Rocksalt or cesium chloride: Investigating the relative stability of the cesium halide structures with random phase approximation based methods

NASA Astrophysics Data System (ADS)

Nepal, Niraj K.; Ruzsinszky, Adrienn; Bates, Jefferson E.

2018-03-01

The ground state structural and energetic properties for rocksalt and cesium chloride phases of the cesium halides were explored using the random phase approximation (RPA) and beyond-RPA methods to benchmark the nonempirical SCAN meta-GGA and its empirical dispersion corrections. The importance of nonadditivity and higher-order multipole moments of dispersion in these systems is discussed. RPA generally predicts the equilibrium volume for these halides within 2.4% of the experimental value, while beyond-RPA methods utilizing the renormalized adiabatic LDA (rALDA) exchange-correlation kernel are typically within 1.8%. The zero-point vibrational energy is small and shows that the stability of these halides is purely due to electronic correlation effects. The rAPBE kernel as a correction to RPA overestimates the equilibrium volume and could not predict the correct phase ordering in the case of cesium chloride, while the rALDA kernel consistently predicted results in agreement with the experiment for all of the halides. However, due to its reasonable accuracy with lower computational cost, SCAN+rVV10 proved to be a good alternative to the RPA-like methods for describing the properties of these ionic solids.

Study on influence of growth conditions on position and shape of crystal/melt interface of alkali lead halide crystals at Bridgman growth

NASA Astrophysics Data System (ADS)

Král, Robert

2012-12-01

Suitable conditions for growth of high quality single crystals of ternary alkali lead halides prepared by a Bridgman method were explored using direct observation of a crystal/melt interface when pulling an ampoule out of a furnace, deliberated striations' induction and measurement of a temperature field in the filled ampoule in the vertical Bridgman arrangement, as model compounds lead chloride and ternary rubidium lead bromide were used. By direct observation only position of the crystal/melt interface was markedly determined, while by induced striations both the position and the shape of the interface were visualized but their contrast had to be intensified by adding admixtures. Performed temperature measurements in the filled ampoule brought both a view of temperature field in the 3D radial symmetry and basic data for comparison of a real temperature field with those obtained by projected modeling.

Fabrication of Low-Loss Halide Glass Fibers.

DTIC Science & Technology

1985-09-01

chalcogenides, have some merit. Well known, also are the polycrystalline halide materials such as KRS-5, TlBr , *TlI and AgCl and their single...tension of the melt zone is high enough to *" eliminate sagging in the fibers. Using this technique, ( TlBr )I (KRS-5), TlBr , CuCl, AgCl, and AgBr have

Phase Segregation in Potassium-Doped Lead Halide Perovskites from 39K Solid-State NMR at 21.1 T.

PubMed

Kubicki, Dominik J; Prochowicz, Daniel; Hofstetter, Albert; Zakeeruddin, Shaik M; Grätzel, Michael; Emsley, Lyndon

2018-06-13

Organic-inorganic lead halide perovskites are a promising family of light absorbers for a new generation of solar cells, with reported efficiencies currently exceeding 22%. A common problem of solar cells fabricated using these materials is that their efficiency depends on their cycling history, an effect known as current-voltage ( J- V) hysteresis. Potassium doping has recently emerged as a universal way to overcome this adverse phenomenon. While the atomistic origins of J- V hysteresis are still not fully understood, it is essential to rationalize the atomic-level effect of protocols that lead to its suppression. Here, using 39 K MAS NMR at 21.1 T we provide for the first time atomic-level characterization of the potassium-containing phases that are formed upon KI doping of multication and multianion lead halide perovskites. We find no evidence of potassium incorporation into 3D perovskite lattices of the recently reported materials. Instead, we observe formation of a mixture of potassium-rich phases and unreacted KI. In the case of Br-containing lead halide perovskites doped with KI, a mixture of KI and KBr ensues, leading to a change in the Br/I ratio in the perovskite phase with respect to the undoped perovskite. Simultaneous Cs and K doping leads to the formation of nonperovskite Cs/K lead iodide phases.

Octahedral tilting instabilities in inorganic halide perovskites

NASA Astrophysics Data System (ADS)

Bechtel, Jonathon S.; Van der Ven, Anton

2018-02-01

Dynamic instabilities, stabilized by anharmonic interactions in cubic and tetragonal halide perovskites at high temperature, play a role in the electronic structure and optoelectronic properties of halide perovskites. In particular, inorganic and hybrid perovskite materials undergo structural phase transitions associated with octahedral tilts of the metal-halide octahedra. We investigate the structural instabilities present in inorganic Cs M X3 perovskites with Pb or Sn on the metal site and Br or I on the X site. Defining primary order parameters in terms of symmetry-adapted collective displacement modes and secondary order parameters in terms of symmetrized Hencky strain components, we unravel the coupling between octahedral tilt modes and macroscopic strains as well as the role of A -site displacements in perovskite phase stability. Symmetry-allowed secondary strain order parameters are enumerated for the 14 unique perovskite tilt systems. Using first-principles calculations to explore the Born-Oppenheimer energy surface in terms of symmetrized order parameters, we find coupling between octahedral tilting and A -site displacements is necessary to stabilize P n m a ground states. Additionally, we show that the relative stability of an inorganic halide perovskite tilt system correlates with the volume decrease from the high-symmetry cubic phase to the low-symmetry distorted phase.

High salinity volatile phases in magmatic Ni-Cu-platinum group element deposits

NASA Astrophysics Data System (ADS)

Hanley, J. J.; Mungall, J. E.

2004-12-01

The role of "deuteric" fluids (exsolved magmatic volatile phases) in the development of Ni-Cu-PGE (platinum group element) deposits in mafic-ultramafic igneous systems is poorly understood. Although considerable field evidence demonstrates unambiguously that fluids modified most large primary Ni-Cu-PGE concentrations, models which hypothesize that fluids alone were largely responsible for the economic concentration of the base and precious metals are not widely accepted. Determination of the trace element composition of magmatic volatile phases in such ore-forming systems can offer considerable insight into the origin of potentially mineralizing fluids in such igneous environments. Laser ablation ICP-MS microanalysis allows researchers to confirm the original metal budget of magmatic volatile phases and quantify the behavior of trace ore metals in the fluid phase in the absence of well-constrained theoretical or experimental predictions of ore metal solubility. In this study, we present new evidence from major deposits (Sudbury, Ontario, Canada; Stillwater Complex, Montana, U.S.A.) that compositionally distinct magmatic brines and halide melt phases were exsolved from crystallizing residual silicate melt and trapped within high-T fluid conduits now comprised of evolved rock compositions (albite-quartz graphic granite, orthoclase-quartz granophyre). Petrographic evidence demonstrates that brines and halide melts coexisted with immiscible carbonic phases at the time of entrapment (light aliphatic hydrocarbons, CO2). Brine and halide melt inclusions are rich in Na, Fe, Mn, K, Pb, Zn, Ba, Sr, Al and Cl, and homogenize by either halite dissolution at high T ( ˜450-700° C) or by melting of the salt phase (700-800° C). LA-ICPMS analyses of single inclusions demonstrate that high salinity volatile phases contained abundant base metals (Cu, Fe, Sn, Bi) and precious metals (Pt, Pd, Au, Ag) at the time of entrapment. Notably, precious metal concentrations in the inclusions

Phase recording for formation of holographic optical elements on silver-halide photographic emulsions

NASA Astrophysics Data System (ADS)

Ganzherli, Nina M.; Gulyaev, Sergey N.; Maurer, Irina A.; Chernykh, Dmitrii F.

2009-05-01

Holographic fabrication methods of regular and nonregular relief-phase structures on silver-halide photographic emulsions are considered. Methods of gelatin photodestruction under short-wave ultra-violet radiation and chemical hardening with the help of dichromated solutions were used as a technique for surface relief formation. The developed techniques permitted us to study specimens of holographic diffusers and microlens rasters with small absorption and high light efficiency.

Liquid-liquid phase transformations and the shape of the melting curve.

PubMed

Makov, G; Yahel, E

2011-05-28

The phase diagram of elemental liquids has been found to be surprisingly rich, including variations in the melting curve and transitions in the liquid phase. The effect of these transitions in the liquid state on the shape of the melting curve is analyzed. First-order phase transitions intersecting the melting curve imply piecewise continuous melting curves, with solid-solid transitions generating upward kinks or minima and liquid-liquid transitions generating downward kinks or maxima. For liquid-liquid phase transitions proposed for carbon, phosphorous selenium, and possibly nitrogen, we find that the melting curve exhibits a kink. Continuous transitions imply smooth extrema in the melting curve, the curvature of which is described by an exact thermodynamic relation. This expression indicates that a minimum in the melting curve requires the solid compressibility to be greater than that of the liquid, a very unusual situation. This relation is employed to predict the loci of smooth maxima at negative pressures for liquids with anomalous melting curves. The relation between the location of the melting curve maximum and the two-state model of continuous liquid-liquid transitions is discussed and illustrated by the case of tellurium. © 2011 American Institute of Physics

Formation of random and regular relief-phase structures on silver halide photographic emulsions by holographic methods

NASA Astrophysics Data System (ADS)

Ganzherli, N. M.; Gulyaev, S. N.; Gurin, A. S.; Kramushchenko, D. D.; Maurer, I. A.; Chernykh, D. F.

2009-07-01

The formation of diffusers and microlens rasters on silver halide emulsions by holographic methods is considered. Two techniques for converting amplitude holographic recording to relief-phase recording, selective curing and irradiation of the emulsion gelatin by short-wavelength UV radiation, are compared.

Mixed-Halide Perovskites with Stabilized Bandgaps.

PubMed

Xiao, Zhengguo; Zhao, Lianfeng; Tran, Nhu L; Lin, Yunhui Lisa; Silver, Scott H; Kerner, Ross A; Yao, Nan; Kahn, Antoine; Scholes, Gregory D; Rand, Barry P

2017-11-08

One merit of organic-inorganic hybrid perovskites is their tunable bandgap by adjusting the halide stoichiometry, an aspect critical to their application in tandem solar cells, wavelength-tunable light emitting diodes (LEDs), and lasers. However, the phase separation of mixed-halide perovskites caused by light or applied bias results in undesirable recombination at iodide-rich domains, meaning open-circuit voltage (V OC ) pinning in solar cells and infrared emission in LEDs. Here, we report an approach to suppress halide redistribution by self-assembled long-chain organic ammonium capping layers at nanometer-sized grain surfaces. Using the stable mixed-halide perovskite films, we are able to fabricate efficient and wavelength-tunable perovskite LEDs from infrared to green with high external quantum efficiencies of up to 5%, as well as linearly tuned V OC from 1.05 to 1.45 V in solar cells.

Regeneration of zinc halide catalyst used in the hydrocracking of polynuclear hydrocarbons

DOEpatents

Gorin, Everett

1978-01-01

Improved recovery of spent molten zinc halide hydro-cracking catalyst is achieved in the oxidative vapor phase regeneration thereof by selective treatment of the zinc oxide carried over by the effluent vapors from the regeneration zone with hydrogen halide gas under conditions favoring the reaction of the zinc oxide with the hydrogen halide, whereby regenerated zinc halide is recovered in a solids-free state with little loss of zinc values.

Silicate and Carbonatite Melts in the Mantle: Adding CO2 to the pMELTS Thermodynamic Model of Silicate Phase Equilibria

NASA Astrophysics Data System (ADS)

Antoshechkina, P. M.; Shorttle, O.

2016-12-01

The current rhyolite-MELTS algorithm includes a mixed H2O-CO2 vapor phase, and a self-consistent speciation model for CO2 and CaCO3 in the silicate liquid (Ghiorso & Gualda 2012; 2015). Although intended primarily to model crustal differentiation and degassing, GG15 captures much of the experimentally-observed melting behavior of CO2-rich mafic lithologies, including generation of small-degree carbonatite melts, a miscibility gap between carbonatite and silicate liquids at low P and a smooth transition to a single carbonated-silicate melt at high P (e.g. Dasgupta et al. 2007). However, solid and liquid carbonate phases were not used in calibration of GG15, and it is suitable only for P < 3 GPa. We present a preliminary model, based on pMELTS (Ghiorso et al. 2002), for melting of nominally-anhydrous carbonated peridotite and pyroxenite. In Antoshechkina et al. (2015; and references therein) we developed a scheme for calibration of molar volumes that directly interfaces with a MySQL database, adapted from LEPR (Hirschmann et al. 2008). Here, we further extend our database, e.g. to include multiple carbonate phases, and combine the calibration scheme with the libalphaMELTS interface to the rhyolite-MELTS, pMELTS, and H2O-CO2 fluid thermodynamic models (see magmasource.caltech.edu/alphamelts). We use a Monte-Carlo type calibration approach to fit the observed phases and compositions, though stop short of a fully Bayesian formulation. The CO2-fluid experimental database has been updated to include more recent and higher P studies, adding approximately 40 pure fluid plus liquid constraints that conform to the selection criteria used in GG15. To further expand the database, we plan to use some or all of: solid carbonate-bearing experiments; coexisting silicate and carbonatite liquids; phase-present, and phase-absent constraints. As a first approximation, we include four carbonate phases: pure calcite and aragonite, and binary solutions for dolomite-ankerite and magnesite

Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals

PubMed Central

2018-01-01

We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic–inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX3 NCs (in which A = Cs+, CH3NH3+, or CH(NH2)2+). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions. PMID:29378131

Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals.

PubMed

Imran, Muhammad; Caligiuri, Vincenzo; Wang, Mengjiao; Goldoni, Luca; Prato, Mirko; Krahne, Roman; De Trizio, Luca; Manna, Liberato

2018-02-21

We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic-inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX 2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX 3 NCs (in which A = Cs + , CH 3 NH 3 + , or CH(NH 2 ) 2 + ). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX 3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI 3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX 3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions.

Microgravity Studies of Liquid-Liquid Phase Transitions in Alumina-Yttria Melts

NASA Technical Reports Server (NTRS)

Guynes, Buddy (Technical Monitor); Weber, Richard; Nordine, Paul

2004-01-01

The scientific objective of this research is to increase the fundamental knowledge base for liquid- phase processing of technologically important oxide materials. The experimental objective is to define conditions and hardware requirements for microgravity flight experiments to test and expand the experimental hypotheses that: 1. Liquid phase transitions can occur in undercooled melts by a diffusionless process. 2. Onset of the liquid phase transition is accompanied by a large change in the temperature dependence of melt viscosity. Experiments on undercooled YAG (Y3A15012)- and rare earth oxide aluminate composition liquids demonstrated a large departure from an Arrhenian temperature dependence of viscosity. Liquid YAG is nearly inviscid at its 2240 K melting point. Glass fibers were pulled from melts undercooled by ca. 600 K indicating that the viscosity is on the order of 100 Pans (1000 Poise) at 1600 K. This value of viscosity is 500 times greater than that obtained by extrapolation of data for temperatures above the melting point of YAG. These results show that the liquids are extremely fragile and that the onset of the highly non-Arrhenian viscosity-temperature relationship occurs at a temperature considerably below the equilibrium melting point of the solid phases. Further results on undercooled alumina-yttria melts containing 23-42 mole % yttrium oxide indicate that a congruent liquid-liquid phase transition occurs in the undercooled liquids. The rates of transition are inconsistent with a diffusion-limited process. This research is directed to investigation of the scientifically interesting phenomena of polyamorphism and fragility in undercooled rare earth oxide aluminum oxide liquids. The results bear on the technologically important problem of producing high value rare earth-based optical materials.

Phase holograms in silver halide emulsions without a bleaching step

NASA Astrophysics Data System (ADS)

Belendez, Augusto; Madrigal, Roque F.; Pascual, Inmaculada V.; Fimia, Antonio

2000-03-01

Phase holograms in holographic emulsions are usually obtained by two bath processes (developing and bleaching). In this work we present a one step method to reach phase holograms with silver-halide emulsions. Which is based on the variation of the conditions of the typical developing processes of amplitude holograms. For this, we have used the well-known chemical developer, AAC, which is composed by ascorbic acid as a developing agent and sodium carbonate anhydrous as accelerator. Agfa 8E75 HD and BB-640 plates were used to obtain these phase gratings, whose colors are between yellow and brown. In function of the parameters of this developing method the resulting diffraction efficiency and optical density of the diffraction gratings were studied. One of these parameters studied is the influence of the grain size. In the case of Agfa plates diffraction efficiency around 18% with density < 1 has been reached, whilst with the BB-640 emulsion, whose grain is smaller than that of the Agfa, diffraction efficiency near 30% has been obtained. The resulting gratings were analyzed through X-ray spectroscopy showing the differences of the structure of the developed silver when amplitude and transmission gratings are obtained. The angular response of both (transmission and amplitude) gratings were studied, where minimal transmission is showed at the Braggs angle in phase holograms, whilst a maximal value is obtained in amplitude gratings.

Defect-induced local variation of crystal phase transition temperature in metal-halide perovskites.

PubMed

Dobrovolsky, Alexander; Merdasa, Aboma; Unger, Eva L; Yartsev, Arkady; Scheblykin, Ivan G

2017-06-26

Solution-processed organometal halide perovskites are hybrid crystalline semiconductors highly interesting for low-cost and efficient optoelectronics. Their properties are dependent on the crystal structure. Literature shows a variety of crystal phase transition temperatures and often a spread of the transition over tens of degrees Kelvin. We explain this inconsistency by demonstrating that the temperature of the tetragonal-to-orthorhombic phase transition in methylammonium lead triiodide depends on the concentration and nature of local defects. Phase transition in individual nanowires was studied by photoluminescence microspectroscopy and super-resolution imaging. We propose that upon cooling from 160 to 140 K, domains of the crystal containing fewer defects stay in the tetragonal phase longer than highly defected domains that readily transform to the high bandgap orthorhombic phase at higher temperatures. The existence of relatively pure tetragonal domains during the phase transition leads to drastic photoluminescence enhancement, which is inhomogeneously distributed across perovskite microcrystals.Understanding crystal phase transition in materials is of fundamental importance. Using luminescence spectroscopy and super-resolution imaging, Dobrovolsky et al. study the transition from the tetragonal to orthorhombic crystal phase in methylammonium lead triiodide nanowires at low temperature.

Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

NASA Technical Reports Server (NTRS)

Schlosser, Herbert

1992-01-01

In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

Thick phase holographic gratings recorded on BB-640 and PFG-01 silver halide materials

NASA Astrophysics Data System (ADS)

Neipp, Cristian; Márquez, Andrés; Pascual, Inmaculada; Beléndez, Augusto

2003-09-01

Photographic emulsions are still widely used to record holographic optical elements. In particular, if high diffraction efficiencies are needed, phase volume holograms are preferably recorded on these emulsions. Two particular techniques producing high-quality volume phase holograms are fixation-free rehalogenating bleaching and the use of silver-halide-sensitized gelatin. In this work we compare these two particular techniques applied to three different red-sensitive emulsions: Agfa 8E75 HD, BB-640, and Slavich PFG-01 emulsions. The differences between these emulsions determine the particular experimental conditions needed to record high-quality volume holograms on them. In this work these differences are analysed, and also their influence on the experimental procedure.

Shock-induced superheating and melting curves of geophysically important minerals

NASA Astrophysics Data System (ADS)

Luo, Sheng-Nian; Ahrens, Thomas J.

2004-06-01

Shock-state temperature and sound-speed measurements on crystalline materials, demonstrate superheating-melting behavior distinct from equilibrium melting. Shocked solid can be superheated to the maximum temperature, Tc'. At slightly higher pressure, Pc, shock melting occurs, and induces a lower shock temperature, Tc. The Hugoniot state, ( Pc, Tc), is inferred to lie along the equilibrium melting curve. The amount of superheating achieved on Hugoniot is, ΘH+= Tc'/ Tc-1. Shock-induced superheating for a number of silicates, alkali halides and metals agrees closely with the predictions of a systematic framework describing superheating at various heating rates [Appl. Phys. Lett. 82 (12) (2003) 1836]. High-pressure melting curves are constructed by integration from ( Pc, Tc) based on the Lindemann law. We calculate the volume and entropy changes upon melting at ( Pc, Tc) assuming the R ln 2 rule ( R is the gas constant) for the disordering entropy of melting [J. Chem. Phys. 19 (1951) 93; Sov. Phys. Usp. 117 (1975) 625; Poirier, J.P., 1991. Introduction to the Physics of the Earth's Interior. Cambridge University Press, Cambridge, 102 pp.]. ( Pc, Tc) and the Lindemann melting curves are in excellent accord with diamond-anvil cell (DAC) results for NaCl, KBr and stishovite. But significant discrepancies exist for transition metals. If we extrapolate the DAC melting data [Phys. Rev. B 63 (2001) 132104] for transition metals (Fe, V, Mo, W and Ta) to 200-400 GPa where shock melting occurs, shock temperature measurement and calculation would indicate ΘH+˜0.7-2.0. These large values of superheating are not consistent with the superheating systematics. The discrepancies could be reconciled by possible solid-solid phase transitions at high pressures. In particular, this work suggests that Fe undergoes a possible solid-solid phase transition at ˜200 GPa and melts at ˜270 GPa upon shock wave loading, and the melting temperature is ˜6300 K at 330 GPa.

Theoretical Prediction of Melting Relations in the Deep Mantle: the Phase Diagram Approach

NASA Astrophysics Data System (ADS)

Belmonte, D.; Ottonello, G. A.; Vetuschi Zuccolini, M.; Attene, M.

2016-12-01

Despite the outstanding progress in computer technology and experimental facilities, understanding melting phase relations in the deep mantle is still an open challenge. In this work a novel computational scheme to predict melting relations at HP-HT by a combination of first principles DFT calculations, polymer chemistry and equilibrium thermodynamics is presented and discussed. The adopted theoretical framework is physically-consistent and allows to compute multi-component phase diagrams relevant to Earth's deep interior in a broad range of P-T conditions by a convex-hull algorithm for Gibbs free energy minimisation purposely developed for high-rank simplexes. The calculated phase diagrams are in turn used as a source of information to gain new insights on the P-T-X evolution of magmas in the deep mantle, providing some thermodynamic constraints to both present-day and early Earth melting processes. High-pressure melting curves of mantle silicates are also obtained as by-product of phase diagram calculation. Application of the above method to the MgO-Al2O3-SiO2 (MAS) ternary system highlights as pressure effects are not only able to change the nature of melting of some minerals (like olivine and pyroxene) from eutectic to peritectic (and vice versa), but also simplify melting relations by drastically reducing the number of phases with a primary phase field at HP-HT conditions. It turns out that mineral phases like Majorite-Pyrope garnet and Anhydrous Phase B (Mg14Si5O24), which are often disregarded in modelling melting processes of mantle assemblages, are stable phases at solidus or liquidus conditions in a P-T range compatible with the mantle transition zone (i.e. P = 16 - 23 GPa and T = 2200 - 2700 °C) when their thermodynamic and thermophysical properties are properly assessed. Financial support to the Senior Author (D.B.) during his stay as Invited Scientist at the Institut de Physique du Globe de Paris (IPGP, Paris) is warmly acknowledged.

Microstructure and hydrogenation properties of a melt-spun non-stoichiometric Zr-based Laves phase alloy

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

Zhang, Tiebang, E-mail: tiebangzhang@nwpu.edu.cn; Zhang, Yunlong; Li, Jinshan

2016-01-15

Alloy with composition of Zr{sub 0.9}Ti{sub 0.1}V{sub 1.7} off normal stoichiometric proportion is selected to investigate the effect of defects introduced by non-stoichiometry on hydrogenation kinetics of Zr–Ti–V Laves phase alloys. Microstructure and phase constituent of melt-spun ribbons have been investigated in this work. The activation process, hydrogenation kinetics, thermodynamics characteristics and hydride phase constituent of as-cast alloy and melt-spun ribbons are also compared. Comparing with the as-cast alloy, the dominant Laves phase ZrV{sub 2} is preserved, V-BCC phase is reduced and α-Zr phase is replaced by a small amount of Zr{sub 3}V{sub 3}O phase in melt-spun ribbons. Melt-spun ribbonsmore » exhibit easy activation and fast initial hydrogen absorption on account of the increased specific surface area. However, the decrease in unit cell volume of the dominant phase leads to the decrease in hydrogen absorption capacity. Melt-spinning technique raises the equilibrium pressure and decreases the stability of hydride due to the decrease of unit cell volume and the elimination of α-Zr phase, respectively. Melt-spun ribbons with fine grains show improved hydrogen absorption kinetics comparing with that of the as-cast alloy. Meanwhile, the prevalent micro twins observed within melt-spun ribbons are believed to account for the improved hydrogen absorption kinetics. - Highlights: • Role of defects on hydrogenation kinetics of Zr-based alloys is proposed. • Microstructure and hydrogenation properties of as-cast/melt-spun alloy are compared. • Melt-spinning technique improves the hydrogenation kinetics of Zr{sub 0.9}Ti{sub 0.1}V{sub 1.7} alloy. • Refined grains and twin defects account for improved hydrogen absorption kinetics.« less

Genetic Control of Methyl Halide Production in Arabidopsis

NASA Astrophysics Data System (ADS)

Rhew, R. C.; Ostergaard, L.; Saltzman, E. S.; Yanofsky, M. F.

2003-12-01

Methyl chloride and methyl bromide are the primary carriers of natural chlorine and bromine to the stratosphere where they catalyze the destruction of ozone, whereas methyl iodide influences aerosol formation and ozone loss in the troposphere. Methyl bromide is also an agricultural fumigant whose use is scheduled to be phased out by international agreement. Despite the economic and environmental importance of these methyl halides, their natural sources and biological production mechanisms are poorly understood. Currently identified sources include oceans, biomass burning, industrial and agricultural use, fuel combustion, salt marshes, wetlands, rice paddies, certain terrestrial plants and fungi, and abiotic processes. We demonstrate that the model plant Arabidopsis thaliana produces and emits methyl halides and that the enzyme primarily responsible for the production is encoded by the HARMLESS TO OZONE LAYER (HOL) gene located on chromosome II. In mutant plants that have a disruption of the HOL gene, methyl halide production is largely eliminated. A phylogenetic analysis using the HOL gene suggests that the ability to produce methyl halides is widespread among vascular plants. This approach provides a genetic basis for understanding and predicting patterns of methyl halide production by plants.

