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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Phosphorus Equilibria Among Mafic Silicate Phases

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 data also indicate that DXVliQP2O5 decrease in the same order, but DOVLiQP2O5 and DOpx/LiQP205 are likely constant, respectively equal to 0.08(3) and 0.007(4), in contrast, DG1ILiQP205 increases from 0.15(3) to 0.36(10) as garnet becomes majoritic, thus silica-enriched, and may also depend on liquid composition (SiO2, P2O5 and Na2O wt%).

Berlin, Jana↗
NASA NTRS2014

Recycling of Oceanic Lithosphere: Water, fO2 and Fe-isotope Constraints

Spinel peridotite and garnet pyroxenite xenoliths from Hawaii provide important clues about the composition of the oceanic lithosphere, and can be used to assess its contribution to mantle heterogeneity upon recycling. The peridotites have lower bulk H2O (approximately 70-114 ppm) than the MORB source, qualitatively consistent with melt depletion. The garnet pyroxenites (high pressure cumulates) have higher H2O (200-460 ppm, up to 550 ppm accounting for phlogopite) and low H2O/Ce ratios (less than 100). The peridotites have relatively light Fe-isotopes (delta Fe -57 = -0.34 to 0.13) that decrease with increasing depletion, while the pyroxenites are significantly heavier (delta Fe-57 up to 0.3). The observed xenolith, as well as MORB and OIB total Fe-isotope variability is larger that can be explained by existing melting models. The high H2O and low H2O/Ce ratios of pyroxenites are similar to estimates of EM-type OIB sources, while their heavy delta Fe-57 are similar to some Society and Cook-Austral basalts. Therefore, recycling of mineralogically enriched oceanic lithosphere (i.e. pyroxenites) may contribute to OIB sources and mantle heterogeneity. The Fe(3+)/Sigma systematics of these xenoliths also suggest that there might be lateral redox gradients within the lithosphere, between juxtaposed oxidized spinel peridotites (deltaFMQ = -0.7 to 1.6, at 15 kb) and more reduced pyroxenites (deltaFMQ = -2 to -0.4, at 20-25kb). Such mineralogically and compositionally imposed fO2 gradients may generate local redox melting due to changes in fluid speciation (e.g. reduced fluids from pyroxenite encountering more oxidized peridotite). Formation of such incipient, small degree melts could further contribute to metasomatic features seen in peridotites, mantle heterogeneity, as well as the low velocity and high electrical conductivity structures near the base of the lithosphere and upper mantle.

Bizmis, M.↗
NASA NTRS2016

Water in the Cratonic Mantle Lithosphere

The fact that Archean and Proterozoic cratons are underlain by the thickest (>200 km) lithosphere on Earth has always puzzled scientists because the dynamic convection of the surrounding asthenosphere would be expected to delaminate and erode these mantle lithospheric "keels" over time. Although density and temperature of the cratonic lithosphere certainly play a role in its strength and longevity, the role of water has only been recently addressed with data on actual mantle samples. Water in mantle lithologies (primarily peridotites and pyroxenites) is mainly stored in nominally anhydrous minerals (olivine, pyroxene, garnet) where it is incorporated as hydrogen bonded to structural oxygen in lattice defects. The property of hydrolytic weakening of olivine [4] has generated the hypothesis that olivine, the main mineral of the upper mantle, may be dehydrated in cratonic mantle lithospheres, contributing to its strength. This presentation will review the distribution of water concentrations in four cratonic lithospheres. The distribution of water contents in olivine from peridotite xenoliths found in kimberlites is different in each craton (Figure 1). The range of water contents of olivine, pyroxene and garnet at each xenolith location appears linked to local metasomatic events, some of which occurred later then the Archean and Proterozoic when these peridotites initially formed via melting. Although the low olivine water contents (<10 ppm wt H2O) at > 6 GPa at the base of the Kaapvaal cratonic lithosphere may contribute to its strength, and prevent its delamination, the wide range of those from Siberian xenoliths is not compatible with providing a high enough viscosity contrast with the asthenophere. The water content in olivine inclusions from Siberian diamonds, on the other hand, have systematically low water contents (<20 ppm wt H2O). The xenoliths may represent a biased sample of the cratonic lithosphere with an over-­abundance of metasomatized peridotites with high water contents. The olivine inclusions, however, may have been protected from metasomatism by their host diamond and record the overall low olivine water content of the cratonic lithosphere. Water may thus still play a role in cratonic keel longevity.

