F-394 piston on 3-ball method in a liquid nitrogen environment. Samples were exposed on the Long Duration Exposure Facility (LDEF) in two locations. Impacts were observed on all specimens except Vycor. Weibull analysis as well as a standard statistical evaluation were conducted. The Weibull analysis revealed no differences between control samples and the two exposed samples. We thus concluded that radiation components of the Earth orbital environment did not degrade the mechanical strength of the samples examined within the limits of experimental error. The upper bound of strength degradation for meteorite impacted samples based upon statistical analysis and observation was 50 percent.

Lithium

USGS Publications Warehouse

Ober, J.

1998-01-01

The lithium industry can be divided into two sectors: ore concentrate producers and chemical producers. Ore concentrate producers mine lithium minerals. They beneficiate the ores to produce material for use in ceramics and glass manufacturing.

Lithium use in batteries

USGS Publications Warehouse

Goonan, Thomas G.

2012-01-01

Lithium has a number of uses but one of the most valuable is as a component of high energy-density rechargeable lithium-ion batteries. Because of concerns over carbon dioxide footprint and increasing hydrocarbon fuel cost (reduced supply), lithium may become even more important in large batteries for powering all-electric and hybrid vehicles. It would take 1.4 to 3.0 kilograms of lithium equivalent (7.5 to 16.0 kilograms of lithium carbonate) to support a 40-mile trip in an electric vehicle before requiring recharge. This could create a large demand for lithium. Estimates of future lithium demand vary, based on numerous variables. Some of those variables include the potential for recycling, widespread public acceptance of electric vehicles, or the possibility of incentives for converting to lithium-ion-powered engines. Increased electric usage could cause electricity prices to increase. Because of reduced demand, hydrocarbon fuel prices would likely decrease, making hydrocarbon fuel more desirable. In 2009, 13 percent of worldwide lithium reserves, expressed in terms of contained lithium, were reported to be within hard rock mineral deposits, and 87 percent, within brine deposits. Most of the lithium recovered from brine came from Chile, with smaller amounts from China, Argentina, and the United States. Chile also has lithium mineral reserves, as does Australia. Another source of lithium is from recycled batteries. When lithium-ion batteries begin to power vehicles, it is expected that battery recycling rates will increase because vehicle battery recycling systems can be used to produce new lithium-ion batteries.

High Pressure Response of Siliceous Materials

DTIC Science & Technology

2013-02-01

quartz, Starphire soda lime silicate glass, hydrated Starphire, BOROFLOAT borosilicate glass, an iron-containing soda lime silicate glass, opal (a hydrated... Opal (hydrated amorphous silica). .............................................................................. 10 2.7. ROBAX glass ceramic...spectrum as a function of stress for BOROFLOAT borosilicate glass. .......... 29 4.8. Raman spectrum as a function of stress for opal (hydrated

Mantle Mineral/Silicate Melt Partitioning

NASA Astrophysics Data System (ADS)

McFarlane, E. A.; Drake, M. J.

1992-07-01

Introduction: The partitioning of elements among mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. It has been proposed that the elevated Mg/Si ratio of the upper mantle of the Earth is a consequence of the flotation of olivine into the upper mantle (Agee and Walker, 1988). Agee and Walker (1988) have generated a model via mass balance by assuming average mineral compositions to generate upper mantle peridotite. This model determines that upper mantle peridotite could result from the addition of 32.7% olivine and 0.9% majorite garnet into the upper mantle, and subtraction of 27.6% perovskite from the upper mantle (Agee and Walker, 1988). The present contribution uses experimental data to examine the consequences of such multiple phase fractionations enabling an independent evaluation of the above mentioned model. Here we use Mg-perovskite/melt partition coefficients from both a synthetic and a natural system (KLB-1) obtained from this laboratory. Also used are partition coefficient values for majorite garnet/melt, beta spinel/melt and olivine/melt partitioning (McFarlane et al., 1991b; McFarlane et al., 1992). Multiple phase fractionations are examined using the equilibrium crystallization equation and partition coefficient values. The mineral proportions determined by Agee and Walker (1988) are converted into weight fractions and used to compute a bulk partition coefficient value. Discussion: There has been a significant debate concerning whether measured values of trace element partition coefficients permit large-scale fractionation of liquidus phases from an early terrestrial magma ocean (Kato et al., 1988a,b; Walker and Agee, 1989; Drake, 1989; Drake et al., 1991; McFarlane et al., 1990, 1991). It should be noted that it is unclear which, if any, numerical values of partition coefficients are appropriate for examining this question, and certainly the assumptions for the current model must be more fully

Electrolytic method for the production of lithium using a lithium-amalgam electrode

DOEpatents

Cooper, John F.; Krikorian, Oscar H.; Homsy, Robert V.

1979-01-01

A method for recovering lithium from its molten amalgam by electrolysis of the amalgam in an electrolytic cell containing as a molten electrolyte a fused-salt consisting essentially of a mixture of two or more alkali metal halides, preferably alkali metal halides selected from lithium iodide, lithium chloride, potassium iodide and potassium chloride. A particularly suitable molten electrolyte is a fused-salt consisting essentially of a mixture of at least three components obtained by modifying an eutectic mixture of LiI-KI by the addition of a minor amount of one or more alkali metal halides. The lithium-amalgam fused-salt cell may be used in an electrolytic system for recovering lithium from an aqueous solution of a lithium compound, wherein electrolysis of the aqueous solution in an aqueous cell in the presence of a mercury cathode produces a lithium amalgam. The present method is particularly useful for the regeneration of lithium from the aqueous reaction products of a lithium-water-air battery.

Silicate Emission in the TW Hydrae Association

NASA Astrophysics Data System (ADS)

Sitko, Michael L.; Lynch, David K.; Russell, Ray W.

2000-11-01

The TW Hydrae association is the nearest young stellar association. Among its members are HD 98800, HR 4796A, and TW Hydrae itself, the nearest known classical T Tauri star. We have observed these three stars spectroscopically between 3 and 13 μm. In TW Hya, the spectrum shows a silicate emission feature that is similar to many other young stars' with protostellar disks. The 11.2 μm feature indicative of significant amounts of crystalline olivine is not as strong as in some young stars and solar system comets. In HR 4796A, the thermal emission in the silicate feature is very weak, suggesting little in the way of (small silicate) grains near the star. The silicate band of HD 98800 (observed by us, but also reported by Sylvester & Skinner) is intermediate in strength between TW Hya and HR 4796A.

[Influence of cations on the laser Raman spectra of silicate glasses].

PubMed

Xiong, Yi; Zhao, Hong-xia; Gan, Fu-xi

2012-04-01

Na2O(K2O)-CaO(MgO)-SiO2, Na2O(K2O)-Al2O3-SiO2, Na2O(K2O)-B2O3-SiO2, Na2O(K2O)-PbO-SiO2 and PbO-BaO-SiO2 glass systems were investigated using laser Raman spectroscopic technique. The modification of short-range structure of glass caused by network modifier cations will influence Raman signature. Alkali and alkali-earth ions can weaken the bridging oxygen bond, thus lower the frequency of Si-O(b)-Si anti-symmetric stretching vibration. When coordina ted by oxygen ions, B3+ can form [BO4] tetrahedron and enter the silicon-oxygen network, but this effect had little impact on the frequency of Raman peaks located in the high-frequency region. Al3+ can also be coordinated by oxygen ions to form [AlO4] tetrahedron. [AlO4] will increase the disorder degree of network while entering network. Ba2+ can increase the density of electron cloud along the Si-O(nb) bond when it bonds with non-bridging oxygen, which will lead to a higher peak intensity of O-Si-O stretching vibration. The Raman peaks of alkli- and alkali-earth silicate glasses are mainly distributed in the region of 400 - 1 200 cm(-1), while in the spectrum of Na2O(K2O)-PbO-SiO2 glass system a 131 cm(-1) peak existed. The authors assigned it to the Pb-O symmetric stretching vibration. Some of the samples were produced in the laboratory according to the average compositions of ancient glasses, so this research is very significant to discriminating ancient silicate glasses of different systems by Laser Raman spectroscopic technique.

Thermal, dynamic and compositional aspects of the core-forming Earth

NASA Technical Reports Server (NTRS)

Stevenson, D. J.

1985-01-01

Core formation is the most important and singular differentiation event in the history of a terrestrial planet. It almost certainly involved the downward migration of a partially or wholly molten iron alloy through a silicate and oxide mantle, and was contemporaneous with accretion. Several important, unresolved issues which have implications for mantle and core geochemistry, the thermal history of the Earth, and the origin of geomagnetism are addressed: whether the early Earth was molten; whether core formation involved low or high pressure geochemistry, or both; early Earth mantle homogenization; whether equilibration established between core forming material and the mantle through which it migrated; and how much iron is stranded and unable to reach the core.

Effect of silicate module of water glass on rheological parameters of poly(sodium acrylate)/sodium silicate hydrogels

NASA Astrophysics Data System (ADS)

Mastalska-Popiawska, J.; Izak, P.

2017-01-01

The poly(sodium acrylate)/sodium silicate hydrogels were synthesized in the presence of sodium thiosulphate and potassium persulphate as the redox initiators and N,N’-methylene-bisacrylamide as the cross-linking monomer. 20 wt% aqueous solution of sodium acrylate was polymerized together with water glass with different silicate modules (M) from 1.74 to 2.29, in three mass ratio of the monomer solution to the water glass 2:1, 1:1 and 1:2. Such obtained hybrid composites were rheologically tested using the oscillation method. It allowed to designate the crossover point during polymerization, as well as to define the viscoelastic properties of the casted hydrogel samples one week after the reaction. The obtained results of the oscillation measurements showed that cross-linking reaction proceeds very quickly and the lower the silicate module is, the process starts faster. After the completion of the reaction the silicate-polymer hydrogels are strongly elastic materials and the highest elasticity characterizes systems with the mass ratio 1:2, i.e. with the highest water glass content.

40 CFR 721.9513 - Modified magnesium silicate polymer (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified magnesium silicate polymer... Specific Chemical Substances § 721.9513 Modified magnesium silicate polymer (generic). (a) Chemical... as modified magnesium silicate polymer (PMN P-98-604) is subject to reporting under this section for...

40 CFR 721.9513 - Modified magnesium silicate polymer (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Modified magnesium silicate polymer... Specific Chemical Substances § 721.9513 Modified magnesium silicate polymer (generic). (a) Chemical... as modified magnesium silicate polymer (PMN P-98-604) is subject to reporting under this section for...

40 CFR 721.9513 - Modified magnesium silicate polymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Modified magnesium silicate polymer... Specific Chemical Substances § 721.9513 Modified magnesium silicate polymer (generic). (a) Chemical... as modified magnesium silicate polymer (PMN P-98-604) is subject to reporting under this section for...

40 CFR 721.9513 - Modified magnesium silicate polymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Modified magnesium silicate polymer... Specific Chemical Substances § 721.9513 Modified magnesium silicate polymer (generic). (a) Chemical... as modified magnesium silicate polymer (PMN P-98-604) is subject to reporting under this section for...

40 CFR 721.9513 - Modified magnesium silicate polymer (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Modified magnesium silicate polymer... Specific Chemical Substances § 721.9513 Modified magnesium silicate polymer (generic). (a) Chemical... as modified magnesium silicate polymer (PMN P-98-604) is subject to reporting under this section for...

Lithium-ion conducting electrolyte salts for lithium batteries.

PubMed

Aravindan, Vanchiappan; Gnanaraj, Joe; Madhavi, Srinivasan; Liu, Hua-Kun

2011-12-16

This paper presents an overview of the various types of lithium salts used to conduct Li(+) ions in electrolyte solutions for lithium rechargeable batteries. More emphasis is paid towards lithium salts and their ionic conductivity in conventional solutions, solid-electrolyte interface (SEI) formation towards carbonaceous anodes and the effect of anions on the aluminium current collector. The physicochemical and functional parameters relevant to electrochemical properties, that is, electrochemical stabilities, are also presented. The new types of lithium salts, such as the bis(oxalato)borate (LiBOB), oxalyldifluoroborate (LiODFB) and fluoroalkylphosphate (LiFAP), are described in detail with their appropriate synthesis procedures, possible decomposition mechanism for SEI formation and prospect of using them in future generation lithium-ion batteries. Finally, the state-of-the-art of the system is given and some interesting strategies for the future developments are illustrated. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High performance discharges in the Lithium Tokamak eXperiment with liquid lithium walls

DOE PAGES

Schmitt, J. C.; Bell, R. E.; Boyle, D. P.; ...

2015-05-15

The first-ever successful operation of a tokamak with a large area (40% of the total plasma surface area) liquid lithium wall has been achieved in the Lithium Tokamak eXperiment (LTX). These results were obtained with a new, electron beam-based lithium evaporation system, which can deposit a lithium coating on the limiting wall of LTX in a five-minute period. Preliminary analyses of diamagnetic and other data for discharges operated with a liquid lithium wall indicate that confinement times increased by 10 x compared to discharges with helium-dispersed solid lithium coatings. Ohmic energy confinement times with fresh lithium walls, solid and liquid,more » exceed several relevant empirical scaling expressions. Spectroscopic analysis of the discharges indicates that oxygen levels in the discharges limited on liquid lithium walls were significantly reduced compared to discharges limited on solid lithium walls. Finally, Tokamak operations with a full liquid lithium wall (85% of the total plasma surface area) have recently started.« less

Modeling Lithium Movement over Multiple Cycles in a Lithium-Metal Battery

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

Ferrese, A; Newman, J

This paper builds on the work by Ferrese et al. [J. Electrochem., 159, A1615 (2012)], where a model of a lithium-metal battery with a LiyCoO2 positive electrode was created in order to predict the movement of lithium in the negative electrode along the negative electrode/separator interface during cell cycling. In this paper, the model is expanded to study the movement of lithium along the lithium-metal anode over multiple cycles. From this model, it is found that when a low percentage of lithium at the negative electrode is utilized, the movement of lithium along the negative electrode/separator interface reaches a quasimore » steady state after multiple cycles. This steady state is affected by the slope of the open-circuit-potential function in the positive electrode, the rate of charge and discharge, the depth of discharge, and the length of the rest periods. However, when a high percent of the lithium at the negative electrode is utilized during cycling, the movement does not reach a steady state and pinching can occur, where the lithium nearest the negative tab becomes progressively thinner after cycling. This is another nonlinearity that leads to a progression of the movement of lithium over multiple cycles. (C) 2014 The Electrochemical Society.« less

The Stability of Hydrous Silicates in Earth's Lower Mantle: Experimental constraints from the System MgO-Al2O3-SiO2-H2O

NASA Astrophysics Data System (ADS)

Walter, M. J.; Thomson, A. R.; Wang, W.; Lord, O. T.; Kleppe, A. K.; Ross, J.; Kohn, S. C.

2014-12-01

Laser-heated diamond anvil cell experiments were performed at pressures from ~ 30 to 125 GPa on bulk compositions in the system MgO-Al2O3-SiO2-H2O (MASH) to constrain the stability of hydrous phases in Earth's lower mantle. Phase identification in run products by synchrotron powder diffraction reveals a consistent set of stability relations for the high-pressure, dense hydrous silicate phases D and H. Experiments show that aluminous phase D is stable to ~ 55 GPa. Aluminous phase H becomes stable at ~ 40 GPa and remains stable to higher pressures throughout the lower mantle depth range in both model peridotitic and basaltic lithologies. Preliminary FEG-probe analyses indicate that Phase H is alumina-rich at ~ 50 GPa, with only 5 to 10 wt% each of MgO and SiO2. Variations in ambient unit cell volumes show that Mg-perovskite becomes more aluminous with pressure throughout the pressure range studied, and that Phase H may become more Mg- and Si-rich with pressure. We also find that at pressures above ~ 90 GPa stishovite is replaced in Si-rich compositions by seifertite, at which point there is a corresponding increase in the Al-content of phase H. The melting curves of MASH compositions have been determined using thermal perturbations in power versus temperature curves, and are observed to be shallow with dT/dP slopes of ~ 4K/GPa. Our results show that hydrated peridotitic or basaltic compositions in the lower mantle should be partially molten at all depths along an adiabatic mantle geotherm. Aluminous Phase H will be stable in colder, hydrated subducting slabs, potentially to the core-mantle boundary. Thus, aluminous phase H is the primary vessel for transport of hydrogen to the deepest mantle, but hydrous silicate melt will be the host of hydrogen at ambient mantle temperatures.