Integral equation theory study on the phase separation in star polymer nanocomposite melts.

PubMed

Zhao, Lei; Li, Yi-Gui; Zhong, Chongli

2007-10-21

The polymer reference interaction site model theory is used to investigate phase separation in star polymer nanocomposite melts. Two kinds of spinodal curves were obtained: classic fluid phase boundary for relatively low nanoparticle-monomer attraction strength and network phase boundary for relatively high nanoparticle-monomer attraction strength. The network phase boundaries are much more sensitive with nanoparticle-monomer attraction strength than the fluid phase boundaries. The interference among the arm number, arm length, and nanoparticle-monomer attraction strength was systematically investigated. When the arm lengths are short, the network phase boundary shows a marked shift toward less miscibility with increasing arm number. When the arm lengths are long enough, the network phase boundaries show opposite trends. There exists a crossover arm number value for star polymer nanocomposite melts, below which the network phase separation is consistent with that of chain polymer nanocomposite melts. However, the network phase separation shows qualitatively different behaviors when the arm number is larger than this value.

Making and Breaking of Lead Halide Perovskites.

PubMed

Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

2016-02-16

A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

Making and Breaking of Lead Halide Perovskites

DOE PAGES

Manser, Joseph S.; Saidaminov, Makhsud I.; Christians, Jeffrey A.; ...

2016-01-20

A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapidmore » degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution

Solid-solid phase transformation via internal stress-induced virtual melting, significantly below the melting temperature. Application to HMX energetic crystal.

PubMed

Levitas, Valery I; Henson, Bryan F; Smilowitz, Laura B; Asay, Blaine W

2006-05-25

We theoretically predict a new phenomenon, namely, that a solid-solid phase transformation (PT) with a large transformation strain can occur via internal stress-induced virtual melting along the interface at temperatures significantly (more than 100 K) below the melting temperature. We show that the energy of elastic stresses, induced by transformation strain, increases the driving force for melting and reduces the melting temperature. Immediately after melting, stresses relax and the unstable melt solidifies. Fast solidification in a thin layer leads to nanoscale cracking which does not affect the thermodynamics or kinetics of the solid-solid transformation. Thus, virtual melting represents a new mechanism of solid-solid PT, stress relaxation, and loss of coherence at a moving solid-solid interface. It also removes the athermal interface friction and deletes the thermomechanical memory of preceding cycles of the direct-reverse transformation. It is also found that nonhydrostatic compressive internal stresses promote melting in contrast to hydrostatic pressure. Sixteen theoretical predictions are in qualitative and quantitative agreement with experiments conducted on the PTs in the energetic crystal HMX. In particular, (a) the energy of internal stresses is sufficient to reduce the melting temperature from 551 to 430 K for the delta phase during the beta --> delta PT and from 520 to 400 K for the beta phase during the delta --> beta PT; (b) predicted activation energies for direct and reverse PTs coincide with corresponding melting energies of the beta and delta phases and with the experimental values; (c) the temperature dependence of the rate constant is determined by the heat of fusion, for both direct and reverse PTs; results b and c are obtained both for overall kinetics and for interface propagation; (d) considerable nanocracking, homogeneously distributed in the transformed material, accompanies the PT, as predicted by theory; (e) the nanocracking does not

Melting along the Hugoniot and solid phase transition for Sn via sound velocity measurements

NASA Astrophysics Data System (ADS)

Song, Ping; Cai, Ling-cang; Tao, Tian-jiong; Yuan, Shuai; Chen, Hong; Huang, Jin; Zhao, Xin-wen; Wang, Xue-jun

2016-11-01

It is very important to determine the phase boundaries for materials with complex crystalline phase structures to construct their corresponding multi-phase equation of state. By measuring the sound velocity of Sn with different porosities, different shock-induced melting pressures along the solid-liquid phase boundary could be obtained. The incipient shock-induced melting of porous Sn samples with two different porosities occurred at a pressure of about 49.1 GPa for a porosity of 1.01 and 45.6 GPa for a porosity of 1.02, based on measurements of the sound velocity. The incipient shock-induced melting pressure of solid Sn was revised to 58.1 GPa using supplemental measurements of the sound velocity. Trivially, pores in Sn decreased the shock-induced melting pressure. Based on the measured longitudinal sound velocity data, a refined solid phase transition and the Hugoniot temperature-pressure curve's trend are discussed. No bcc phase transition occurs along the Hugoniot for porous Sn; further investigation is required to understand the implications of this finding.

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites.

PubMed

Sutter-Fella, Carolin M; Ngo, Quynh P; Cefarin, Nicola; Gardner, Kira L; Tamura, Nobumichi; Stan, Camelia V; Drisdell, Walter S; Javey, Ali; Toma, Francesca M; Sharp, Ian D

2018-06-13

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2 ) 2 CsPb-halide (FACsPb-) and CH 3 NH 3 Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials. However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.

A phase-field approach to nonequilibrium phase transformations in elastic solids via an intermediate phase (melt) allowing for interface stresses.

PubMed

Momeni, Kasra; Levitas, Valery I

2016-04-28

A phase-field approach for phase transformations (PTs) between three different phases at nonequilibrium temperatures is developed. It includes advanced mechanics, thermodynamically consistent interfacial stresses, and interface interactions. A thermodynamic Landau-Ginzburg potential developed in terms of polar order parameters satisfies the desired instability and equilibrium conditions for homogeneous phases. The interfacial stresses were introduced with some terms from large-strain formulation even though the small-strain assumption was utilized. The developed model is applied to study the PTs between two solid phases via a highly disordered intermediate phase (IP) or an intermediate melt (IM) hundreds of degrees below the melting temperature. In particular, the β ↔ δ PTs in HMX energetic crystals via IM are analyzed. The effects of various parameters (temperature, ratios of widths and energies of solid-solid (SS) to solid-melt (SM) interfaces, elastic energy, and interfacial stresses) on the formation, stability, and structure of the IM within a propagating SS interface are studied. Interfacial and elastic stresses within a SS interphase and their relaxation and redistribution with the appearance of a partial or complete IM are analyzed. The energy and structure of the critical nucleus (CN) of the IM are studied as well. In particular, the interfacial stresses increase the aspect-ratio of the CN. Although including elastic energy can drastically reduce the energy of the CN of the IM, the activation energy of the CN of the IM within the SS interface increases when interfacial tension is taken into account. The developed thermodynamic potential can also be modified to model other multiphase physical phenomena, such as multi-variant martensitic PTs, grain boundary and surface-induced pre-melting and PTs, as well as developing phase diagrams for IPs.

Peroxidative oxidation of halides catalysed by myeloperoxidase. Effect of fluoride on halide oxidation.

PubMed

Zgliczyński, J M; Stelmaszyńska, T; Olszowska, E; Krawczyk, A; Kwasnowska, E; Wróbel, J T

1983-01-01

It was found that all halides can compete with cyanide for binding with myeloperoxidase. The lower is the pH, the higher is the affinity of halides. The apparent dissociation constants (Kd) of myeloperoxidase-cyanide complex were determined in the presence of F-, Cl-, Br- and I- in the pH range of 4 to 7. In slightly acidic pH (4 - 6) fluoride and chloride exhibit a higher affinity towards the enzyme than bromide and iodide. Taking into account competition between cyanide and halides for binding with myeloperoxidase the dissociation constants of halide-myeloperoxidase complexes were calculated. All halides except fluoride can be oxidized by H2O2 in the presence of myeloperoxidase. However, since fluoride can bind with myeloperoxidase, it can competitively inhibit the oxidation of other halides. Fluoride was a competitive inhibitor with respect to other halides as well as to H2O2. Inhibition constants (Ki) for fluoride as a competitive inhibitor with respect to H2O2 increased from iodide oxidation through bromide to chloride oxidation.

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites

DOE PAGES

Sutter-Fella, Carolin M.; Ngo, Quynh P.; Cefarin, Nicola; ...

2018-04-30

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. In this paper, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2) 2CsPb-halide (FACsPb-) and CH 3NH 3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials.more » However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Finally, because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.« less

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites

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

Sutter-Fella, Carolin M.; Ngo, Quynh P.; Cefarin, Nicola

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. In this paper, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2) 2CsPb-halide (FACsPb-) and CH 3NH 3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials.more » However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Finally, because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.« less

Thermodynamic reactivity, growth and characterization of mercurous halide crystals

NASA Technical Reports Server (NTRS)

Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Singh, M.; Glicksman, M. E.; Paradies, C.

1992-01-01

Thermodynamic calculations were carried out for the Hg-X-O system (X = Cl, Br, I) to identify the potential sources of contamination and relative stability of oxides and oxy-halide phases. The effect of excess mercury vapor pressure on the optical quality of mercurous halide crystal was studied by growing several mercurous chloride crystals from mercury-rich composition. The optical quality of crystals was examined by birefringence interferometry and laser scattering studies. Crystals grown in slightly mercury-rich composition showed improved optical quality relative to stoichiometric crystals.

Continuous melting through a hexatic phase in confined bilayer water

NASA Astrophysics Data System (ADS)

Zubeltzu, Jon; Corsetti, Fabiano; Fernández-Serra, M. V.; Artacho, Emilio

2016-06-01

Liquid water is not only of obvious importance but also extremely intriguing, displaying many anomalies that still challenge our understanding of such an a priori simple system. The same is true when looking at nanoconfined water: The liquid between constituents in a cell is confined to such dimensions, and there is already evidence that such water can behave very differently from its bulk counterpart. A striking finding has been reported from computer simulations for two-dimensionally confined water: The liquid displays continuous or discontinuous melting depending on its density. In order to understand this behavior, we have analyzed the melting exhibited by a bilayer of nanoconfined water by means of molecular dynamics simulations. At high density we observe the continuous melting to be related to the phase change of the oxygens only, with the hydrogens remaining liquidlike throughout. Moreover, we find an intermediate hexatic phase for the oxygens between the liquid and a triangular solid ice phase, following the Kosterlitz-Thouless-Halperin-Nelson-Young theory for two-dimensional melting. The liquid itself tends to maintain the local structure of the triangular ice, with its two layers being strongly correlated yet with very slow exchange of matter. The decoupling in the behavior of the oxygens and hydrogens gives rise to a regime in which the complexity of water seems to disappear, resulting in what resembles a simple monoatomic liquid. This intrinsic tendency of our simulated water may be useful for understanding novel behaviors in other confined and interfacial water systems.

Experimental research of phase transitions in a melt of high-purity aluminum

NASA Astrophysics Data System (ADS)

Vorontsov, V. B.; Pershin, V. K.

2017-12-01

This scientific work is devoted to the studying of the genetic connection structures of solid and liquid phases. In this paper Fourier analysis of acoustic emission (AE) signals accompanying heating of high purity aluminum from the melting point up to 860 °C was performed. The experimental data allowed to follow the dynamics of disorder zones in the melt with increasing melt temperature up to their complete destruction. The presented results of spectral analysis of the signals were analyzed from the standpoint of the theory of cluster melting metals.

Local polar fluctuations in lead halide perovskite crystals

DOE PAGES

Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; ...

2017-03-28

Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH 3NH 3PbBr 3) and all-inorganic (CsPbBr 3) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. Furthermore, MD simulations indicatemore » that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr 3.« less

Preparation of highly pure α-MnBi phase via melt-spinning

NASA Astrophysics Data System (ADS)

Gabay, A. M.; Hadjipanayis, G. C.; Cui, J.

2018-05-01

High concentration of the magnetically hard α phase in the Mn-Bi alloys is important for the development of these alloys as rare-earth-free permanent magnets. Among several explored manufacturing methods, melt-spinning followed by annealing is known to be suitable of producing the most pure α structure. In this work, a series of melt-spun Mn100-xBix alloys was prepared with x = 43 - 51 at a wheel speed of 67 m/s by ejecting the alloys through orifices 0.17 mm and 0.27 mm in diameter. The smaller orifice diameter favored formation of an amorphous phase in the as-spun alloys as well as a higher saturation magnetization Ms in the alloys subsequently annealed at 300 °C. Although the most pure, 98 vol.%, α phase was obtained for the off-stoichiometric Mn55Bi45 composition, the Ms of this material was lowered, possibly because the excess Mn atoms induced antiferromagnetic coupling in the α phase. The highest Ms of 78 emu/g was obtained for a composition closer to the Mn50Bi50 stoichiometry, despite the slightly lower purity of α phase. Evolution of the room-temperature coercivity with the formation of the α phase in the melt-spun alloys was studied for the Mn55Bi45 ribbons compacted at 275 °C; the coercivity values of around 1 kOe obtained through this simple procedure are not sufficient for permanent magnet applications.

Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films

NASA Astrophysics Data System (ADS)

Wehrenfennig, Christian; Liu, Mingzhen; Snaith, Henry J.; Johnston, Michael B.; Herz, Laura M.

2014-08-01

The optoelectronic properties of the mixed hybrid lead halide perovskite CH3NH3PbI3-xClx have been subject to numerous recent studies related to its extraordinary capabilities as an absorber material in thin film solar cells. While the greatest part of the current research concentrates on the behavior of the perovskite at room temperature, the observed influence of phonon-coupling and excitonic effects on charge carrier dynamics suggests that low-temperature phenomena can give valuable additional insights into the underlying physics. Here, we present a temperature-dependent study of optical absorption and photoluminescence (PL) emission of vapor-deposited CH3NH3PbI3-xClx exploring the nature of recombination channels in the room- and the low-temperature phase of the material. On cooling, we identify an up-shift of the absorption onset by about 0.1 eV at about 100 K, which is likely to correspond to the known tetragonal-to-orthorhombic transition of the pure halide CH3NH3PbI3. With further decreasing temperature, a second PL emission peak emerges in addition to the peak from the room-temperature phase. The transition on heating is found to occur at about 140 K, i.e., revealing significant hysteresis in the system. While PL decay lifetimes are found to be independent of temperature above the transition, significantly accelerated recombination is observed in the low-temperature phase. Our data suggest that small inclusions of domains adopting the room-temperature phase are responsible for this behavior rather than a spontaneous increase in the intrinsic rate constants. These observations show that even sparse lower-energy sites can have a strong impact on material performance, acting as charge recombination centres that may detrimentally affect photovoltaic performance but that may also prove useful for optoelectronic applications such as lasing by enhancing population inversion.

Metamorphism and partial melting of ordinary chondrites: Calculated phase equilibria

NASA Astrophysics Data System (ADS)

Johnson, T. E.; Benedix, G. K.; Bland, P. A.

2016-01-01

Constraining the metamorphic pressures (P) and temperatures (T) recorded by meteorites is key to understanding the size and thermal history of their asteroid parent bodies. New thermodynamic models calibrated to very low P for minerals and melt in terrestrial mantle peridotite permit quantitative investigation of high-T metamorphism in ordinary chondrites using phase equilibria modelling. Isochemical P-T phase diagrams based on the average composition of H, L and LL chondrite falls and contoured for the composition and abundance of olivine, ortho- and clinopyroxene, plagioclase and chromite provide a good match with values measured in so-called equilibrated (petrologic type 4-6) samples. Some compositional variables, in particular Al in orthopyroxene and Na in clinopyroxene, exhibit a strong pressure dependence when considered over a range of several kilobars, providing a means of recognising meteorites derived from the cores of asteroids with radii of several hundred kilometres, if such bodies existed at that time. At the low pressures (<1 kbar) that typify thermal metamorphism, several compositional variables are good thermometers. Although those based on Fe-Mg exchange are likely to have been reset during slow cooling, those based on coupled substitution, in particular Ca and Al in orthopyroxene and Na in clinopyroxene, are less susceptible to retrograde diffusion and are potentially more faithful recorders of peak conditions. The intersection of isopleths of these variables may allow pressures to be quantified, even at low P, permitting constraints on the minimum size of parent asteroid bodies. The phase diagrams predict the onset of partial melting at 1050-1100 °C by incongruent reactions consuming plagioclase, clinopyroxene and orthopyroxene, whose compositions change abruptly as melting proceeds. These predictions match natural observations well and support the view that type 7 chondrites represent a suprasolidus continuation of the established petrologic

Constraints on Mantle Plume Melting Conditions in the Martian Mantle Based on Improved Melting Phase Relationships of Olivine-Phyric Shergottite Yamato 980459

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Rapp, Jennifer F.; Usui, Tomohiro; Draper, David S.; Filiberto, Justin

2016-01-01

Martian meteorite Yamato 980459 (hereafter Y98) is an olivine-phyric shergottite that has been interpreted as closely approximating a martian mantle melt [1-4], making it an important constraint on adiabatic decompression melting models. It has long been recognized that low pressure melting of the Y98 composition occurs at extremely high temperatures relative to martian basalts (1430 degC at 1 bar), which caused great difficulties in a previous attempt to explain Y98 magma generation via a mantle plume model [2]. However, previous studies of the phase diagram were limited to pressures of 2 GPa and less [2, 5], whereas decompression melting in the present-day martian mantle occurs at pressures of 3-7 GPa, with the shallow boundary of the melt production zone occurring just below the base of the thermal lithosphere [6]. Recent experimental work has now extended our knowledge of the Y98 melting phase relationships to 8 GPa. In light of this improved petrological knowledge, we are therefore reassessing the constraints that Y98 imposes on melting conditions in martian mantle plumes. Two recently discovered olivine- phyric shergottites, Northwest Africa (NWA) 5789 and NWA 6234, may also be primary melts from the martian mantle [7, 8]. However, these latter meteorites have not been the subject of detailed experimental petrology studies, so we focus here on Y98.

The dry-heat loss effect of melt-spun phase change material fibres.

PubMed

Tjønnås, Maria Suong; Færevik, Hilde; Sandsund, Mariann; Reinertsen, Randi E

2015-01-01

Phase change materials (PCM) have the ability to store latent heat when they change phases, a property that gives clothing that incorporates PCM its cooling effect. This study investigated the effect of dry-heat loss (cooling) of a novel melt-spun PCM fibre on the basis of the area covered, mass, the latent heat of fusion and melting temperature, compared to a known PCM clothing product. PCM fibres with melting temperatures of 28.4 and 32.0°C and PCM packs with melting temperatures of 28.0 and 32.0°C were studied. The results showed that the PCM fibres had a larger initial peak cooling effect than that of the PCM packs. The duration of the cooling effect of PCM fibres was primarily dependent on the PCM mass and the latent heat of fusion capacity, and secondly on the covered area and melting temperature of the PCM. This study investigates the cooling effect of PCM fibres on a thermal manikin. The PCM fibres had a high but short-lasting cooling effect. This study contributes to the knowledge of how the body's temperature regulation may be affected by the cooling properties of clothing that incorporates PCM.

Phase behavior and reactive transport of partial melt in heterogeneous mantle model

NASA Astrophysics Data System (ADS)

Jordan, J.; Hesse, M. A.

2013-12-01

The reactive transport of partial melt is the key process that leads to the chemical and physical differentiation of terrestrial planets and smaller celestial bodies. The essential role of the lithological heterogeneities during partial melting of the mantle is increasingly recognized. How far can enriched melts propagate while interacting with the ambient mantle? Can the melt flow emanating from a fertile heterogeneity be localized through a reactive infiltration feedback in a model without exogenous factors or contrived initial conditions? A full understanding of the role of heterogeneities requires reactive melt transport models that account for the phase behavior of major elements. Previous work on reactive transport in the mantle focuses on trace element partitioning; we present the first nonlinear chromatographic analysis of reactive melt transport in systems with binary solid solution. Our analysis shows that reactive melt transport in systems with binary solid solution leads to the formation of two separate reaction fronts: a slow melting/freezing front along which enthalpy change is dominant and a fast dissolution/precipitation front along which compositional changes are dominated by an ion-exchange process over enthalpy change. An intermediate state forms between these two fronts with a bulk-rock composition and enthalpy that are not necessarily bounded by the bulk-rock composition and enthalpy of either the enriched heterogeneity or the depleted ambient mantle. The formation of this intermediate state makes it difficult to anticipate the porosity changes and hence the stability of reaction fronts. Therefore, we develop a graphical representation for the solution that allows identification of the intermediate state by inspection, for all possible bulk-rock compositions and enthalpies of the heterogeneity and the ambient mantle. We apply the analysis to the partial melting of an enriched heterogeneity. This leads to the formation of moving precipitation

Sulfur in Hydrous, Oxidized Basaltic Magmas: Phase Equilibria and Melt Solubilities

NASA Astrophysics Data System (ADS)

Pichavant, M.; Scaillet, B.; di Carlo, I.; Rotolo, S.; Metrich, N.

2006-05-01

Basaltic magmas from subduction zone settings are typically S-rich and may be the ultimate source of sulfur in vapor phases emitted during eruptions of more silicic systems. To understand processes of sulfur recycling in subduction zones, the behaviour of S in hydrous, oxidized, mafic arc magmas must be known. Although experimental data on S-bearing basaltic melts are available for dry conditions, and under both reduced and oxidized fO2, no study has yet examined the effect of S in hydrous mafic melts. In this work, 3 starting compositions were investigated, a basaltic andesite, a K basalt and a picritic basalt. For each composition, experimental data for S-added (1 wt % elemental sulfur) and S-free charges were obtained under similar P-T- H2O-fO2. All experiments were performed at 4 kbar and at either 950 ° C (basaltic andesite), 1100 ° C (K basalt) or 1150 ° C (picritic basalt). These were carried out in an internally heated vessel pressurized with Ar-H2 mixtures and fitted with a drop-quench device, and lasted for between 15 and 99 h. Either Au (950 ° C) or AuPd alloys (1100 and 1150 ° C) were used as containers. These latter perform satisfactorily under strongly oxidizing conditions, i.e., for fO2 above NNO+1 at 1100 and 1150 ° C. Below NNO+1, Pd- Au-S-Fe phases appear in the charges, suggesting extensive interaction between S and the capsule material. Experimental redox conditions, determined from Ni-Pd-O sensors, ranged between NNO+1.3 to +4.1 (basaltic andesite), +0.6 to +2.0 (K basalt), and +0.3 to +3.6 (picritic basalt). H2O concentrations in melt ranged from 8.2 wt % (basaltic andesite), decreasing to 2.2-3.9 wt % (K basalt) and 2.5-5.0 wt % (picritic basalt). All 3 compositions studied crystallize anhydrite and Fe-Ni-S-O sulphide as saturating S-bearing phases, anhydrite at high fO2 and sulphide at lower fO2, although melt composition also influences their stability. Anhydrite is present at a fO2 as low as NNO+1.5 in the K basalt. In the picritic

The Oxidation State of Europium in Halide Glasses

PubMed Central

Weber, J.K.R.; Vu, M.; Paßlick, C.; Schweizer, S.; Brown, D.E.; Johnson, C.E.; Johnson, J.A.

2012-01-01

The luminescent properties of divalent europium ions can be exploited to produce storage phosphors for x-ray imaging applications. The relatively high cost and limited availability of divalent europium halides makes it desirable to synthesize them from the readily available trivalent salts. In this work, samples of pure EuCl3 and fluoride glass melts doped with EuCl3 were processed at 700-800 °C in an inert atmosphere furnace. The Eu oxidation state in the resulting materials was determined using fluorescence and Mössbauer spectroscopy. Heat treatment of pure EuCl3 for 10 minutes at 710 °C resulted in a material comprising approximately equal amounts of Eu2+ and Eu3+. Glasses made using mixtures of EuCl2 and EuCl3 in the starting material contained both oxidation states. This paper describes the sample preparation and analysis and discusses the results in the context of chemical equilibria in the melts. PMID:22101252

Thermodynamic Model of the Na-Al-Si-O-F Melts

NASA Astrophysics Data System (ADS)

Dolejs, D.; Baker, D. R.

2004-05-01

Fluorine is a common volatile element in magmatic-hydrothermal systems, but its solution mechanisms in highly polymerized silicate melts are poorly known. We have developed a thermodynamic model for fluorosilicate liquids which links experimentally determined phase equilibria and spectroscopic information on melt structure. The model is applicable to crystallization of fluoride minerals or fluoride-silicate immiscibility in natural felsic melts. Configurational properties of the liquid are defined by mixing of alkali fluoride, polyhedral aluminofluoride and silicofluoride species and non-bridging terminations of the silicate network. Abundances of individual structural species are described by a homogeneous equilibrium, representing melt depolymerization: F- (free) + O0 (bridging) = F0 (terminal) + O- (non-bridging), which is a replacement of one oxygen bridge, Si-O-Si, by two terminations, Si-F | Na-O-Si. In cryolite-bearing systems, the self-dissociation of octahedral aluminofluoride complexes: Na3[AlF6] = Na[AlF4] + 2 NaF, and the short-range order between (O,F)-corners and (Si,NaAl)-centers of tetrahedra: Si-O-Si + 2 [NaAl]-F = [NaAl]-O-[NaAl] + 2 Si-F, represent two additional interaction mechanisms. Portrayal of these equilibria in ternary Thompson reaction space allows to decrease the number of interaction mechanisms by linearly combining melt depolymerization with tetrahedral short-range order. In this formulation, the interaction parameters are incorporated directly in configurational properties, thus the complete melt speciation can be calculated, and the activities of any macroscopic species are readily derived. The model has been applied to subsystems of the Na2O-NaAlO2-SiO2-F2O-1 compositional space. Activity-composition relationships in the villiaumite-sodium silicate binaries require clustering of silicate tetrahedra in fluoride solvent. Phase-equilibria in cryolite-nepheline and cryolite-albite systems illustrate an overall increase of Na3AlF6 self

Hetero-phase fluctuations in the pre-melting region in ionic crystals

NASA Astrophysics Data System (ADS)

Matsunaga, S.; Tamaki, S.