Peslier, A. H.↗
NASA NTRS2017

Heterogeneity of Water Concentrations in the Mantle Lithosphere Beneath Hawaii

The amount and distribution of water in the oceanic mantle lithosphere has implications on its strength and of the role of volatiles during plume/lithosphere interaction. The latter plays a role in the Earth's deep water cycle as water-rich plume lavas could re-enrich an oceanic lithosphere depleted in water at the ridge, and when this heterogeneous lithosphere gets recycled back into the deep mantle. The main host of water in mantle lithologies are nominally anhydrous minerals like olivine, pyroxene and garnet, where hydrogen (H) is incorporated in mineral defects by bonding to structural oxygen. Here, we report water concentrations by Fourier transform infrared spectrometry (FTIR) on olivine, clino- and orthopyroxenes (Cpx & Opx) from spinel peridotites from the Pali vent and garnet pyroxenite xenoliths from Aliamanu vent, both part of the rejuvenated volcanism at Oahu (Hawaii). Pyroxenes from the Aliamanu pyroxenites have high water concentrations, similar to the adjacent Salt Lake Crater (SLC) pyroxenites (Cpx ~400-500 ppm H2O, Opx ~200 ppm H2O). This confirms that pyroxenite cumulates form water-rich lithologies within the oceanic lithosphere. In contrast, the Pali peridotites have much lower water concentrations than the SLC ones (<25 ppm vs. 50-96 ppm H2O respectively) despite being relatively fertile with >10% modal Cpx and low spinel Cr# (0.09-0.10). The contrast between the two peridotite suites is also evident in their trace elements and radiogenic isotopes. The Pali Cpx are depleted in light REE, consistent with minimal metasomatism. Those of SLC have enriched light REE patterns and Nd and Hf isotopes consistent with metasomatism by alkaline melts. These observations are consistent with heterogeneous water distribution in the oceanic lithosphere that may be related to metasomatism, as well as relatively dry peridotites cross-cut by narrow (?) water-rich melt reaction zones.

Bizimis, M.↗
NASA NTRS2017

Water and Metasomatism in the Slave Cratonic Lithosphere (Canada): An FTIR Study

Water in the mantle influences melting, viscosity, seismic velocity, and electrical conductivity. The role played by water in the long-term stabilization of cratonic roots is currently being debated. This study focuses on water contents of mantle minerals (olivine, pyroxene and garnet) from xenoliths found in kimberlites of the Archean Slave craton. 19 mantle xenoliths from central Lac de Gras, and 10 from northern Jericho were analyzed by FTIR for water, and their equilibration depths span the several compositional layers identified beneath the region. At both locations, the shallow peridotites have lower water contents in their olivines (11-30 ppm H2O) than those from the deeper layers (28-300 ppm H2O). The driest olivines, however, are not at the base of the cratonic lithosphere (>6 GPa) as in the Kaapvaal craton. Instead, the deepest olivines are hydrous (31-72 ppm H2O at Lac de Gras and 275 ppm H2O at Jericho). Correlations of water in clinopyroxene and garnet with their other trace element contents are consistent with water being added by metasomatism by melts resembling kimberlite precursors in the mantle approx.0.35 Ga ago beneath Lac de Gras. The northern Jericho xenoliths are derived from a region of the Slave craton that is even more chemically stratified, and was affected at depth by the 1.27 Ga Mackenzie igneous events. Metasomatism at Jericho may be responsible for the particularly high olivine water contents (up to 300 ppm H2O) compared to those at Lac de Gras, which will be investigated by acquiring trace-element data on these xenoliths. These data indicate that several episodes of metasomatic rehydration occurred in the deep part of the Slave craton mantle lithosphere, with the process being more intense in the northern part beneath Jericho, likely related to a translithospheric suture serving as a channel to introduce fluids and/or melts in the northern region. Consequently, rehydration of the lithosphere does not necessarily cause cratonic root delamination and these peridotites may represent localized metasomatic zones - the wall rocks to kimberlite magma passage.