Carbon Dioxide Cycling And The Climate of Ancient Earth

NASA Technical Reports Server (NTRS)

Zahnle, Kevin; Sleep, Norman H.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

The continental cycle of silicate weathering and metamorphism dynamically buffers atmospheric CO2 and climate. Feedback is provided by the strong temperature dependence of silicate weathering. Here we argue that hydrothermal alteration of oceanic basalts also dynamically buffers CO2. The oceanic cycle links with the mantle via subduction and the midocean ridges. Feedback is provided by the dependence of carbonatization on dissolved carbonates in seawater. Unlike the continental cycle, the oceanic cycle has no thermostat. Currently the continental cycle is more important, but earlier in Earth's history, especially if heat flow were higher than it is now, more vigorous plate tectonics would have made the oceanic cycle dominant. We find that CO2 greenhouses thick enough to defeat the faint early sun are implausible and that, if no other greenhouse gases are invoked, very cold climates are expected for much of the Proterozoic and the Archean. We echo current fashion and favor biogenic methane as the chief supplement to CO2. Fast weathering and probable subduction of abundant impact ejecta would have reduced CO2 levels still further in the Hadean. Despite its name, the Hadean would have been the coldest era in the history of the Earth.

Carbon Dioxide Cycling and the Climate of Ancient Earth

NASA Technical Reports Server (NTRS)

Zahnle, Kevin; Sleep, Norman H.

2001-01-01

The continental cycle of silicate weathering and metamorphism dynamically buffers atmospheric CO2 and climate. Feedback is provided by the strong temperature dependence of silicate weathering. Here we argue that hydrothermal alteration of oceanic basalts also dynamically buffers CO2. The oceanic cycle links with the mantle via subduction and the midocean ridges. Feedback is provided by the dependence of carbonatization on dissolved carbonates in seawater. Unlike the continental cycle, the oceanic cycle has no thermostat. Currently the continental cycle is more important, but earlier in Earth's history, especially if heat flow were higher than it is now, more vigorous plate tectonics would have made the oceanic cycle dominant. We find that CO2 greenhouses thick enough to defeat the faint early Sun are implausible and that, if no other greenhouse gases are invoked, very cold climates are expected for much of the Proterozoic and the Archean. We echo current fashion and favor biogenic methane as the chief supplement to CO2. Fast weathering and probable subduction of abundant impact ejecta would have reduced CO2 levels still further in the Hadean. Despite its name, the Hadean would have been the coldest era in the history of the Earth.

The Mineralogy of Circumstellar Silicates Preserved in Cometary Dust

NASA Technical Reports Server (NTRS)

Keller, L. P.; Messenger, S.

2010-01-01

Interplanetary dust particles (IDPs) contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula. Cometary IDPs have remained relatively unaltered since their accretion because of the lack of parent body thermal and aqueous alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these particles because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars. Five circumstellar grains have been identified including three amorphous silicate grains and two polycrystalline aggregates. All of these grains are between 0.2 and 0.5 micrometers in size. The isotopic compositions of all five presolar silicate grains fall within the range of presolar oxides and silicates, having large (17)O-enrichments and normal (18)O/(16)O ratios (Group 1 grains from AGB and RG stars). The amorphous silicates are chemically heterogeneous and contain nanophase FeNi metal and FeS grains in a Mg-silicate matrix. Two of the amorphous silicate grains are aggregates with subgrains showing variable Mg/Si ratios in chemical maps. The polycrystalline grains show annealed textures (equilibrium grains boundaries, uniform Mg/Fe ratios), and consist of 50-100 nm enstatite and pyrrhotite grains with lesser forsterite. One of the polycrystalline aggregates contains a subgrain of diopside. The polycrystalline aggregates form by subsolidus annealing of amorphous precursors. The bulk compositions of the five grains span a wide range in Mg/Si ratios from 0.4 to 1.2 (avg. 0.86). The average Fe/Si (0.40) and S/Si (0.21) ratios show a much narrower range of values and are approximately 50% of their solar

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.

Solid-state lithium battery

DOEpatents

Ihlefeld, Jon; Clem, Paul G; Edney, Cynthia; Ingersoll, David; Nagasubramanian, Ganesan; Fenton, Kyle Ross

2014-11-04

The present invention is directed to a higher power, thin film lithium-ion electrolyte on a metallic substrate, enabling mass-produced solid-state lithium batteries. High-temperature thermodynamic equilibrium processing enables co-firing of oxides and base metals, providing a means to integrate the crystalline, lithium-stable, fast lithium-ion conductor lanthanum lithium tantalate (La.sub.1/3-xLi.sub.3xTaO.sub.3) directly with a thin metal foil current collector appropriate for a lithium-free solid-state battery.

Tin isotope fractionation during magmatic processes and the isotope composition of the bulk silicate Earth

NASA Astrophysics Data System (ADS)

Wang, Xueying; Amet, Quentin; Fitoussi, Caroline; Bourdon, Bernard

2018-05-01

Tin is a moderately volatile element whose isotope composition can be used to investigate Earth and planet differentiation and the early history of the Solar System. Although the Sn stable isotope composition of several geological and archaeological samples has been reported, there is currently scarce information about the effect of igneous processes on Sn isotopes. In this study, high-precision Sn isotope measurements of peridotites and basalts were obtained by MC-ICP-MS with a double-spike technique. The basalt samples display small variations in δ124/116Sn ranging from -0.01 ± 0.11 to 0.27 ± 0.11‰ (2 s.d.) relative to NIST SRM 3161a standard solution, while peridotites have more dispersed and more negative δ124Sn values ranging from -1.04 ± 0.11 to -0.07 ± 0.11‰ (2 s.d.). Overall, basalts are enriched in heavy Sn isotopes relative to peridotites. In addition, δ124Sn in peridotites become more negative with increasing degrees of melt depletion. These results can be explained by different partitioning behavior of Sn4+ and Sn2+ during partial melting. Sn4+ is overall more incompatible than Sn2+ during partial melting, resulting in Sn4+-rich silicate melt and Sn2+-rich residue. As Sn4+ has been shown experimentally to be enriched in heavy isotopes relative to Sn2+, the effect of melting is to enrich residual peridotites in relatively more compatible Sn2+, which results in isotopically lighter peridotites and isotopically heavier mantle-derived melts. This picture can be disturbed partly by the effect of refertilization. Similarly, the presence of enriched components such as recycled oceanic crust or sediments could explain part of the variations in Sn isotopes in oceanic basalts. The most primitive peridotite analyzed in this study was used for estimating the Sn isotope composition of the BSE, with δ124Sn = -0.08 ± 0.11‰ (2 s.d.) relative to the Sn NIST SRM 3161a standard solution. Altogether, this suggests that Sn isotopes may be a powerful probe of

Effect of water on the fluorine and chlorine partitioning behavior between olivine and silicate melt.

PubMed

Joachim, Bastian; Stechern, André; Ludwig, Thomas; Konzett, Jürgen; Pawley, Alison; Ruzié-Hamilton, Lorraine; Clay, Patricia L; Burgess, Ray; Ballentine, Christopher J

2017-01-01

Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth's mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280 °C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F-Cl-Br-I-H 2 O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H 2 O (D Cl ol/melt = 1.6 ± 0.9 × 10 -4 ) to 0.33 (6) wt% H 2 O (D Cl ol/melt = 2.2 ± 1.1 × 10 -4 ). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65-78, 2015), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F-Cl-Br-I-H 2 O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280 °C and 0.3 GPa with ( R 2  = 0.99): [Formula: see text]. The observed fluorine partitioning behavior supports the theory suggested by Crépisson et al. (Earth Planet Sci Lett 390:287-295, 2014) that fluorine and water are incorporated as clumped OH/F defects in the olivine structure. Results of this study further suggest that fluorine concentration estimates in OIB source regions are at least 10% lower than previously expected (Joachim et al. Chem Geol 416:65-78, 2015), implying that consideration of the effect of water on the fluorine partitioning behavior between Earth's mantle minerals and

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

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.

Synthesis of non-siliceous mesoporous oxides.

PubMed

Gu, Dong; Schüth, Ferdi

2014-01-07

Mesoporous non-siliceous oxides have attracted great interest due to their unique properties and potential applications. Since the discovery of mesoporous silicates in 1990s, organic-inorganic assembly processes by using surfactants or block copolymers as soft templates have been considered as a feasible path for creating mesopores in metal oxides. However, the harsh sol-gel conditions and low thermal stabilities have limited the expansion of this method to various metal oxide species. Nanocasting, using ordered mesoporous silica or carbon as a hard template, has provided possibilities for preparing novel mesoporous materials with new structures, compositions and high thermal stabilities. This review concerns the synthesis, composition, and parameter control of mesoporous non-siliceous oxides. Four synthesis routes, i.e. soft-templating (surfactants or block copolymers as templates), hard-templating (mesoporous silicas or carbons as sacrificial templates), colloidal crystal templating (3-D ordered colloidal particles as a template), and super lattice routes, are summarized in this review. Mesoporous metal oxides with different compositions have different properties. Non-siliceous mesoporous oxides are comprehensively described, including a discussion of constituting elements, synthesis, and structures. General aspects concerning pore size control, atomic scale crystallinity, and phase control are also reviewed.

Fast accretion of the earth with a late moon-forming giant impact.

PubMed

Yu, Gang; Jacobsen, Stein B

2011-10-25

Constraints on the formation history of the Earth are critical for understanding of planet formation processes. (182)Hf-(182)W chronometry of terrestrial rocks points to accretion of Earth in approximately 30 Myr after the formation of the solar system, immediately followed by the Moon-forming giant impact (MGI). Nevertheless, some N-body simulations and (182)Hf-(182)W and (87)Rb-(87)Sr chronology of some lunar rocks have been used to argue for a later formation of the Moon at 52 to > 100 Myr. This discrepancy is often explained by metal-silicate disequilibrium during giant impacts. Here we describe a model of the (182)W isotopic evolution of the accreting Earth, including constraints from partitioning of refractory siderophile elements (Ni, Co, W, V, and Nb) during core formation, which can explain the discrepancy. Our modeling shows that the concentrations of the siderophile elements of the mantle are consistent with high-pressure metal-silicate equilibration in a terrestrial magma ocean. Our analysis shows that the timing of the MGI is inversely correlated with the time scale of the main accretion stage of the Earth. Specifically, the earliest time the MGI could have taken place right at approximately 30 Myr, corresponds to the end of main-stage accretion at approximately 30 Myr. A late MGI (> 52 Myr) requires the main stage of the Earth's accretion to be completed rapidly in < 10.7 ± 2.5 Myr. These are the two end member solutions and a continuum of solutions exists in between these extremes.

A Cesium Rare-Earth Silicate Cs3 RESi6 O15 (RE=Dy-Lu, Y, In): The Parent of an Unusual Structural Class Featuring a Remarkable 57 Å Unit Cell Axis.

PubMed

Terry, Rylan; Vinton, Daniel; McMillen, Colin D; Kolis, Joseph W

2018-02-19

The structure of Cs 3 RESi 6 O 15 , where RE=Dy-Lu, Y, In, is unusual in that it contains octahedrally coordinated rare-earth ions; their relative orientation dictates the structure, as they rotate about the c-axis supported by the cyclic Si 6 O 15 framework. The repeat unit of the rotation is eight units generating a very long (ca. 57 Å) unit cell axis. This unusual repeat unit is created by the structural flexibility of the hexasilicate ring, which is in turn affected by the size of the rare earth ion as well as the size of alkali ion residing within the silicate layers. Previous work showed for the smaller Sc 3+ ion, the rotation of the octahedra is not sufficient to achieve closure at an integral repeat unit and an incommensurate structure results. The products are prepared as large, high quality single crystals using a high-temperature (650 °C) hydrothermal method with CsOH and F - mineralizers. The presence of fluoride is essential to the formation of the product. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isotopes as clues to the origin and earliest differentiation history of the Earth.

PubMed

Jacobsen, Stein B; Ranen, Michael C; Petaev, Michael I; Remo, John L; O'Connell, Richard J; Sasselov, Dimitar D

2008-11-28

Measurable variations in (182)W/(183)W, (142)Nd/(144)Nd, (129)Xe/(130)Xe and (136)XePu/(130)Xe in the Earth and meteorites provide a record of accretion and formation of the core, early crust and atmosphere. These variations are due to the decay of the now extinct nuclides (182)Hf, (146)Sm, (129)I and (244)Pu. The (l82)Hf-(182)W system is the best accretion and core-formation chronometer, which yields a mean time of Earth's formation of 10Myr, and a total time scale of 30Myr. New laser shock data at conditions comparable with those in the Earth's deep mantle subsequent to the giant Moon-forming impact suggest that metal-silicate equilibration was rapid enough for the Hf-W chronometer to reliably record this time scale. The coupled (146)Sm-(147)Sm chronometer is the best system for determining the initial silicate differentiation (magma ocean crystallization and proto-crust formation), which took place at ca 4.47Ga or perhaps even earlier. The presence of a large (129)Xe excess in the deep Earth is consistent with a very early atmosphere formation (as early as 30Myr); however, the interpretation is complicated by the fact that most of the atmospheric Xe may be from a volatile-rich late veneer.

Water-bearing, high-pressure Ca-silicates

NASA Astrophysics Data System (ADS)

Németh, Péter; Leinenweber, Kurt; Ohfuji, Hiroaki; Groy, Thomas; Domanik, Kenneth J.; Kovács, István J.; Kovács, Judit S.; Buseck, Peter R.

2017-07-01

Water-bearing minerals provide fundamental knowledge regarding the water budget of the mantle and are geophysically significant through their influence on the rheological and seismic properties of Earth's interior. Here we investigate the CaO-SiO2-H2O system at 17 GPa and 1773 K, corresponding to mantle transition-zone condition, report new high-pressure (HP) water-bearing Ca-silicates and reveal the structural complexity of these phases. We document the HP polymorph of hartrurite (Ca3SiO5), post-hartrurite, which is tetragonal with space group P4/ncc, a = 6.820 (5), c = 10.243 (8) Å, V = 476.4 (8) Å3, and Z = 4, and is isostructural with Sr3SiO5. Post-hartrurite occurs in hydrous and anhydrous forms and coexists with larnite (Ca2SiO4), which we find also has a hydrous counterpart. Si is 4-coordinated in both post-hartrurite and larnite. In their hydrous forms, H substitutes for Si (4H for each Si; hydrogrossular substitution). Fourier transform infrared (FTIR) spectroscopy shows broad hydroxyl absorption bands at ∼3550 cm-1 and at 3500-3550 cm-1 for hydrous post-hartrurite and hydrous larnite, respectively. Hydrous post-hartrurite has a defect composition of Ca2.663Si0.826O5H1.370 (5.84 weight % H2O) according to electron-probe microanalysis (EPMA), and the Si deficiency relative to Ca is also observed in the single-crystal data. Hydrous larnite has average composition of Ca1.924Si0.851O4H0.748 (4.06 weight % H2O) according to EPMA, and it is in agreement with the Si occupancy obtained using X-ray data collected on a single crystal. Superlattice reflections occur in electron-diffraction patterns of the hydrous larnite and could indicate crystallographic ordering of the hydroxyl groups and their associated cation defects. Although textural and EPMA-based compositional evidence suggests that hydrous perovskite may occur in high-Ca-containing (or low silica-activity) systems, the FTIR measurement does not show a well-defined hydroxyl absorption band for this

EPR and ENDOR Studies of Point Defects in Lithium Tetraborate Crystals

DTIC Science & Technology

2012-12-14

the US and its allies. Terrorist groups have shown interest in seeking and deploying weapons of mass destruction and mass disruption--weapons that...5]. Lithium tetraborate, has been grown pure and doped with many different elements including transition metals, actinides , and rare earth...microwave cavity is said to be “ critically coupled” when there is no reflected microwave power. Absorption of microwaves, which occurs when the magnetic

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.

Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell

NASA Technical Reports Server (NTRS)

Attia, Alan I. (Inventor); Halpert, Gerald (Inventor); Huang, Chen-Kuo (Inventor); Surampudi, Subbarao (Inventor)

1995-01-01

The method includes steps for forming a carbon electrode composed of graphitic carbon particles adhered by an ethylene propylene diene monomer binder. An effective binder composition is disclosed for achieving a carbon electrode capable of subsequent intercalation by lithium ions. The method also includes steps for reacting the carbon electrode with lithium ions to incorporate lithium ions into graphitic carbon particles of the electrode. An electrical current is repeatedly applied to the carbon electrode to initially cause a surface reaction between the lithium ions and to the carbon and subsequently cause intercalation of the lithium ions into crystalline layers of the graphitic carbon particles. With repeated application of the electrical current, intercalation is achieved to near a theoretical maximum. Two differing multi-stage intercalation processes are disclosed. In the first, a fixed current is reapplied. In the second, a high current is initially applied, followed by a single subsequent lower current stage. Resulting carbon/lithium-ion electrodes are well suited for use as an anode in a reversible, ambient temperature, lithium cell.

Barrier Properties of Layered-Silicate Reinforced Ethylenepropylenediene Monomer/Chloroprene Rubber Nanorubbers.

PubMed

Wu, Chang Mou; Hsieh, Wen Yen; Cheng, Kuo Bin; Lai, Chiu-Chun; Lee, Kuei Chi

2018-05-09

The triacetin and nitroglycerin barrier properties of layered-silicate reinforced ethylenepropylenediene monomer/chloroprene rubber (EPDM/CR) nanorubbers were investigated as rocket-propellant inhibitors. EPDM/CR nanorubbers with intercalated structures were formulated and prepared by the melt-compounding method. The triacetin permeability and nitroglycerin absorption were observed to decrease with increasing layered-silicate content. The layered silicates also improved the flame retardancies of the nanorubbers by forming silicate reinforced carbonaceous chars. Layered-silicate reinforced EPDM/CR nanorubbers are potentially effective rocket propellant-inhibiting materials.

Water in silicate melts

NASA Astrophysics Data System (ADS)

McMillan, Paul; Stolper, Edward

Water is one of the more important volatile species in magmas, both in terms of its abundance and its influence on the properties of a given magma. Many workers in the geological sciences have measured, modeled, and speculated on the interaction of water with silicate melts as a function of pressure. At the same time, glass and materials scientists have collected a considerable body of data on the effect of water on the properties of liquid and glassy silicates at 1 atmosphere (1.01325×105 N m-2) and below. A special session on “Solubility and Transport Properties of Water in Silicate Melts” was held during the 1983 AGU Spring Meeting, May 30-June 3, in Baltimore. The session had three main objectives: (1) review the present data base and discuss the status of current models in order to identify areas where further work is needed; (2) introduce interested geologists to the large body of work being carried out in the glass and materials sciences; and (3) consider static properties, such as thermodynamic relations, structure of hydrous melts, and dynamic properties including diffusion and viscosity. This report summarizes the major topics discussed. More detailed information may be found in the published abstracts (Eos, May 3, 1983, pp. 338-343).

Microfabrics in Siliceous Hotsprings: Yellowstone National Park, Wyoming

NASA Technical Reports Server (NTRS)

Guidry, S. A.; Chafetz, H. S.; Westall, F.

2001-01-01

Microfabrics shed light on the mechanisms governing siliceous sinter precipitation, the profound effects of microorganisms, as well as a conventional facies model for siliceous hotsprings. Additional information is contained in the original extended abstract.

Grain Boundary Engineering of Lithium-Ion-Conducting Lithium Lanthanum Titanate for Lithium-Air Batteries

DTIC Science & Technology

2015-01-01

Tojo T, Sakurai Y. Synthesis and lithium - ion conductivity for perovskite-type Li3/8Sr7/16Ta3/4Zr1/4O3 solid electrolyte by powder-bed sintering...battery performance is limited by the electrolytic membrane, which needs high Li-ionic conductivity. Lithium lanthanum titanate (Li3xLa(2/3)-xTiO3, or...of the A-site ions and lithium ion conductivity in the perovskite solid solution La0.67-xLi3xTiO3 (x=0.11). Journal of Solid State Ionics. 1999;121

Barrier Properties of Layered-Silicate Reinforced Ethylenepropylenediene Monomer/Chloroprene Rubber Nanorubbers

PubMed Central

Hsieh, Wen Yen; Cheng, Kuo Bin; Lai, Chiu-Chun; Lee, Kuei Chi

2018-01-01

The triacetin and nitroglycerin barrier properties of layered-silicate reinforced ethylenepropylenediene monomer/chloroprene rubber (EPDM/CR) nanorubbers were investigated as rocket-propellant inhibitors. EPDM/CR nanorubbers with intercalated structures were formulated and prepared by the melt-compounding method. The triacetin permeability and nitroglycerin absorption were observed to decrease with increasing layered-silicate content. The layered silicates also improved the flame retardancies of the nanorubbers by forming silicate reinforced carbonaceous chars. Layered-silicate reinforced EPDM/CR nanorubbers are potentially effective rocket propellant-inhibiting materials. PMID:29747427

The nature, fabrication, and applications of photosensitive, bulk, germano-silicate glass

NASA Astrophysics Data System (ADS)

Heaney, Alan Douglas

2000-08-01

The photosensitive nature of germano-silicate glass is widely used to create fiber-optic devices. This thesis examines the cause of photosensitivity in germano- silicate glass. The results of this research elucidate the role that germanium oxygen deficient defects play in the photosensitivity of hydrogen-loaded, germano-silicate glass. We find that defects are not vital to the photosensitivity of hydrogen-loaded, germano-silicate glass but they do enhance the effect. Quantitative measurements show that germanium oxygen deficient defects promote the formation of OH, GeH, and GeH2 when hydrogen-loaded, germano-silicate glass is exposed to ultraviolet light. A sol-gel process for fabricating germano-silicate glass in bulk samples has been developed. The sol-gel process produces high-quality, germano-silicate glass which can be tailored to contain defects or be relatively free of defects. Control over the glass defect concentration allows us to use sol-gel derived glass for comparative studies of the photosensitive process and for device applications. The unique properties of germano-silicate glass make it a likely choice for use in optical applications. To prove the feasibility of bulk devices, chirped-pulse amplification is demonstrated using gratings written in bulk germano-silicate glass.

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.

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.

The young age of Earth

NASA Astrophysics Data System (ADS)

Zhang, Youxue

1998-09-01

Patterson (1956) established that the age of Earth is close to that of meteorites. Over the last 20 years, workers argued for younger age for core differentiation based on Pb-Pb model ages and tungsten isotopic data and for gas retention based on I-Xe modeling. However, disagreement is abundant, and the young age of Earth has not been widely accepted. In this work, I examine all radiogenic noble gases in the atmosphere and use a model-independent approach and total inversion to show that (1) the Xe-closure age of Earth is 109 ± 23 million years younger than the formation of meteorite Bjurbole (˜4560 Ma) and (2) all radiogenic components of noble gases in the atmosphere can be quantitatively accounted for by production and degassing ˜60% of the bulk silicate earth. The agreement between the 129I- 129Xe clock and 244Pu- 238U- 136Xe- 134Xe- 132Xe- 131Xe clock suggests that the volatility of iodine does not affect the 129I- 129Xe clock. Earth's Xe-closure age is 4.45 ± 0.02 Ga, consistent with the model age of Pb and the 146Sm- 142Nd, 147Sm- 143Nd and 182Hf- 182W systematics. On the basis of the consistency of these ages, 4.45 ± 0.02 Ga probably represents the time when the last Martian-sized planetesimal hit Earth and reinitialized the global clocks.

Comment on "The shape and composition of interstellar silicate grains"

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

Bradley, J P; Ishii, H

2007-09-27

In the paper entitled 'The shape and composition of interstellar silicate grains' (A & A, 462, 667-676 (2007)), Min et al. explore non-spherical grain shape and composition in modeling the interstellar 10 and 20 {micro}m extinction features. This progression towards more realistic models is vitally important to enabling valid comparisons between dust observations and laboratory measurements. Min et al. proceed to compare their model results with GEMS (glass with embedded metals and sulfides) from IDPs (interplanetary dust particles) and to discuss the nature and origin of GEMS. Specifically, they evaluate the hypothesis of Bradley (1994) that GEMS are interstellar (IS)more » amorphous silicates. From a comparison of the mineralogy, chemical compositions, and infrared (IR) spectral properties of GEMS with their modeling results, Min et al. conclude: 'GEMS are, in general, not unprocessed leftovers from the diffuse ISM'. This conclusion is based, however, on erroneous and incomplete GEMS data. It is important to clarify first that Bradley (1994) never proposed that GEMS are unprocessed leftovers from the diffuse ISM, nor did he suggest that individual subnanogram mass GEMS are a representative sampling of the enormous mass of silicates in the diffuse ISM. Bradley (1994) simply showed that GEMS properties are consistent with those of IS amorphous silicates. It is widely accepted that circumstellar outflows are important sources of IS silicates, and whether GEMS are processed or not, the circumstellar heritage of some has been rigorously confirmed through measurements of non-solar oxygen (O) isotope abundances (Messenger et al., 2003; Floss et al., 2006). Keller et al. (2000) assert that even GEMS without detectable O isotope anomalies are probably also extrasolar IS silicates because they are embedded in carbonaceous material with non-solar D/H isotopic composition. (Much of the silicate dust in the ISM may be isotopically homogenized (Zhukovska et al., 2007

Origin of silicic crust by rifting and bimodal plume volcanism in the Afar Depression

NASA Astrophysics Data System (ADS)

Ghatak, A.; Basu, A. R.; Ebinger, C. J.

2010-12-01

The youngest mantle plume province worldwide occurs at the seismically and volcanically active East African - Red Sea - Gulf of Aden (Afar) triple junction, where one or more upwellings has impinged the thick cratonic lithosphere since ~45 Ma. A spectacular example of magmatism in the Afar depression is seen in the present to < 2 Ma old bimodal fissural mafic and peralkaline silicic eruptions in the ~60 km-long Dabbahu-Manda Hararo (DMH) Rift. In this study we report major, trace elements, and Nd-Sr-Pb isotopes in recent basaltic and silicic rocks originating from the center of the DMH rift segment, exposed along the rift axis and flanks of this segment. The rare earth element (REE) patterns of the silicic rocks and basalts are different in two significant ways: (1) the silicic rocks show a prominent positive Ce-anomaly that is extremely rare in volcanic rocks; and (2) this positive Ce-anomaly is accompanied by a strong negative Eu-anomaly. These anomalies are absent in the basaltic rocks. The positive Ce-anomaly is probably due to interaction in a magma chamber, similar in composition to the basalts, with deep saline aquifer or brines that typically show positive Ce-anomaly. The REE patterns of the two lava groups are interpreted to be due to fractional crystallization of plagioclase in a magma chamber similar in REE composition as the basalts that erupted in the DMH segments. We interpret the silicic rocks to be residues after ~20% fractional crystallization of plagioclase in the DMH basalts. The Nd-Pb isotopic composition of the basalts and rhyolites of the DMH are similar to the Ethiopian plume as defined by the ~30 Ma old Ethiopian flood basalts. Based on their high 3He/4He ratios (R/RA ~30) and Nd-Sr-Pb isotopic data, the source of the Ethiopian plume is generally believed to be in the lower mantle. Therefore, the similarity of the Nd-Pb and Pb-Pb isotopic variations between the Ethiopian plume and the DMH lavas indicates that these lavas were sourced from

What can the Hf–W System tell Us About the Mechanism and Timing of Earth's Core Formation?

NASA Astrophysics Data System (ADS)

Fischer, R. A.; Nimmo, F.; O'Brien, D. P.

2018-05-01

Strong tradeoff between effects of depth and extent of metal-silicate equilibration and formation timescale on the Hf-W system. Whole mantle equilibration requires k = 0.4. Later formation times require less equilibration to match Earth's anomaly.

Stability and Solid Solutions of Hydrous Alumino-Silicates in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Panero, W. R.; Caracas, R.

2017-12-01

The degree to which the Earth's mantle stores and cycles water in excess of the storage capacity of nominally anhydrous minerals is dependent upon the stability of hydrous phases under mantle-relevant pressures, temperatures, and compositions. Two hydrous phases, phase D and phase H are stable to the pressures and temperatures of the Earth's lower mantle, suggesting that the Earth's lower mantle may participate in the cycling of water. Each phase has a wide solid solution series between MgSi2O6H2-Al2SiO6H2 and MgSiO4H2-2δAlOOH-SiO2, respectively, yet most work addresses end-member compositions for analysis of stability and elastic properties. We present the results of density functional theory calculations on the stability, structure, bonding, partitioning, and elasticity of hydrous phases D and H in the Al2O3-SiO2-MgO-H2O system, addressing the solid solution series through a statistical sampling of site occupancy and calculation of the partition function from the grand canonical ensemble. We find that the addition of Al to the endmember compositions stabilizes each phase to higher temperatures through additional configurational entropy. We further find that solid solutions tend not to undergo hydrogen-bond symmetrization as is found in the end member compositions as a result of non-symmetric bonding environments.

Molten salt lithium cells

DOEpatents

Raistrick, I.D.; Poris, J.; Huggins, R.A.

1980-07-18

Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and light weight. One type of lithium-based cell utilizes a molten salt electrolyte and is operated in the temperature range of about 400 to 500/sup 0/C. Such high temperature operation accelerates corrosion problems and a substantial amount of energy is lost through heat transfer. The present invention provides an electrochemical cell which may be operated at temperatures between about 100 to 170/sup 0/C. The cell is comprised of an electrolyte, which preferably includes lithium nitrate, and a lithium or lithium alloy electrode.

Molten salt lithium cells

DOEpatents

Raistrick, Ian D.; Poris, Jaime; Huggins, Robert A.

1983-01-01

Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and light weight. One type of lithium-based cell utilizes a molten salt electrolyte and is operated in the temperature range of about 400.degree.-500.degree. C. Such high temperature operation accelerates corrosion problems and a substantial amount of energy is lost through heat transfer. The present invention provides an electrochemical cell (10) which may be operated at temperatures between about 100.degree.-170.degree. C. Cell (10) comprises an electrolyte (16), which preferably includes lithium nitrate, and a lithium or lithium alloy electrode (12).

Molten salt lithium cells

DOEpatents

Raistrick, Ian D.; Poris, Jaime; Huggins, Robert A.

1982-02-09

Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and light weight. One type of lithium-based cell utilizes a molten salt electrolyte and is operated in the temperature range of about 400.degree.-500.degree. C. Such high temperature operation accelerates corrosion problems and a substantial amount of energy is lost through heat transfer. The present invention provides an electrochemical cell (10) which may be operated at temperatures between about 100.degree.-170.degree. C. Cell (10) comprises an electrolyte (16), which preferably includes lithium nitrate, and a lithium or lithium alloy electrode (12).

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.

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.

Fundamental Investigation of Silicon Anode in Lithium-Ion Cells

NASA Technical Reports Server (NTRS)

Wu, James J.; Bennett, William R.

2012-01-01

Silicon is a promising and attractive anode material to replace graphite for high capacity lithium ion cells since its theoretical capacity is 10 times of graphite and it is an abundant element on Earth. However, there are challenges associated with using silicon as Li-ion anode due to the significant first cycle irreversible capacity loss and subsequent rapid capacity fade during cycling. Understanding solid electrolyte interphase (SEI) formation along with the lithium ion insertion/de-insertion kinetics in silicon anodes will provide greater insight into overcoming these issues, thereby lead to better cycle performance. In this paper, cyclic voltammetry and electrochemical impedance spectroscopy are used to build a fundamental understanding of silicon anodes. The results show that it is difficult to form the SEI film on the surface of a Si anode during the first cycle; the lithium ion insertion and de-insertion kinetics for Si are sluggish, and the cell internal resistance changes with the state of lithiation after electrochemical cycling. These results are compared with those for extensively studied graphite anodes. The understanding gained from this study will help to design better Si anodes, and the combination of cyclic voltammetry with impedance spectroscopy provides a useful tool to evaluate the effectiveness of the design modifications on the Si anode performance.