2008-06-01

The theory of the pre-melting phenomena in ionic crystals on the basis of the concept of the hetero phase fluctuation has been applied to KCl and AgCl crystal. The large scale molecular dynamics simulations (MD) in KCl and AgCl crystals are also performed to examine the ionic configuration in premelting region in the vicinity of their melting points. The size of the liquid like clusters are estimated by the theory and MD. The structural features of liquid like clusters are discussed by MD results using the Lindemann instability condition. The ionic conductivities in the pre-melting region are also discussed on the same theoretical basis.

Melting and Vaporization of the 1223 Phase in the System (Tl-Pb-Ba-Sr-Ca-Cu-O)

PubMed Central

Cook, L. P.; Wong-Ng, W.; Paranthaman, P.

1996-01-01

The melting and vaporization of the 1223 [(Tl,Pb):(Ba,Sr):Ca:Cu] oxide phase in the system (Tl-Pb-Ba-Sr-Ca-Cu-O) have been investigated using a combination of dynamic methods (differential thermal analysis, thermogravimetry, effusion) and post-quenching characterization techniques (powder x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectrometry). Vaporization rates, thermal events, and melt compositions were followed as a function of thallia loss from a 1223 stoichiometry. Melting and vaporization equilibria of the 1223 phase are complex, with as many as seven phases participating simultaneously. At a total pressure of 0.1 MPa the 1223 phase was found to melt completely at (980 ± 5) °C in oxygen, at a thallia partial pressure (pTl2O) of (4.6 ± 0.5) kPa, where the quoted uncertainties are standard uncertainties, i.e., 1 estimated standard deviation. The melting reaction involves five other solids and a liquid, nominally as follows: 1223→1212+(Ca,Sr)2CuO3+(Sr,Ca)CuO2+BaPbO3+(Ca,Sr)O+Liquid Stoichiometries of the participating phases have been determined from microchemical analysis, and substantial elemental substitution on the 1212 and 1223 crystallographic sites is indicated. The 1223 phase occurs in equilibrium with liquids from its melting point down to at least 935 °C. The composition of the lowest melting liquid detected for the bulk compositions of this study has been measured using microchemical analysis. Applications to the processing of superconducting wires and tapes are discussed. PMID:27805086

Dynamical Scaling and Phase Coexistence in Topologically Constrained DNA Melting.

PubMed

Fosado, Y A G; Michieletto, D; Marenduzzo, D

2017-09-15

There is a long-standing experimental observation that the melting of topologically constrained DNA, such as circular closed plasmids, is less abrupt than that of linear molecules. This finding points to an important role of topology in the physics of DNA denaturation, which is, however, poorly understood. Here, we shed light on this issue by combining large-scale Brownian dynamics simulations with an analytically solvable phenomenological Landau mean field theory. We find that the competition between melting and supercoiling leads to phase coexistence of denatured and intact phases at the single-molecule level. This coexistence occurs in a wide temperature range, thereby accounting for the broadening of the transition. Finally, our simulations show an intriguing topology-dependent scaling law governing the growth of denaturation bubbles in supercoiled plasmids, which can be understood within the proposed mean field theory.

Using a Spreadsheet To Explore Melting, Dissolving and Phase Diagrams.

ERIC Educational Resources Information Center

Goodwin, Alan

2002-01-01

Compares phase diagrams relating to the solubilities and melting points of various substances in textbooks with those generated by a spreadsheet using data from the literature. Argues that differences between the diagrams give rise to new chemical insights. (Author/MM)

Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films

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

Sutter-Fella, Carolin M.; Li, Yanbo; Cefarin, Nicola

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, we present a protocol for the fabrication of this material via the low-pressure vapor assisted solution process (LP-VASP) method, which yields ~19% power conversion efficiency in planar heterojunction perovskite solar cells. First, we report the synthesis of methylammonium iodide (CH 3NH 3I) and methylammonium bromide (CH 3NH 3Br) from methylamine and the corresponding halide acid (HI or HBr). Then, we describe the fabrication of pinhole-free, continuous methylammonium-lead halide perovskite (CH 3NH 3PbX 3 with X = I, Br, Cl and their mixture) filmsmore » with the LP-VASP. This process is based on two steps: i) spin-coating of a homogenous layer of lead halide precursor onto a substrate, and ii) conversion of this layer to CH 3NH 3PbI 3-xBr x by exposing the substrate to vapors of a mixture of CH 3NH 3I and CH 3NH 3Br at reduced pressure and 120 °C. Through slow diffusion of the methylammonium halide vapor into the lead halide precursor, we achieve slow and controlled growth of a continuous, pinhole-free perovskite film. The LP-VASP allows synthetic access to the full halide composition space in CH 3NH 3PbI 3-xBr x with 0 ≤ x ≤ 3. Depending on the composition of the vapor phase, the bandgap can be tuned between 1.6 eV ≤ E g ≤ 2.3 eV. In addition, by varying the composition of the halide precursor and of the vapor phase, we can also obtain CH 3NH 3PbI 3-xCl x. Films obtained from the LP-VASP are reproducible, phase pure as confirmed by X-ray diffraction measurements, and show high photoluminescence quantum yield. The process does not require the use of a glovebox.« less

Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films

DOE PAGES

Sutter-Fella, Carolin M.; Li, Yanbo; Cefarin, Nicola; ...

2017-09-08

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, we present a protocol for the fabrication of this material via the low-pressure vapor assisted solution process (LP-VASP) method, which yields ~19% power conversion efficiency in planar heterojunction perovskite solar cells. First, we report the synthesis of methylammonium iodide (CH 3NH 3I) and methylammonium bromide (CH 3NH 3Br) from methylamine and the corresponding halide acid (HI or HBr). Then, we describe the fabrication of pinhole-free, continuous methylammonium-lead halide perovskite (CH 3NH 3PbX 3 with X = I, Br, Cl and their mixture) filmsmore » with the LP-VASP. This process is based on two steps: i) spin-coating of a homogenous layer of lead halide precursor onto a substrate, and ii) conversion of this layer to CH 3NH 3PbI 3-xBr x by exposing the substrate to vapors of a mixture of CH 3NH 3I and CH 3NH 3Br at reduced pressure and 120 °C. Through slow diffusion of the methylammonium halide vapor into the lead halide precursor, we achieve slow and controlled growth of a continuous, pinhole-free perovskite film. The LP-VASP allows synthetic access to the full halide composition space in CH 3NH 3PbI 3-xBr x with 0 ≤ x ≤ 3. Depending on the composition of the vapor phase, the bandgap can be tuned between 1.6 eV ≤ E g ≤ 2.3 eV. In addition, by varying the composition of the halide precursor and of the vapor phase, we can also obtain CH 3NH 3PbI 3-xCl x. Films obtained from the LP-VASP are reproducible, phase pure as confirmed by X-ray diffraction measurements, and show high photoluminescence quantum yield. The process does not require the use of a glovebox.« less

Melting of KCl and pressure calibration from in situ ionic conductivity measurements in a multi-anvil apparatus

NASA Astrophysics Data System (ADS)

Li, J.; Dong, J.; Zhu, F.

2017-12-01

will examine the effect of solid-state phase transition on the melting curves of halides and test the validity of various melting theories.

Metal-halide mixtures for latent heat energy storage

NASA Technical Reports Server (NTRS)

Chen, K.; Manvi, R.

1981-01-01

Some candidates for alkali metal and alkali halide mixtures suitable for thermal energy storage at temperatures 600 C are identified. A solar thermal system application which offer advantages such as precipitation of salt crystals away from heat transfer surfaces, increased thermal conductivity of phase change materials, corrosion inhibition, and a constant monotectic temperature, independent of mixture concentrations. By using the lighters, metal rich phase as a heat transfer medium and the denser, salt rich phase as a phase change material for latent heat storage, undesirable solidification on the heat transfer surface may be prevented, is presented.

Metal-halide mixtures for latent heat energy storage

NASA Astrophysics Data System (ADS)

Chen, K.; Manvi, R.

Some candidates for alkali metal and alkali halide mixtures suitable for thermal energy storage at temperatures 600 C are identified. A solar thermal system application which offer advantages such as precipitation of salt crystals away from heat transfer surfaces, increased thermal conductivity of phase change materials, corrosion inhibition, and a constant monotectic temperature, independent of mixture concentrations. By using the lighters, metal rich phase as a heat transfer medium and the denser, salt rich phase as a phase change material for latent heat storage, undesirable solidification on the heat transfer surface may be prevented, is presented.

Predicting the thermodynamic stability of double-perovskite halides from density functional theory

DOE PAGES

Han, Dan; Zhang, Tao; Huang, Menglin; ...

2018-05-24

Recently, a series of double-perovskite halide compounds such as Cs 2AgBiCl 6 and Cs 2AgBiBr 6 have attracted intensive interest as promising alternatives to the solar absorber material CH 3NH 3PbI 3 because they are Pb-free and may exhibit enhanced stability. The thermodynamic stability of a number of double-perovskite halides has been predicted based on density functional theory (DFT) calculations of compound formation energies. In this paper, we found that the stability prediction can be dependent on the approximations used for the exchange-correlation functionals, e.g., the DFT calculations using the widely used Perdew, Burke, Ernzerhof (PBE) functional predict that Csmore » 2AgBiBr 6 is thermodynamically unstable against phase-separation into the competing phases such as AgBr, Cs 2AgBr 3, Cs 3Bi 2Br 9, etc., obviously inconsistent with the good stability observed experimentally. The incorrect prediction by the PBE calculation results from its failure to predict the correct ground-state structures of AgBr, AgCl, and CsCl. By contrast, the DFT calculations based on local density approximation, optB86b-vdW, and optB88-vdW functionals predict the ground-state structures of these binary halides correctly. Furthermore, the optB88-vdW functional is found to give the most accurate description of the lattice constants of the double-perovskite halides and their competing phases. Given these two aspects, we suggest that the optB88-vdW functional should be used for predicting thermodynamic stability in the future high-throughput computational material design or the construction of the Materials Genome database for new double-perovskite halides. As a result, using different exchange-correlation functionals has little influence on the dispersion of the conduction and the valence bands near the electronic bandgap; however, the calculated bandgap can be affected indirectly by the optimized lattice constant, which varies for different functionals.« less

Predicting the thermodynamic stability of double-perovskite halides from density functional theory

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

Han, Dan; Zhang, Tao; Huang, Menglin

Recently, a series of double-perovskite halide compounds such as Cs 2AgBiCl 6 and Cs 2AgBiBr 6 have attracted intensive interest as promising alternatives to the solar absorber material CH 3NH 3PbI 3 because they are Pb-free and may exhibit enhanced stability. The thermodynamic stability of a number of double-perovskite halides has been predicted based on density functional theory (DFT) calculations of compound formation energies. In this paper, we found that the stability prediction can be dependent on the approximations used for the exchange-correlation functionals, e.g., the DFT calculations using the widely used Perdew, Burke, Ernzerhof (PBE) functional predict that Csmore » 2AgBiBr 6 is thermodynamically unstable against phase-separation into the competing phases such as AgBr, Cs 2AgBr 3, Cs 3Bi 2Br 9, etc., obviously inconsistent with the good stability observed experimentally. The incorrect prediction by the PBE calculation results from its failure to predict the correct ground-state structures of AgBr, AgCl, and CsCl. By contrast, the DFT calculations based on local density approximation, optB86b-vdW, and optB88-vdW functionals predict the ground-state structures of these binary halides correctly. Furthermore, the optB88-vdW functional is found to give the most accurate description of the lattice constants of the double-perovskite halides and their competing phases. Given these two aspects, we suggest that the optB88-vdW functional should be used for predicting thermodynamic stability in the future high-throughput computational material design or the construction of the Materials Genome database for new double-perovskite halides. As a result, using different exchange-correlation functionals has little influence on the dispersion of the conduction and the valence bands near the electronic bandgap; however, the calculated bandgap can be affected indirectly by the optimized lattice constant, which varies for different functionals.« less

The aluminum electrode in AlCl3-alkali-halide melts.

NASA Technical Reports Server (NTRS)

Holleck, G. L.; Giner, J.

1972-01-01

Passivation phenomena have been observed upon cathodic and anodic polarization of the Al electrode in AlCl3-KCl-NaCl melts between 100 and 160 C. They are caused by formation of a solid salt layer at the electrode surface resulting from concentration changes upon current flow. The anodic limiting currents increased with temperature and with decreasing AlCl3 content of the melt. Current voltage curves obtained on a rotating aluminum disk showed a linear relationship between the anodic limiting current and omega to the minus 1/2 power. Upon cathodic polarization, dendrite formation occurs at the Al electrode. The activation overvoltage in AlCl3-KCl-NaCl was determined by galvanostatic current step methods. An apparent exchange current density of 270 mA/sq cm at 130 C and a double layer capacity of 40 plus or minus 10 microfarad/sq cm were measured.

Experimental Phase Relations of Hydrous, Primitive Melts: Implications for variably depleted mantle melting in arcs and the generation of primitive high-SiO2 melts

NASA Astrophysics Data System (ADS)

Weaver, S.; Wallace, P. J.; Johnston, A.

2010-12-01

There has been considerable experimental and theoretical work on how the introduction of H2O-rich fluids into the mantle wedge affects partial melting in arcs and chemical evolution of mantle melts as they migrate through the mantle. Studies aimed at describing these processes have become largely quantitative, with an emphasis on creating models that suitably predict the production and evolution of melts and describe the thermal state of arcs worldwide. A complete experimental data set that explores the P-T conditions of melt generation and subsequent melt extraction is crucial to the development, calibration, and testing of these models. This work adds to that data set by constraining the P-T-H2O conditions of primary melt extraction from two end-member subduction zones, a continental arc (Mexico) and an intraoceanic arc (Aleutians). We present our data in context with primitive melts found worldwide and with other experimental studies of melts produced from fertile and variably depleted mantle sources. Additionally, we compare our experimental results to melt compositions predicted by empirical and thermodynamic models. We used a piston-cylinder apparatus and employed an inverse approach in our experiments, constraining the permissible mantle residues with which our melts could be in equilibrium. We confirmed our inverse approach with forced saturation experiments at the P-T-H2O conditions of melt-mantle equilibration. Our experimental results show that a primitive, basaltic andesite melt (JR-28) from monogenetic cinder cone Volcan Jorullo (Central Mexico) last equilibrated with a harzburgite mantle residue at 1.2-1.4 GPa and 1150-1175°C with H2O contents in the range of 5.5-7 wt% H2O prior to ascent and eruption. Phase relations of a tholeiitic high-MgO basaltic melt (ID-16) from the Central Aleutians (Okmok) show the conditions of last equilibration with a fertile lherzolite mantle residue at shallower (1.2 GPa) but hotter (1275°C) conditions with

Thermochromic halide perovskite solar cells.

PubMed

Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A; Xie, Chenlu; Cui, Fan; Alivisatos, A Paul; Limmer, David T; Yang, Peidong

2018-03-01

Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

Thermochromic halide perovskite solar cells

NASA Astrophysics Data System (ADS)

Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S.; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A.; Xie, Chenlu; Cui, Fan; Alivisatos, A. Paul; Limmer, David T.; Yang, Peidong

2018-03-01

Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

Reduced sediment melting at 7.5-12 GPa: phase relations, geochemical signals and diamond nucleation

NASA Astrophysics Data System (ADS)

Brey, G. P.; Girnis, A. V.; Bulatov, V. K.; Höfer, H. E.; Gerdes, A.; Woodland, A. B.

2015-08-01

Melting of carbonated sediment in the presence of graphite or diamond was experimentally investigated at 7.5-12 GPa and 800-1600 °C in a multianvil apparatus. Two starting materials similar to GLOSS of Plank and Langmuir (Chem Geol 145:325-394, 1998) were prepared from oxides, carbonates, hydroxides and graphite. One mixture (Na-gloss) was identical in major element composition to GLOSS, and the other was poorer in Na and richer in K (K-gloss). Both starting mixtures contained ~6 wt% CO2 and 7 wt% H2O and were doped at a ~100 ppm level with a number of trace elements, including REE, LILE and HFSE. The near-solidus mineral assemblage contained a silica polymorph (coesite or stishovite), garnet, kyanite, clinopyroxene, carbonates (aragonite and magnesite-siderite solid solution), zircon, rutile, bearthite and hydrous phases (phengite and lawsonite at <9 GPa and the hydrous aluminosilicates topaz-OH and phase egg at >10 GPa). Hydrous phases disappear at ~900 °C, and carbonates persist up to 1000-1100 °C. At temperatures >1200 °C, the mineral assemblage consists of coesite or stishovite, kyanite and garnet. Clinopyroxene stability depends strongly on the Na content in the starting mixture; it remains in the Na-gloss composition up to 1600 °C at 12 GPa, but was not observed in K-gloss experiments above 1200 °C. The composition of melt or fluid changes gradually with increasing temperature from hydrous carbonate-rich (<10 wt% SiO2) at 800-1000 °C to volatile-rich silicate liquids (up to 40 wt% SiO2) at high temperatures. Trace elements were analyzed in melts and crystalline phases by LA ICP MS. The garnet-melt and clinopyroxene-melt partition coefficients are in general consistent with results from the literature for volatile-free systems and silicocarbonate melts derived by melting carbonated peridotites. Most trace elements are strongly incompatible in kyanite and silica polymorphs ( D < 0.01), except for V, Cr and Ni, which are slightly compatible in kyanite

Hybrid Lead Halide Layered Perovskites with Silsesquioxane Interlayers.

PubMed

Kataoka, Sho; Kaburagi, Wako; Mochizuki, Hiroyuki; Kamimura, Yoshihiro; Sato, Kazuhiko; Endo, Akira

2018-01-01

Hybrid organic-lead halide perovskites exhibit remarkable properties as semiconductors and light absorbers. Here, we report the formation of silsesquioxane-lead halide hybrid layered perovskites. We prepared silsesquioxane with a cubic cage-like structure and fabricated hybrid silsesquioxane-lead halide layered perovskites in a self-assembled manner. It is demonstrated that the silsesquioxane maintain their cage-like structure between lead halide perovskite layers. The silsesquioxane-lead halide perovskites also show excitonic absorption and emission in the visible light region similar to typical lead halide layered perovskites.

Heat capacity of molten halides.

PubMed

Redkin, Alexander A; Zaikov, Yurii P; Korzun, Iraida V; Reznitskikh, Olga G; Yaroslavtseva, Tatiana V; Kumkov, Sergey I

2015-01-15

The heat capacities of molten salts are very important for their practical use. Experimental investigation of this property is challenging because of the high temperatures involved and the corrosive nature of these materials. It is preferable to combine experimental investigations with empirical relationships, which allows for the evaluation of the heat capacity of molten salt mixtures. The isobaric molar heat capacities of all molten alkali and alkaline-earth halides were found to be constant for each group of salts. The value depends on the number of atoms in the salt, and the molar heat capacity per atom is constant for all molten halide salts with the exception of the lithium halides. The molar heat capacities of molten halides do not change when the anions are changed.

Methods for producing single crystal mixed halide perovskites

DOEpatents

Zhu, Kai; Zhao, Yixin

2017-07-11

An aspect of the present invention is a method that includes contacting a metal halide and a first alkylammonium halide in a solvent to form a solution and maintaining the solution at a first temperature, resulting in the formation of at least one alkylammonium halide perovskite crystal, where the metal halide includes a first halogen and a metal, the first alkylammonium halide includes the first halogen, the at least one alkylammonium halide perovskite crystal includes the metal and the first halogen, and the first temperature is above about 21.degree. C.

Induced amphotropic and thermotropic ionic liquid crystallinity in phosphonium halides: "lubrication" by hydroxyl groups.

PubMed

Ma, Kefeng; Somashekhar, B S; Gowda, G A Nagana; Khetrapal, C L; Weiss, Richard G

2008-03-18

The influence of covalently attaching hydroxymethylene to the methyl groups of methyl-tri-n-alkylphosphonium halides (where the alkyl chains are decyl, tetradecyl, or octadecyl and the halide is chloride or bromide) or adding methanol as a solute to the salts on their solid, liquid-crystalline (smectic A2), and isotropic phases has been investigated using a variety of experimental techniques. These structural and compositional changes are found to induce liquid crystallinity in some cases and to enhance the temperature range and lower the onset temperature of the liquid-crystalline phases in some others. The results are interpreted in terms of the lengths of the three n-alkyl chains attached to the phosphorus cation, the nature of the halide anion, the influence of H-bonding interactions at the head group regions of the layered phases, and other solvent-solute interactions. The fact that at least 1 molar equiv of methanol must be added to effect complete (isothermal) conversion of a solid methyl-tri-n-alkylphosphonium salt to a liquid crystal demonstrates a direct and strong association between individual methanol molecules and the phosphonium salts. Possible applications of such systems are suggested.

Melt-Vapor Phase Diagram of the Te-S System

NASA Astrophysics Data System (ADS)

Volodin, V. N.; Trebukhov, S. A.; Kenzhaliyev, B. K.; Nitsenko, A. V.; Burabaeva, N. M.

2018-03-01

The values of partial pressure of saturated vapor of the constituents of the Te-S system are determined from boiling points. The boundaries of the melt-vapor phase transition at atmospheric pressure and in vacuum of 2000 and 100 Pa are calculated on the basis of partial pressures. A phase diagram that includes vapor-liquid equilibrium fields whose boundaries allow us to assess the behavior of elements upon distillation fractioning is plotted. It is established that the separation of elements is possible at the first evaporation-condensation cycle. Complications can be caused by crystallization of a sulfur solid solution in tellurium.

Halide removal from aqueous solution by novel silver-polymeric materials.

PubMed

A M S, Polo; I, Velo-Gala; M, Sánchez-Polo; U, von Gunten; J J, López-Peñalver; J, Rivera-Utrilla

2016-12-15

The objective of this study was to analyze the behavior of a new material, silver-doped polymeric cloth (Ag-cloth), in the removal of bromide and iodide from waters. Silver is immobilized on the cloth, guaranteeing selective adsorption of the halide ions as retained silver halides that therefore do not pass into the solution. Results indicate that Ag 0 reacts with H 2 O 2 in the first phases of the process, yielding Ag + and superoxide radical; however, as the process advances, this radical favors Ag + reduction. Increases in the concentration of H 2 O 2 augment the capacity of the Ag-cloth to remove halides from the medium up to a maximum concentration (55μM), above which the removal capacity remains constant (Xm≅1.3-1.8mg halide/g Ag-cloth). Thus, when there is excess H 2 O 2 in the medium, secondary competitive reactions that take place in the process guarantee a constant Ag + concentration, which defines the maximum adsorption capacity of Ag-cloth, reducing its ability to remove halides. Ag-cloth has a higher capacity to remove iodide than bromide, and the presence of organic matter or chloride reduces its capacity to remove iodide or bromide from water. The results obtained shown that the capacity of Ag 0 with H 2 O 2 significantly varies as a function of the medium pH from 1mg Br - /g Ag-cloth at very low pH to 1.6mg/g Ag-cloth at pH9. Copyright © 2016 Elsevier B.V. All rights reserved.

Model of melting (crystallization) process of the condensed disperse phase in the smoky plasmas

NASA Astrophysics Data System (ADS)

Dragan, G. S.; Kolesnikov, K. V.; Kutarov, V. V.

2018-01-01

The paper presents an analysis of the causes of a formation of spatial ordered grain structures in a smoky plasma. We are modeling the process of melting (crystallization) of a condensed phase in this environment taking into account the screened electrostatic interaction and the diffusion-drift force. We discuss an influence of the charge on the melting temperatures.

Local Polar Fluctuations in Lead Halide Perovskite Crystals

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

Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.

2017-03-01

Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH3NH3PbBr3) and all-inorganic (CsPbBr3) leadhalide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-tohead Cs motion coupledmore » to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3.« less

Evaluation of Low Melting Halide Systems for Battery Applications.

DTIC Science & Technology

1983-04-01

prominent peak at 95 cm-1 . The spectrum of the other sample exhibits 124 -4 ,4 -4 -44 .. t - CD - 0o - N. 0 uN C)(j QCD oca CD u C 125. the same peaks... lattice with 6-fold coordination about in this region can be drawn. However. his isotherms have aluminum and melts at 192.4 ’C with a AH° of 35.3 kJ the...temperature in the composition of SbC.AICI is favored by the relatively large direction of increasing aluminum bromide content. just as lattice energy of

Lasing in robust cesium lead halide perovskite nanowires

PubMed Central

Eaton, Samuel W.; Lai, Minliang; Gibson, Natalie A.; Wong, Andrew B.; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R.; Yang, Peidong

2016-01-01

The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic–inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry–Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm−2 with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 109 excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

Lasing in robust cesium lead halide perovskite nanowires

DOE PAGES

Eaton, Samuel W.; Lai, Minliang; Gibson, Natalie A.; ...

2016-02-09

The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic-inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored andmore » handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry-Pérot lasing occurs in CsPbBr 3 nanowires with an onset of 5 μJ cm -2 with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 10 9 excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication.« less

Effect of Halide Flux on Physicochemical Properties of MgCl2-Based Molten Salts for Accelerating Zirconium Production: Thermodynamic Assessment

NASA Astrophysics Data System (ADS)

Shin, Jae Hong; Park, Joo Hyun

2016-09-01

The effective halide flux additive for increasing the density of MgCl2 mixture and for decreasing the activity of MgCl2 was investigated in order to improve the reaction efficiency between gaseous ZrCl4 and fresh Mg melt to produce zirconium sponge. Thermochemical computation using FactSageTM software was primarily carried out, followed by the experimental confirmation. The addition of CaCl2, BaCl2, MgF2, and CaF2 to the molten MgCl2 increases the density of the melts, indicating that these halide additives can be a candidate to increase the density of the MgCl2-based molten salts. Among them, BaCl2, MgF2, and CaF2 are the useful additives. The activity of MgCl2 can be reduced by the addition of BaCl2, KCl, NaCl, MgF2, and CaF2, among which the CaF2 is the most effective additive to reduce the activity of MgCl2 with the strongest negative deviation from an ideality. Thus, the addition of CaF2 to the MgCl2, forming the MgCl2-CaF2 binary melt, is the most effective way not only to increase the density of the melt but also to decrease the activity of MgCl2, which was experimentally confirmed. Consequently, the production rate of zirconium sponge by magnesiothermic reduction process can be accelerated by the addition of CaF2.