Kilgore, McKensie↗
NASA NTRS2017

Dynamic Control of Refractive Index During Pulsed-Laser-Deposited Waveguide Growth

Engineering the optical properties of waveguides is important for the optimization of their guided optical mode characteristics. Here, we document the dynamic control of the refractive index and composition of crystalline films, via the substrate temperature, during pulsed-laser-deposition growth of Er(1%)-doped yttrium gallium garnet on <100>-orientated single-crystal yttrium aluminium garnet. An increasing substrate temperature is observed to reduce the gallium content in the grown film, with a corresponding reduction of refractive index. We demonstrate the ability to accurately control the refractive index via this technique and use it to grow a complex multi-core crystal waveguide. Our results highlight the potential of using pulsed laser deposition to fabricate crystal films with bespoke optical properties and thus engineer passive and active waveguide devices in situ.

Temperature↗
DOE OSTI2023

Optimizing the tuning range of the Fermilab Recycler 53MHz RF cavities by exploiting the avoided crossing of the tuner and cavity modes

The electromagnetic eigenmodes of the Fermilab Recycler RF cavities were simulated with ACE3P running on NERSC's 'Perlmutter' supercomputer in an attempt to optimize their tuning range to comfortably support slip-stacking. A theory, based on coupled circuits and avoided crossings, was developed to explain the origins of the tuning range for tuner-cavity waveguide systems. This provided a logical, rigorous method to carry out this optimization, although engineering problems due to high voltages in the tuner and the operational $\mu$ range of the garnet had to be carefully implemented. It was shown that the desired goal of 10kHz of tuning was not attainable with the current cavity specifications. The maximum tuning range obtained was 5.59kHz for a single tuner with a coaxial line of length 63in. A double tuner cavity was also studied using the simulation software, although with little improvement in the tuning range. A promising technique to improve the tuning range involving the desynchronization of the garnets' magnetic permeabilities is proposed.

43 PARTICLE ACCELERATORS↗
DOE OSTI2025

Pristine Interface between Lithium Lanthanum Zirconate and Lithium Manganese Oxide by Pulsed Laser Deposition

Solid state lithium-ion batteries have garnered increasing interest in recent years due to several potential advantages over liquid-electrolyte based systems. The possibility of integrating the lithium garnet oxide, Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO), with the high voltage cathode, spinel Li x Mn 2 O 4 (LMO), is evaluated here. Thin film bilayer structures are prepared by pulsed laser deposition on MgO (001) substrates and characterized by x-ray diffraction and transmission electron microscopy. The LLZTO is grown by an alternating layer-by-layer deposition of LLZTO and Li 3 N and subsequently annealed for several hours at 575 °C to promote crystallinity. Growth of crystalline LMO with a pristine interface to LLZTO is achieved by gentle heat treatment (500 °C) to remove surface carbonate from the electrolyte and by cathode growth at a low temperature of 250 °C. Higher temperature depositions (330 – 450 °C) result in reaction between the two materials and the appearance of Li 2 MnO 3 , which may be in part due to the presence of excess lithium in the electrolyte layer. Because fully lithiated LiMn 2 O 4 has a voltage of ≈3.7 V versus Li+/Li, the observation of a well-defined interface, free of impurity phases and with no interdiffusion of elements, indicates LLZTO is stable to at least 3.7 V.

Garnet LLZO↗
DOE OSTI2021

Spin waves in YIG based magnonic networks: Design and technological aspects

Microwaveguides for spin waves based on yttrium iron garnet films and cross-like structures built on such waveguides are experimentally studied. Additionally, effects of the waveguides geometry, location of the microantennas for excitation and detection of the spin waves, and geometry of the waveguides junctions on the spin wave excitation and propagation efficiency are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Molten Lithium-Brass/Zinc Chloride System as High-Performance and Low-Cost Battery

Batteries with high safety, low cost, and reasonable energy density are essential for grid-scale energy storage and still remain elusive. In this paper, we report a solid electrolyte-based liquid lithium-brass/zinc chloride (SELL-brass/ZnCl 2 ) battery using garnet-type lithium-ion solid electrolyte, lithium anode, and brass/ZnCl 2 cathode. The chemistry of the cell reaction and the ability of being assembled in discharged state ensures a high safety. The use of low-cost ZnCl 2 cathode can realize a low cell material cost of $16 kWh –1 . The adoption of lithium anode guarantees a high theoretical energy density of 750 Wh kg –1 and 2,250 Wh L –1 . Moreover, by using brass powder as a Zn source in the cathode, the Zn particle growth issue is successfully solved, and a good cycling stability of the battery can be obtained. As full cell performance and scalability are also verified, our SELL-brass/ZnCl 2 battery shows a high potential for practical use in grid energy storage.