Testing Conducted for Lithium-Ion Cell and Battery Verification

NASA Technical Reports Server (NTRS)

Reid, Concha M.; Miller, Thomas B.; Manzo, Michelle A.

2004-01-01

The NASA Glenn Research Center has been conducting in-house testing in support of NASA's Lithium-Ion Cell Verification Test Program, which is evaluating the performance of lithium-ion cells and batteries for NASA mission operations. The test program is supported by NASA's Office of Aerospace Technology under the NASA Aerospace Flight Battery Systems Program, which serves to bridge the gap between the development of technology advances and the realization of these advances into mission applications. During fiscal year 2003, much of the in-house testing effort focused on the evaluation of a flight battery originally intended for use on the Mars Surveyor Program 2001 Lander. Results of this testing will be compared with the results for similar batteries being tested at the Jet Propulsion Laboratory, the Air Force Research Laboratory, and the Naval Research Laboratory. Ultimately, this work will be used to validate lithium-ion battery technology for future space missions. The Mars Surveyor Program 2001 Lander battery was characterized at several different voltages and temperatures before life-cycle testing was begun. During characterization, the battery displayed excellent capacity and efficiency characteristics across a range of temperatures and charge/discharge conditions. Currently, the battery is undergoing lifecycle testing at 0 C and 40-percent depth of discharge under low-Earth-orbit (LEO) conditions.

The Lithium Battery: assessing the neurocognitive profile of lithium in bipolar disorder.

PubMed

Malhi, Gin S; McAulay, Claire; Gershon, Samuel; Gessler, Danielle; Fritz, Kristina; Das, Pritha; Outhred, Tim

2016-03-01

The aim of the present study was to characterize the neurocognitive effects of lithium in bipolar disorder to inform clinical and research approaches for further investigation. Key words pertaining to neurocognition in bipolar disorder and lithium treatment were used to search recognized databases to identify relevant literature. The authors also retrieved gray literature (e.g., book chapters) known to them and examined pertinent articles from bibliographies. A limited number of studies have examined the effects of lithium on neurocognition in bipolar disorder and, although in some domains a consistent picture emerges, in many domains the findings are mixed. Lithium administration appears to reshape key components of neurocognition - in particular, psychomotor speed, verbal memory, and verbal fluency. Notably, it has a sophisticated neurocognitive profile, such that while lithium impairs neurocognition across some domains, it seemingly preserves others - possibly those vulnerable to the effects of bipolar disorder. Furthermore, its effects are likely to be direct and indirect (via mood, for example) and cumulative with duration of treatment. Disentangling the components of neurocognition modulated by lithium in the context of a fluctuating and complex illness such as bipolar disorder is a significant challenge but one that therefore demands a stratified and systematic approach, such as that provided by the Lithium Battery. In order to delineate the effects of lithium therapy on neurocognition in bipolar disorder within both research and clinical practice, a greater understanding and measurement of the relatively stable neurocognitive components is needed to examine those that indeed change with lithium treatment. In order to achieve this, we propose a Lithium Battery-Clinical and a Lithium Battery-Research that can be applied to these respective settings. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

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

A stable organic-inorganic hybrid layer protected lithium metal anode for long-cycle lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Zhu, Jinhui; Yang, Jun; Zhou, Jingjing; Zhang, Tao; Li, Lei; Wang, Jiulin; Nuli, Yanna

2017-10-01

A stable organic-inorganic hybrid layer (OIHL) is direct fabricated on lithium metal surface by the interfacial reaction of lithium metal foil with 1-chlorodecane and oxygen/carbon dioxide mixed gas. This favorable OIHL is approximately 30 μm thick and consists of lithium alkyl carbonate and lithium chloride. The lithium-oxygen batteries with OIHL protected lithium metal anode exhibit longer cycle life (340 cycles) than those with bare lithium metal anode (50 cycles). This desirable performance can be ascribed to the robust OIHL which prevents the growth of lithium dendrites and the corrosion of lithium metal.

Heterogeneous Nucleation of Protein Crystals on Fluorinated Layered Silicate

PubMed Central

Ino, Keita; Udagawa, Itsumi; Iwabata, Kazuki; Takakusagi, Yoichi; Kubota, Munehiro; Kurosaka, Keiichi; Arai, Kazuhito; Seki, Yasutaka; Nogawa, Masaya; Tsunoda, Tatsuo; Mizukami, Fujio; Taguchi, Hayao; Sakaguchi, Kengo

2011-01-01

Here, we describe an improved system for protein crystallization based on heterogeneous nucleation using fluorinated layered silicate. In addition, we also investigated the mechanism of nucleation on the silicate surface. Crystallization of lysozyme using silicates with different chemical compositions indicated that fluorosilicates promoted nucleation whereas the silicates without fluorine did not. The use of synthesized saponites for lysozyme crystallization confirmed that the substitution of hydroxyl groups contained in the lamellae structure for fluorine atoms is responsible for the nucleation-inducing property of the nucleant. Crystallization of twelve proteins with a wide range of pI values revealed that the nucleation promoting effect of the saponites tended to increase with increased substitution rate. Furthermore, the saponite with the highest fluorine content promoted nucleation in all the test proteins regardless of their overall net charge. Adsorption experiments of proteins on the saponites confirmed that the density of adsorbed molecules increased according to the substitution rate, thereby explaining the heterogeneous nucleation on the silicate surface. PMID:21818343

Molybdenum Valence in Basaltic Silicate Melts

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Pando, K.

2010-01-01

The moderately siderophile element molybdenum has been used as an indicator in planetary differentiation processes, and is particularly relevant to core formation [for example, 1-6]. However, models that apply experimental data to an equilibrium differentiation scenario infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Partitioning behavior of molybdenum, a multivalent element with a transition near the J02 of interest for core formation (IW-2) will be sensitive to changes in JO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo6+ can be either octahedrally or tetrahedrally coordinated. Here we present first XANES measurements of Mo valence in basaltic run products at a range of P, T, and JO2 and further quantify the valence transition of Mo.

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.

The Role of Gas-Silicate Chemisorption Reactions in Modifying Planetary Crusts and Surfaces

NASA Astrophysics Data System (ADS)

King, P. L.; Henley, R. W.; Wykes, J. L.; Renggli, C.; Troitzsch, U.; Clark, D.; O'Neill, H. S.

2014-12-01

Evidence for gas-solid reactions is found throughout the solar system: for example, sulfidation reactions in some meteorites and secondary phases coating lunar pyroclastic glasses. On Earth, the products of gas-solid reactions are documented in volcanic systems, metalliferous mineral deposits, impact craters, and on dust or meteorites after passage through the atmosphere - such reactions are also likely on the surfaces of Mars and Venus. To understand the chemical dynamics of such gas-solid reactions, we are undertaking systematic experiments and thermochemical modelling. Experiments were conducted in a vertical gas-mixing furnace at 600 - 800 °C and 1 bar, using SO2and a range of Ca-bearing materials: labradorite, feldspar glass and anorthosite (rock). In each case, anhydrite formed rapidly. In shorter experiments with labradorite, isolated anhydrite is observed surrounded by 'moats' of Ca-depleted silicate. In longer experiments, anhydrite is found as clusters of crystals that, in some cases, extend from the substrate forming precarious 'towers' (Figure). Anhydrite fills cracks in porous samples. We propose that the nucleation and rapid growth of anhydrite on the surface of these Ca-rich phases occurs by chemisorption of SO2(g) molecules with slightly negatively charged oxygen onto available near-surface calcium with slight positive charge. Anhydrite growth is sustained by SO2(g) chemisorption and Ca migration through the reacting silicate lattice, accelerated by increased bond lengths at high temperature. Significantly, the chemisorption reaction indicates that SO2 disproportionates to form both oxidized sulfur (as anhydrite) and a reduced sulfur species (e.g., an S* radical ion). On Earth, in the presence of H2O, the predominant reduced sulfur species is H2S, through an overall reaction: 3CaAl2Si2O8 + 4 SO2(g)+ H2O(g) → 3CaSO4 + 3Al2SiO5 + 3SiO2 + H2S(g)The reduced sulfur may react with gas phase Fe, Ni, Zn and Cu cluster compounds to form metal sulfides

The chlorine abundance of Earth: Implications for a habitable planet

NASA Astrophysics Data System (ADS)

Sharp, Z. D.; Draper, D. S.

2013-05-01

The Cl, Br and I contents of Earth are depleted by a factor of 10 relative to predicted values from chondritic and solar abundances. Possible explanations for the apparent discrepancy include (1) unrecognized sequestration of Cl in the core, (2) a much higher nebular volatility than normally presumed or (3) a preferential loss of the heavy halogens during planetary accretion. We tested the first assumption by conducting high pressure-temperature equilibration experiments between silicate and metal. At 15 GPa and 1900 °C, the DCl(metal-silicate) value for Cl is less than 0.007, indicating that the core is not a significant reservoir for Cl. The concentration of Cl in all chondritic classes follows a depletion trend very similar to that of Na and Mn, arguing against a low condensation temperature for Cl. Instead, we propose that the depletion of the heavy halogens is due to their unique hydrophilic behavior. Almost half of Earth's Cl and Br inventory resides in the ocean and evaporites, demonstrating the unique affinity for aqueous solutions for these elements. During planetary accretion, there would have been a strong sequestration of halogens into the crustal reservoir. 'Collisional erosion' during planetary accretion provides a mechanism that would uniquely strip the heavy halogens out of an accreting Earth. Had such loss not occurred, the salinity of the oceans would be 10× the present value, and complex life would probably never have evolved.

Effects of selective fusion on the thermal history of the earth's mantle

USGS Publications Warehouse

Lee, W.H.K.

1968-01-01

A comparative study on the thermal history of the earth's mantle was made by numerical solutions of the heat equation including and excluding selective fusion of silicates. Selective fusion was approximated by melting in a multicomponent system and redistribution of radioactive elements. Effects of selective fusion on the thermal models are (1) lowering (by several hundred degrees centigrade) and stabilizing the internal temperature distribution, and (2) increasing the surface heat-flow. It was found that models with selective fusion gave results more compatible with observations of both present temperature and surface heat-flow. The results therefore suggest continuous differentiation of the earth's mantle throughout geologic time, and support the hypothesis that the earth's atmosphere, oceans, and crust have been accumulated throughout the earth's history by degassing and selective fusion of the mantle. ?? 1968.

Experimental investigation on V isotope equilibrium fractionation factor between metal and silicate melt

NASA Astrophysics Data System (ADS)

Zhang, S.; Zhang, H.; Huang, F.

2017-12-01

Equilibrium fractionation factors of stable isotopes between metal and silicate melt are of vital importance for understanding the isotope variations within meteorites and planetary bodies. The V isotope composition (reported as δ51V = 1000 × [(51V/50Vsample/51V/50VAA)-1] ) of the bulk silicate Earth (BSE) has been estimated as δ51V = -0.7 ± 0.2‰ (2sd) [1], which is significantly heavier than most meteorites by 1‰ [2]. Such isotopic offset may provide insights for the core formation and core-mantle segregation. Therefore, it is important to understand V isotope equilibrium fractionation factor between silicate melt and metal. Nielsen et al. (2014) [2] had performed 3 experiments using starting materials of pure Fe metal and An50Di28Fo22 composition, revealing no resolvable V isotope fractionation. However, it is not clear whether chemical compositions in the melts can affect V isotope fractionations. Therefore, we experimentally calibrated equilibrium V isotope fractionation between Fe metallic and basaltic melt, with particular focus on the effect of Ni and other light elements. Experiments were performed at 1 GPa and 1600 oC using a 3/4″ end-loaded piston cylinder. The starting materials consisted of 1:1 mixture of pure Fe metal and basaltic composition [3]. The isotope equilibrium was assessed using time series experiments combined with the reverse reaction method. Carbon saturation and C-free experiments were achieved by using graphite and silica capsules, respectively. The Ni series experiments were doped with 6 wt% Ni into the starting Fe metal. The metal and silicate phases of samples were mechanically separated, V was purified using a chromatographic technique, and V isotope ratios were measured using MC-ICP-MS [4]. Carbon saturation, C-free experiments and Ni series experiment all show non-resolvable V isotope fractionation between metal and basaltic melt, which indicates that the presence of C and Ni could not affect V isotope fractionation

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P.; Armand, Michel; Zaghib, Karim

2017-04-01

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries.

PubMed

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P; Armand, Michel; Zaghib, Karim

2017-04-10

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Manufacturing of Protected Lithium Electrodes for Advanced Lithium-Air, Lithium-Water & Lithium-Sulfur Batteries

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

Visco, Steven J

The global demand for rechargeable batteries is large and growing rapidly. Assuming the adoption of electric vehicles continues to increase, the need for smaller, lighter, and less expensive batteries will become even more pressing. In this vein, PolyPlus Battery Company has developed ultra-light high performance batteries based on its proprietary protected lithium electrode (PLE) technology. The Company’s Lithium-Air and Lithium-Seawater batteries have already demonstrated world record performance (verified by third party testing), and we are developing advanced lithium-sulfur batteries which have the potential deliver high performance at low cost. In this program PolyPlus Battery Company teamed with Corning Incorporated tomore » transition the PLE technology from bench top fabrication using manual tooling to a pre- commercial semi-automated pilot line. At the inception of this program PolyPlus worked with a Tier 1 battery manufacturing engineering firm to design and build the first-of-its-kind pilot line for PLE production. The pilot line was shipped and installed in Berkeley, California several months after the start of the program. PolyPlus spent the next two years working with and optimizing the pilot line and now produces all of its PLEs on this line. The optimization process successfully increased the yield, throughput, and quality of PLEs produced on the pilot line. The Corning team focused on fabrication and scale-up of the ceramic membranes that are key to the PLE technology. PolyPlus next demonstrated that it could take Corning membranes through the pilot line process to produce state-of-the-art protected lithium electrodes. In the latter part of the program the Corning team developed alternative membranes targeted for the large rechargeable battery market. PolyPlus is now in discussions with several potential customers for its advanced PLE-enabled batteries, and is building relationships and infrastructure for the transition into manufacturing. It

Biomass-derived carbonaceous positive electrodes for sustainable lithium-ion storage

NASA Astrophysics Data System (ADS)

Liu, Tianyuan; Kavian, Reza; Chen, Zhongming; Cruz, Samuel S.; Noda, Suguru; Lee, Seung Woo

2016-02-01

Biomass derived carbon materials have been widely used as electrode materials; however, in most cases, only electrical double layer capacitance (EDLC) is utilized and therefore, only low energy density can be achieved. Herein, we report on redox-active carbon spheres that can be simply synthesized from earth-abundant glucose via a hydrothermal process. These carbon spheres exhibit a specific capacity of ~210 mA h gCS-1, with high redox potentials in the voltage range of 2.2-3.7 V vs. Li, when used as positive electrode in lithium cells. Free-standing, flexible composite films consisting of the carbon spheres and few-walled carbon nanotubes deliver high specific capacities up to ~155 mA h gelectrode-1 with no obvious capacity fading up to 10 000 cycles, proposing to be promising positive electrodes for lithium-ion batteries or capacitors. Furthermore, considering that the carbon spheres were obtained in an aqueous glucose solution and no toxic or hazardous reagents were used, this process opens up a green and sustainable method for designing high performance, environmentally-friendly energy storage devices.Biomass derived carbon materials have been widely used as electrode materials; however, in most cases, only electrical double layer capacitance (EDLC) is utilized and therefore, only low energy density can be achieved. Herein, we report on redox-active carbon spheres that can be simply synthesized from earth-abundant glucose via a hydrothermal process. These carbon spheres exhibit a specific capacity of ~210 mA h gCS-1, with high redox potentials in the voltage range of 2.2-3.7 V vs. Li, when used as positive electrode in lithium cells. Free-standing, flexible composite films consisting of the carbon spheres and few-walled carbon nanotubes deliver high specific capacities up to ~155 mA h gelectrode-1 with no obvious capacity fading up to 10 000 cycles, proposing to be promising positive electrodes for lithium-ion batteries or capacitors. Furthermore, considering

A review of lithium and non-lithium based solid state batteries

NASA Astrophysics Data System (ADS)

Kim, Joo Gon; Son, Byungrak; Mukherjee, Santanu; Schuppert, Nicholas; Bates, Alex; Kwon, Osung; Choi, Moon Jong; Chung, Hyun Yeol; Park, Sam

2015-05-01

Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks, including expensive sealing agents and inherent hazards of fire and leakages. All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used, and a detailed literature review of various important advances made in research. The paper exhaustively studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium based systems. Non-lithium based solid state batteries are attaining widespread commercial applications, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.