Shallow halogen vacancies in halide optoelectronic materials

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

Shi, Hongliang; Du, Mao -Hua

2014-11-05

Halogen vacancies (V H) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep V H contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH 3NH 3PbI 3 and TlBr. Both CH 3NH 3PbI 3 and TlBr have been found to have shallow V H, in contrast to commonly seen deep V H in halides. In this paper, several halide optoelectronic materials, i.e., CH 3NH 3PbI 3, CH 3NH 3SnI 3 (photovoltaic materials), TlBr, and CsPbBrmore » 3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether V H is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns 2 ions both play important roles in creating shallow V H in halides such as CH 3NH 3PbI 3, CH 3NH 3SnI 3, and TlBr. The key to identifying halides with shallow V H is to find the right crystal structures and compounds that suppress cation orbital hybridization at V H, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at V H. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow V H as good electronic and optoelectronic materials.« less

Shallow halogen vacancies in halide optoelectronic materials

NASA Astrophysics Data System (ADS)

Shi, Hongliang; Du, Mao-Hua

2014-11-01

Halogen vacancies (VH ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., C H3N H3Pb I3 and TlBr. Both C H3N H3Pb I3 and TlBr have been found to have shallow VH , in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., C H3N H3Pb I3 , C H3N H3Sn I3 (photovoltaic materials), TlBr, and CsPbB r3 (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of n s2 ions both play important roles in creating shallow VH in halides such as C H3N H3Pb I3 , C H3N H3Sn I3 , and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH , such as those with large cation-cation distances and low anion coordination numbers and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH . The results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

Modeling the hydration of mono-atomic anions from the gas phase to the bulk phase: the case of the halide ions F-, Cl-, and Br-.

PubMed

Trumm, Michael; Martínez, Yansel Omar Guerrero; Réal, Florent; Masella, Michel; Vallet, Valérie; Schimmelpfennig, Bernd

2012-01-28

In this work, we investigate the hydration of the halide ions fluoride, chloride, and bromide using classical molecular dynamics simulations at the 10 ns scale and based on a polarizable force-field approach, which treats explicitly the cooperative bond character of strong hydrogen bond networks. We have carried out a thorough analysis of the ab initio data at the MP2 or CCSD(T) level concerning anion/water clusters in gas phase to adjust the force-field parameters. In particular, we consider the anion static polarizabilities computed in gas phase using large atomic basis sets including additional diffuse functions. The information extracted from trajectories in solution shows well structured first hydration shells formed of 6.7, 7.0, and 7.6 water molecules at about 2.78 Å, 3.15 Å, and 3.36 Å for fluoride, chloride, and bromide, respectively. These results are in excellent agreement with the latest neutron- and x-ray diffraction studies. In addition, our model reproduces several other properties of halide ions in solution, such as diffusion coefficients, description of hydration processes, and exchange reactions. Moreover, it is also able to reproduce the electrostatic properties of the anions in solution (in terms of anion dipole moment) as reported by recent ab initio quantum simulations. All the results show the ability of the proposed model in predicting data, as well as the need of accounting explicitly for the cooperative character of strong hydrogen bonds to reproduce ab initio potential energy surfaces in a mean square sense and to build up a reliable force field. © 2012 American Institute of Physics

Method for producing hydrocarbon fuels and fuel gas from heavy polynuclear hydrocarbons by the use of molten metal halide catalysts

DOEpatents

Gorin, Everett

1979-01-01

In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst in a hydrocracking zone, thereafter separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide and thereafter regenerating the spent molten metal halide by incinerating the spent molten metal halide by combustion of carbon and sulfur compounds in the spent molten metal halide in an incineration zone, the improvement comprising: (a) contacting the heavy feedstocks and hydrogen in the presence of the molten metal halide in the hydrocracking zone at reaction conditions effective to convert from about 60 to about 90 weight percent of the feedstock to lighter hydrocarbon fuels; (b) separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide; (c) contacting the spent molten metal halide with oxygen in a liquid phase gasification zone at a temperature and pressure sufficient to vaporize from about 25 to about 75 weight percent of the spent metal halide, the oxygen being introduced in an amount sufficient to remove from about 60 to about 90 weight percent of the carbon contained in the spent molten metal halide to produce a fuel gas and regenerated metal halide; and (d) incinerating the spent molten metal halide by combusting carbon and sulfur compounds contained therein.

Metastable phase formation in undercooled Fe-Co melts under terrestrial and parabolic flight conditions

NASA Astrophysics Data System (ADS)

Hermann, R.; Löser, W.; Lindenkreuz, H. G.; Yang-Bitterlich, W.; Mickel, Ch.; Diefenbach, A.; Schneider, S.; Dreier, W.

2007-12-01

Soft magnetic Fe-Co alloys display primary fcc phase solidification for>19,5 at% Co in conventional near-equilibrium solidification processes. Undercooled Fe-Co melt drops within the composition range of 30 to 50 at% Co have been investigated with the electromagnetic levitation technique. The solidification kinetics was measured in situ using a high-resolution Siphotodiode. Melt drops were undercooled up to 263 K below the liquidus temperature and subsequently quenched onto a chill substrate in order to characterize the solidification sequence and microstructure. The transition from stable fcc phase to metastable bcc primary phase solidification has been observed after reaching a critical undercooling level. The critical undercooling increases with rising Co content. The growth velocity drops obviously after transition to metastable bcc phase formation. Parabolic flight experiments were performed in order to study the phase selection under reduced gravity conditions. Under microgravity conditions, a much smaller critical undercooling and an increased life time of the metastable bcc phase were obtained. This result was validated with TEM investigations. The appearance of Fe-O particles gives an indirect hint for an intermediate fcc phase formation from the metastable bcc phase at elevated temperature.

Phase diagrams of block copolymer melts by dissipative particle dynamics simulations

NASA Astrophysics Data System (ADS)

Gavrilov, Alexey A.; Kudryavtsev, Yaroslav V.; Chertovich, Alexander V.

2013-12-01

Phase diagrams for monodisperse and polydisperse diblock copolymer melts and a random multiblock copolymer melt are constructed using dissipative particle dynamics simulations. A thorough visual analysis and calculation of the static structure factor in several hundreds of points at each of the diagrams prove the ability of mesoscopic molecular dynamics to predict the phase behavior of polymer systems as effectively as the self-consistent field-theory and Monte Carlo simulations do. It is demonstrated that the order-disorder transition (ODT) curve for monodisperse diblocks can be precisely located by a spike in the dependence of the mean square pressure fluctuation on χN, where χ is the Flory-Huggins parameter and N is the chain length. For two other copolymer types, the continuous ODTs are observed. Large polydispersity of both blocks obeying the Flory distribution in length does not shift the ODT curve but considerably narrows the domains of the cylindrical and lamellar phases partially replacing them with the wormlike micelle and perforated lamellar phases, respectively. Instead of the pure 3d-bicontinuous phase in monodisperse diblocks, which could be identified as the gyroid, a coexistence of the 3d phase and cylindrical micelles is detected in polydisperse diblocks. The lamellar domain spacing D in monodisperse diblocks follows the strong-segregation theory prediction, D/N1/2 ˜ (χN)1/6, whereas in polydisperse diblocks it is almost independent of χN at χN < 100. Completely random multiblock copolymers cannot form ordered microstructures other than lamellas at any composition.

Three-Phase Melting Curves in the Binary System of Carbon Dioxide and Water

NASA Astrophysics Data System (ADS)

Abramson, E. H.

2017-10-01

Invariant, three-phase melting curves, of ice VI in equilibrium with solid CO2, of ice VII in equilibrium with solid CO2, and of solid CO2 in simultaneous equilibrium with a majority aqueous and a majority CO2 fluid, were explored in the binary system of carbon dioxide and water. Diamond-anvil cells were used to develop pressures of 5 GPa. Water exhibits a large melting temperature depression (73°C less than its pure melting temperature of 253°C at 5 GPa) indicative of large concentrations of CO2 in the aqueous solution. The melting point of water-saturated CO2 does not show a measureable departure from that of the pure system at temperatures lower than ∼200°C and only 10°C at 5 GPa (from 327°C).

Calcium looping process for high purity hydrogen production integrated with capture of carbon dioxide, sulfur and halides

DOEpatents

Ramkumar, Shwetha; Fan, Liang-Shih

2013-07-30

A process for producing hydrogen comprising the steps of: (i) gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam, sulfur and halide contaminants in the form of H.sub.2S, COS, and HX, wherein X is a halide; (ii) passing the raw synthesis gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO.sub.2, sulfur and halides in a solid-phase calcium-containing product comprising CaCO.sub.3, CaS and CaX.sub.2; (iii) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (iv) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO.sub.2, in the presence of synthesis gas, in the presence of H.sub.2 and O.sub.2, under partial vacuum, and combinations thereof.

Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

ERIC Educational Resources Information Center

Waas, Jack R.

2006-01-01

Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing

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

Dandeneau, Christopher S.; Hong, Tao; Brinkman, Kyle S.

Melt processing of multi-phase ceramic waste forms offers potential advantages over traditional solid-state synthesis methods given both the prevalence of melters currently in use and the ability to reduce the possibility of airborne radionuclide contamination. In this work, multi-phase ceramics with a targeted hollandite composition of Ba 1.0Cs 0.3Cr 1.0Al 0.3Fe 1.0Ti 5.7O 16 were fabricated by melt processing at 1675 °C and hot isostatic pressing (HIP) at 1250 and 1300 °C. X-ray diffraction analysis (XRD) confirmed hollandite as the major phase in all specimens. Zirconolite/pyrochlore peaks and weaker perovskite reflections were observed after melt processing, while HIP samples displayedmore » prominent perovskite peaks and low-intensity zirconolite reflections. Melt processing produced specimens with large (>50 μm) well-defined hollandite grains, while HIP yielded samples with a more fine-grained morphology. Elemental analysis showed “islands” rich in Cs and Ti across the surface of the 1300 °C HIP sample, suggesting partial melting and partitioning of Cs into multiple phases. Photoemission data revealed multiple Cs 3d spin-orbit pairs for the HIP samples, with the lower binding energy doublets likely corresponding to Cs located in more leachable phases. Among all specimens examined, the melt-processed sample exhibited the lowest fractional release rates for Rb and Cs. However, the retention of Sr and Mo was greater in the HIP specimens.« less

Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing

DOE PAGES

Dandeneau, Christopher S.; Hong, Tao; Brinkman, Kyle S.; ...

2018-02-08

Melt processing of multi-phase ceramic waste forms offers potential advantages over traditional solid-state synthesis methods given both the prevalence of melters currently in use and the ability to reduce the possibility of airborne radionuclide contamination. In this work, multi-phase ceramics with a targeted hollandite composition of Ba 1.0Cs 0.3Cr 1.0Al 0.3Fe 1.0Ti 5.7O 16 were fabricated by melt processing at 1675 °C and hot isostatic pressing (HIP) at 1250 and 1300 °C. X-ray diffraction analysis (XRD) confirmed hollandite as the major phase in all specimens. Zirconolite/pyrochlore peaks and weaker perovskite reflections were observed after melt processing, while HIP samples displayedmore » prominent perovskite peaks and low-intensity zirconolite reflections. Melt processing produced specimens with large (>50 μm) well-defined hollandite grains, while HIP yielded samples with a more fine-grained morphology. Elemental analysis showed “islands” rich in Cs and Ti across the surface of the 1300 °C HIP sample, suggesting partial melting and partitioning of Cs into multiple phases. Photoemission data revealed multiple Cs 3d spin-orbit pairs for the HIP samples, with the lower binding energy doublets likely corresponding to Cs located in more leachable phases. Among all specimens examined, the melt-processed sample exhibited the lowest fractional release rates for Rb and Cs. However, the retention of Sr and Mo was greater in the HIP specimens.« less

Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing

NASA Astrophysics Data System (ADS)

Dandeneau, Christopher S.; Hong, Tao; Brinkman, Kyle S.; Vance, Eric R.; Amoroso, Jake W.

2018-04-01

Melt processing of multi-phase ceramic waste forms offers potential advantages over traditional solid-state synthesis methods given both the prevalence of melters currently in use and the ability to reduce the possibility of airborne radionuclide contamination. In this work, multi-phase ceramics with a targeted hollandite composition of Ba1.0Cs0.3Cr1.0Al0.3Fe1.0Ti5.7O16 were fabricated by melt processing at 1675 °C and hot isostatic pressing (HIP) at 1250 and 1300 °C. X-ray diffraction analysis (XRD) confirmed hollandite as the major phase in all specimens. Zirconolite/pyrochlore peaks and weaker perovskite reflections were observed after melt processing, while HIP samples displayed prominent perovskite peaks and low-intensity zirconolite reflections. Melt processing produced specimens with large (>50 μm) well-defined hollandite grains, while HIP yielded samples with a more fine-grained morphology. Elemental analysis showed "islands" rich in Cs and Ti across the surface of the 1300 °C HIP sample, suggesting partial melting and partitioning of Cs into multiple phases. Photoemission data revealed multiple Cs 3d spin-orbit pairs for the HIP samples, with the lower binding energy doublets likely corresponding to Cs located in more leachable phases. Among all specimens examined, the melt-processed sample exhibited the lowest fractional release rates for Rb and Cs. However, the retention of Sr and Mo was greater in the HIP specimens.

Coulometric thermometric titration of halides in molten calcium nitrate tetrahydrate.

PubMed

Zsigrai, I J; Bartusz, D B

1983-01-01

A method for coulometric thermometric precipitation titrations of chloride, bromide and iodide in molten calcium nitrate tetrahydrate at 55 degrees with coulometrically generated silver ions has been developed. The change in temperature during the titration is followed with the aid of a thermistor bridge coupled to a recorder. To minimize the temperature effect of the passage of current through the melt, two thermistors are connected in opposition in the bridge, with one in the anodic and the other in the cathodic cell compartment. Amounts of 62-80 mumole of halide have been determined with relative error below 0.4% and relative standard deviation less than 2.7%. The relative error in determination of 40 mumole of iodide was + 2%.

A Comparative Study of Continental vs. Intraoceanic Arc Mantle Melting: Experimentally Determined Phase Relations of Hydrous, Primitive Melts

NASA Astrophysics Data System (ADS)

Weaver, S.; Johnston, A.; Wallace, P. J.

2009-12-01

It is widely recognized that H2O and other volatiles play a crucial role in mantle melting in subduction zones. This work is a comparative study focused on determining the H2O-undersaturated, near-liquidus phase relations for two primitive subduction related compositions with the goal of determining the P-T-H2O conditions of mantle melting beneath arcs. These samples, JR-28, a calc-alkaline basalt from Volcan Jorullo, Mexico, and ID-16, a tholeiitic basalt from Okmok Volcano, Aleutian Islands, have major element compositions that indicate they are primary, mantle-derived melts. H2O-undersaturated piston cylinder experiments have been carried out at upper mantle pressures and temperatures (1.0-2.0 GPa and 1100-1350°C). The near-liquidus mineralogy of these two compositions has been mapped in P-T- H2O space in order to constrain the conditions under which these melts are multiply saturated with a mantle residue (lherzolite or harzburgite). Previous studies of dissolved volatiles in olivine-hosted melt inclusions have provided an estimate of pre-eruptive H2O-contents for JR-28 at ≥5 wt% H2O and experiments have been carried out accordingly. Preliminary results for JR-28 at 5 wt% H2O show olivine ± Cr-rich spinel on the liquidus at 1.0 GPa and enstatite as the liquidus phase at higher pressures (1.3 to 2.0 GPa). Ca-rich pyroxene appears in only one experiment 50°C below the liquidus at 1.5 GPa. These data show that JR-28 melts are multiply saturated with a harzburgite assemblage at ~1175°C and ~1.2 GPa at 5 wt% H2O. Experiments at 7 wt% H2O show similar results, although the olivine/Cr-spinel stability field expands at the expense of the enstatite stability field. Consequently, the olivine-enstatite cotectic is shifted to higher pressures and slightly cooler temperatures. The relatively high SiO2 content in the bulk rock (~52 wt% SiO2) supports the hypothesis that JR-28 last equilibrated with a depleted or harzburgite residue rather than a more fertile mantle

Tin in granitic melts: The role of melting temperature and protolith composition

NASA Astrophysics Data System (ADS)

Wolf, Mathias; Romer, Rolf L.; Franz, Leander; López-Moro, Francisco Javier

2018-06-01

Granite bound tin mineralization typically is seen as the result of extreme magmatic fractionation and late exsolution of magmatic fluids. Mineralization, however, also could be obtained at considerably less fractionation if initial melts already had enhanced Sn contents. We present chemical data and results from phase diagram modeling that illustrate the dominant roles of protolith composition, melting conditions, and melt extraction/evolution for the distribution of Sn between melt and restite and, thus, the Sn content of melts. We compare the element partitioning between leucosome and restite of low-temperature and high-temperature migmatites. During low-temperature melting, trace elements partition preferentially into the restite with the possible exception of Sr, Cd, Bi, and Pb, that may be enriched in the melt. In high-temperature melts, Ga, Y, Cd, Sn, REE, Pb, Bi, and U partition preferentially into the melt whereas Sc, V, Cr, Co, Ni, Mo, and Ba stay in the restite. This contrasting behavior is attributed to the stability of trace element sequestering minerals during melt generation. In particular muscovite, biotite, titanite, and rutile act as host phases for Sn and, therefore prevent Sn enrichment in the melt as long as they are stable phases in the restite. As protolith composition controls both the mineral assemblage and modal contents of the various minerals, protolith composition eventually also controls the fertility of a rock during anatexis, restite mineralogy, and partitioning behavior of trace metals. If a particular trace element is sequestered in a phase that is stable during partial melting, the resulting melt is depleted in this element whereas the restite becomes enriched. Melt generation at high temperature may release Sn when Sn-hosts become unstable. If melt has not been lost before the breakdown of Sn-hosts, Sn contents in the melt will increase but never will be high. In contrast, if melt has been lost before the decomposition of Sn

Partial Melting of the Indarch (EH4) Meteorite : A Textural, Chemical and Phase Relations View of Melting and Melt Migration

NASA Technical Reports Server (NTRS)

McCoy, Timothy J.; Dickinson, Tamara L.; Lofgren, Gary E.

2000-01-01

To Test whether Aubrites can be formed by melting of enstatite Chondrites and to understand igneous processes at very low oxygen fugacities, we have conducted partial melting experiments on the Indarch (EH4) chondrite at 1000-1500 C. Silicate melting begins at 1000 C. Substantial melt migration occurs at 1300-1400 C and metal migrates out of the silicate change at 1450 C and approx. 50% silicate partial melting. As a group, our experiments contain three immiscible metallic melts 9Si-, and C-rich), two immiscible sulfide melts(Fe-and FeMgMnCa-rich) and Silicate melt. Our partial melting experiments on the Indarch (EH4) enstatite Chondrite suggest that igneous processes at low fO2 exhibit serveral unique features. The complete melting of sulfides at 1000 C suggest that aubritic sulfides are not relicts. Aubritic oldhamite may have crystallized from Ca and S complexed in the silicate melt. Significant metal-sulfide melt migration might occur at relatively low degrees of silicate partial melting. Substantial elemental exchange occurred between different melts (e.g., between sulfide and silicate, Si between silicate and metal), a feature not observed during experiments at higher fO2. This exchange may help explain the formation of aubrites from known enstatite chondrites.

Gas Phase Chromatography of some Group 4, 5, and 6 Halides

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

Sylwester, Eric Robert

1998-10-01

Gas phase chromatography using The Heavy Element Volatility Instrument (HEVI) and the On Line Gas Apparatus (OLGA III) was used to determine volatilities of ZrBr 4, HfBr 4, RfBr 4, NbBr 5, TaOBr 3, HaCl 5, WBr 6, FrBr, and BiBr 3. Short-lived isotopes of Zr, Hf, Rf, Nb, Ta, Ha, W, and Bi were produced via compound nucleus reactions at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory and transported to the experimental apparatus using a He gas transport system. The isotopes were halogenated, separated from the other reaction products, and their volatilities determined by isothermal gas phase chromatography.more » Adsorption Enthalpy (ΔH a) values for these compounds were calculated using a Monte Carlo simulation program modeling the gas phase chromatography column. All bromides showed lower volatility than molecules of similar molecular structures formed as chlorides, but followed similar trends by central element. Tantalum was observed to form the oxybromide, analogous to the formation of the oxychloride under the same conditions. For the group 4 elements, the following order in volatility and ΔH a was observed: RfBr 4 > ZrBr 4 > HfBr 4. The ΔH a values determined for the group 4, 5, and 6 halides are in general agreement with other experimental data and theoretical predictions. Preliminary experiments were performed on Me-bromides. A new measurement of the half-life of 261Rf was performed. 261Rf was produced via the 248Cm( 18O, 5n) reaction and observed with a half-life of 74 -6 +7 seconds, in excellent agreement with the previous measurement of 78 -6 +11 seconds. We recommend a new half-life of 75±7 seconds for 261Rf based on these two measurements. Preliminary studies in transforming HEVI from an isothermal (constant temperature) gas phase chromatography instrument to a thermochromatographic (variable temperature) instrument have been completed. Thermochromatography is a technique that can be used to study the volatility and ΔH a of longer

Process and composition for drying of gaseous hydrogen halides

DOEpatents

Tom, Glenn M.; Brown, Duncan W.

1989-08-01

A process for drying a gaseous hydrogen halide of the formula HX, wherein X is selected from the group consisting of bromine, chlorine, fluorine, and iodine, to remove water impurity therefrom, comprising: contacting the water impurity-containing gaseous hydrogen halide with a scavenger including a support having associated therewith one or more members of the group consisting of: (a) an active scavenging moiety selected from one or more members of the group consisting of: (i) metal halide compounds dispersed in the support, of the formula MX.sub.y ; and (ii) metal halide pendant functional groups of the formula -MX.sub.y-1 covalently bonded to the support, wherein M is a y-valent metal, and y is an integer whose value is from 1 to 3; (b) corresponding partially or fully alkylated compounds and/or pendant functional groups, of the metal halide compounds and/or pendant functional groups of (a); wherein the alkylated compounds and/or pendant functional groups, when present, are reactive with the gaseous hydrogen halide to form the corresponding halide compounds and/or pendant functional groups of (a); and M being selected such that the heat of formation, .DELTA.H.sub.f of its hydrated halide, MX.sub.y.(H.sub.2 O).sub.n, is governed by the relationship: .DELTA.H.sub.f .gtoreq.n.times.10.1 kilocalories/mole of such hydrated halide compound wherein n is the number of water molecules bound to the metal halide in the metal halide hydrate. Also disclosed is an appertaining scavenger composition and a contacting apparatus wherein the scavenger is deployed in a bed for contacting with the water impurity-containing gaseous hydrogen halide.

Melt focusing and geochemical evolution at mid-ocean ridges: simulations of reactive two-phase flow

NASA Astrophysics Data System (ADS)

Keller, T.; Katz, R. F.; Hirschmann, M. M.

2017-12-01

The geochemical character of MORB and related off-axis volcanic products reflects the signature of chemical reservoirs in the mantle, the processes of melt transport from source to surface, or both. Focusing of partial melt to the ridge axis controls the proportion of deep, volatile- and incompatible-rich melts that contribute to MORB formation. However, the effect of volatiles, including CO2 and H2O, on melt segregation and focusing remains poorly understood. We investigate this transport using 2-D numerical simulations of reactive two-phase flow. The phases are solid mantle and liquid magma. Major elements and volatiles are represented by a system with 4 or 6 pseudo-components. This captures accepted features of mantle melting with volatiles. The fluid-dynamical model is McKenzie's formulation [1], while melting and reactive transport use the R_DMC method [2,3]. Trace element transport is computed for 5 idealized elements between highly incompatible and compatible behavior. Our results indicate that volatiles cause channelized melt transport, which leads to fluctuations in volume and composition of melt focused to the axis. The volatile-induced expansion of the melting regime at depth, however, has no influence on melt focusing. Up to 50% of deep, volatile-rich melts are not focused to the axis, but are emplaced along the oceanic LAB. There, crystallization of accumulated melt leads to enrichment of volatiles and incompatibles in the deep lithosphere. This has implications for volatile recycling by subduction, seismic properties of the oceanic LAB, and potential sources for seamount volcanism. Results from a suite of simulations, constrained by catalogued observational data [4,5,6], enable prediction of global MORB and volatile output and systematic variations of major, volatile and trace element concentrations as a function of mantle conditions and dynamic properties. REFERENCES[1] McKenzie (1984), doi:10.1093/petrology/25.3.713.[2] Rudge, Bercovici & Spiegelman

Greater-than-bulk melting temperatures explained: Gallium melts Gangnam style

NASA Astrophysics Data System (ADS)

Gaston, Nicola; Steenbergen, Krista

2014-03-01

The experimental discovery of superheating in gallium clusters contradicted the clear and well-demonstrated paradigm that the melting temperature of a particle should decrease with its size. However the extremely sensitive dependence of melting temperature on size also goes to the heart of cluster science, and the interplay between the effects of electronic and geometric structure. We have performed extensive first-principles molecular dynamics calculations, incorporating parallel tempering for an efficient exploration of configurational phase space. This is necessary, due to the complicated energy landscape of gallium. In the nanoparticles, melting is preceded by a transitions between phases. A structural feature, referred to here as the Gangnam motif, is found to increase with the latent heat and appears throughout the observed phase changes of this curious metal. We will present our detailed analysis of the solid-state isomers, performed using extensive statistical sampling of the trajectory data for the assignment of cluster structures to known phases of gallium. Finally, we explain the greater-than-bulk melting through analysis of the factors that stabilise the liquid structures.

Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence

PubMed Central

Xing, Guichuan; Wu, Bo; Wu, Xiangyang; Li, Mingjie; Du, Bin; Wei, Qi; Guo, Jia; Yeow, Edwin K. L.; Sum, Tze Chien; Huang, Wei

2017-01-01

The slow bimolecular recombination that drives three-dimensional lead-halide perovskites' outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 1015 cm−3, defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence. PMID:28239146

Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence.

PubMed

Xing, Guichuan; Wu, Bo; Wu, Xiangyang; Li, Mingjie; Du, Bin; Wei, Qi; Guo, Jia; Yeow, Edwin K L; Sum, Tze Chien; Huang, Wei

2017-02-27

The slow bimolecular recombination that drives three-dimensional lead-halide perovskites' outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 10 15  cm -3 , defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence.

Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

NASA Technical Reports Server (NTRS)

Dickson, C. R.; Gould, R. K.; Felder, W.

1981-01-01

High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

Melt coaxial electrospinning: a versatile method for the encapsulation of solid materials and fabrication of phase change nanofibers.

PubMed

McCann, Jesse T; Marquez, Manuel; Xia, Younan

2006-12-01

We have developed a method based on melt coaxial electrospinning for fabricating phase change nanofibers consisting of long-chain hydrocarbon cores and composite sheaths. This method combines melt electrospinning with a coaxial spinneret and allows for nonpolar solids such as paraffins to be electrospun and encapsulated in one step. Shape-stabilized, phase change nanofibers have many potential applications as they are able to absorb, hold, and release large amounts of thermal energy over a certain temperature range by taking advantage of the large heat of fusion of long-chain hydrocarbons. We have focused on compounds with melting points near room temperature (octadecane) and body temperature (eicosane) as these temperature ranges are most valuable in practice. We have produced thermally stable, phase change materials up to 45 wt % octadecane, as measured by differential scanning calorimetry. In addition, the resultant fibers display novel segmented morphologies for the cores due to the rapid solidification of the hydrocarbons driven by evaporative cooling of the carrier solution. Aside from the fabrication of phase change nanofibers, the melt coaxial method is promising for applications related to microencapsulation and controlled release of drugs.

Stability of the bcc phase of 4He close to the melting curve: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Belonoshko, A. B.; Koči, L.; Rosengren, A.

2012-01-01

We have investigated whether the Aziz [J. Chem. Phys.JCPSA60021-960610.1063/1.438007 70, 4330 (1979)] model for 4He renders the body-centered cubic phase more stable than the face-centered cubic phase in the proximity of the melting curve. Using molecular dynamics, we have simulated these solid phases in equilibrium with the liquid at a number of densities. In contrast to previous free energy molecular dynamics calculations, the model stabilizes the body-centered cubic phase. The stability field is just 5∘ wide below the melting curve at pressures around 140 Kbar and about 70∘ wide at pressures around 750 Kbar. Considering that the body-centered cubic phase is dynamically unstable at low temperature, this result bears striking similarities to transition metal phase diagrams.

Consequences of viscous anisotropy for melt localization in a deforming, two-phase aggregate

NASA Astrophysics Data System (ADS)

Takei, Y.; Katz, R. F.

2012-12-01

Melt localization in the deforming, partially molten mantle has been of interest because it affects the melt extraction rate, mantle deformability, and chemical interaction between the melt and host rock. Experimental studies have reported the spontaneous segregation of melt into melt-rich bands in samples deformed under simple shear and torsion (Holtzman et al, 2003, King et al, 2010). Efforts to clarify the instability mechanism have so far revealed that rheological properties of partially molten rocks control the occurrence of instability. Porosity-weakening viscosity, empirically written as exp(- λ × f) with porosity f and constant λ(= 25-45), plays an essential role in the destabilization of porosity perturbation in the shear flow of a two-phase aggregate (eg., pure shear flow, simple shear flow): the perturbation growth rate is proportional to the product of shear strain rate and the factor λ (Stevenson, 1989). The stress exponent n of the viscosity affects the angle of the perturbation plane with maximum growthrate, where n=3-6 (power-law creep) explains the experimentally observed low angle to the shear plane (Katz et al, 2006). However, in-situ experimental measurements of n indicate that it takes values as low as unity without affecting the observed orientation of melt bands. Viscous anisotropy provides an alternative explanation for the observed band angles. It is produced by the stress-induced microstructural anisotropy (Daines and Kohlstedt, 1997; Zimmermann et al., 1999; Takei, 2010), and it enhances the coupling between melt migration and matrix shear deformation (Takei and Holtzman, 2009). Even without any porosity perturbation, viscous anisotropy destabilizes simple patterns of two-phase flow with a stress/strain gradient (eg., Poiseuille flow, torsional flow) and gives rise to shear-induced melt localization: the growth rate of this mechanism depends on the shear strain rate and the compaction length relative to the spatial scale of the

PREPARATION OF HALIDES OF PLUTONIUM

DOEpatents

Garner, C.S.; Johns, I.B.

1958-09-01

A dry chemical method is described for preparing plutonium halides, which consists in contacting plutonyl nitrate with dry gaseous HCl or HF at an elevated temperature. The addition to the reaction gas of a small quantity of an oxidizing gas or a reducing gas will cause formation of the tetra- or tri-halide of plutonium as desired.

Melting phase relations in the MgSiO3-CaSiO3 system at 24 GPa

NASA Astrophysics Data System (ADS)

Nomura, Ryuichi; Zhou, Youmo; Irifune, Tetsuo

2017-12-01

The Earth's lower mantle is composed of bridgmanite, ferropericlase, and CaSiO3-rich perovskite. The melting phase relations between each component are key to understanding the melting of the Earth's lower mantle and the crystallization of the deep magma ocean. In this study, melting phase relations in the MgSiO3-CaSiO3 system were investigated at 24 GPa using a multi-anvil apparatus. The eutectic composition is (Mg,Ca)SiO3 with 81-86 mol% MgSiO3. The solidus temperature is 2600-2620 K. The solubility of CaSiO3 component into bridgmanite increases with temperature, reaching a maximum of 3-6 mol% at the solidus, and then decreases with temperature. The same trend was observed for the solubility of MgSiO3 component into CaSiO3-rich perovskite, with a maximum of 14-16 mol% at the solidus. The asymmetric regular solutions between bridgmanite and CaSiO3-rich perovskite and between MgSiO3 and CaSiO3 liquid components well reproduce the melting phase relations constrained experimentally. [Figure not available: see fulltext.

Permeation of halide anions through phospholipid bilayers occurs by the solubility-diffusion mechanism

NASA Technical Reports Server (NTRS)

Paula, S.; Volkov, A. G.; Deamer, D. W.

1998-01-01

Two alternative mechanisms are frequently used to describe ionic permeation of lipid bilayers. In the first, ions partition into the hydrophobic phase and then diffuse across (the solubility-diffusion mechanism). The second mechanism assumes that ions traverse the bilayer through transient hydrophilic defects caused by thermal fluctuations (the pore mechanism). The theoretical predictions made by both models were tested for halide anions by measuring the permeability coefficients for chloride, bromide, and iodide as a function of bilayer thickness, ionic radius, and sign of charge. To vary the bilayer thickness systematically, liposomes were prepared from monounsaturated phosphatidylcholines (PC) with chain lengths between 16 and 24 carbon atoms. The fluorescent dye MQAE (N-(ethoxycarbonylmethyl)-6-methoxyquinolinium bromide) served as an indicator for halide concentration inside the liposomes and was used to follow the kinetics of halide flux across the bilayer membranes. The observed permeability coefficients ranged from 10(-9) to 10(-7) cm/s and increased as the bilayer thickness was reduced. Bromide was found to permeate approximately six times faster than chloride through bilayers of identical thickness, and iodide permeated three to four times faster than bromide. The dependence of the halide permeability coefficients on bilayer thickness and on ionic size were consistent with permeation of hydrated ions by a solubility-diffusion mechanism rather than through transient pores. Halide permeation therefore differs from that of a monovalent cation such as potassium, which has been accounted for by a combination of the two mechanisms depending on bilayer thickness.

Quantum vortex melting and phase diagram in the layered organic superconductor κ -(BEDT-TTF)2Cu(NCS ) 2

NASA Astrophysics Data System (ADS)

Uji, S.; Fujii, Y.; Sugiura, S.; Terashima, T.; Isono, T.; Yamada, J.

2018-01-01

Resistance and magnetic torque measurements have been performed to investigate vortex phases for a layered organic superconductor κ -(BEDT-TTF) 2Cu (NCS) 2 [BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene], which is modeled as stacks of Josephson junctions. At 25 mK, the out-of-plane resistivity increases at 0.6 T, has a step feature up to 4 T, and then increases again, whereas the in-plane resistivity monotonically increases above 4 T. The results show that both pancake vortices (PVs) and Josephson vortices (JVs) are in solid phases for μ0H <0.6 T, but only JVs are in a liquid phase for 0.6 <μ0H <4 T. For μ0H >4 T, both PVs and JVs are in liquid phases. These melting transitions are predominantly induced by quantum fluctuations (not by thermal fluctuations). In the magnetic torque curves, the irreversibility transition is clearly observed, roughly corresponding to the melting transition of the PVs but no anomaly is found at the JV melting transition. The detailed vortex phase diagram is determined in a wide temperature region.

Phase composition and microstructure of WC-Co alloys obtained by selective laser melting

NASA Astrophysics Data System (ADS)

Khmyrov, Roman S.; Shevchukov, Alexandr P.; Gusarov, Andrey V.; Tarasova, Tatyana V.

2018-03-01

Phase composition and microstructure of initial WC, BK8 (powder alloy 92 wt.% WC-8 wt.% Co), Co powders, ball-milled powders with four different compositions (1) 25 wt.% WC-75 wt.% Co, (2) 30 wt.% BK8-70 wt.% Co, (3) 50 wt.% WC-50 wt.% Co, (4) 94 wt.% WC-6 wt.% Co, and bulk alloys obtained by selective laser melting (SLM) from as-milled powders in as-melted state and after heat treatment were investigated by scanning electron microscopy and X-ray diffraction analysis. Initial and ball-milled powders consist of WC, hexagonal α-Co and face-centered cubic β-Co. The SLM leads to the formation of major new phases W3Co3C, W4Co2C and face-centered cubic β-Co-based solid solution. During the heat treatment, there occurs partial decomposition of the face-centered cubic β-Co-based solid solution with the formation of W2C and hexagonal α-Co solid solution. The microstructure of obtained bulk samples, in general, corresponds to the observed phase composition.

Hydrogen-alkali exchange between silicate melts and two-phase aqueous mixtures: an experimental investigation

NASA Astrophysics Data System (ADS)

Williams, Thomas J.; Candela, Philip A.; Piccoli, Philip M.

Experiments were performed in the three-phase system high-silica rhyolite melt + low-salinity aqueous vapor + hydrosaline brine, to investigate the exchange equilibria for hydrogen, potassium, and sodium in magmatic-hydrothermal systems at 800 °C and 100 MPa, and 850 °C and 50 MPa. The Kaqm/meltH,Na and Kaqm/meltH,K for hydrogen-sodium exchange between a vapor + brine mixture and a silicate melt are inversely proportional to the total chloride concentration (ΣCl) in the vapor + brine mixture indicating that HCl/NaCl and HCl/KCl are higher in the low-salinity aqueous vapor relative to high-salinity brine. The equilibrium constants for vapor/melt and brine/melt exchange were extracted from regressions of Kaqm/meltH,Na and Kaqm/meltH,K versus the proportion of aqueous vapor relative to brine in the aqueous mixture (Faqv) at P and T, expressed as a function of ΣCl. No significant pressure effect on the empirically determined exchange constants was observed for the range of pressures investigated. Model equilibrium constants are: Kaqv/meltH,Na(vapor/melt)=26(+/-1.3) at 100 MPa (800 °C), and 19( +/- 7.0) at 50 MPa (850 °C) Kaqv/meltH,K=14(+/-1.1) at 100 MPa (800 °C), and 24(+/-12) at 50 MPa (850 °C) Kaqb/meltH,b(brine/melt)= 1.6(+/-0.7) at 100 MPa (800 °C), and 3.9(+/-2.3) at 50 MPa (850 °C) and Kaqb/meltH,K=2.7(+/-1.2) at 100 MPa (800 °C) and 3.8(+/-2.3) at 50 MPa (850 °C). Values for Kaqv/meltH,K and Kaqb/meltH,K were used to calculate KCl/HCl in the aqueous vapor and brine as a function of melt aluminum saturation index (ASI: molar Al2O3/(K2O+Na2O+CaO) and pressure. The model log KCl/HCl values show that a change in melt ASI from peraluminous (ASI = 1.04) to moderately metaluminous (ASI = 1.01) shifts the cooling pathway (in temperature-log KCl/HCl space) of the aqueous vapor toward the andalusite+muscovite+K-feldspar reaction point.

Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

PubMed

Chen, Kun; Tüysüz, Harun

2015-11-09

The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bulk assembly of organic metal halide nanotubes

DOE PAGES

Lin, Haoran; Zhou, Chenkun; Tian, Yu; ...

2017-10-16

The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C 6H 13N 4) 3Pb 2Br 7. In a metal halide nanotube, six face-sharing metal halide dimers (Pb 2Br 9 5–) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C 6H 13N 4 +). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resultingmore » in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ~7%. Finally, having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.« less

Phase separation of comb polymer nanocomposite melts.

PubMed

Xu, Qinzhi; Feng, Yancong; Chen, Lan

2016-02-07

In this work, the spinodal phase demixing of branched comb polymer nanocomposite (PNC) melts is systematically investigated using the polymer reference interaction site model (PRISM) theory. To verify the reliability of the present method in characterizing the phase behavior of comb PNCs, the intermolecular correlation functions of the system for nonzero particle volume fractions are compared with our molecular dynamics simulation data. After verifying the model and discussing the structure of the comb PNCs in the dilute nanoparticle limit, the interference among the side chain number, side chain length, nanoparticle-monomer size ratio and attractive interactions between the comb polymer and nanoparticles in spinodal demixing curves is analyzed and discussed in detail. The results predict two kinds of distinct phase separation behaviors. One is called classic fluid phase boundary, which is mediated by the entropic depletion attraction and contact aggregation of nanoparticles at relatively low nanoparticle-monomer attraction strength. The second demixing transition occurs at relatively high attraction strength and involves the formation of an equilibrium physical network phase with local bridging of nanoparticles. The phase boundaries are found to be sensitive to the side chain number, side chain length, nanoparticle-monomer size ratio and attractive interactions. As the side chain length is fixed, the side chain number has a large effect on the phase behavior of comb PNCs; with increasing side chain number, the miscibility window first widens and then shrinks. When the side chain number is lower than a threshold value, the phase boundaries undergo a process from enlarging the miscibility window to narrowing as side chain length increases. Once the side chain number overtakes this threshold value, the phase boundary shifts towards less miscibility. With increasing nanoparticle-monomer size ratio, a crossover of particle size occurs, above which the phase separation

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics.

PubMed

Hoke, Eric T; Slotcavage, Daniel J; Dohner, Emma R; Bowring, Andrea R; Karunadasa, Hemamala I; McGehee, Michael D

2015-01-01

We report on reversible, light-induced transformations in (CH 3 NH 3 )Pb(Br x I 1- x ) 3 . Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.

Method for recovering hydrocarbons from molten metal halides

DOEpatents

Pell, Melvyn B.

1979-01-01

In a process for hydrocracking heavy carbonaceous materials by contacting such carbonaceous materials with hydrogen in the presence of a molten metal halide catalyst to produce hydrocarbons having lower molecular weights and thereafter recovering the hydrocarbons so produced from the molten metal halide, an improvement comprising injecting into the spent molten metal halide, a liquid low-boiling hydrocarbon stream is disclosed.

Divergent electronic structures of isoelectronic metalloclusters: tungsten(II) halides and rhenium(III) chalcogenide halides.

PubMed

Gray, Thomas G

2009-03-02

Same but different: DFT calculations on hexanuclear tungsten(II) halide clusters [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I) indicate a breakdown in the isoelectronic analogy between themselves and the isostructural rhenium(III) chalcogenide clusters [Re(6)S(8)X(6)](4-) (see figure).The hexanuclear tungsten(II) halide clusters and the sulfido-halide clusters of rhenium(III) are subsets of a broad system of 24-electron metal-metal bonded assemblies that share a common structure. Tungsten(II) halide clusters and rhenium(III) sulfide clusters luminesce from triplet excited states upon ultraviolet or visible excitation; emission from both cluster series has been extensively characterized elsewhere. Reported here are density-functional theory studies of the nine permutations of [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I). Ground-state properties including geometries, harmonic vibrational frequencies, and orbital energy-level diagrams, have been calculated. Comparison is made to the sulfide clusters of rhenium(III), of which [Re(6)S(8)Cl(6)](4-) is representative. [W(6)X(8)X'(6)](2-) and [Re(6)S(8)Cl(6)](4-) possess disparate electronic structures owing to the greater covalency of the metal-sulfur bond and hence of the [Re(6)S(8)](2+) core. Low-lying virtual orbitals are raised in energy in [Re(6)S(8)Cl(6)](4-) with the result that the LUMO+7 (or LUMO+8 in some cases) of tungsten(II) halide clusters is the LUMO of [Re(6)S(8)Cl(6)](4-) species. An inversion of the HOMO and HOMO-1 between the two cluster series also occurs. Time-dependent density-functional calculations using asymptotically correct functionals do not recapture the experimentally observed periodic trend in [W(6)X(14)](2-) luminescence (E(em) increasing in the order [W(6)Cl(14)](2-) < [W(6)Br(14)](2-) < [W(6)I(14)](2-)), predicting instead that emission energies decrease with incorporation of the heavier halides. This circumstance is either a gross failure of the time-dependent formalism of DFT or it indicates extensive

METHOD OF PREPARING METAL HALIDES

DOEpatents

Hendrickson, A.V.

1958-11-18

The conversion of plutonium halides from plutonium peroxide can be done by washing the peroxide with hydrogen peroxide, drying the peroxide, passing a dry gaseous hydrohalide over the surface of the peroxide at a temperature of about lOO icient laborato C until the reaction rate has stabillzed, and then ralsing the reaction temperature to between 400 and 600 icient laborato C until the conversion to plutonium halide is substantially complete.

Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation.

PubMed

Zhao, Xin-Gang; Yang, Ji-Hui; Fu, Yuhao; Yang, Dongwen; Xu, Qiaoling; Yu, Liping; Wei, Su-Huai; Zhang, Lijun

2017-02-22

Hybrid organic-inorganic halide perovskites with the prototype material of CH 3 NH 3 PbI 3 have recently attracted intense interest as low-cost and high-performance photovoltaic absorbers. Despite the high power conversion efficiency exceeding 20% achieved by their solar cells, two key issues-the poor device stabilities associated with their intrinsic material instability and the toxicity due to water-soluble Pb 2+ -need to be resolved before large-scale commercialization. Here, we address these issues by exploiting the strategy of cation-transmutation to design stable inorganic Pb-free halide perovskites for solar cells. The idea is to convert two divalent Pb 2+ ions into one monovalent M + and one trivalent M 3+ ions, forming a rich class of quaternary halides in double-perovskite structure. We find through first-principles calculations this class of materials have good phase stability against decomposition and wide-range tunable optoelectronic properties. With photovoltaic-functionality-directed materials screening, we identify 11 optimal materials with intrinsic thermodynamic stability, suitable band gaps, small carrier effective masses, and low excitons binding energies as promising candidates to replace Pb-based photovoltaic absorbers in perovskite solar cells. The chemical trends of phase stabilities and electronic properties are also established for this class of materials, offering useful guidance for the development of perovskite solar cells fabricated with them.

Effects of nanoparticles on melting process with phase-change using the lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Ibrahem, Ahmed M.; El-Amin, Mohamed F.; Sun, Shuyu

In this work, the problem of nanoparticles dispersion effects on coupled heat transfer and solid-liquid phase change has been studied. The lattice Boltzmann method (LBM) enthalpy-based is employed. The collision model of lattice Bhatnagar-Gross-Krook (LBGK) is used to solve the problem of 1D melting by conduction. On the other hand, we use the model of multi-distribution functions (MDF) to calculate the density, the velocity and the temperature for the problem of 2D melting by free convection, associated with different boundary conditions. In these simulations, the volume fractions of copper nanoparticles (0-2%) added to water-base fluid and Rayleigh numbers of 103-105. We use the Chapman-Enskog expansion to derive the governing macroscopic quantities from the mesoscopic lattice Boltzmann equation. The results obtained by these models have been compared to an analytical solution or other numerical methods. The effects of nanoparticles on conduction and natural convection during the melting process have been investigated. Moreover, the influences of nanoparticles on moving of the phase change front, the thermal conductivity and the latent heat of fusion are also studied.

TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

DOEpatents

Fried, S.

1951-03-20

Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

Structure and property of metal melt I: The number of residual bonds after solid-liquid phase changes

NASA Astrophysics Data System (ADS)

Mi, Guangbao; Li, Peijie; He, Liangju

2010-09-01

Based on the mechanism of metal solid-liquid phase change and the theory of liquid metal’s micro-inhomogeneity, a physical model is established between latent heats of fusion and vaporization and the numbers of residual bonds and short-range ordered atoms at the melting point inside a metal melt. Meanwhile, the mathematical derivation and proof are also offered. This model produces the numbers of residual bonds and short-range ordered atoms after the solid-liquid phase change only by using basic parameters and thermophysical properties of the crystal structure. Therefore, it presents a more effective way to analyze the melt’s structural information. By using this model, this study calculates the numbers of residual bonds and short-range ordered atoms in Al and Ni melts. The calculated results are consistent with the experimental results. Simultaneously, this study discusses the atomic number’s influence on the numbers of residual bonds and short-range ordered atoms in the melts within the first (IA) and second main group (IIA) elements.

Unraveling the Role of Monovalent Halides in Mixed-Halide Organic-Inorganic Perovskites.

PubMed

Deepa, Melepurath; Ramos, F Javier; Shivaprasad, S M; Ahmad, Shahzada

2016-03-16

The performance of perovskite solar cells is strongly influenced by the composition and microstructure of the perovskite. A recent approach to improve the power conversion efficiencies utilized mixed-halide perovskites, but the halide ions and their roles were not directly studied. Unraveling their precise location in the perovskite layer is of paramount importance. Here, we investigated four different perovskites by using X-ray photoelectron spectroscopy, and found that among the three studied mixed-halide perovskites, CH3 NH3 Pb(I0.74 Br0.26 )3 and CH3 NH3 PbBr3-x Clx show peaks that unambiguously demonstrate the presence of iodide and bromide in the former, and bromide and chloride in the latter. The CH3 NH3 PbI3-x Clx perovskite shows anomalous behavior, the iodide content far outweighs that of the chloride; a small proportion of chloride, in all likelihood, resides deep within the TiO2 /absorber layer. Our study reveals that there are many distinguishable structural differences between these perovskites, and that these directly impact the photovoltaic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ca-Fe and Alkali-Halide Alteration of an Allende Type B CAI: Aqueous Alteration in Nebular or Asteroidal Settings

NASA Technical Reports Server (NTRS)

Ross, D. K.; Simon, J. I.; Simon, S. B.; Grossman, L.

2012-01-01

Ca-Fe and alkali-halide alteration of CAIs is often attributed to aqueous alteration by fluids circulating on asteroidal parent bodies after the various chondritic components have been assembled, although debate continues about the roles of asteroidal vs. nebular modification processes [1-7]. Here we report de-tailed observations of alteration products in a large Type B2 CAI, TS4 from Allende, one of the oxidized subgroup of CV3s, and propose a speculative model for aqueous alteration of CAIs in a nebular setting. Ca-Fe alteration in this CAI consists predominantly of end-member hedenbergite, end-member andradite, and compositionally variable, magnesian high-Ca pyroxene. These phases are strongly concentrated in an unusual "nodule" enclosed within the interior of the CAI (Fig. 1). The Ca, Fe-rich nodule superficially resembles a clast that pre-dated and was engulfed by the CAI, but closer inspection shows that relic spinel grains are enclosed in the nodule, and corroded CAI primary phases interfinger with the Fe-rich phases at the nodule s margins. This CAI also contains abundant sodalite and nepheline (alkali-halide) alteration that occurs around the rims of the CAI, but also penetrates more deeply into the CAI. The two types of alteration (Ca-Fe and alkali-halide) are adjacent, and very fine-grained Fe-rich phases are associated with sodalite-rich regions. Both types of alteration appear to be replacive; if that is true, it would require substantial introduction of Fe, and transport of elements (Ti, Al and Mg) out of the nodule, and introduction of Na and Cl into alkali-halide rich zones. Parts of the CAI have been extensively metasomatized.

Preparation of 2-in.-diameter (001) β-Ga2O3 homoepitaxial wafers by halide vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Thieu, Quang Tu; Wakimoto, Daiki; Koishikawa, Yuki; Sasaki, Kohei; Goto, Ken; Konishi, Keita; Murakami, Hisashi; Kuramata, Akito; Kumagai, Yoshinao; Yamakoshi, Shigenobu

2017-11-01

The homoepitaxial growth of thick β-Ga2O3 layers on 2-in.-diameter (001) wafers was demonstrated by halide vapor phase epitaxy. Growth rates of 3 to 4 µm/h were confirmed for growing intentionally Si-doped n-type layers. A homoepitaxial layer with an average thickness and carrier concentration of 10.9 µm and 2.7 × 1016 cm-3 showed standard deviations of 1.8 µm (16.5%) and 0.5 × 1016 cm-3 (19.7%), respectively. Ni Schottky barrier diodes fabricated directly on a 5.3-µm-thick homoepitaxial layer with a carrier concentration of 3.4 × 1016 cm-3 showed reasonable reverse and forward characteristics, i.e., breakdown voltages above 200 V and on-resistances of 3.8-7.7 mΩ cm2 at room temperature.

Theory of metal atom-water interactions and alkali halide dimers

NASA Technical Reports Server (NTRS)

Jordan, K. D.; Kurtz, H. A.

1982-01-01

Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

When Is Melting Not Really Melting?