25 ENERGY STORAGE↗
DOE OSTI2020

Effect of Liquid Electrolyte Soaking on the Interfacial Resistance of Li 7 La 3 Zr 2 O 1 2 for All-Solid-State Lithium Batteries

In this work, the impact of liquid electrolyte soaking on the interfacial resistance between the garnet-structured Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte and metallic lithium has been studied. Lithium carbonate (Li 2 CO 3 ) formed by inadvertent exposure of LLZO to ambient conditions is generally known to increase interfacial impedance and decrease lithium wettability. Soaking LLZO powders and pellets in the electrolyte containing lithium tetrafluoroborate (LiBF 4 ) shows a significantly reduced interfacial resistance and improved contact between lithium and LLZO. Raman spectroscopy, X-ray diffraction, and soft X-ray absorption spectroscopy reveal how Li 2 CO 3 is continuously removed with increasing soaking time. On-line mass spectrometry and free energy calculations show how LiBF 4 reacts with surface carbonate to form carbon dioxide. Using a very simple and scalable process that does not involve heat-treatment and expensive coating techniques, we show that the Li–LLZO interfacial resistance can be reduced by an order of magnitude.

25 ENERGY STORAGE↗
DOE OSTI2020

Inhomogeneous broadening and splitting of lines in spectra of YAG : Tm

The shape and fine structure of lines due to Tm{sup 3+} f −f electronic transitions in multifunctional Y{sub 3}Al{sub 5}O{sub 12} garnet crystals have been studied by high-resolution spectroscopy. The observed inhomogeneously broadened lines have a Lorentzian shape, suggesting that point defects make a predominant contribution to the inhomogeneous broadening. Moreover, Y{sub Al} antisite defects, which are formed during high-temperature melt growth, produce spectral satellites near the main lines. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1963

The satellite ferrimagnetic power limiter

To limit the 4080-mc local oscillator signal power input to the beat oscillator modulator of the Telstar satellite communications repeater, a subsidiary absorption limiter was used which consisted of an optically polished sphere of single-crystal yttrium iron garnet (YIG), placed in a resonant transmission cavity between the amplified 4080-mc output of the traveling-wave tube and the BO modulator input. The limiter holds the output power nearly constant above a given input threshold; below this threshold the YIG is linear and introduces only a small loss. The threshold is determined, for a given sample at a given frequency, by the external magnetic bias field. Temperature compensation over the desired range was obtained by orienting the crystal with the dc magnetic field along a [100] or “hard” axis. The total weight of the limiter package, including the bias magnet and cavity, is 13 ounces.

YTTRIUM-IRON GARNET /YIG/ CRYSTAL↗
DOE OSTI2023

A Guideline to Mitigate Interfacial Degradation Processes in Solid‐State Batteries Caused by Cross Diffusion

Abstract Diffusion of transition metals across the cathode–electrolyte interface is identified as a key challenge for the practical realization of solid‐state batteries. This is related to the formation of highly resistive interphases impeding the charge transport across the materials. Herein, the hypothesis that formation of interphases is associated with the incorporation of Co into the Li 7 La 3 Zr 2 O 12 lattice representing the starting point of a cascade of degradation processes is investigated. It is shown that Co incorporates into the garnet structure preferably four‐fold coordinated as Co 2+ or Co 3+ depending on oxygen fugacity. The solubility limit of Co is determined to be around 0.16 per formula unit, whereby concentrations beyond this limit causes a cubic‐to‐tetragonal phase transition. Moreover, the temperature‐dependent Co diffusion coefficient is determined, for example, D 700 °C = 9.46 × 10 −14 cm 2 s −1 and an activation energy E a = 1.65 eV, suggesting that detrimental cross diffusion will take place at any relevant process condition. Additionally, the optimal protective Al 2 O 3 coating thickness for relevant temperatures is studied, which allows to create a process diagram to mitigate any degradation with a minimum compromise on electrochemical performance. This study provides a tool to optimize processing conditions toward developing high energy density solid‐state batteries.

Chemistry↗