Properties of Tricalcium Silicate Sealers.

PubMed

Khalil, Issam; Naaman, Alfred; Camilleri, Josette

2016-10-01

Sealers based on tricalcium silicate cement aim at an interaction of the sealer with the root canal wall, alkalinity with potential antimicrobial activity, and the ability to set in a wet field. The aim of this study was to characterize and investigate the properties of a new tricalcium silicate-based sealer and verify its compliance to ISO 6876 (2012). A new tricalcium silicate-based sealer (Bio MM; St Joseph University, Beirut, Lebanon), BioRoot RCS (Septodont, St Maure de Fosses, France), and AH Plus (Dentsply, DeTrey, Konstanz, Germany) were investigated. Characterization using scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction analysis was performed. Furthermore, sealer setting time, flow, film thickness, and radiopacity were performed following ISO specifications. pH and ion leaching in solution were assessed by pH analysis and inductively coupled plasma. Bio MM and BioRoot RCS were both composed of tricalcium silicate and tantalum oxide in Bio MM and zirconium oxide in BioRoot RCS. In addition, the Bio MM contained calcium carbonate and a phosphate phase. The inorganic components of AH Plus were calcium tungstate and zirconium oxide. AH Plus complied with the ISO norms for both flow and film thickness. BioRoot RCS and Bio MM exhibited a lower flow and a higher film thickness than that specified for sealer cements in ISO 6876. All test sealers exhibited adequate radiopacity. Bio MM interacted with physiologic solution, thus showing potential for bioactivity. Sealer properties were acceptable and comparable with other sealers available clinically. Copyright © 2016 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

PubMed Central

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P.; Armand, Michel; Zaghib, Karim

2017-01-01

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron–hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries. PMID:28393912

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

Magnetic mineralogy and rock magnetic properties of silicate and carbonatite rocks from Oldoinyo Lengai volcano (Tanzania)

NASA Astrophysics Data System (ADS)

Mattsson, H. B.; Balashova, A.; Almqvist, B. S. G.; Bosshard-Stadlin, S. A.; Weidendorfer, D.

2018-06-01

Oldoinyo Lengai, a stratovolcano in northern Tanzania, is most famous for being the only currently active carbonatite volcano on Earth. The bulk of the volcanic edifice is dominated by eruptive products produced by silica-undersaturated, peralkaline, silicate magmas (effusive, explosive and/or as cumulates at depth). The recent (2007-2008) explosive eruption produced the first ever recorded pyroclastic flows at this volcano and the accidental lithics incorporated into the pyroclastic flows represent a broad variety of different rock types, comprising both extrusive and intrusive varieties, in addition to various types of cumulates. This mix of different accidental lithics provides a unique insight into the inner workings of the world's only active carbonatite volcano. Here, we focus on the magnetic mineralogy and the rock magnetic properties of a wide selection of samples spanning the spectrum of Oldoinyo Lengai rock types compositionally, as well from a textural point of view. Here we show that the magnetic properties of most extrusive silicate rocks are dominated by magnetite-ulvöspinel solid solutions, and that pyrrhotite plays a larger role in the magnetic properties of the intrusive silicate rocks. The natrocarbonatitic lavas, for which the volcano is best known for, show distinctly different magnetic properties in comparison with the silicate rocks. This discrepancy may be explained by abundant alabandite crystals/blebs in the groundmass of the natrocarbonatitic lavas. A detailed combination of petrological/mineralogical studies with geophysical investigations is an absolute necessity in order to understand, and to better constrain, the overall architecture and inner workings of the subvolcanic plumbing system. The results presented here may also have implications for the quest in order to explain the genesis of the uniquely natrocarbonatitic magmas characteristic of Oldoinyo Lengai.

Results of a real-time irradiation of lithium P/N and conventional N/P silicon solar cells.

NASA Technical Reports Server (NTRS)

Reynard, D. L.; Peterson, D. G.

1972-01-01

Eight types of lithium-diffused P/N and three types of conventional 10 ohm-cm N/P silicon solar cells were irradiated at four different temperatures with a strontium-90 radioisotope at a rate typical of that expected in earth orbit. The six-month irradiation confirmed earlier accelerator results, showed that certain cell types outperform others at the various temperatures, and, in general, verified the recent improvements and potential usefulness of lithium solar cells. The experimental approach and statistical methods and analyses employed yielded increased confidence in the validity of the results. Injection level effects were observed to be significant.

Early Earth(s) Across Time and Space

NASA Astrophysics Data System (ADS)

Mojzsis, S.

2014-04-01

The geochemical and cosmochemical record of our solar system is the baseline for exploring the question: "when could life appear on a world similar to our own?" Data arising from direct analysis of the oldest terrestrial rocks and minerals from the first 500 Myr of Earth history - termed the Hadean Eon - inform us about the timing for the establishment of a habitable silicate world. Liquid water is the key medium for life. The origin of water, and its interaction with the crust as revealed in the geologic record, guides our exploration for a cosmochemically Earth-like planets. From the time of primary planetary accretion to the start of the continuous rock record on Earth at ca. 3850 million years ago, our planet experienced a waning bolide flux that partially or entirely wiped out surface rocks, vaporized oceans, and created transient serpentinizing atmospheres. Arguably, "Early Earths" across the galaxy may start off as ice planets due to feeble insolation from their young stars, occasionally punctuated by steam atmospheres generated by cataclysmic impacts. Alternatively, early global environments conducive to life spanned from a benign surface zone to deep into crustal rocks and sediments. In some scenarios, nascent biospheres benefit from the exogenous delivery of essential bio-elements via leftovers of accretion, and the subsequent establishment of planetary-scale hydrothermal systems. If what is now known about the early dynamical regime of the Earth serves as any measure of the potential habitability of worlds across space and time, several key boundary conditions emerge. These are: (i) availability and long-term stability of liquid water; (ii) presence of energy resources; (iii) accessibility of organic raw materials; (iv) adequate inventory of radioisotopes to drive internal heating; (v) gross compositional parameters such as mantle/core mass ratio, and (vi) P-T conditions at or near the surface suitable for sustaining biological activity. Life could

Three-dimensionally ordered macroporous Li2FeSiO4/C composite as a high performance cathode for advanced lithium ion batteries

NASA Astrophysics Data System (ADS)

Ding, Zhengping; Liu, Jiatu; Ji, Ran; Zeng, Xiaohui; Yang, Shuanglei; Pan, Anqiang; Ivey, Douglas G.; Wei, Weifeng

2016-10-01

Li2MSiO4 (M = Mn, Fe, Co, Ni, et al.) has received great attention because of the theoretical possibility to reversibly deintercalate two Li+ ions from the structure. However, the silicates still suffer from low electronic conductivity, sluggish lithium ion diffusion and structural instability upon deep cycling. In order to solve these problems, a "hard-soft" templating method has been developed to synthesize three-dimensionally ordered macroporous (3DOM) Li2FeSiO4/C composites. The 3DOM Li2FeSiO4/C composites show a high reversible capacity (239 mAh g-1) with ∼1.50 lithium ion insertion/extraction, a capacity retention of nearly 100% after 420 cycles and excellent rate capability. The enhanced electrochemical performance is ascribed to the interconnected carbon framework that improves the electronic conductivity and the 3DOM structure that offers short Li ion diffusion pathways and restrains volumetric changes.

Mineral stimulation of subsurface microorganisms: release of limiting nutrients from silicates

USGS Publications Warehouse

Roger, Jennifer Roberts; Bennett, Philip C.

2004-01-01

Microorganisms play an important role in the weathering of silicate minerals in many subsurface environments, but an unanswered question is whether the mineral plays an important role in the microbial ecology. Silicate minerals often contain nutrients necessary for microbial growth, but whether the microbial community benefits from their release during weathering is unclear. In this study, we used field and laboratory approaches to investigate microbial interactions with minerals and glasses containing beneficial nutrients and metals. Field experiments from a petroleum-contaminated aquifer, where silicate weathering is substantially accelerated in the contaminated zone, revealed that phosphorus (P) and iron (Fe)-bearing silicate glasses were preferentially colonized and weathered, while glasses without these elements were typically barren of colonizing microorganisms, corroborating previous studies using feldspars. In laboratory studies, we investigated microbial weathering of silicates and the release of nutrients using a model ligand-promoted pathway. A metal-chelating organic ligand 3,4 dihydroxybenzoic acid (3,4 DHBA) was used as a source of chelated ferric iron, and a carbon source, to investigate mineral weathering rate and microbial metabolism.In the investigated aquifer, we hypothesize that microbes produce organic ligands to chelate metals, particularly Fe, for metabolic processes and also form stable complexes with Al and occasionally with Si. Further, the concentration of these ligands is apparently sufficient near an attached microorganism to destroy the silicate framework while releasing the nutrient of interest. In microcosms containing silicates and glasses with trace phosphate mineral inclusions, microbial biomass increased, indicating that the microbial community can use silicate-bound phosphate inclusions. The addition of a native microbial consortium to microcosms containing silicates or glasses with iron oxide inclusions correlated to

Siderophile Element Partitioning between Sulfide- and Silicate melts.

NASA Astrophysics Data System (ADS)

Hackler, S.; Rohrbach, A.; Loroch, D. C.; Klemme, S.; Berndt, J.

2017-12-01

Different theories concerning the formation of the Earth are debated. Either Earth accreted mostly `dry' or volatile elements were delivered late after core formation was largely inactive [1, 2], or volatile rich material was accreted during the main stages of accretion and core formation [3, 4, 5]. The partitioning behavior of siderophile volatile elements (SVE; S, Se, Te, Tl, Ag, Au, Cd, Bi, Pb, Sn, Cu, Ge, and In) may provide first order constraints whether these element concentrations in Earth's mantle were established before or after core-mantle differentiation or perhaps during both periods by multi stage core formation [6]. A special interest is laid into chalcophile element behavior with respective to the possible formation and segregation of a hadean matte [7]. To examine the influence of sulfur on SVE partitioning between metal-silicate melts, we performed experiments simulating a magma ocean stage evolving from sulfur poor- (low fO2) to more oxidizing sulfur rich- (Fe, Ni)-S melts ( 20 wt% S) towards the end of accretion. We carried out partitioning experiments under various P-T-fO2 conditions with a Bristol type end loaded piston cylinder apparatus (<3 GPa) and a 1000 t walker-type multi-anvil press (3-20 GPa). Our results will be presented at the meeting. References: [1] Albarède F. (2009) Nature, 461, 1227-1233. [2] Ballhaus C. et al. (2013) EPSL, 362, 237-245. [3] Fischer-Gödde M. and Kleine T. (2017) Nature, 541, 525 527. [4] Wade J. and Wood B. J. (2005) EPSL, 236, 78-95. [5] Rubie D. et al. (2016) Science, 253, 1141-1144. [6] Rubie D. et al. (2011) EPSL, 301, 31-42. [7] O'Neill H. St. C. (1991) GCA, 55, 1159-1172.

Heteroaromatic-based electrolytes for lithium and lithium-ion batteries

DOEpatents

Cheng, Gang; Abraham, Daniel P.

2017-04-18

The present invention provides an electrolyte for lithium and/or lithium-ion batteries comprising a lithium salt in a liquid carrier comprising heteroaromatic compound including a five-membered or six-membered heteroaromatic ring moiety selected from the group consisting of a furan, a pyrazine, a triazine, a pyrrole, and a thiophene, the heteroaromatic ring moiety bearing least one carboxylic ester or carboxylic anhydride substituent bound to at least one carbon atom of the heteroaromatic ring. Preferred heteroaromatic ring moieties include pyridine compounds, pyrazine compounds, pyrrole compounds, furan compounds, and thiophene compounds.

Lithium metal oxide electrodes for lithium batteries

DOEpatents

Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kang, Sun-Ho

2010-06-08

An uncycled preconditioned electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula xLi.sub.2-yH.sub.yO.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 in which 0lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M' is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. The xLi.sub.2-yH.sub.y.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 material is prepared by preconditioning a precursor lithium metal oxide (i.e., xLi.sub.2M'O.sub.3.(1-x)LiMO.sub.2) with a proton-containing medium with a pH<7.0 containing an inorganic acid. Methods of preparing the electrodes are disclosed, as are electrochemical cells and batteries containing the electrodes.

A Non-Arrhenian Viscosity Model for Natural Silicate Melts with Applications to Volcanology

NASA Astrophysics Data System (ADS)

Russell, J. K.; Giordano, D.; Dingwell, D. B.

2005-12-01

silicate melts converge to a common, but unknown, high-T limit (e.g., A) and that all compositional dependence is accommodated for by B and C. We adopt a linear compositional dependence for B and C: B = σi=1..n [xi βi] C = σi=1..n [xi γi] where xi's are the mole fractions of oxide components (n=8) and βi and γi are adjustable parameters. The model, therefore, comprises 2 · n+1 adjustable parameters which are optimized for against the experimental database including a common value of A and compositional coefficeints for B and C. The new model reproduces the original database to within experimental uncertainty and can predict the viscosity of silicate melts across the full range of conditions found in Nature. References Cited: [1] Friedman et al., 1963. J Geophys Res 68, 6523-6535. [2] Bottinga Y & Weill D 1972. Am J Sci 272, 438- 475. [3] Shaw HR 1972. Am J Sci 272, 438- 475. [4] Persikov ES 1991. Adv Phys Geochem 9, 1-40. [5] Prusevich AA 1988. Geol Geofiz 29, 67-69. [6] Baker DR 1996. Am Min 81, 126-134. [7] Hess KU & Dingwell DB 1996. Am Min 81, 1297- 1300. [8] Zhang, et al. 2003. Am min 88, 1741- 1752. [9] Russell et al. 2002. Eur J Min 14, 417-428. [10] Russell et al. 2003. Am Min 8, 1390- 1394. [11] Russell JK & Giordano D In Press. Geochim Cosmochim Acta. [12] Giordano D & Dingwell DB 2003. Earth Planet. Sci. Lett. 208, 337-349.

Rare-earth gate oxides for GaAs MOSFET application

NASA Astrophysics Data System (ADS)

Kwon, Kwang-Ho; Yang, Jun-Kyu; Park, Hyung-Ho; Kim, Jongdae; Roh, Tae Moon

2006-08-01

Rare-earth oxide films for gate dielectric on n-GaAs have been investigated. The oxide films were e-beam evaporated on S-passivated GaAs, considering interfacial chemical bonding state and energy band structure. Rare-earth oxides such as Gd 2O 3, (Gd xLa 1- x) 2O 3, and Gd-silicate were employed due to high resistivity and no chemical reaction with GaAs. Structural and bonding properties were characterized by X-ray photoemission, absorption, and diffraction. The electrical characteristics of metal-oxide-semiconductor (MOS) diodes were correlated with material properties and energy band structures to guarantee the feasibility for MOS field effect transistor (FET) application. Gd 2O 3 films were grown epitaxially on S-passivated GaAs (0 0 1) at 400 °C. The passivation induced a lowering of crystallization temperature with an epitaxial relationship of Gd 2O 3 (4 4 0) and GaAs (0 0 1). A better lattice matching relation between Gd 2O 3 and GaAs substrate was accomplished by the substitution of Gd with La, which has larger ionic radius. The in-plane relationship of (Gd xLa 1- x) 2O 3 (4 4 0) with GaAs (0 0 1) was found and the epitaxial films showed an improved crystalline quality. Amorphous Gd-silicate film was synthesized by the incorporation of SiO 2 into Gd 2O 3. These amorphous Gd-silicate films excluded defect traps or current flow path due to grain boundaries and showed a relatively larger energy band gap dependent on the contents of SiO 2. Energy band parameters such as Δ EC, Δ EV, and Eg were effectively controlled by the film composition.