ERIC Educational Resources Information Center

Mangiaracina, Mike

2017-01-01

This 5E cycle of lessons takes students through a fun and thorough study of Silly Putty's properties, progressing from an initial observation of a "melting snowman" toy in the Engage phase to making and "marketing" their own homemade putty in the Evaluate phase. Along the way, students use evidence to construct their own…

Improved Heat-of-Fusion Energy Storage

NASA Technical Reports Server (NTRS)

Chen, K. H.; Manvi, R.

1982-01-01

Alkali metal/alkali-halide mixtures proposed for preventing solid buildup during energy recovery. When mixture melts (by absorption of heat of fusion), it forms two immiscible liquids. Salt-rich phase is heavier and has higher melting/recrysallization temperature; so during energy recovery salt crystallizes in this phase first. Since heat exchanger for energy recovery is in lighter metal-rich phase, solids do not form and there is no reduction of heat-recovery efficiency.

Role of a gas phase in the kinetics of zinc and iron reduction with carbon from slag melts

NASA Astrophysics Data System (ADS)

Chumarev, V. M.; Selivanov, E. N.

2013-03-01

The influence of the mass transfer conditions in the gas phase having formed at the carbon-slag melt interface on CO regeneration is approximately estimated in the framework of a two-stage scheme of metal reduction from slag melts by carbon. The effect of zinc vapors on the combined reduction of iron and zinc from slags is considered. The influence of the slag composition and temperature on the critical concentration of zinc oxide above which no iron forms as an individual phase is explained.

Colloidal thallium halide nanocrystals with reasonable luminescence, carrier mobility and diffusion length.

PubMed

Mir, Wasim J; Warankar, Avinash; Acharya, Ashutosh; Das, Shyamashis; Mandal, Pankaj; Nag, Angshuman

2017-06-01

Colloidal lead halide based perovskite nanocrystals (NCs) have been recently established as an interesting class of defect-tolerant NCs with potential for superior optoelectronic applications. The electronic band structure of thallium halides (TlX, where X = Br and I) show a strong resemblance to lead halide perovskites, where both Pb 2+ and Tl + exhibit a 6s 2 inert pair of electrons and strong spin-orbit coupling. Although the crystal structure of TlX is not perovskite, the similarities of its electronic structure with lead halide perovskites motivated us to prepare colloidal TlX NCs. These TlX NCs exhibit a wide bandgap (>2.5 eV or <500 nm) and the potential to exhibit a reduced density of deep defect states. Optical pump terahertz (THz) probe spectroscopy with excitation fluence in the range of 0.85-5.86 × 10 13 photons per cm 2 on NC films shows that the TlBr NCs possess high effective carrier mobility (∼220 to 329 cm 2 V -1 s -1 ), long diffusion length (∼0.77 to 0.98 μm), and reasonably high photoluminescence efficiency (∼10%). This combination of properties is remarkable compared to other wide-bandgap (>2.5 eV) semiconductor NCs, which suggests a reduction in the deep-defect states in the TlX NCs. Furthermore, the ultrafast carrier dynamics and temperature-dependent reversible structural phase transition together with its influence on the optical properties of the TlX NCs are studied.

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites.

PubMed

Bischak, Connor G; Hetherington, Craig L; Wu, Hao; Aloni, Shaul; Ogletree, D Frank; Limmer, David T; Ginsberg, Naomi S

2017-02-08

The distinct physical properties of hybrid organic-inorganic materials can lead to unexpected nonequilibrium phenomena that are difficult to characterize due to the broad range of length and time scales involved. For instance, mixed halide hybrid perovskites are promising materials for optoelectronics, yet bulk measurements suggest the halides reversibly phase separate upon photoexcitation. By combining nanoscale imaging and multiscale modeling, we find that the nature of halide demixing in these materials is distinct from macroscopic phase separation. We propose that the localized strain induced by a single photoexcited charge interacting with the soft, ionic lattice is sufficient to promote halide phase separation and nucleate a light-stabilized, low-bandgap, ∼8 nm iodide-rich cluster. The limited extent of this polaron is essential to promote demixing because by contrast bulk strain would simply be relaxed. Photoinduced phase separation is therefore a consequence of the unique electromechanical properties of this hybrid class of materials. Exploiting photoinduced phase separation and other nonequilibrium phenomena in hybrid materials more generally could expand applications in sensing, switching, memory, and energy storage.

Melt focusing and CO2 extraction at mid-ocean ridges: simulations of reactive two-phase flow

NASA Astrophysics Data System (ADS)

Keller, T.; Katz, R. F.; Hirschmann, M. M.

2016-12-01

The deep CO2 cycle is the result of fluxes between near-surface and mantle reservoirs. Outgassing from mid-ocean ridges is one of the primary fluxes of CO2 from the asthenosphere into the ocean-atmosphere reservoir. Focusing of partial melt to the ridge axis crucially controls this flux. However, the role of volatiles, in particular CO2 and H2O, on melt transport processes beneath ridges remains poorly understood. We investigate this transport using numerical simulations of two-phase, multi-component magma/mantle dynamics. The phases are solid mantle and liquid magma; the components are dunite, MORB, hydrated basalt, and carbonated basalt. These effective components capture accepted features of mantle melting with volatiles. The fluid-dynamical model is McKenzie's formulation [1], while melting and reactive transport use the R_DMC method [2,3]. Our results indicate that volatiles cause channelized melt transport, which leads to significant variability in volume and composition of focused melt. The volatile-induced expansion of the melting regime at depth, however, has no influence on melt focusing; distal volatile-rich melts are not focused to the axis. Up to 50% of these melts are instead emplaced along the oceanic LAB. There, crystallization of accumulated melt leads to enrichment of CO2 and H2O in the deep lithosphere, which has implications for LAB rheology and volatile recycling by subduction. Results from a suite of simulations, constrained by catalogued observational data [4,5,6] enable predictions of global MOR CO2 output. By combining observational constraints with self-consistent numerical simulations we obtain a range of CO2 output from the global ridge system of 28-110 Mt CO2/yr, corresponding to mean CO2 contents of 50-200 ppm in the mantle. REFERENCES[1] McKenzie (1984), doi:10.1093/petrology/25.3.713.[2] Rudge, Bercovici & Spiegelman (2011), doi:10.1111/j.1365-246X.2010.04870.x.[3] Keller & Katz (2016), doi:10.1093/petrology/egw030.[4] Dalton

Investigation of surface halide modification of nitrile butadiene rubber

NASA Astrophysics Data System (ADS)

Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

2017-12-01

The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

Advances in the growth of alkaline-earth halide single crystals for scintillator detectors

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

Boatner, Lynn A; Ramey, Joanne Oxendine; Kolopus, James A

2014-01-01

Alkaline-earth scintillators such as strontium iodide and other alkaline-earth halides activated with divalent europium represent some of the most efficient and highest energy resolution scintillators for use as gamma-ray detectors in a wide range of applications. These applications include the areas of nuclear nonproliferation, homeland security, the detection of undeclared nuclear material, nuclear physics and materials science, medical diagnostics, space physics, high energy physics, and radiation monitoring systems for first responders, police, and fire/rescue personnel. Recent advances in the growth of large single crystals of these scintillator materials hold the promise of higher crystal yields and significantly lower detector productionmore » costs. In the present work, we describe new processing protocols that, when combined with our molten salt filtration methods, have led to advances in achieving a significant reduction of cracking effects during the growth of single crystals of SrI2:Eu2+. In particular, we have found that extended pumping on the molten crystal-growth charge under vacuum for time periods extending up to 48 hours is generally beneficial in compensating for variations in the alkaline-earth halide purity and stoichiometry of the materials as initially supplied by commercial sources. These melt-pumping and processing techniques are now being applied to the purification of CaI2:Eu2+ and some mixed-anion europium-doped alkaline-earth halides prior to single-crystal growth by means of the vertical Bridgman technique. The results of initial studies of the effects of aliovalent doping of SrI2:Eu2+ on the scintillation characteristics of this material are also described.« less

Unraveling luminescence mechanisms in zero-dimensional halide perovskites

DOE PAGES

Han, Dan; Shi, Hongliang; Ming, Wenmei; ...

2018-01-01

Zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6 ) 4− are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials.

Unraveling luminescence mechanisms in zero-dimensional halide perovskites

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

Han, Dan; Shi, Hongliang; Ming, Wenmei

Zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6 ) 4− are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials.

Unraveling luminescence mechanisms in zero-dimensional halide perovskites

DOE PAGES

Han, Dan; Shi, Hongliang; Ming, Wenmei; ...

2018-05-18

Here, zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6) 4– are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials.

Myeloperoxidase-Halide-Hydrogen Peroxide Antibacterial System

PubMed Central

Klebanoff, Seymour J.

1968-01-01

An antibacterial effect of myeloperoxidase, a halide, such as iodide, bromide, or chloride ion, and H2O2 on Escherichia coli or Lactobacillus acidophilus is described. When L. acidophilus was employed, the addition of H2O2 was not required; however, the protective effect of catalase suggested that, in this instance, H2O2 was generated by the organisms. The antibacterial effect was largely prevented by preheating the myeloperoxidase at 80 C or greater for 10 min or by the addition of a number of inhibitors; it was most active at the most acid pH employed (5.0). Lactoperoxidase was considerably less effective than was myeloperoxidase when chloride was the halide employed. Myeloperoxidase, at high concentrations, exerted an antibacterial effect on L. acidophilus in the absence of added halide, which also was temperature- and catalase-sensitive. Peroxidase was extracted from intact guinea pig leukocytes by weak acid, and the extract with peroxidase activity had antibacterial properties which were similar, in many respects, to those of the purified preparation of myeloperoxidase. Under appropriate conditions, the antibacterial effect was increased by halides and by H2O2 and was decreased by catalase, as well as by cyanide, azide, Tapazole, and thiosulfate. This suggests that, under the conditions employed, the antibacterial properties of a weak acid extract of guinea pig leukocytes is due, in part, to its peroxidase content, particularly if a halide is present in the reaction mixture. A heat-stable antibacterial agent or agents also appear to be present in the extract. PMID:4970226

Shock temperatures in silica glass - Implications for modes of shock-induced deformation, phase transformation, and melting with pressure

NASA Technical Reports Server (NTRS)

Schmitt, Douglas R.; Ahrens, Thomas J.

1989-01-01

Observations of shock-induced radiative thermal emissions are used to determine the gray body temperatures and emittances of silica glass under shock compression between 10 and 30 GPa. The results suggest that fused quartz deforms heterogeneously in this shock pressure range. It is shown that the 10-16 GPa range coincides with the permanent densification region, while the 16-30 GPa range coincides with the inferred mixed phase region along the silica glass Hugoniot. Low emittances in the mixed phase region are thought to represent the melting temperature of the high-pressure phase, stishovite. Also, consideration is given to the effects of pressure on melting relations for the system SiO2-Mg2SiO4.

Systematic analysis of the unique band gap modulation of mixed halide perovskites.

PubMed

Kim, Jongseob; Lee, Sung-Hoon; Chung, Choong-Heui; Hong, Ki-Ha

2016-02-14

Solar cells based on organic-inorganic hybrid metal halide perovskites have been proven to be one of the most promising candidates for the next generation thin film photovoltaic cells. Mixing Br or Cl into I-based perovskites has been frequently tried to enhance the cell efficiency and stability. One of the advantages of mixed halides is the modulation of band gap by controlling the composition of the incorporated halides. However, the reported band gap transition behavior has not been resolved yet. Here a theoretical model is presented to understand the electronic structure variation of metal mixed-halide perovskites through hybrid density functional theory. Comparative calculations in this work suggest that the band gap correction including spin-orbit interaction is essential to describe the band gap changes of mixed halides. In our model, both the lattice variation and the orbital interactions between metal and halides play key roles to determine band gap changes and band alignments of mixed halides. It is also presented that the band gap of mixed halide thin films can be significantly affected by the distribution of halide composition.

Melting Processes at the Base of the Mantle Wedge: Melt Compositions and Melting Reactions for the First Melts of Vapor-Saturated Lherzolite

NASA Astrophysics Data System (ADS)

Grove, T. L.; Till, C. B.

2014-12-01

Vapor-saturated melting experiments have been performed at pressures near the base of the mantle wedge (3.2 GPa). The starting composition is a metasomatized lherzolite containing 3 wt. % H2O. Near-solidus melts and coexisting mineral phases have been characterized in experiments that span 925 to 1100 oC with melt % varying from 6 to 9 wt. %. Olivine, orthopyroxene, clinopyroxene and garnet coexist with melt over the entire interval and rutile is also present at < 1000 oC. Melt is andesitic in composition and varies from 60 wt. % SiO2 at 950 oC to 52 wt. % at 1075 oC. The Al2O3 contents of the melt are 13 to 14 wt. %, and CaO contents range from 1 and 4 wt. %. Melting is peritectic with orthopyroxene + liquid produced by melting of garnet + olivine + high-Ca pyroxene. In addition to quenched melt, we observe a quenched silicate component that is rhyolitic (>72 % SiO2) that we interpret as a precipitate from the coexisting supercritical H2O-rich vapor. Extrapolation of the measured compositional variation toward the solidus suggests that the first melt may be very SiO2 rich (i.e., granitic). We suggest that these granitic melts are the first melts of the mantle near the slab-wedge interface. As these SiO2-rich melts ascend into shallower, hotter overlying mantle, they continue to interact with the surrounding mantle and evolve in composition. These first melts may elucidate the geochemical and physical processes that accompany the beginnings of H2O flux melting.

Highly luminescent colloidal nanoplates of perovskite cesium lead halide and their oriented assemblies

DOE PAGES

Bekenstein, Yehonadav; Koscher, Brent A.; Eaton, Samuel W.; ...

2015-12-15

Anisotropic colloidal quasi-two-dimensional nanoplates (NPLs) hold great promise as functional materials due to their combination of low dimensional optoelectronic properties and versatility through colloidal synthesis. Recently, lead-halide perovskites have emerged as important optoelectronic materials with excellent efficiencies in photovoltaic and light-emitting applications. Here we report the synthesis of quantum confined all inorganic cesium lead halide nanoplates in the perovskite crystal structure that are also highly luminescent (PLQY 84%). The controllable self-assembly of nanoplates either into stacked columnar phases or crystallographic-oriented thin-sheet structures is demonstrated. Furthermore, the broad accessible emission range, high native quantum yields, and ease of self-assembly make perovskitemore » NPLs an ideal platform for fundamental optoelectronic studies and the investigation of future devices.« less

Petrological Geodynamics of Mantle Melting II. AlphaMELTS + Multiphase Flow: Dynamic Fractional Melting

NASA Astrophysics Data System (ADS)

Tirone, Massimiliano

2018-03-01

In this second installment of a series that aims to investigate the dynamic interaction between the composition and abundance of the solid mantle and its melt products, the classic interpretation of fractional melting is extended to account for the dynamic nature of the process. A multiphase numerical flow model is coupled with the program AlphaMELTS, which provides at the moment possibly the most accurate petrological description of melting based on thermodynamic principles. The conceptual idea of this study is based on a description of the melting process taking place along a 1-D vertical ideal column where chemical equilibrium is assumed to apply in two local sub-systems separately on some spatial and temporal scale. The solid mantle belongs to a local sub-system (ss1) that does not interact chemically with the melt reservoir which forms a second sub-system (ss2). The local melt products are transferred in the melt sub-system ss2 where the melt phase eventually can also crystallize into a different solid assemblage and will evolve dynamically. The main difference with the usual interpretation of fractional melting is that melt is not arbitrarily and instantaneously extracted from the mantle, but instead remains a dynamic component of the model, hence the process is named dynamic fractional melting (DFM). Some of the conditions that may affect the DFM model are investigated in this study, in particular the effect of temperature, mantle velocity at the boundary of the mantle column. A comparison is made with the dynamic equilibrium melting (DEM) model discussed in the first installment. The implications of assuming passive flow or active flow are also considered to some extent. Complete data files of most of the DFM simulations, four animations and two new DEM simulations (passive/active flow) are available following the instructions in the supplementary material.

40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted aliphatic acid halide... Specific Chemical Substances § 721.530 Substituted aliphatic acid halide (generic name). (a) Chemical... acid halide (PMN P-84-491) is subject to reporting under this section for the significant new uses...

40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Substituted aliphatic acid halide... Specific Chemical Substances § 721.530 Substituted aliphatic acid halide (generic name). (a) Chemical... acid halide (PMN P-84-491) is subject to reporting under this section for the significant new uses...

Resonance Raman and excitation energy dependent charge transfer mechanism in halide-substituted hybrid perovskite solar cells.

PubMed

Park, Byung-wook; Jain, Sagar M; Zhang, Xiaoliang; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

2015-02-24

Organo-metal halide perovskites (OMHPs) are materials with attractive properties for optoelectronics. They made a recent introduction in the photovoltaics world by methylammonium (MA) lead triiodide and show remarkably improved charge separation capabilities when chloride and bromide are added. Here we show how halide substitution in OMHPs with the nominal composition CH3NH3PbI2X, where X is I, Br, or Cl, influences the morphology, charge quantum yield, and local interaction with the organic MA cation. X-ray diffraction and photoluminescence data demonstrate that halide substitution affects the local structure in the OMHPs with separate MAPbI3 and MAPbCl3 phases. Raman spectroscopies as well as theoretical vibration calculations reveal that this at the same time delocalizes the charge to the MA cation, which can liberate the vibrational movement of the MA cation, leading to a more adaptive organic phase. The resonance Raman effect together with quantum chemical calculations is utilized to analyze the change in charge transfer mechanism upon electronic excitation and gives important clues for the mechanism of the much improved photovoltage and photocurrent also seen in the solar cell performance for the materials when chloride compounds are included in the preparation.

Lead-free Halide Perovskites via Functionality-directed Materials Screening

NASA Astrophysics Data System (ADS)

Zhang, Lijun; Yang, Dongwen; Lv, Jian; Zhao, Xingang; Yang, Ji-Hui; Yu, Liping; Wei, Su-Huai; Zunger, Alex

Hybrid organic-inorganic halide perovskites with the prototype material of CH3NH3PbI3 have recently attracted much interest as low-cost and high-performance photovoltaic absorbers but one would like to improve their stability and get rid of toxic Pb. We used photovoltaic-functionality-directed materials screening approach to rationally design via first-principles DFT calculations Pb-free halide perovskites. Screening criteria involve thermodynamic and crystallographic stability, as well as solar band gaps, light carrier effective masses, exciton binding, etc. We considered both single atomic substitutions in AMX3 normal perovskites (altering chemical constituents of A, M and X individually) as well as double substitution of 2M into B+C in A2BCX6 double-perovskites. Chemical trends in phase stabilities and optoelectronic properties are discussed with some promising cases exhibiting solar cell efficiencies comparable to that of CH3NH3PbI3. L.Z. founded by Recruitment Program of Global Youth Experts and National Key Research and Development Program of China, and A.Z. by DOE EERE Sun Shot of USA.

Depletion-mode vertical Ga2O3 trench MOSFETs fabricated using Ga2O3 homoepitaxial films grown by halide vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Sasaki, Kohei; Thieu, Quang Tu; Wakimoto, Daiki; Koishikawa, Yuki; Kuramata, Akito; Yamakoshi, Shigenobu

2017-12-01

We developed depletion-mode vertical Ga2O3 trench metal-oxide-semiconductor field-effect transistors by using n+ contact and n- drift layers. These epilayers were grown on an n+ (001) Ga2O3 single-crystal substrate by halide vapor phase epitaxy. Cu and HfO2 were used for the gate metal and dielectric film, respectively. The mesa width and gate length were approximately 2 and 1 µm, respectively. The devices showed good DC characteristics, with a specific on-resistance of 3.7 mΩ cm2 and clear current modulation. An on-off ratio of approximately 103 was obtained.

Light-melt adhesive based on dynamic carbon frameworks in a columnar liquid-crystal phase

NASA Astrophysics Data System (ADS)

Saito, Shohei; Nobusue, Shunpei; Tsuzaka, Eri; Yuan, Chunxue; Mori, Chigusa; Hara, Mitsuo; Seki, Takahiro; Camacho, Cristopher; Irle, Stephan; Yamaguchi, Shigehiro

2016-07-01

Liquid crystal (LC) provides a suitable platform to exploit structural motions of molecules in a condensed phase. Amplification of the structural changes enables a variety of technologies not only in LC displays but also in other applications. Until very recently, however, a practical use of LCs for removable adhesives has not been explored, although a spontaneous disorganization of LC materials can be easily triggered by light-induced isomerization of photoactive components. The difficulty of such application derives from the requirements for simultaneous implementation of sufficient bonding strength and its rapid disappearance by photoirradiation. Here we report a dynamic molecular LC material that meets these requirements. Columnar-stacked V-shaped carbon frameworks display sufficient bonding strength even during heating conditions, while its bonding ability is immediately lost by a light-induced self-melting function. The light-melt adhesive is reusable and its fluorescence colour reversibly changes during the cycle, visualizing the bonding/nonbonding phases of the adhesive.

Absence of B1-B2 structural transition in lithium halides under hydrostatic pressure

NASA Astrophysics Data System (ADS)

de Coss, Romeo; Murrieta, Gabriel

2005-03-01

We have investigated the B1-B2 structural transition in LiF, LiCl, LiBr, and LiI under hydrostatic pressure by means of first-principles total-energy calculations using the Full- Potential LAPW method. In order to analyze the gradient effects, we have performed calculations using the local density approximation (LDA) and the generalized gradient approximation (GGA), for the exchange and correlation potential. In agreement with the experimental observations, we find that even for pressures higher than 100 GPa, the Li halides do not present the B1-B2 structural transition. In order to understand this behavior, we have calculated the distribution of the electron densities. From the analysis of the distribution of electron densities for the Li halides in the B1 and B2 phases, we find that for this group of ionic compounds the B1 phase have a distribution of electron densities more homogeneous than in the B2 phase, preventing the B1-B2 structural transition. This work was partially supported by Consejo Nacional de Ciencia y Tecnolog'ia (CONACYT, M'exico) under Grant No. 43830-F.

Electrolytic systems and methods for making metal halides and refining metals

DOEpatents

Holland, Justin M.; Cecala, David M.

2015-05-26

Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

Melt-gas phase equilibria and state diagrams of the selenium-tellurium system

NASA Astrophysics Data System (ADS)

Volodin, V. N.; Trebukhov, S. A.; Burabaeva, N. M.; Nitsenko, A. V.

2017-05-01

The partial pressures of saturated vapor of the components in the Se-Te system are determined and presented in the form of temperature-concentration dependences from which the boundaries of the melt-gas phase transition are calculated at atmospheric pressure and vacuums of 2000 and 100 Pa. The existence of azeotropic mixtures is revealed. It is found that the points of inseparably boiling melts correspond to 7.5 at % of Se and 995°C at 101325 Pa, 10.9 at % at 673°C and 19.5 at % at 522°C in vacuums of 2000 and 100 Pa, respectively. A complete state diagram is constructed, including the fields of gas-liquid equilibria at atmospheric and low pressures, the boundaries of which allow us to assess the behavior of selenium and tellurium upon distillation fractionation.

Composition-Graded Cesium Lead Halide Perovskite Nanowires with Tunable Dual-Color Lasing Performance.

PubMed

Huang, Ling; Gao, Qinggang; Sun, Ling-Dong; Dong, Hao; Shi, Shuo; Cai, Tong; Liao, Qing; Yan, Chun-Hua

2018-05-21

Cesium lead halide (CsPbX 3 ) perovskite has emerged as a promising low-threshold multicolor laser material; however, realizing wavelength-tunable lasing output from a single CsPbX 3 nanostructure is still constrained by integrating different composition. Here, the direct synthesis of composition-graded CsPbBr x I 3- x nanowires (NWs) is reported through vapor-phase epitaxial growth on mica. The graded composition along the NW, with an increased Br/I from the center to the ends, comes from desynchronized deposition of cesium lead halides and temperature-controlled anion-exchange reaction. The graded composition results in varied bandgaps along the NW, which induce a blueshifted emission from the center to the ends. As an efficient gain media, the nanowire exerts position-dependent lasing performance, with a different color at the ends and center respectively above the threshold. Meanwhile, dual-color lasing with a wavelength separation of 35 nm is activated simultaneously at a site with an intermediate composition. This position-dependent dual-color lasing from a single nanowire makes these metal halide perovskites promising for applications in nanoscale optical devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of PbCl{sub 2} content in PbI{sub 2} solution of DMF on the absorption, crystal phase, morphology of lead halide thin films and photovoltaic performance in planar perovskite solar cells

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

Wang, Mao; Shi, Chengwu, E-mail: shicw506@foxmail.com; Zhang, Jincheng

2015-11-15

In this paper, the influence of PbCl{sub 2} content in PbI{sub 2} solution of DMF on the absorption, crystal phase and morphology of lead halide thin films was systematically investigated and the photovoltaic performance of the corresponding planar perovskite solar cells was evaluated. The result revealed that the various thickness lead halide thin film with the small sheet-like, porous morphology and low crystallinity can be produced by adding PbCl{sub 2} powder into PbI{sub 2} solution of DMF as a precursor solution. The planar perovskite solar cell based on the 300-nm-thick CH{sub 3}NH{sub 3}PbI{sub 3−x}Cl{sub x} thin film by the precursormore » solution with the mixture of 0.80 M PbI{sub 2} and 0.20 M PbCl{sub 2} exhibited the optimum photoelectric conversion efficiency of 10.12% along with an open-circuit voltage of 0.93 V, a short-circuit photocurrent density of 15.70 mA cm{sup −2} and a fill factor of 0.69. - Graphical abstract: The figure showed the surface and cross-sectional SEM images of lead halide thin films using the precursor solutions: (a) 0.80 M PbI{sub 2}, (b) 0.80 M PbI{sub 2}+0.20 M PbCl{sub 2}, (c) 0.80 M PbI{sub 2}+0.40 M PbCl{sub 2}, and (d) 0.80 M PbI{sub 2}+0.60 M PbCl{sub 2}. With the increase of the PbCl{sub 2} content in precursor solution, the size of the lead halide nanosheet decreased and the corresponding thin films gradually turned to be porous with low crystallinity. - Highlights: • Influence of PbCl{sub 2} content on absorption, crystal phase and morphology of thin film. • Influence of perovskite film thickness on photovoltaic performance of solar cell. • Lead halide thin film with small sheet-like, porous morphology and low crystallinity. • Planar solar cell with 300 nm-thick perovskite thin film achieved PCE of 10.12%.« less

Phase Transitions and Melting in Magnesium to 200 GPa and 4500 K

NASA Astrophysics Data System (ADS)

Stinton, G.; MacLeod, S.; Cynn, H.; Errandonea, D.; Proctor, J.; Meng, Y.; McMahon, M.

2013-06-01

Magnesium is a ``simple'' nearly free-electron metal up to around 100 GPa. Despite similarly-simple group II metals being the subject of numerous studies that have revealed complex high-pressure behaviour, Mg has very few high-pressure diffraction studies, particularly above room temperature. Here we describe such studies to above 200 GPa at 300 K, combined with resistive- and laser-heating experiments to 4500 K and 100 GPa. The hcp-bcc transition at ~50 GPa exhibits a large region of phase co-existence at all temperatures up to 800 K, and the transition pressure is found to decrease with temperature at the rate of ~3.4 GPa per 100 K, somewhat smaller than the rate calculated by Mehta et al.,. At lower pressures, below the melting curve at 10 GPa, we find the dhcp phase to be stable, in agreement with Errandonea et al.. Laser heating studies to 4500 K and 100 GPa show that Mg remains bcc up to the melting curve, our measurement of which is in good agreement with the previous ``speckle'' studies of Errandonea et al.. This work was performed under the auspices of the US DOE by LLNL under Contract DE-AC52-07NA27344.

Discovery of a Frank-Kasper [sigma] Phase in Sphere-Forming Block Copolymer Melts

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

Lee, Sangwoo; Bluemle, Michael J.; Bates, Frank S.

Sphere-forming block copolymers are known to self-assemble into body-centered cubic crystals near the order-disorder transition temperature. Small-angle x-ray scattering and transmission electron microscopy experiments on diblock and tetrablock copolymer melts have revealed an equilibrium phase characterized by a large tetragonal unit cell containing 30 microphase-separated spheres. This structure, referred to as the sigma ({sigma}) phase by Frank and Kasper more than 50 years ago, nucleates and grows from the body-centered cubic phase similar to its occurrence in metal alloys and is a crystal approximant to dodecagonal quasicrystals. Formation of the {sigma} phase in undiluted linear block copolymers (and certain branchedmore » dendrimers) appears to be mediated by macromolecular packing frustration, an entropic contribution to the interparticle interactions that control the sphere-packing geometry.« less

Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries

NASA Astrophysics Data System (ADS)

Zevgolis, Alysia; Wood, Brandon C.; Mehmedović, Zerina; Hall, Alex T.; Alves, Thomaz C.; Adelstein, Nicole

2018-04-01

Alloying of anions is a promising engineering strategy for tuning ionic conductivity in halide-based inorganic solid electrolytes. We explain the alloying effects in Li3InBr6-xClx, in terms of strain, chemistry, and microstructure, using first-principles molecular dynamics simulations and electronic structure analysis. We find that strain and bond chemistry can be tuned through alloying and affect the activation energy and maximum diffusivity coefficient. The similar conductivities of the x = 3 and x = 6 compositions can be understood by assuming that the alloy separates into Br-rich and Cl-rich regions. Phase-separation increases diffusivity at the interface and in the expanded Cl-region, suggesting microstructure effects are critical. Similarities with other halide superionic conductors are highlighted.

Optical properties of C-doped bulk GaN wafers grown by halide vapor phase epitaxy

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

Khromov, S.; Hemmingsson, C.; Monemar, B.

2014-12-14

Freestanding bulk C-doped GaN wafers grown by halide vapor phase epitaxy are studied by optical spectroscopy and electron microscopy. Significant changes of the near band gap (NBG) emission as well as an enhancement of yellow luminescence have been found with increasing C doping from 5 × 10{sup 16} cm{sup −3} to 6 × 10{sup 17} cm{sup −3}. Cathodoluminescence mapping reveals hexagonal domain structures (pits) with high oxygen concentrations formed during the growth. NBG emission within the pits even at high C concentration is dominated by a rather broad line at ∼3.47 eV typical for n-type GaN. In the area without pits,more » quenching of the donor bound exciton (DBE) spectrum at moderate C doping levels of 1–2 × 10{sup 17} cm{sup −3} is observed along with the appearance of two acceptor bound exciton lines typical for Mg-doped GaN. The DBE ionization due to local electric fields in compensated GaN may explain the transformation of the NBG emission.« less

Local melting in Al-Mg-Zn-alloys

NASA Astrophysics Data System (ADS)

Droenen, Per-Erik; Ryum, Nils

1994-03-01

The internal melting of several Al-Mg-Zn-alloys has been studied by rapid upquenching in a salt bath of specimens slowly cooled at a rate of 2 °C/h down to 375 °C. The melting reaction was studied metallographically in the light- and electron-scanning microscope, and local concentrations were measured in the microprobe. Local melting of both the equilibrium phases T and η was observed to occur. There were, however, essential differences between the melting kinetics for the two phases. While the T-phase particles melted spontaneously at temperatures at or above the invariant temperature, 489 °C, and after some period of time at lower temperatures, the η-phase particles either melted spontaneously at or above the invariant temperature, T - 475 °C, or dissolved into the matrix at temperatures below 475 °C. This difference in behavior can be accounted for if the α(Al)-η section is not a quasi-binary section. The industrial implications of the internal melting in these alloys are discussed and compared to the same reaction in the Al-Mg-Si alloys. A model is developed in the Appendix to quantify the different behaviors of these two classes of alloys.

A study of Lux-Flood acid-base reactions in KBr melts at 800°C

NASA Astrophysics Data System (ADS)

Rebrova, T. P.; Cherginets, V. L.; Ponomarenko, T. V.

2009-11-01

The dissociation of CO{3/2-} (p K = 2.4 ± 0.2) and precipitation of MgO (p L MgO = 10.66 ± 0.1) in a KBr melt at 800°C were studied potentiometrically with the use of a Pt(O2)|ZrO2|(Y2O3) membrane oxygen electrode. The direct calibration of the electrochemical circuit allowed only the equilibrium concentration of O2- (of strong bases) to be determined in the melt. The total concentration of oxygen-containing impurities, including CO{3/2-} and CO{4/2-} weak bases, can be found by the potentiometric titration of a sample of KBr by adding MgCl2 (Mg2+), a strong Lux-Flood acid, which causes the decomposition of these oxygen-containing anions. This reaction can also be used to remove oxo anions from alkali metal halide melts.

Entropy in halide perovskites

NASA Astrophysics Data System (ADS)

Katan, Claudine; Mohite, Aditya D.; Even, Jacky

2018-05-01

Claudine Katan, Aditya D. Mohite and Jacky Even discuss the possible impact of various entropy contributions (stochastic structural fluctuations, anharmonicity and lattice softness) on the optoelectronic properties of halide perovskite materials and devices.

A Victim of Halide Ion Segregation. How Light Soaking Affects Solar Cell Performance of Mixed Halide Lead Perovskites

DOE PAGES

Samu, Gergely F.; Janaky, Csaba; Kamat, Prashant V.

2017-07-24

Photoinduced segregation in mixed halide perovskites has a direct influence on decreasing the solar cell efficiency as segregated I-rich domains serve as charge recombination centers. Here, the changes in the external quantum efficiency mirror the spectral loss in the absorption; however, the time scale of the IPCE recovery in the dark is slower than the absorption recovery, showing the intricate nature of the photoinduced halide segregation and charge collection in solar cell devices.

A benchmark initiative on mantle convection with melting and melt segregation

NASA Astrophysics Data System (ADS)

Schmeling, Harro; Dohmen, Janik; Wallner, Herbert; Noack, Lena; Tosi, Nicola; Plesa, Ana-Catalina; Maurice, Maxime

2015-04-01

In recent years a number of mantle convection models have been developed which include partial melting within the asthenosphere, estimation of melt volumes, as well as melt extraction with and without redistribution at the surface or within the lithosphere. All these approaches use various simplifying modelling assumptions whose effects on the dynamics of convection including the feedback on melting have not been explored in sufficient detail. To better assess the significance of such assumptions and to provide test cases for the modelling community we initiate a benchmark comparison. In the initial phase of this endeavor we focus on the usefulness of the definitions of the test cases keeping the physics as sound as possible. The reference model is taken from the mantle convection benchmark, case 1b (Blanckenbach et al., 1989), assuming a square box with free slip boundary conditions, the Boussinesq approximation, constant viscosity and a Rayleigh number of 1e5. Melting is modelled assuming a simplified binary solid solution with linearly depth dependent solidus and liquidus temperatures, as well as a solidus temperature depending linearly on depletion. Starting from a plume free initial temperature condition (to avoid melting at the onset time) three cases are investigated: Case 1 includes melting, but without thermal or dynamic feedback on the convection flow. This case provides a total melt generation rate (qm) in a steady state. Case 2 includes batch melting, melt buoyancy (melt Rayleigh number Rm), depletion buoyancy and latent heat, but no melt percolation. Output quantities are the Nusselt number (Nu), root mean square velocity (vrms) and qm approaching a statistical steady state. Case 3 includes two-phase flow, i.e. melt percolation, assuming a constant shear and bulk viscosity of the matrix and various melt retention numbers (Rt). These cases should be carried out using the Compaction Boussinseq Approximation (Schmeling, 2000) or the full compaction

Oxidation of hydrogen halides to elemental halogens

DOEpatents

Rohrmann, Charles A.; Fullam, Harold T.

1985-01-01

A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

About the Shape of the Melting Line as a Possible Precursor of a Liquid-Liquid Phase Transition

NASA Astrophysics Data System (ADS)

Imre, Attila R.; Rzoska, Sylwester J.

Several simple, non-mesogenic liquids can exists in two or more different liquid forms. When the liquid-liquid line, separating two liquid forms, meets the melting line, one can expect some kind of break on the melting line, caused by the different freezing/melting behaviour of the two liquid forms. Unfortunately recently several researchers are using this vein of thinking in reverse; seeing some irregularity on the melting line, they will expect a break and the appearance of a liquid-liquid line. In this short paper, we are going to show, that in the case of the high-pressure nitrogen studied recently by Mukherjee and Boehler, the high-pressure data can be easily described by a smooth, break-free function, the modified Simon-Glatzel equation. In this way, the break, suggested by them and consequently the suggested appearance of a new liquid phase of the nitrogen might be artefacts.

Temperature-dependent excitonic photoluminescence of hybrid organometal halide perovskite films.

PubMed

Wu, Kewei; Bera, Ashok; Ma, Chun; Du, Yuanmin; Yang, Yang; Li, Liang; Wu, Tom

2014-11-07

Organometal halide perovskites have recently attracted tremendous attention due to their potential for photovoltaic applications, and they are also considered as promising materials in light emitting and lasing devices. In this work, we investigated in detail the cryogenic steady state photoluminescence properties of a prototypical hybrid perovskite CH3NH3PbI3-xClx. The evolution of the characteristics of two excitonic peaks coincides with the structural phase transition around 160 K. Our results further revealed an exciton binding energy of 62.3 ± 8.9 meV and an optical phonon energy of 25.3 ± 5.2 meV, along with an abnormal blue-shift of the band gap in the high-temperature tetragonal phase.

Melting of superheated molecular crystals

NASA Astrophysics Data System (ADS)

Cubeta, Ulyana; Bhattacharya, Deepanjan; Sadtchenko, Vlad

2017-07-01

Melting dynamics of micrometer scale, polycrystalline samples of isobutane, dimethyl ether, methyl benzene, and 2-propanol were investigated by fast scanning calorimetry. When films are superheated with rates in excess of 105 K s-1, the melting process follows zero-order, Arrhenius-like kinetics until approximately half of the sample has transformed. Such kinetics strongly imply that melting progresses into the bulk via a rapidly moving solid-liquid interface that is likely to originate at the sample's surface. Remarkably, the apparent activation energies for the phase transformation are large; all exceed the enthalpy of vaporization of each compound and some exceed it by an order of magnitude. In fact, we find that the crystalline melting kinetics are comparable to the kinetics of dielectric α-relaxation in deeply supercooled liquids. Based on these observations, we conclude that the rate of non-isothermal melting for superheated, low-molecular-weight crystals is limited by constituent diffusion into an abnormally dense, glass-like, non-crystalline phase.

Melting of 2D colloidal crystals

NASA Astrophysics Data System (ADS)

Maret, G.; Eisenmann, C.; Gasser, U.; Vongruenberg, H. H.; Keim, P.; Zahn, K.

2004-11-01

We study melting of 2D crystals of super-paramagnetic colloidal particles confined by gravity to a flat air-water interface. The effective system temperature is given by the strength of the dipolar inter-particle interaction controlled by an external magnetic field B. Particle positions are obtained by video-microscopy. In vertical B-field crystals are hexagonal and we find all features of the 2-step melting scenario predicted by KTHNY-theory. In particular, quantitative agreement is found for the translational and orientational order parameters related to bound and isolated dislocations and disclinations. From particle position fluctuations wave-vector (q) dependent normal-mode spring constants are obtained in agreement with phonon band structure calculations. The elastic constants (q=0 limit) soften near melting in quantitative agreement with KTHNY. By tilting B away from vertical anisotropic 2D crystals are generated; at small tilting angles they melt through a quasi-hexatic phase, while at higher tilts a centered rectangular phase is found which melts into a 2D smectic-like phase through orientation-dependent dislocations.

A multiphysics phase field model on melting and kinetic superheating of aluminum nanolayer and nanoparticle

NASA Astrophysics Data System (ADS)

Hwang, Yong Seok

It has been found during the last decade that a nanoscale melting of metal has very distinctive features compared to its microscale counterpart. It has been observed that a highly non-equilibrium state can result in extreme superheating of a solid state, which cannot be explained well by thermodynamic theories based on equilibrium or nucleation. An endeavor to find the superheating limit and mechanisms of melting and superheating becomes more complicated when various physical phenomena are involved at the similar scales. The main goal of this research is to establish a multiphysics model and to reveal the mechanism of melting and kinetic superheating of a metal nanostructure at high heating rates. The model includes elastodynamics, a fast heating of metal considering a delayed heat transfer between electron gas and lattice phonon and couplings among physical phenomena, and phase transformation incorporated with thermal fluctuation. The model successfully reproduces two independent experiments and several novel nanoscale physical phenomena are discovered. For example, the depression of the melting temperature of Al nanolayer under plane stress condition, the threshold heating rate, 1011 K/s, for kinetic superheating, a large temperature drop in a 5 nm collision region of the two solid-melt interfaces, and a strong effect of geometry on kinetic superheating in Al core-shell nanostructure at high heating rate.

Melts of garnet lherzolite: experiments, models and comparison to melts of pyroxenite and carbonated lherzolite

USGS Publications Warehouse

Grove, Timothy L.; Holbig, Eva S.; Barr, Jay A.; Till, Christy B.; Krawczynski, Michael J.

2013-01-01

Phase equilibrium experiments on a compositionally modified olivine leucitite from the Tibetan plateau have been carried out from 2.2 to 2.8 GPa and 1,380–1,480 °C. The experiments-produced liquids multiply saturated with spinel and garnet lherzolite phase assemblages (olivine, orthopyroxene, clinopyroxene and spinel ± garnet) under nominally anhydrous conditions. These SiO2-undersaturated liquids and published experimental data are utilized to develop a predictive model for garnet lherzolite melting of compositionally variable mantle under anhydrous conditions over the pressure range of 1.9–6 GPa. The model estimates the major element compositions of garnet-saturated melts for a range of mantle lherzolite compositions and predicts the conditions of the spinel to garnet lherzolite phase transition for natural peridotite compositions at above-solidus temperatures and pressures. We compare our predicted garnet lherzolite melts to those of pyroxenite and carbonated lherzolite and develop criteria for distinguishing among melts of these different source types. We also use the model in conjunction with a published predictive model for plagioclase and spinel lherzolite to characterize the differences in major element composition for melts in the plagioclase, spinel and garnet facies and develop tests to distinguish between melts of these three lherzolite facies based on major elements. The model is applied to understand the source materials and conditions of melting for high-K lavas erupted in the Tibetan plateau, basanite–nephelinite lavas erupted early in the evolution of Kilauea volcano, Hawaii, as well as younger tholeiitic to alkali lavas from Kilauea.

A review of bacterial methyl halide degradation: biochemistry, genetics and molecular ecology

USGS Publications Warehouse

McDonald, I.R.; Warner, K.L.; McAnulla, C.; Woodall, C.A.; Oremland, R.S.; Murrell, J.C.

2002-01-01

Methyl halide-degrading bacteria are a diverse group of organisms that are found in both terrestrial and marine environments. They potentially play an important role in mitigating ozone depletion resulting from methyl chloride and methyl bromide emissions. The first step in the pathway(s) of methyl halide degradation involves a methyltransferase and, recently, the presence of this pathway has been studied in a number of bacteria. This paper reviews the biochemistry and genetics of methyl halide utilization in the aerobic bacteria Methylobacterium chloromethanicum CM4T, Hyphomicrobium chloromethanicum CM2T, Aminobacter strain IMB-1 and Aminobacter strain CC495. These bacteria are able to use methyl halides as a sole source of carbon and energy, are all members of the α-Proteobacteria and were isolated from a variety of polluted and pristine terrestrial environments. An understanding of the genetics of these bacteria identified a unique gene (cmuA) involved in the degradation of methyl halides, which codes for a protein (CmuA) with unique methyltransferase and corrinoid functions. This unique functional gene, cmuA, is being used to develop molecular ecology techniques to examine the diversity and distribution of methyl halide-utilizing bacteria in the environment and hopefully to understand their role in methyl halide degradation in different environments. These techniques will also enable the detection of potentially novel methyl halide-degrading bacteria.

Melting Curve of Molecular Crystal GeI4

NASA Astrophysics Data System (ADS)

Fuchizaki, Kazuhiro; Hamaya, Nozomu

2014-07-01

In situ synchrotron x-ray diffraction measurements were carried out to determine the melting curve of the molecular crystal GeI4. We found that the melting line rapidly increases with a pressure up to about 3 GPa, at which it abruptly breaks. Such a strong nonlinear shape of the melting curve can be approximately captured by the Kumari-Dass-Kechin equation. The parameters involved in the equation could be determined from the equation of state for the crystalline phase, which was also established in the present study. The melting curve predicted from the equation approaches the actual melting curve as the degree of approximation involved in obtaining the equation is improved. However, the treatment is justifiable only if the slope of the melting curve is everywhere continuous. We believe that this is not the case for GeI4's melting line at the breakpoint, as inferred from the nature of breakdown of the Kraut-Kennedy and the Magalinskii-Zubov relationships.The breakpoint may then be a triple point among the crystalline phase and two possible liquid phases.

Process for oxidation of hydrogen halides to elemental halogens

DOEpatents

Lyke, Stephen E.

1992-01-01

An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

Internal stress-induced melting below melting temperature at high-rate laser heating

NASA Astrophysics Data System (ADS)

Hwang, Yong Seok; Levitas, Valery I.

2014-06-01

In this Letter, continuum thermodynamic and phase field approaches (PFAs) predicted internal stress-induced reduction in melting temperature for laser-irradiated heating of a nanolayer. Internal stresses appear due to thermal strain under constrained conditions and completely relax during melting, producing an additional thermodynamic driving force for melting. Thermodynamic melting temperature for Al reduces from 933.67 K for a stress-free condition down to 898.1 K for uniaxial strain and to 920.8 K for plane strain. Our PFA simulations demonstrated barrierless surface-induced melt nucleation below these temperatures and propagation of two solid-melt interfaces toward each other at the temperatures very close to the corresponding predicted thermodynamic equilibrium temperatures for the heating rate Q ≤1.51×1010K/s. At higher heating rates, kinetic superheating competes with a reduction in melting temperature and melting under uniaxial strain occurs at 902.1 K for Q = 1.51 × 1011 K/s and 936.9 K for Q = 1.46 × 1012 K/s.

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites

NASA Astrophysics Data System (ADS)

Bischak, Connor G.; Hetherington, Craig L.; Wu, Hao; Aloni, Shaul; Ogletree, D. Frank; Limmer, David T.; Ginsberg, Naomi S.

2017-02-01

Nonequilibrium processes occurring in functional materials can significantly impact device efficiencies and are often difficult to characterize due to the broad range of length and time scales involved. In particular, mixed halide hybrid perovskites are promising for optoelectronics, yet the halides reversibly phase separate when photo-excited, significantly altering device performance. By combining nanoscale imaging and multiscale modeling, we elucidate the mechanism underlying this phenomenon, demonstrating that local strain induced by photo-generated polarons promotes halide phase separation and leads to nucleation of light-stabilized iodide-rich clusters. This effect relies on the unique electromechanical properties of hybrid materials, characteristic of neither their organic nor inorganic constituents alone. Exploiting photo-induced phase separation and other nonequilibrium phenomena in hybrid materials, generally, could enable new opportunities for expanding the functional applications in sensing, photoswitching, optical memory, and energy storage.

Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency.

PubMed

Zhou, Chenkun; Lin, Haoran; Tian, Yu; Yuan, Zhao; Clark, Ronald; Chen, Banghao; van de Burgt, Lambertus J; Wang, Jamie C; Zhou, Yan; Hanson, Kenneth; Meisner, Quinton J; Neu, Jennifer; Besara, Tiglet; Siegrist, Theo; Lambers, Eric; Djurovich, Peter; Ma, Biwu

2018-01-21

Single crystalline zero-dimensional (0D) organic-inorganic hybrid materials with perfect host-guest structures have been developed as a new generation of highly efficient light emitters. Here we report a series of lead-free organic metal halide hybrids with a 0D structure, (C 4 N 2 H 14 X) 4 SnX 6 (X = Br, I) and (C 9 NH 20 ) 2 SbX 5 (X = Cl), in which the individual metal halide octahedra (SnX 6 4- ) and quadrangular pyramids (SbX 5 2- ) are completely isolated from each other and surrounded by the organic ligands C 4 N 2 H 14 X + and C 9 NH 20 + , respectively. The isolation of the photoactive metal halide species by the wide band gap organic ligands leads to no interaction or electronic band formation between the metal halide species, allowing the bulk materials to exhibit the intrinsic properties of the individual metal halide species. These 0D organic metal halide hybrids can also be considered as perfect host-guest systems, with the metal halide species periodically doped in the wide band gap matrix. Highly luminescent, strongly Stokes shifted broadband emissions with photoluminescence quantum efficiencies (PLQEs) of close to unity were realized, as a result of excited state structural reorganization of the individual metal halide species. Our discovery of highly luminescent single crystalline 0D organic-inorganic hybrid materials as perfect host-guest systems opens up a new paradigm in functional materials design.

The Kinetics of Phase Transformations During Tempering in Laser Melted High Chromium Cast Steel

NASA Astrophysics Data System (ADS)

Li, M. Y.; Wang, Y.; Han, B.

2012-06-01

The precipitation of secondary carbides in the laser melted high chromium cast steels during tempering at 300-650 °C for 2 h in air furnace was characterized and the present phases was identified, by using transmission electron microscopy. Laser melted high chromium cast steel consists of austenitic dendrites and interdendritic M23C6 carbides. The austenite has such a strong tempering stability that it remains unchanged at temperature below 400 °C and the secondary hardening phenomenon starts from 450 °C to the maximum value of 672 HV at 560 °C. After tempering at 450 °C fine M23C6 carbides precipitate from the supersaturated austenite preferentially. In addition, the dislocation lines and slip bands still exist inside the austenite. While tempering at temperature below 560 °C, the secondary hardening simultaneously results from the martensite phase transformation and the precipitation of carbides as well as dislocation strengthening within a refined microstructure. Moreover, the formation of the ferrite matrix and large quality of coarse lamellar M3C carbides when the samples were tempered at 650 °C contributes to the decrease of hardness.

Berezinskii-Kosterlitz-Thouless transition and two-dimensional melting

NASA Astrophysics Data System (ADS)

Ryzhov, V. N.; Tareyeva, E. E.; Fomin, Yu D.; Tsiok, E. N.

2017-12-01

The main aspects of the theory of phase transitions in two-dimensional degenerate systems (Berezinskii-Kosterlitz-Thouless, or BKT, transitions) are reviewed in detail, including the transition mechanism, the renormalization group as a tool for describing the transition, and how the transition scenario can possibly depend on the core energy of topological defects (in particular, in thin superconducting films). Various melting scenarios in two-dimensional systems are analyzed, and the current status of actual experiments and computer simulations in the field is examined. Whereas in three dimensions melting always occurs as a single first-order transition, in two dimensions, as shown by Halperin, Nelson, and Young, melting via two continuous BKT transitions with an intermediate hexatic phase characterized by quasi-long-range orientational order is possible. But there is also a possibility for a first-order phase transition to occur. Recently, one further melting scenario, different from that occurring in the Berezinskii-Kosterlitz-Thouless-Halperin-Nelson-Young theory, has been proposed, according to which a solid can melt in two stages: a continuous BKT-type solid-hexatic transition and then a first-order hexatic-phase-isotropic-liquid phase transition. Particular attention is given to the melting scenario as a function of the potential shape and to the random pinning effect on two-dimensional melting. In particular, it is shown that random pinning can alter the melting scenario fundamentally in the case of a first-order transition. Also considered is the melting of systems with potentials having a negative curvature in the repulsion region-potentials that are successfully used in describing the anomalous properties of water in two dimensions. This review is an extended version of the report “Old and new in the physics of phase transitions” presented at the scientific session of the Physical Sciences Division of the Russian Academy of Sciences on 21 December

On high-pressure melting of tantalum

NASA Astrophysics Data System (ADS)

Luo, Sheng-Nian; Swift, Damian C.