Lithium purification technique

DOEpatents

Keough, Robert F.; Meadows, George E.

1985-01-01

A method for purifying liquid lithium to remove unwanted quantities of nitrogen or aluminum. The method involves precipitation of aluminum nitride by adding a reagent to the liquid lithium. The reagent will be either nitrogen or aluminum in a quantity adequate to react with the unwanted quantity of the impurity to form insoluble aluminum nitride. The aluminum nitride can be mechanically separated from the molten liquid lithium.

Lithium purification technique

DOEpatents

Keough, R.F.; Meadows, G.E.

1984-01-10

A method for purifying liquid lithium to remove unwanted quantities of nitrogen or aluminum. The method involves precipitation of aluminum nitride by adding a reagent to the liquid lithium. The reagent will be either nitrogen or aluminum in a quantity adequate to react with the unwanted quantity of the impurity to form insoluble aluminum nitride. The aluminum nitride can be mechanically separated from the molten liquid lithium.

Chondritic Mn/Na ratio and limited post-nebular volatile loss of the Earth

NASA Astrophysics Data System (ADS)

Siebert, Julien; Sossi, Paolo A.; Blanchard, Ingrid; Mahan, Brandon; Badro, James; Moynier, Frédéric

2018-03-01

The depletion pattern of volatile elements on Earth and other differentiated terrestrial bodies provides a unique insight as to the nature and origin of planetary building blocks. The processes responsible for the depletion of volatile elements range from the early incomplete condensation in the solar nebula to the late de-volatilization induced by heating and impacting during planetary accretion after the dispersion of the H2-rich nebular gas. Furthermore, as many volatile elements are also siderophile (metal-loving), it is often difficult to deconvolve the effect of volatility from core formation. With the notable exception of the Earth, all the differentiated terrestrial bodies for which we have samples have non-chondritic Mn/Na ratios, taken as a signature of post-nebular volatilization. The bulk silicate Earth (BSE) is unique in that its Mn/Na ratio is chondritic, which points to a nebular origin for the depletion; unless the Mn/Na in the BSE is not that of the bulk Earth (BE), and has been affected by core formation through the partitioning of Mn in Earth's core. Here we quantify the metal-silicate partitioning behavior of Mn at deep magma ocean pressure and temperature conditions directly applicable to core formation. The experiments show that Mn becomes more siderophile with increasing pressure and temperature. Modeling the partitioning of Mn during core formation by combining our results with previous data at lower P-T conditions, we show that the core likely contains a significant fraction (20 to 35%) of Earth's Mn budget. However, we show that the derived Mn/Na value of the bulk Earth still lies on the volatile-depleted end of a trend defined by chondritic meteorites in a Mn/Na vs Mn/Mg plot, which tend to higher Mn/Na with increasing volatile depletion. This suggests that the material that formed the Earth recorded similar chemical fractionation processes for moderately volatile elements as chondrites in the solar nebula, and experienced limited post

Lithium: for harnessing renewable energy

USGS Publications Warehouse

Bradley, Dwight; Jaskula, Brian W.

2014-01-01

Lithium, which has the chemical symbol Li and an atomic number of 3, is the first metal in the periodic table. Lithium has many uses, the most prominent being in batteries for cell phones, laptops, and electric and hybrid vehicles. Worldwide sources of lithium are broken down by ore-deposit type as follows: closed-basin brines, 58%; pegmatites and related granites, 26%; lithium-enriched clays, 7%; oilfield brines, 3%; geothermal brines, 3%; and lithium-enriched zeolites, 3% (2013 statistics). There are over 39 million tons of lithium resources worldwide. Of this resource, the USGS estimates there to be approximately 13 million tons of current economically recoverable lithium reserves. To help predict where future lithium supplies might be located, USGS scientists study how and where identified resources are concentrated in the Earth’s crust, and they use that knowledge to assess the likelihood that undiscovered resources also exist.

Elasticity of Deep-Earth Materials at High P and T: Implication for Earths Lower Mantle

NASA Astrophysics Data System (ADS)

Bass, Jay; Sinogeikin, S. V.; Mattern, Estelle; Jackson, J. M.; Matas, J.; Wang, J.; Ricard, Y.

2005-03-01

Brillouin spectroscopy allows measurements of sound velocities and elasticity on phases of geophysical interest at high Pressures and Temperatures. This technique was used to measure the properties of numerous important phases of Earths deep interior. Emphasis is now on measurements at elevated P-T conditions, and measurements on dense polycrystals. Measurements to 60 GPa were made using diamond anvil cells. High temperature is achieved by electrical resistance and laser heating. Excellent results are obtained for polycrystalline samples of dense oxides such as silicate spinels, and (Mg,Al)(Si,Al)O3 --perovskites. A wide range of materials can now be characterized. These and other results were used to infer Earths average lower mantle composition and thermal structure by comparing mineral properties at lower mantle P-T conditions to global Earth models. A formal inversion procedure was used. Inversions of density and bulk sound velocity do not provide robust compositional and thermal models. Including shear properties in the inversions is important to obtain unique solutions. We discuss the range of models consistent with present lab results, and data needed to further refine lower mantle models.

Nanostructured electrolytes for stable lithium electrodeposition in secondary batteries.

PubMed

Tu, Zhengyuan; Nath, Pooja; Lu, Yingying; Tikekar, Mukul D; Archer, Lynden A

2015-11-17

Secondary batteries based on lithium are the most important energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceous host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to some extent even aluminum. Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost of ceramic electrolytes that meet the

Characterizing Amorphous Silicates in Extraterrestrial Materials

NASA Astrophysics Data System (ADS)

Fu, X.; Wang, A.; Krawczynski, M. J.

2015-12-01

Amorphous silicates are common in extraterrestrial materials. They are seen in the matrix of carbonaceous chondrites as well as in planetary materials. Tagish Lake is one of the most primitive carbonaceous meteorites in which TEM and XRD analyses found evidence for poorly crystalline phyllosilicate-like species; Raman spectra revealed amorphous silicates with variable degree of polymerization and low crystallinity. On Mars, CheMin discovered amorphous phases in all analyzed samples, and poorly crystalline smectite in mudstone samples. These discoveries pose questions on the crystallinity of phyllosilicates found by remote sensing on Mars, which is directly relevant to aqueous alteration during geologic history of Mars. Our goal is to use spectroscopy to better characterize amorphous silicates. We use three approaches: (1) using silicate glasses synthesized with controlled chemistry to study the effects of silicate polymerization and (2) using phyllosilicates synthesized with controlled hydrothermal treatment to study the effect of crystallinity on vibrational spectroscopy, finally (3) to use the developed correlations in above two steps to study amorphous phases in meteorites, and those found in future missions to Mars. In the 1st step, silicate glasses were synthesized from pure oxides in a range of NBO/T ratios (from 0 to 4). Depending on the targeted NBO/T and composition of mixed oxides, temperatures for each experiment fell in a range from 1260 to 1520 °C, run for ~ 4 hrs. The melt was quenched in liquid N2 or water. Homogeneity of glass was checked under optical microscopy. Raman spectra were taken over 100 spots on small chips free of bubbles and crystals. We have observed that accompanying an increase of NBO/T, there is a strengthening and a position shift of the Raman peak near 1000 cm-1 (Si-Onon-bridging stretching mode), and the weakening of broad Raman peaks near 500 cm-1 (ring breathing mode) and 700cm-1 (Si-Obridging-Si mode). We are building the

FE and MG Isotopic Analyses of Isotopically Unusual Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Messenger, S.; Ito, M.; Rahman, Z.

2011-01-01

Interstellar and circumstellar silicate grains are thought to be Mg-rich and Fe-poor, based on astronomical observations and equilibrium condensation models of silicate dust formation in stellar outflows. On the other hand, presolar silicates isolated from meteorites have surprisingly high Fe contents and few Mg-rich grains are observed. The high Fe contents in meteoritic presolar silicates may indicate they formed by a non-equilibrium condensation process. Alternatively, the Fe in the stardust grains could have been acquired during parent body alteration. The origin of Fe in presolar silicates may be deduced from its isotopic composition. Thus far, Fe isotopic measurements of presolar silicates are limited to the Fe-54/Fe-56 ratios of 14 grains. Only two slight anomalies (albeit solar within error) were observed. However, these measurements suffered from contamination of Fe from the adjacent meteorite matrix, which diluted any isotopic anomalies. We have isolated four presolar silicates having unusual O isotopic compositions by focused ion beam (FIB) milling and obtained their undiluted Mg and Fe isotopic compositions. These compositions help to identify the grains stellar sources and to determine the source of Fe in the grains.

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

PubMed Central

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; Zhao, Jie; Yan, Kai; Cui, Yi

2016-01-01

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm−2 in both carbonate and ether electrolyte. The advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes. PMID:26987481

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

DOE PAGES

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; ...

2016-03-18

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

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

Liu, Yayuan; Lin, Dingchang; Liang, Zheng

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

Recovery of Lithium from Geothermal Brine with Lithium-Aluminum Layered Double Hydroxide Chloride Sorbents.

PubMed

Paranthaman, Mariappan Parans; Li, Ling; Luo, Jiaqi; Hoke, Thomas; Ucar, Huseyin; Moyer, Bruce A; Harrison, Stephen

2017-11-21

We report a three-stage bench-scale column extraction process to selectively extract lithium chloride from geothermal brine. The goal of this research is to develop materials and processing technologies to improve the economics of lithium extraction and production from naturally occurring geothermal and other brines for energy storage applications. A novel sorbent, lithium aluminum layered double hydroxide chloride (LDH), is synthesized and characterized with X-ray powder diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometry (ICP-OES), and thermogravimetric analysis. Each cycle of the column extraction process consists of three steps: (1) loading the sorbent with lithium chloride from brine; (2) intermediate washing to remove unwanted ions; (3) final washing for unloading the lithium chloride ions. Our experimental analysis of eluate vs feed concentrations of Li and competing ions demonstrates that our optimized sorbents can achieve a recovery efficiency of ∼91% and possess excellent Li apparent selectivity of 47.8 compared to Na ions and 212 compared to K ions, respectively in the brine. The present work demonstrates that LDH is an effective sorbent for selective extraction of lithium from brines, thus offering the possibility of effective application of lithium salts in lithium-ion batteries leading to a fundamental shift in the lithium supply chain.

Lithium metal oxide electrodes for lithium batteries

DOEpatents

Thackeray, Michael M [Naperville, IL; Kim, Jeom-Soo [Naperville, IL; Johnson, Christopher S [Naperville, IL

2008-01-01

An uncycled electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula Li.sub.(2+2x)/(2+x)M'.sub.2x/(2+x)M.sub.(2-2x)/(2+x)O.sub.2-.delta., in which 0.ltoreq.x<1 and .delta. is less than 0.2, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M' is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. Methods of preconditioning the electrodes are disclosed as are electrochemical cells and batteries containing the electrodes.

Lanthanum Nitrate As Electrolyte Additive To Stabilize the Surface Morphology of Lithium Anode for Lithium-Sulfur Battery.

PubMed

Liu, Sheng; Li, Guo-Ran; Gao, Xue-Ping

2016-03-01

Lithium-sulfur (Li-S) battery is regarded as one of the most promising candidates beyond conventional lithium ion batteries. However, the instability of the metallic lithium anode during lithium electrochemical dissolution/deposition is still a major barrier for the practical application of Li-S battery. In this work, lanthanum nitrate, as electrolyte additive, is introduced into Li-S battery to stabilize the surface of lithium anode. By introducing lanthanum nitrate into electrolyte, a composite passivation film of lanthanum/lithium sulfides can be formed on metallic lithium anode, which is beneficial to decrease the reducibility of metallic lithium and slow down the electrochemical dissolution/deposition reaction on lithium anode for stabilizing the surface morphology of metallic Li anode in lithium-sulfur battery. Meanwhile, the cycle stability of the fabricated Li-S cell is improved by introducing lanthanum nitrate into electrolyte. Apparently, lanthanum nitrate is an effective additive for the protection of lithium anode and the cycling stability of Li-S battery.

An approach to beneficiation of spent lithium-ion batteries for recovery of materials

NASA Astrophysics Data System (ADS)

Marinos, Danai

Lithium ion batteries are one of the most commonly used batteries. A large amount of these have been used over the past 25 years and the use is expected to rise more due to their use in automotive batteries. Lithium ion batteries cannot be disposed into landfill due to safety reasons and cost. Thus, over the last years, there has been a lot of effort to find ways to recycle lithium ion batteries. A lot of valuable materials are present in a lithium ion battery making their recycling favorable. Many attempts, including pyrometallurgical and hydrometallurgical methods, have been researched and some of them are already used by the industry. However, further improvements are needed to the already existing processes, to win more valuable materials, use less energy and be more environmentally benign. The goal of this thesis is to find a low-temperature, low-energy method of recovering lithium from the electrolyte and to develop pathways for complete recycling of the battery. The research consists of the following parts: Pure LiPF6 powder, which is the electrolyte material, was characterized using x- ray diffraction analysis and DSC/TGA analysis. The LiPF6 powder was titrated using acid (HCl, HNO3, H2SO4), bases (NH4 OH) and distilled water. It was concluded that distilled water was the best solvent to selectively leach lithium from lithium-ion batteries. Leaching conditions were optimized including time, temperature, solid/liquid ratio and stirring velocity. All the samples were tested using ICP for chemical composition. Because leaching could be performed at room temperature, leaching was conducted in a flotation machine that was able to separate plastics by creating bubbles with no excess reagents use. The solution that contained lithium had to be concentrated more in order for lithium to be able to precipitate and it was shown that the solution could be concentrated by using the same solution over and over again. The next set of experiments was composed of battery

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, Li; Jacobsen, Stein; Sasselov, Dimitar D.

2015-01-01

We propose to use evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet's rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called 'late veneer'. The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet's surface, which are crucial for life to occur. We plan to build an integrative model of Earth-like planets from the bottom up. We would like to infer their chemical compositions from their mass-radius relations and their host stars' elemental abundances, and understand the origins of volatile contents (especially water) on their surfaces, and thereby shed light on the origins of life on them.

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.

Thin-film Rechargeable Lithium Batteries

DOE R&D Accomplishments Database

Dudney, N. J.; Bates, J. B.; Lubben, D.

1995-06-01

Thin film rechargeable lithium batteries using ceramic electrolyte and cathode materials have been fabricated by physical deposition techniques. The lithium phosphorous oxynitride electrolyte has exceptional electrochemical stability and a good lithium conductivity. The lithium insertion reaction of several different intercalation materials, amorphous V{sub 2}O{sub 5}, amorphous LiMn{sub 2}O{sub 4}, and crystalline LiMn{sub 2}O{sub 4} films, have been investigated using the completed cathode/electrolyte/lithium thin film battery.

Grain Growth and Silicates in Dense Clouds

NASA Technical Reports Server (NTRS)

Pendeleton, Yvonne J.; Chiar, J. E.; Ennico, K.; Boogert, A.; Greene, T.; Knez, C.; Lada, C.; Roellig, T.; Tielens, A.; Werner, M.;

Monitoring the Hazards of Silicic Volcanoes with Remote Sensing

NASA Technical Reports Server (NTRS)

Fink, Jonathan; Wessels, Rick; Eisinger, Chris; Ramsey, Michael; Hellman, Melanie; Kuhn, Sally

2004-01-01

This report details the final progress on the Solid Earth and Natural Hazards project: Monitoring of Hazards of Silicic Volcanoes with Remote Sensing (SENH99-0000-0159). The original award went to Arizona State University (ASU) with Dr. Jonathan Fink as the P.I. and Dr. Michael Ramsey as the Co-I. In May 2000, Dr. Ramsey left ASU to take a tenure-track faculty position at the University of Pittsburgh. The principle investigators and NASA Headquarters agreed to split the grant award at the HQ level and therefore avoid the double overhead charges that would arise from a university subcontract. The objectives of the science were divided, and coordinated yearly progress reports have been submitted from each University. This report details the final progress on work carried out at Arizona State. A report by Dr. Ramsey at the University of Pittsburgh has already been submitted. The work from both institutions is closely related and this report will reflect that connection.

Safe and recyclable lithium-ion capacitors using sacrificial organic lithium salt.

PubMed

Jeżowski, P; Crosnier, O; Deunf, E; Poizot, P; Béguin, F; Brousse, T

2018-02-01

Lithium-ion capacitors (LICs) shrewdly combine a lithium-ion battery negative electrode capable of reversibly intercalating lithium cations, namely graphite, together with an electrical double-layer positive electrode, namely activated carbon. However, the beauty of this concept is marred by the lack of a lithium-cation source in the device, thus requiring a specific preliminary charging step. The strategies devised thus far in an attempt to rectify this issue all present drawbacks. Our research uncovers a unique approach based on the use of a lithiated organic material, namely 3,4-dihydroxybenzonitrile dilithium salt. This compound can irreversibly provide lithium cations to the graphite electrode during an initial operando charging step without any negative effects with respect to further operation of the LIC. This method not only restores the low CO 2 footprint of LICs, but also possesses far-reaching potential with respect to designing a wide range of greener hybrid devices based on other chemistries, comprising entirely recyclable components.

METHOD FOR PRODUCING ISOTOPIC METHANES FROM LITHIUM CARBONATE AND LITHIUM HYDRIDE

DOEpatents

Frazer, J.W.

1959-10-27

A process is descrlbed for the production of methane and for the production of methane containing isotopes of hydrogen and/or carbon. Finely divided lithium hydrlde and litldum carbonate reactants are mixed in intimate contact and subsequently compacted under pressures of from 5000 to 60,000 psl. The compacted lithium hydride and lithium carbenate reactunts are dispised in a gas collecting apparatus. Subsequently, the compact is heated to a temperature in the range 350 to 400 deg C whereupon a solid-solid reaction takes place and gaseous methane is evolved. The evolved methane is contaminated with gaseous hydrogen and a very small amount of CO/sub 2/; however, the desired methane product is separated from sald impurities by well known chemical processes, e.g., condensation in a cold trap. The product methane contalns isotopes of carbon and hydrogen, the Isotopic composition being determined by the carbon isotopes originally present In the lithium carbonate and the hydrogen isotopes originally present in the lithium hydride.

New promising lithium malonatoborate salts for high voltage lithium ion batteries

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

Sun, Xiao -Guang; Wan, Shun; Guang, Hong Yu

Here, three new lithium salts, lithium difluoro-2-methyl-2-fluoromalonaoborate (LiDFMFMB), lithium difluoro-2-ethyl-2-fluoromalonaoborate (LiDFEFMB), and lithium difluoro-2-propyl-2-fluoro malonaoborate (LiDFPFMB), have been synthesized and evaluated for application in lithium ion batteries. These new salts are soluble in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt.) and 1.0 M salt solutions can be easily prepared. The ionic conductivities of these new salts are close to those of LiBF 4 and LiPF 6. Cyclic voltammograms reveal that these new salt based electrolytes can passivate both natural graphite and high voltage spinel LiNi 0.5Mn 1.5O 4 (LNMO) to form effective solidmore » electrolyte interphases (SEIs). In addition, these new salts based electrolytes exhibit good cycling stability with high coulombic efficiencies in both LiNi 0.5Mn 1.5O 4 and graphite based half-cells and full cells.« less

New promising lithium malonatoborate salts for high voltage lithium ion batteries

DOE PAGES

Sun, Xiao -Guang; Wan, Shun; Guang, Hong Yu; ...

2016-12-01

Here, three new lithium salts, lithium difluoro-2-methyl-2-fluoromalonaoborate (LiDFMFMB), lithium difluoro-2-ethyl-2-fluoromalonaoborate (LiDFEFMB), and lithium difluoro-2-propyl-2-fluoro malonaoborate (LiDFPFMB), have been synthesized and evaluated for application in lithium ion batteries. These new salts are soluble in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt.) and 1.0 M salt solutions can be easily prepared. The ionic conductivities of these new salts are close to those of LiBF 4 and LiPF 6. Cyclic voltammograms reveal that these new salt based electrolytes can passivate both natural graphite and high voltage spinel LiNi 0.5Mn 1.5O 4 (LNMO) to form effective solidmore » electrolyte interphases (SEIs). In addition, these new salts based electrolytes exhibit good cycling stability with high coulombic efficiencies in both LiNi 0.5Mn 1.5O 4 and graphite based half-cells and full cells.« less

Safe and recyclable lithium-ion capacitors using sacrificial organic lithium salt

NASA Astrophysics Data System (ADS)

Jeżowski, P.; Crosnier, O.; Deunf, E.; Poizot, P.; Béguin, F.; Brousse, T.

2018-02-01

Lithium-ion capacitors (LICs) shrewdly combine a lithium-ion battery negative electrode capable of reversibly intercalating lithium cations, namely graphite, together with an electrical double-layer positive electrode, namely activated carbon. However, the beauty of this concept is marred by the lack of a lithium-cation source in the device, thus requiring a specific preliminary charging step. The strategies devised thus far in an attempt to rectify this issue all present drawbacks. Our research uncovers a unique approach based on the use of a lithiated organic material, namely 3,4-dihydroxybenzonitrile dilithium salt. This compound can irreversibly provide lithium cations to the graphite electrode during an initial operando charging step without any negative effects with respect to further operation of the LIC. This method not only restores the low CO2 footprint of LICs, but also possesses far-reaching potential with respect to designing a wide range of greener hybrid devices based on other chemistries, comprising entirely recyclable components.

Lithium Azide as an Electrolyte Additive for All-Solid-State Lithium-Sulfur Batteries.

PubMed

Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Bondarchuk, Oleksandr; Rodriguez-Martinez, Lide M; Zhang, Heng; Armand, Michel

2017-11-27

Of the various beyond-lithium-ion battery technologies, lithium-sulfur (Li-S) batteries have an appealing theoretical energy density and are being intensely investigated as next-generation rechargeable lithium-metal batteries. However, the stability of the lithium-metal (Li°) anode is among the most urgent challenges that need to be addressed to ensure the long-term stability of Li-S batteries. Herein, we report lithium azide (LiN 3 ) as a novel electrolyte additive for all-solid-state Li-S batteries (ASSLSBs). It results in the formation of a thin, compact and highly conductive passivation layer on the Li° anode, thereby avoiding dendrite formation, and polysulfide shuttling. It greatly enhances the cycling performance, Coulombic and energy efficiencies of ASSLSBs, outperforming the state-of-the-art additive lithium nitrate (LiNO 3 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

History of Nebular Processing Traced by Silicate Stardust in IDPS

NASA Technical Reports Server (NTRS)

Messenger, Scott R.; Keller, L. P.; Nakamura-Messenger, K.

2010-01-01

Chondritic porous interplanetary dust particles (CP-IDPs) may be the best preserved remnants of primordial solar system materials, in part because they were not affected by parent body hydrothermal alteration. Their primitive characteristics include fine grained, unequilibrated, anhydrous mineralogy, enrichment in volatile elements, and abundant molecular cloud material and silicate stardust. However, while the majority of CP-IDP materials likely derived from the Solar System, their formation processes and provenance are poorly constrained. Stardust abundances provide a relative measure of the extent of processing that the Solar System starting materials has undergone in primitive materials. For example, among primitive meteorites silicate stardust abundances vary by over two orders of magnitude (less than 10-200 ppm). This range of abundances is ascribed to varying extents of aqueous processing in the meteorite parent bodies. The higher average silicate stardust abundances among CP-IDPs (greater than 375 ppm) are thus attributable to the lack of aqueous processing of these materials. Yet, silicate stardust abundances in IDPs also vary considerably. While the silicate stardust abundance in IDPs having anomalous N isotopic compositions was reported to be 375 ppm, the abundance in IDPs lacking N anomalies is less than 10 ppm. Furthermore, these values are significantly eclipsed among some IDPs with abundances ranging from 2,000 ppm to 10,000 ppm. Given that CP-IDPs have not been significantly affected by parent body processes, the difference in silicate stardust abundances among these IDPs must reflect varying extents of nebular processing. Here we present recent results of a systematic coordinated mineralogical/isotopic study of large cluster IDPs aimed at (1) characterizing the mineralogy of presolar silicates and (2) delineating the mineralogical and petrographic characteristics of IDPs with differing silicate stardust abundances. One of the goals of this study is

Microstructures of Rare Silicate Stardust from Nova and Supernovae

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Rahman, Z.; Messenger, S

2011-01-01

Most silicate stardust analyzed in the laboratory and observed around stellar environments derives from O-rich red giant and AGB stars [1,2]. Supernova (SN) silicates and oxides are comparatively rare, and fewer than 10 grains from no-va or binary star systems have been identified to date. Very little is known about dust formation in these stellar environments. Mineralogical studies of only three O-rich SN [3-5] and no nova grains have been performed. Here we report the microstructure and chemical makeup of two SN silicates and one nova grain.

Direct observation of lithium polysulfides in lithium-sulfur batteries using operando X-ray diffraction

NASA Astrophysics Data System (ADS)

Conder, Joanna; Bouchet, Renaud; Trabesinger, Sigita; Marino, Cyril; Gubler, Lorenz; Villevieille, Claire

2017-06-01

In the on going quest towards lithium-battery chemistries beyond the lithium-ion technology, the lithium-sulfur system is emerging as one of the most promising candidates. The major outstanding challenge on the route to commercialization is controlling the so-called polysulfide shuttle, which is responsible for the poor cycling efficiency of the current generation of lithium-sulfur batteries. However, the mechanistic understanding of the reactions underlying the polysulfide shuttle is still incomplete. Here we report the direct observation of lithium polysulfides in a lithium-sulfur cell during operation by means of operando X-ray diffraction. We identify signatures of polysulfides adsorbed on the surface of a glass-fibre separator and monitor their evolution during cycling. Furthermore, we demonstrate that the adsorption of the polysulfides onto SiO2 can be harnessed for buffering the polysulfide redox shuttle. The use of fumed silica as an electrolyte additive therefore significantly improves the specific charge and Coulombic efficiency of lithium-sulfur batteries.

Silicon K-edge XANES spectra of silicate minerals

NASA Astrophysics Data System (ADS)

Li, Dien; Bancroft, G. M.; Fleet, M. E.; Feng, X. H.

1995-03-01

Silicon K-edge x-ray absorption near-edge structure (XANES) spectra of a selection of silicate and aluminosilicate minerals have been measured using synchrotron radiation (SR). The spectra are qualitatively interpreted based on MO calculation of the tetrahedral SiO{4/4-}cluster. The Si K-edge generally shifts to higher energy with increased polymerization of silicates by about 1.3 eV, but with considerable overlap for silicates of different polymerization types. The substitution of Al for Si shifts the Si K-edge to lower energy. The chemical shift of Si K-edge is also sensitive to cations in more distant atom shells; for example, the Si K-edge shifts to lower energy with the substitution of Al for Mg in octahedral sites. The shifts of the Si K-edge show weak correlation with average Si-O bond distance (dSi-O), Si-O bond valence (sSi-O) and distortion of SiO4 tetrahedra, due to the crystal structure complexity of silicate minerals and multiple factors effecting the x-ray absorption processes.

Io's Volcanism: Thermo-Physical Models of Silicate Lava Compared with Observations of Thermal Emission

NASA Technical Reports Server (NTRS)

Davies, Ashely G.

1996-01-01

Analyses of thermal infrared outbursts from the jovian satellite Io indicate that at least some of these volcanic events are due to silicate lava. Analysis of the January 9, 1990 outburst indicates that this was an active eruption consisting of a large lava flow (with mass eruption rate of order 10(exp 5) cubic m/sec) and a sustained area at silicate liquidus temperatures. This is interpreted as a series of fire fountains along a rift zone. A possible alternative scenario is that of an overflowing lava lake with extensive fire fountaining. The January 9, 1990 event is unique as multispectral observations with respect to time were obtained. In this paper, a model is presented for the thermal energy lost by active and cooling silicate lava flows and lakes on Io. The model thermal emission is compared with Earth-based observations and Voyager IRIS data. The model (a) provides an explanation of the thermal anomalies on Io's surface; (b) provides constraints on flow behavior and extent and infers some flow parameters; and (c) determines flow geometry and change in flow size with time, and the temperature of each part of the flow or lava lake surface as a function of its age. Models of heat output from active lava flows or inactive but recently emplaced lava flows or overturning lava lakes alone are unable to reproduce the observations. If the January 9, 1990 event is the emplacement of a lava flow, the equivalent of 27 such events per year would yield a volume of material sufficient, if uniformly distributed, to resurface all of Io at a rate of 1 cm/year.

Lithium-induced downbeat nystagmus.

PubMed

Schein, Flora; Manoli, Pierre; Cathébras, Pascal

2017-09-01

We report the case of a 76-year old lady under lithium carbonate for a bipolar disorder who presented with a suspected optic neuritis. A typical lithium-induced downbeat nystagmus was observed. Discontinuation of lithium therapy resulted in frank improvement in visual acuity and disappearance of the nystagmus.

Lithium ion cell safety

NASA Astrophysics Data System (ADS)

Tobishima, Shin-ichi; Takei, Koji; Sakurai, Yoji; Yamaki, Jun-ichi

The safety characteristics of recent commercial lithium ion cells are examined in relation to their use for cellular phones. These are prismatic cells with an aluminum cell housing (can) and a 500-600 mA h capacity. They have one of two types of 4-V class cathodes, lithium cobalt oxide (LiCoO 2) or lithium manganese oxide (LiMn 2O 4). This report provides results of the safety tests that we performed on lithium ion cells and outlines our views regarding their safety.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, L.; Jacobsen, S. B.; Sasselov, D. D.

2015-12-01

We propose to use the evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet's rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called "late veneer". The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet's surface, which are crucial for life to occur. Here we build an integrative model of Earth-like planets from the bottom up. Thus the chemical compositions of Earth-like planets could be inferred from their mass-radius relations and their host stars' elemental abundances, and the origins of volatile contents (especially water) on their surfaces could be understood, and thereby shed light on the origins of life on them. This elemental abundance model could be applied to other rocky exoplanets in exoplanet systems.

Self-organization of the earth's biosphere-geochemical or geophysiological?

NASA Technical Reports Server (NTRS)

Schwartzman, David W.; Shore, Steven N.; Volk, Tyler; Mcmenamin, Mark

1994-01-01

We explore the implications of indicating the biosphere's self-organization by the trend over time of the net entropic flow from the Earth's surface, the actual physical boundary of virtually all biotic mass. This flow, derived from the radiative surface entropy budget, is approximately inversely related to the surface temperature when the solar incident flux remains constant. In the geophysiological ('gaian') interpretation, biospheric self-organization has increased with the progressive colonization of the continents and evolutionary developments in the land biota, as a result of surface cooling arising from biotic enhancement of weathering. The key site for this self-organization is at the interface between land and atmosphere, the soil, where carbon is sequestered by its reaction (as carbonic and organic acids) with calcium magnesium silicates. Along with disequilibrium (steady-state) levels of carbon dioxide in the atmosphere, the occurrence of differentiated soil is the critical material evidence for biospheric self-organization, whether it be geophysiological or geochemical (ie., purely result of inorganic reactions). The computed equilibrium levels of carbon dioxide and corresponding equilibrium temperatures in the past are dramatically different from the steady-state levels. With future solar luminosity increase, the biospheric capacity for climatic regulation will decrease, leading to the ending of self-organization some two billion years from now. The Earth's surface will then approach chemical equilibrium with respect to the carbonate-silicate cycle.

SILICATES FOR CORROSION CONTROL IN BUILDING POTABLE WATER SYSTEMS

EPA Science Inventory

Silicates have been used to control the corrosion of drinking water distribution system materials. Previous work has shown that they are particularly useful in reducing the release of zinc from galvanized materials in hot water systems. Negatively charged silicate species were re...

Lithium-air batteries, method for making lithium-air batteries

DOEpatents

Vajda, Stefan; Curtiss, Larry A.; Lu, Jun; Amine, Khalil; Tyo, Eric C.

2016-11-15

The invention provides a method for generating Li.sub.2O.sub.2 or composites of it, the method uses mixing lithium ions with oxygen ions in the presence of a catalyst. The catalyst comprises a plurality of metal clusters, their alloys and mixtures, each cluster consisting of between 3 and 18 metal atoms. The invention also describes a lithium-air battery which uses a lithium metal anode, and a cathode opposing the anode. The cathode supports metal clusters, each cluster consisting of size selected clusters, taken from a range of between approximately 3 and approximately 18 metal atoms, and an electrolyte positioned between the anode and the cathode.

Two-Dimensional Phosphorene-Derived Protective Layers on a Lithium Metal Anode for Lithium-Oxygen Batteries.

PubMed

Kim, Youngjin; Koo, Dongho; Ha, Seongmin; Jung, Sung Chul; Yim, Taeeun; Kim, Hanseul; Oh, Seung Kyo; Kim, Dong-Min; Choi, Aram; Kang, Yongku; Ryu, Kyoung Han; Jang, Minchul; Han, Young-Kyu; Oh, Seung M; Lee, Kyu Tae

2018-05-04

Lithium-oxygen (Li-O 2 ) batteries are desirable for electric vehicles because of their high energy density. Li dendrite growth and severe electrolyte decomposition on Li metal are, however, challenging issues for the practical application of these batteries. In this connection, an electrochemically active two-dimensional phosphorene-derived lithium phosphide is introduced as a Li metal protective layer, where the nanosized protective layer on Li metal suppresses electrolyte decomposition and Li dendrite growth. This suppression is attributed to thermodynamic properties of the electrochemically active lithium phosphide protective layer. The electrolyte decomposition is suppressed on the protective layer because the redox potential of lithium phosphide layer is higher than that of electrolyte decomposition. Li plating is thermodynamically unfavorable on lithium phosphide layers, which hinders Li dendrite growth during cycling. As a result, the nanosized lithium phosphide protective layer improves the cycle performance of Li symmetric cells and Li-O 2 batteries with various electrolytes including lithium bis(trifluoromethanesulfonyl)imide in N,N-dimethylacetamide. A variety of ex situ analyses and theoretical calculations support these behaviors of the phosphorene-derived lithium phosphide protective layer.

Nitrogen solubility in the deep mantle and the origin of Earth's primordial nitrogen budget

NASA Astrophysics Data System (ADS)

Yoshioka, Takahiro; Wiedenbeck, Michael; Shcheka, Svyatoslav; Keppler, Hans

2018-04-01

The solubility of nitrogen in the major minerals of the Earth's transition zone and lower mantle (wadsleyite, ringwoodite, bridgmanite, and Ca-silicate perovskite) coexisting with a reduced, nitrogen-rich fluid phase was measured. Experiments were carried out in multi-anvil presses at 14 to 24 GPa and 1100 to 1800 °C close to the Fe-FeO buffer. Starting materials were enriched in 15N and the nitrogen concentrations in run products were measured by secondary ion mass spectrometry. Observed nitrogen (15N) solubilities in wadsleyite and ringwoodite typically range from 10 to 250 μg/g and strongly increase with temperature. Nitrogen solubility in bridgmanite is about 20 μg/g, while Ca-silicate perovskite incorporates about 30 μg/g under comparable conditions. Partition coefficients of nitrogen derived from coexisting phases are DNwadsleyite/olivine = 5.1 ± 2.1, DNringwoodite/wadsleyite = 0.49 ± 0.29, and DNbridgmanite/ringwoodite = 0.24 (+ 0.30 / - 0.19). Nitrogen solubility in the solid, iron-rich metal phase coexisting with the silicates was also measured and reached a maximum of nearly 1 wt.% 15N at 23 GPa and 1400 °C. These data yield a partition coefficient of nitrogen between iron metal and bridgmanite of DNmetal/bridgmanite ∼ 98, implying that in a lower mantle containing about 1% of iron metal, about half of the nitrogen still resides in the silicates. The high nitrogen solubility in wadsleyite and ringwoodite may be responsible for the low nitrogen concentrations often observed in ultradeep diamonds from the transition zone. Overall, the solubility data suggest that the transition zone and the lower mantle have the capacity to store at least 33 times the mass of nitrogen presently residing in the atmosphere. By combining the nitrogen solubility data in minerals with data on nitrogen solubility in silicate melts, mineral/melt partition coefficients of nitrogen can be estimated, from which the behavior of nitrogen during magma ocean crystallization can

Advanced Micro/Nanostructures for Lithium Metal Anodes

PubMed Central

Zhang, Rui; Li, Nian‐Wu; Cheng, Xin‐Bing; Yin, Ya‐Xia

2017-01-01

Owning to their very high theoretical capacity, lithium metal anodes are expected to fuel the extensive practical applications in portable electronics and electric vehicles. However, unstable solid electrolyte interphase and lithium dendrite growth during lithium plating/stripping induce poor safety, low Coulombic efficiency, and short span life of lithium metal batteries. Lately, varies of micro/nanostructured lithium metal anodes are proposed to address these issues in lithium metal batteries. With the unique surface, pore, and connecting structures of different nanomaterials, lithium plating/stripping processes have been regulated. Thus the electrochemical properties and lithium morphologies have been significantly improved. These micro/nanostructured lithium metal anodes shed new light on the future applications for lithium metal batteries. PMID:28331792

Highly Stable Lithium Metal Batteries Enabled by Regulating the Solvation of Lithium Ions in Nonaqueous Electrolytes.

PubMed

Zhang, Xue-Qiang; Chen, Xiang; Cheng, Xin-Bing; Li, Bo-Quan; Shen, Xin; Yan, Chong; Huang, Jia-Qi; Zhang, Qiang

2018-05-04

Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO 3 ) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiN x O y on a working lithium metal anode with dendrite-free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO 3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first-principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

EFFECT OF SILICATE ON GRAM STAINING AND VIABILITY OF PNEUMOCOCCI AND OTHER BACTERIA

PubMed Central

MacLeod, Colin M.; Roe, Amy S.

1956-01-01

Application of silicate solutions to living or heat-killed pneumococci and to certain "viridans" streptococci causes their conversion from a Gram-positive to a Gram-negative state. The original staining properties can be restored by suspending the silicate-treated bacteria in alkaline solutions of various salts but not by simple washing in water. Living pneumococci and the strains of streptococci whose staining properties are similarly affected are killed when suspended in silicate solutions. In other Gram-positive species silicate causes conversion to Gram negativity but restoration to positivity occurs upon washing in water. In a third group of Gram-positive organisms silicate has no effect on the Gram reaction. The viability of organisms in these two groups is unaffected by silicate under the conditions employed. No effect on staining or viability of Gram-negative bacteria has been observed. The effects of silicate on staining and viability are inhibited by nutrient broth or whole serum but not by purified serum albumin. Lecithin, choline, and other substituted ammonium compounds also inhibit the effects of silicate on pneumococci. PMID:13306854

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.

Carbonation of metal silicates for long-term CO2 sequestration

DOEpatents

Blencoe, James G; Palmer, Donald A; Anovitz, Lawrence M; Beard, James S

2014-03-18

In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

Cathode material for lithium batteries

DOEpatents

Park, Sang-Ho; Amine, Khalil

2013-07-23

A method of manufacture an article of a cathode (positive electrode) material for lithium batteries. The cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material.

Cathode material for lithium batteries

DOEpatents

Park, Sang-Ho; Amine, Khalil

2015-01-13

A method of manufacture an article of a cathode (positive electrode) material for lithium batteries. The cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material.

Initiation of clement surface conditions on the earliest Earth

PubMed Central

Sleep, N. H.; Zahnle, K.; Neuhoff, P. S.

2001-01-01

In the beginning the surface of the Earth was extremely hot, because the Earth as we know it is the product of a collision between two planets, a collision that also created the Moon. Most of the heat within the very young Earth was lost quickly to space while the surface was still quite hot. As it cooled, the Earth's surface passed monotonically through every temperature regime between silicate vapor to liquid water and perhaps even to ice, eventually reaching an equilibrium with sunlight. Inevitably the surface passed through a time when the temperature was around 100°C at which modern thermophile organisms live. How long this warm epoch lasted depends on how long a thick greenhouse atmosphere can be maintained by heat flow from the Earth's interior, either directly as a supplement to insolation, or indirectly through its influence on the nascent carbonate cycle. In both cases, the duration of the warm epoch would have been controlled by processes within the Earth's interior where buffering by surface conditions played little part. A potentially evolutionarily significant warm period of between 105 and 107 years seems likely, which nonetheless was brief compared to the vast expanse of geological time. PMID:11259665

Initiation of clement surface conditions on the earliest Earth.

PubMed

Sleep, N H; Zahnle, K; Neuhoff, P S

2001-03-27

In the beginning the surface of the Earth was extremely hot, because the Earth as we know it is the product of a collision between two planets, a collision that also created the Moon. Most of the heat within the very young Earth was lost quickly to space while the surface was still quite hot. As it cooled, the Earth's surface passed monotonically through every temperature regime between silicate vapor to liquid water and perhaps even to ice, eventually reaching an equilibrium with sunlight. Inevitably the surface passed through a time when the temperature was around 100 degrees C at which modern thermophile organisms live. How long this warm epoch lasted depends on how long a thick greenhouse atmosphere can be maintained by heat flow from the Earth's interior, either directly as a supplement to insolation, or indirectly through its influence on the nascent carbonate cycle. In both cases, the duration of the warm epoch would have been controlled by processes within the Earth's interior where buffering by surface conditions played little part. A potentially evolutionarily significant warm period of between 10(5) and 10(7) years seems likely, which nonetheless was brief compared to the vast expanse of geological time.

Lithium and Pregnancy

MedlinePlus

... best live chat Live Help Fact Sheets Share Lithium Wednesday, 01 November 2017 In every pregnancy, a ... risk. This sheet talks about whether exposure to lithium may increase the risk for birth defects over ...

The Effect of Pressure on Siderophile-Element (Ni, Co, Mo, W, and P) Metal-Silicate Partition Coefficients

NASA Astrophysics Data System (ADS)

Righter, K.; Drake, M. J.

1995-09-01

Quantification of the effect of pressure on siderophile element metal-silicate partition coefficients (D) is essential in modelling the accretion histories of the the Earth and terrestrial planets [1], as metal-silicate equilibria may have been set over a range of pressures [2]. We report siderophile element partition coefficients from metal-silicate equilibrium experiments done at 10 and 15 kb, and 1300 degrees C. These new results show that metal-silicate partition coefficients for Ni (Fig. 1), Co, and P decrease with increasing pressure (at constant T and relative fO(sub)2), while those for Mo and W increase. Experiments were done in a 1/2" piston cylinder apparatus, with T, P and fO(sub)2 controlled and monitored as described in a previous study [3]. Synthetic basalt [see 3] powder, doped with 5 wt% levels of either MoO3, WO3 or apatite, was loaded into Fe54Ni29Co17 or Fe64Ni36 tubing, which was closed either by welding or plugging the open ends with small, tapered caps of the same alloy composition. The samples were quenched after 4 to 6 hrs. The metal and glass in the run products are then analyzed by electron microprobe to obtain a solid metal/liquid silicate (SM/LS) partition coefficient for a given element (D = wt% element in metal/ wt% element in glass). For several experiments, NiS was added as a sulfur source, and thus stabilizing a sulfur-bearing metallic liquid. For these experiments, both solid metal/ liquid silicate and liquid metal/ liquid silicate (LM/LS) partition coefficients are reported (Table 1). In order to isolate the effect of pressure on siderophile element partition coefficients, we have compared our results at high pressures to calculated 1 bar values at the same T and fO(sub)2 as our experiments (based on experiments of [4 - 11]; see results for Ni in Fig. 1; data from [3] and this study). The effect of pressure and other intensive variables on metal-silicate D's can be quantified using the thermodynamically-based relation: lnD (metal/silicate

Improving Ionic Conductivity and Lithium-Ion Transference Number in Lithium-Ion Battery Separators.

PubMed

Zahn, Raphael; Lagadec, Marie Francine; Hess, Michael; Wood, Vanessa

2016-12-07

The microstructure of lithium-ion battery separators plays an important role in separator performance; however, here we show that a geometrical analysis falls short in predicting the lithium-ion transport in the electrolyte-filled pore space. By systematically modifying the surface chemistry of a commercial polyethylene separator while keeping its microstructure unchanged, we demonstrate that surface chemistry, which alters separator-electrolyte interactions, influences ionic conductivity and lithium-ion transference number. Changes in separator surface chemistry, particularly those that increase lithium-ion transference numbers can reduce voltage drops across the separator and improve C-rate capability.

Low Temperature Life-cycle Testing of a Lithium-ion Battery for Low-earth-orbiting Spacecraft

NASA Technical Reports Server (NTRS)

Reid, Concha

2004-01-01

A flight-qualified, lithium-ion (Li-ion) battery developed for the Mars Surveyor Program 2001 lander is undergoing life-testing at low temperature under a low-Earth-orbit (LEO) profile to assess its capability to provide long term energy storage for aerospace missions. NASA has embarked upon an ambitious course to return humans to the moon by 2015-2020 in preparation for robotic and human exploration of Mars and robotic exploration of the moons of outer planets. Li-ion batteries are excellent candidates to provide power and energy storage for multiple aspects of these missions due to their low specific energy, low energy density, and excellent low temperature performance. Laboratory testing of Li-ion technology is necessary in order to assess lifetime, characterize multi-cell battery-level performance under aerospace conditions, and to gauge safety aspects of the technology. Life-cycle testing provides an opportunity to examine battery-level performance and the dynamics of individual cells in the stack over the entire life of the battery. Data generated through this testing will be critical to establish confidence in the technology for its widespread use in manned and unmanned mission. This paper discusses the performance of the 28 volt, 25 ampere-hour battery through 6000 LEO cycles, which corresponds to one year on LEO orbit. Testing is being performed at 0 C and 40% depth-of-discharge. Individual cell behaviors and their effect on the performance of the battery are described. Capacity, impedance, energy efficiency and end-of-discharge voltage at 1000 cycle intervals are reported. Results from this life-testing will help contribute to the database on battery-level performance of aerospace Li-ion batteries and low temperature cycling under LEO conditions.

Fast accretion of the Earth with a late Moon-forming giant impact

PubMed Central

Yu, Gang; Jacobsen, Stein B.

2011-01-01

Constraints on the formation history of the Earth are critical for understanding of planet formation processes. 182Hf-182W chronometry of terrestrial rocks points to accretion of Earth in approximately 30 Myr after the formation of the solar system, immediately followed by the Moon-forming giant impact (MGI). Nevertheless, some N-body simulations and 182Hf-182W and 87Rb-87Sr chronology of some lunar rocks have been used to argue for a later formation of the Moon at 52 to > 100 Myr. This discrepancy is often explained by metal-silicate disequilibrium during giant impacts. Here we describe a model of the 182W isotopic evolution of the accreting Earth, including constraints from partitioning of refractory siderophile elements (Ni, Co, W, V, and Nb) during core formation, which can explain the discrepancy. Our modeling shows that the concentrations of the siderophile elements of the mantle are consistent with high-pressure metal-silicate equilibration in a terrestrial magma ocean. Our analysis shows that the timing of the MGI is inversely correlated with the time scale of the main accretion stage of the Earth. Specifically, the earliest time the MGI could have taken place right at approximately 30 Myr, corresponds to the end of main-stage accretion at approximately 30 Myr. A late MGI (> 52 Myr) requires the main stage of the Earth’s accretion to be completed rapidly in < 10.7 ± 2.5 Myr. These are the two end member solutions and a continuum of solutions exists in between these extremes. PMID:22006299

Lithium compensation for full cell operation

DOEpatents

Xiao, Jie; Zheng, Jianming; Chen, Xilin; Lu, Dongping; Liu, Jun; Jiguang, Jiguang

2016-05-17

Disclosed herein are embodiments of a lithium-ion battery system comprising an anode, an anode current collector, and a layer of lithium metal in contact with the current collector, but not in contact with the anode. The lithium compensation layer dissolves into the electrolyte to compensate for the loss of lithium ions during usage of the full cell. The specific placement of the lithium compensation layer, such that there is no direct physical contact between the lithium compensation layer and the anode, provides certain advantages.

Dual-Layered Film Protected Lithium Metal Anode to Enable Dendrite-Free Lithium Deposition.