2007-01-01

The issues related to high-pressure melting of Ta are discussed within the context of diamond-anvil cell (DAC) and shock wave experiments, theoretical calculations and common melting models. The discrepancies between the extrapolations of the DAC melting curve and the melting point inferred from shock wave experiments, cannot be reconciled either by superheating or solid-solid phase transition. The failure to reproduce low-pressure DAC melting curve by melting models such as dislocation-mediated melting and the Lindemann law, and molecular dynamics and quantum mechanics-based calculations, undermines their predictions at moderate and high pressures. Despite claims to the contrary, the melting curve of Ta (as well as Mo and W) remains inconclusive at high pressures.

Solubility of alkali metal halides in the ionic liquid [C4C1im][OTf].

PubMed

Kuzmina, O; Bordes, E; Schmauck, J; Hunt, P A; Hallett, J P; Welton, T

2016-06-28

The solubilities of the metal halides LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbCl, CsCl, CsI, were measured at temperatures ranging from 298.15 to 378.15 K in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4C1im][OTf]). Li(+), Na(+) and K(+) salts with anions matching the ionic liquid have also been investigated to determine how well these cations dissolve in [C4C1im][OTf]. This study compares the influence of metal cation and halide anion on the solubility of salts within this ionic liquid. The highest solubility found was for iodide salts, and the lowest solubility for the three fluoride salts. There is no outstanding difference in the solubility of salts with matching anions in comparison to halide salts. The experimental data were correlated employing several phase equilibria models, including ideal mixtures, van't Hoff, the λh (Buchowski) equation, the modified Apelblat equation, and the non-random two-liquid model (NRTL). It was found that the van't Hoff model gave the best correlation results. On the basis of the experimental data the thermodynamic dissolution parameters (ΔH, ΔS, and ΔG) were determined for the studied systems together with computed gas phase metathesis parameters. Dissolution depends on the energy difference between enthalpies of fusion and dissolution of the solute salt. This demonstrates that overcoming the lattice energy of the solid matrix is the key to the solubility of inorganic salts in ionic liquids.

Alkali metal and alkali earth metal gadolinium halide scintillators

DOEpatents

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

2016-08-02

The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

Effect of halide ions on the photodegradation of ibuprofen in aqueous environments.

PubMed

Li, Fuhua; Kong, Qingqing; Chen, Ping; Chen, Min; Liu, Guoguang; Lv, Wenying; Yao, Kun

2017-01-01

Typically contained within ambient surface waters and certain industrial wastewaters, are plentiful halide ions, which possess varying degrees of photosensitivity. The effects of halide ions on the photodegradation of ibuprofen (IBP) were investigated under UV irradiation using a 500 W mercury lamp as a light source. Studies of the mechanism of halide ions were inclusive of both their light shielding effects and quenching experiments. The results indicated that chloride ion has a slight inhibition against IBP photodegradation under neutral condition, and significant inhibition is observed with bromide ions and iodide ions. In addition to the observed increased rate of IBP photodegradation in conjunction with elevated pH in solution, the inhibitory effect of halide ions was different. When the pH value of the IBP solution was 5, chloride ions were seen to facilitate the photodegradation of IBP. Halide ions can inhibit IBP photodegradation by means of a light attenuation effect. All of the halide ions significantly facilitated the generation of 1 O 2 . Copyright © 2016 Elsevier Ltd. All rights reserved.

The melting and solidification of nanowires

NASA Astrophysics Data System (ADS)

Florio, B. J.; Myers, T. G.

2016-06-01

A mathematical model is developed to describe the melting of nanowires. The first section of the paper deals with a standard theoretical situation, where the wire melts due to a fixed boundary temperature. This analysis allows us to compare with existing results for the phase change of nanospheres. The equivalent solidification problem is also examined. This shows that solidification is a faster process than melting; this is because the energy transfer occurs primarily through the solid rather than the liquid which is a poorer conductor of heat. This effect competes with the energy required to create new solid surface which acts to slow down the process, but overall conduction dominates. In the second section, we consider a more physically realistic boundary condition, where the phase change occurs due to a heat flux from surrounding material. This removes the singularity in initial melt velocity predicted in previous models of nanoparticle melting. It is shown that even with the highest possible flux the melting time is significantly slower than with a fixed boundary temperature condition.

Solvation structure of the halides from x-ray absorption spectroscopy

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

Antalek, Matthew; Hedman, Britt; Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu

2016-07-28

Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, andmore » a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (−0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions.« less

Structural, dynamical, and transport properties of the hydrated halides: How do At{sup −} bulk properties compare with those of the other halides, from F{sup −} to I{sup −}?

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

Réal, Florent, E-mail: florent.real@univ-lille1.fr; Severo Pereira Gomes, André; Guerrero Martínez, Yansel Omar

2016-03-28

The properties of halides from the lightest, fluoride (F{sup −}), to the heaviest, astatide (At{sup −}), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force-field parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I{sup −} and At{sup −}, were computed in the gas phase using large and diffuse atomic basis sets,more » and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I{sup −} and At{sup −} in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F{sup −}, Cl{sup −}, and Br{sup −} ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At{sup −} in liquid water at ambient conditions to be 68 kcal mol{sup −1}, a value also close the I{sup −} one, about 70 kcal mol{sup −1}. In all, our simulation results for I{sup −} are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At{sup −} ion are predictive, as no theoretical or experimental data are available to date.« less

Shock melting method to determine melting curve by molecular dynamics: Cu, Pd, and Al.

PubMed

Liu, Zhong-Li; Zhang, Xiu-Lu; Cai, Ling-Cang

2015-09-21

A melting simulation method, the shock melting (SM) method, is proposed and proved to be able to determine the melting curves of materials accurately and efficiently. The SM method, which is based on the multi-scale shock technique, determines melting curves by preheating and/or prepressurizing materials before shock. This strategy was extensively verified using both classical and ab initio molecular dynamics (MD). First, the SM method yielded the same satisfactory melting curve of Cu with only 360 atoms using classical MD, compared to the results from the Z-method and the two-phase coexistence method. Then, it also produced a satisfactory melting curve of Pd with only 756 atoms. Finally, the SM method combined with ab initio MD cheaply achieved a good melting curve of Al with only 180 atoms, which agrees well with the experimental data and the calculated results from other methods. It turned out that the SM method is an alternative efficient method for calculating the melting curves of materials.

Effects of halides on plasmid-mediated silver resistance in Escherichia coli.

PubMed

Gupta, A; Maynes, M; Silver, S

1998-12-01

Silver resistance of sensitive Escherichia coli J53 and resistance plasmid-containing J53(pMG101) was affected by halides in the growth medium. The effects of halides on Ag+ resistance were measured with AgNO3 and silver sulfadiazine, both on agar and in liquid. Low concentrations of chloride made the differences in MICs between sensitive and resistant strains larger. High concentrations of halides increased the sensitivities of both strains to Ag+.

On the phase evolution of AlCoCrCuFeMnSix high entropy alloys prepared by mechanical alloying and arc melting route

NASA Astrophysics Data System (ADS)

Kumar, Anil; Chopkar, Manoj

2018-05-01

Effect of Si addition on phase formation of AlCoCrCuFeMnSix (x=0, 0.3, 0.6 and 0.9) high entropy alloy have been investigated in this work. The alloys are prepared by mechanical alloying and vacuum arc melting technique. The X-ray diffraction results reveals the formation of mixture of face centered and body centered cubic solid solution phases in milled powders. The addition of Si favours body centered cubic structure formation during milling process. Whereas, after melting the milled powders, body centered phases formed during milling is partial transformed into sigma phases. XRD results were also correlated with the SEM elemental mapping of as casted samples. Addition of Si favours σ phase formation in the as cast samples.

Cu-In Halide Perovskite Solar Absorbers.

PubMed

Zhao, Xin-Gang; Yang, Dongwen; Sun, Yuanhui; Li, Tianshu; Zhang, Lijun; Yu, Liping; Zunger, Alex

2017-05-17

The long-term chemical instability and the presence of toxic Pb in otherwise stellar solar absorber APbX 3 made of organic molecules on the A site and halogens for X have hindered their large-scale commercialization. Previously explored ways to achieve Pb-free halide perovskites involved replacing Pb 2+ with other similar M 2+ cations in ns 2 electron configuration, e.g., Sn 2+ or by Bi 3+ (plus Ag + ), but unfortunately this showed either poor stability (M = Sn) or weakly absorbing oversized indirect gaps (M = Bi), prompting concerns that perhaps stability and good optoelectronic properties might be contraindicated. Herein, we exploit the electronic structure underpinning of classic Cu[In,Ga]Se 2 (CIGS) chalcopyrite solar absorbers to design Pb-free halide perovskites by transmuting 2Pb to the pair [B IB + C III ] such as [Cu + Ga] or [Ag + In] and combinations thereof. The resulting group of double perovskites with formula A 2 BCX 6 (A = K, Rb, Cs; B = Cu, Ag; C = Ga, In; X = Cl, Br, I) benefits from the ionic, yet narrow-gap character of halide perovskites, and at the same time borrows the advantage of the strong Cu(d)/Se(p) → Ga/In(s/p) valence-to-conduction-band absorption spectra known from CIGS. This constitutes a new group of CuIn-based Halide Perovskite (CIHP). Our first-principles calculations guided by such design principles indicate that the CIHPs class has members with clear thermodynamic stability, showing direct band gaps, and manifesting a wide-range of tunable gap values (from zero to about 2.5 eV) and combination of light electron and heavy-light hole effective masses. Materials screening of candidate CIHPs then identifies the best-of-class Rb 2 [CuIn]Cl 6 , Rb 2 [AgIn]Br 6 , and Cs 2 [AgIn]Br 6 , having direct band gaps of 1.36, 1.46, and 1.50 eV, and theoretical spectroscopic limited maximal efficiency comparable to chalcopyrites and CH 3 NH 3 PbI 3 . Our finding offers a new routine for designing new-type Pb-free halide perovskite solar

Internal stress-induced melting below melting temperature at high-rate laser heating

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

Hwang, Yong Seok, E-mail: yshwang@iastate.edu; Levitas, Valery I., E-mail: vlevitas@iastate.edu

In this Letter, continuum thermodynamic and phase field approaches (PFAs) predicted internal stress-induced reduction in melting temperature for laser-irradiated heating of a nanolayer. Internal stresses appear due to thermal strain under constrained conditions and completely relax during melting, producing an additional thermodynamic driving force for melting. Thermodynamic melting temperature for Al reduces from 933.67 K for a stress-free condition down to 898.1 K for uniaxial strain and to 920.8 K for plane strain. Our PFA simulations demonstrated barrierless surface-induced melt nucleation below these temperatures and propagation of two solid-melt interfaces toward each other at the temperatures very close to the corresponding predicted thermodynamicmore » equilibrium temperatures for the heating rate Q≤1.51×10{sup 10}K/s. At higher heating rates, kinetic superheating competes with a reduction in melting temperature and melting under uniaxial strain occurs at 902.1 K for Q = 1.51 × 10{sup 11 }K/s and 936.9 K for Q = 1.46 × 10{sup 12 }K/s.« less

On the correlation between hydrogen bonding and melting points in the inositols

PubMed Central

Bekö, Sándor L.; Alig, Edith; Schmidt, Martin U.; van de Streek, Jacco

2014-01-01

Inositol, 1,2,3,4,5,6-hexahydroxycyclohexane, exists in nine stereoisomers with different crystal structures and melting points. In a previous paper on the relationship between the melting points of the inositols and the hydrogen-bonding patterns in their crystal structures [Simperler et al. (2006 ▶). CrystEngComm 8, 589], it was noted that although all inositol crystal structures known at that time contained 12 hydrogen bonds per molecule, their melting points span a large range of about 170 °C. Our preliminary investigations suggested that the highest melting point must be corrected for the effect of molecular symmetry, and that the three lowest melting points may need to be revised. This prompted a full investigation, with additional experiments on six of the nine inositols. Thirteen new phases were discovered; for all of these their crystal structures were examined. The crystal structures of eight ordered phases could be determined, of which seven were obtained from laboratory X-ray powder diffraction data. Five additional phases turned out to be rotator phases and only their unit cells could be determined. Two previously unknown melting points were measured, as well as most enthalpies of melting. Several previously reported melting points were shown to be solid-to-solid phase transitions or decomposition points. Our experiments have revealed a complex picture of phases, rotator phases and phase transitions, in which a simple correlation between melting points and hydrogen-bonding patterns is not feasible. PMID:25075320

Effect of boron additions on phase formation and magnetic properties of TbCu7-type melt spun SmFe ribbons

NASA Astrophysics Data System (ADS)

Zheng, Chuanjiang; Yu, Dunbo; Li, Kuoshe; Luo, Yang; Jin, Jinling; Lu, Shuo; Li, Hongwei; Mao, Yongjun; Quan, Ningtao

2016-08-01

Melt spun ribbons of a series of SmFe12Bx (x=0.0, 0.5, 0.75, 1.0, 1.25, and 1.5) have been prepared by the melt spinning technique. Sm-Fe-B melt spun ribbons with single phase TbCu7-type structure were prepared from the SmFe12Bx (x=0.5, 0.75, and 1.0) alloys at the surface velocity around 40 m/s. The addition of boron not only inhibits the appearance of soft magnetic phase α-Fe, but also enhances the ability of amorphous formation for melt spun Sm-Fe ribbons. The concentration of boron atoms, however, exceeds the limit of the solubility (x>1.0) of Sm-Fe alloys, which does not impede the appearance of α-Fe but accelerates the formation of metastable phase Sm2Fe23B3 that is unfavorable to their magnetic properties. Moreover, it is found that the addition of boron whose concentration is 0.0≤x≤0.75 can stabilize the metastable TbCu7-type structure because of the increase of the lattice parameter ratio c/a. The magnetic properties of as-annealed SmFe12B1.0 melt spun ribbons with an energy product of 2.19MGOe, a coercivity of 2.36 kOe and a remanence of 4.8 kGs have been achieved. The microstructural characteristics of as-annealed melt spun SmFe12 and SmFe12B1.0 ribbons have been discussed as well. The following sequence of the hyperfine field H(6l)

Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

PubMed

Duan, Zonghui; Wang, Shuai; Yi, Ningbo; Gu, Zhiyuan; Gao, Yisheng; Song, Qinghai; Xiao, Shumin

2017-06-21

Lasing actions in organo-lead halide perovskite films have been heavily studied in the past few years. However, due to the disordered nature of synthesized perovskite films, the lasing actions are usually understood as random lasers that are formed by multiple scattering. Herein, we demonstrate the miscellaneous lasing actions in organo-lead halide perovskite films. In addition to the random lasers, we show that a single or a few perovskite microparticles can generate laser emissions with their internal resonances instead of multiple scattering among them. We experimentally observed and numerically confirmed whispering gallery (WG)-like microlasers in polygon shaped and other deformed microparticles. Meanwhile, owing to the nature of total internal reflection and the novel shape of the nanoparticle, the size of the perovskite WG laser can be significantly decreased to a few hundred nanometers. Thus, wavelength-scale lead halide perovskite lasers were realized for the first time. All of these laser behaviors are complementary to typical random lasers in perovskite film and will help the understanding of lasing actions in complex lead halide perovskite systems.

Evaporation-induced gas-phase flows at selective laser melting

NASA Astrophysics Data System (ADS)

Zhirnov, I.; Kotoban, D. V.; Gusarov, A. V.

2018-02-01

Selective laser melting is the method for 3D printing from metals. A solid part is built from powder layer-by-layer. A continuum-wave laser beam scans every powder layer to fuse powder. The process is studied with a high-speed CCD camera at the frame rate of 104 fps and the resolution up to 5 µm per pixel. Heat transfer and evaporation in the laser-interaction zone are numerically modeled. Droplets are ejected from the melt pool in the direction around the normal to the melt surface and the powder particles move in the horizontal plane toward the melt pool. A vapor jet is observed in the direction of the normal to the melt surface. The velocities of the droplets, the powder particles, and the jet flow and the mass loss due to evaporation are measured. The gas flow around the vapor jet is calculated by Landau's model of submerged jet. The measured velocities of vapor, droplets, and powder particles correlate with the calculated flow field. The obtained results show the importance of evaporation and the flow of the vapor and the ambient gas. These gas-dynamic phenomena can explain the formation of the denudated zones and the instability at high-energy input.

Melting of stripe phases and its signature in the single-particle spectral function

NASA Astrophysics Data System (ADS)

Raczkowski, Marcin; Assaad, Fakher F.

2010-12-01

Motivated by the recent experimental data [J. Fink, E. Schierle, E. Weschke, J. Geck, D. Hawthorn, V. Soltwisch, H. Wadati, H.-H. Wu, H. A. Dürr, N. Wizent, B. Büchner, and G. A. Sawatzky, Phys. Rev. B 79, 100502 (2009)10.1103/PhysRevB.79.100502] indicating the existence of a pure stripe charge order over unprecedently wide temperature range in La1.8-xEu0.2SrxCuO4 , we investigate the temperature-induced melting of the metallic stripe phase. In spite of taking into account local dynamic correlations within a real-space dynamical mean-field theory of the Hubbard model, we observe a mean-field-like melting of the stripe order irrespective of the choice of the next-nearest-neighbor hopping. The temperature dependence of the single-particle spectral function shows the stripe induced formation of a flat band around the antinodal points accompanied by the opening a gap in the nodal direction.

Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

NASA Astrophysics Data System (ADS)

Reo, G.; Frank, M. R.; Loocke, M. P.; Macey, C. J.

2017-12-01

Magmatic sulfide ore deposits account for over 80% of the world's platinum group element (PGE) reserves. Layered mafic intrusions (LMIs), a type of magmatic sulfide ore deposit, contain alternating layers of silicate and sulfide mineralization that are thought to have coexisted as an immiscible silicate + sulfide melt pair. Platinum and palladium, the most common PGEs found in LMIs, heavily favor the sulfide melt. Nernst partition coefficients for Pt (D = wt% of Pt in sulfide/wt% of Pt in silicate) range from 102 to 109. This study examined the Pt- and Pd-bearing phases that formed from the quenched sulfide melts to better constrain the PGE-rich sulfide layers of LMIs system. Experiments were conducted with a basalt melt, sulfide melt, and Pt-Pd metal in a vertical tube furnace at 1100°C and 1 atm and with oxygen fugacity buffered to QFM (quartz-fayalite-magnetite). Following the experiments, run products containing both sulfide and silicate glasses (quenched melts) were analyzed by a Shimadzu EPMA-1720HT Electron Probe Microanalyzer. The focus here is on the quenched Fe-rich sulfides whereas data on the partitioning of Pt and Pd between the coexisting silicate and sulfide melts will be presented in the future. The sulfide samples were imaged in back-scattering mode and major and trace element concentrations of separate metal-rich phases in the sulfide matrix were ascertained through wavelength-dispersive x-ray spectroscopy. Three discernable PGE-rich phases were found to have exsolved from the sulfide matrix upon quenching of the sulfide melt. All of these phases had Fe and S of 21-24 and 16-22 wt.%, respectively. An irregularly shaped Pd- and Cu-rich sulfide phase ( 36 and 14 wt.%, respectively) makes up the majority of the exsolution product. A separate Pd- and Ni-rich phase ( 22 and 14 wt%, respectively) can be found as grains or rims adjacent to the exsolved Pd- and Cu-rich phase. A third Pd- and Pt-rich phase ( 26 and 18 wt.%, respectively) exhibits a

Effects of Halides on Plasmid-Mediated Silver Resistance in Escherichia coli

PubMed Central

Gupta, Amit; Maynes, Maria; Silver, Simon

1998-01-01

Silver resistance of sensitive Escherichia coli J53 and resistance plasmid-containing J53(pMG101) was affected by halides in the growth medium. The effects of halides on Ag+ resistance were measured with AgNO3 and silver sulfadiazine, both on agar and in liquid. Low concentrations of chloride made the differences in MICs between sensitive and resistant strains larger. High concentrations of halides increased the sensitivities of both strains to Ag+. PMID:9835606

Cu-catalyzed Suzuki-Miyaura reactions of primary and secondary benzyl halides with arylboronates.

PubMed

Sun, Yan-Yan; Yi, Jun; Lu, Xi; Zhang, Zhen-Qi; Xiao, Bin; Fu, Yao

2014-09-28

A copper-catalyzed Suzuki-Miyaura coupling of benzyl halides with arylboronates is described. Varieties of primary benzyl halides as well as more challenging secondary benzyl halides with β hydrogens or steric hindrance could be successfully converted into the corresponding products. Thus it provides access to diarylmethanes, diarylethanes and triarylmethanes.

Formation of Low Symmetry Ordered Phases in Block Polymer Melts

NASA Astrophysics Data System (ADS)

Bates, Frank

Until recently the phase behavior of asymmetric AB diblock copolymers in the melt state was universally accepted as a solved problem: spherical domains packed on a body centered cubic (BCC) lattice. Recent experiments with low molecular weight diblocks have upended this picture, beginning with the discovery of the Frank-Kasper sigma phase in poly(isoprene)- b-poly(lactide) (PI-PLA) followed recently by the identification of a dodecagonal quasicrystal phase (DDQC) as a metastable state that evolves from the supercooled disordered liquid. Self-consistent mean-field theory shows that introducing conformational asymmetry (bA >bB where b is the statistical segment length) opens a window in the phase portrait at fA <<1/2 that supports the formation of various low symmetry ordered phases. However, contrary to the widely accepted mean-field picture, the disordered state near the order-disorder transition (ODT) is highly structured and rapid cooling of this micellar fluid several tens of degrees below the ODT temperature arrests macromolecular chain exchange transitioning the material from an ergodic to non-ergodic state. We have explored the evolution of order following such temperature quenches and during subsequent reheating using synchrotron small-angle X-ray scattering (SAXS) revealing surprising analogies with the behavior of metal alloys. This presentation will associate the formation of ordered low symmetry phases with the concept of sphericity, the tendency for the self-assembled nanoparticles to be spherical in competition with the constraints imposed by periodic and aperiodic packing without voids and subject to the condition of incompressibility. Supported by NSF-DMR-1104368. This work was conducted in collaboration with Kyungtae Kim, Morgan Schulze, Akash Arora, Ronald Lewis, Timothy Gillard, Sangwoo Lee, Kevin Dorfman and Marc Hillmyer.

Electrochemical Doping of Halide Perovskites with Ion Intercalation.

PubMed

Jiang, Qinglong; Chen, Mingming; Li, Junqiang; Wang, Mingchao; Zeng, Xiaoqiao; Besara, Tiglet; Lu, Jun; Xin, Yan; Shan, Xin; Pan, Bicai; Wang, Changchun; Lin, Shangchao; Siegrist, Theo; Xiao, Qiangfeng; Yu, Zhibin

2017-01-24

Halide perovskites have recently been investigated for various solution-processed optoelectronic devices. The majority of studies have focused on using intrinsic halide perovskites, and the intentional incoporation of dopants has not been well explored. In this work, we discovered that small alkali ions, including lithium and sodium ions, could be electrochemically intercalated into a variety of halide and pseudohalide perovskites. The ion intercalation caused a lattice expansion of the perovskite crystals and resulted in an n-type doping of the perovskites. Such electrochemical doping improved the conductivity and changed the color of the perovskites, leading to an electrochromism with more than 40% reduction of transmittance in the 450-850 nm wavelength range. The doped perovskites exhibited improved electron injection efficiency into the pristine perovskite crystals, resulting in bright light-emitting diodes with a low turn-on voltage.

The gas phase emitter effect of lanthanum within ceramic metal halide lamps and its dependence on the La vapor pressure and operating frequency

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

Ruhrmann, C.; Hoebing, T.; Bergner, A.

2015-08-07

The gas phase emitter effect increases the lamp lifetime by lowering the work function and, with it, the temperature of the tungsten electrodes of metal halide lamps especially for lamps in ceramic vessels due to their high rare earth pressures. It is generated by a monolayer on the electrode surface of electropositive atoms of certain emitter elements, which are inserted into the lamp bulb by metal iodide salts. They are vaporized, dissociated, ionized, and deposited by an emitter ion current onto the electrode surface within the cathodic phase of lamp operation with a switched-dc or ac-current. The gas phase emittermore » effect of La and the influence of Na on the emitter effect of La are studied by spatially and phase-resolved pyrometric measurements of the electrode tip temperature, La atom, and ion densities by optical emission spectroscopy as well as optical broadband absorption spectroscopy and arc attachment images by short time photography. An addition of Na to the lamp filling increases the La vapor pressure within the lamp considerably, resulting in an improved gas phase emitter effect of La. Furthermore, the La vapor pressure is raised by a heating of the cold spot. In this way, conditions depending on the La vapor pressure and operating frequency are identified, at which the temperature of the electrodes becomes a minimum.« less

Some physical aspects of fluid-fluxed melting

NASA Astrophysics Data System (ADS)

Patiño Douce, A.

2012-04-01

Fluid-fluxed melting is thought to play a crucial role in the origin of many terrestrial magmas. We can visualize the fundamental physics of the process as follows. An infinitesimal amount of fluid infiltrates dry rock at the temperature of its dry solidus. In order to restore equilibrium the temperature must drop, so that enthalpy is released and immediately reabsorbed as enthalpy of melting. The amount of melt produced must be such that the energy balance and thermodynamic equilibrium conditions are simultaneously satisfied. We wish to understand how an initially dry rock melts in response to progressive fluid infiltration, under both batch and fractional melting constraints. The simplest physical model for this process is a binary system in which one of the components makes up a pure solid phase and the other component a pure fluid phase, and in which a binary melt phase exists over certain temperature range. Melting point depression is calculated under the assumption of ideal mixing. The equations of energy balance and thermodynamic equilibrium are solved simultaneously for temperature and melt fraction, using an iterative procedure that allows addition of fluid in infinitesimal increments. Batch melting and fractional melting are simulated by allowing successive melt increments to remain in the system (batch) or not (fractional). Despite their simplified nature, these calculations reveal some important aspects of fluid-fluxed melting. The model confirms that, if the solubility of the fluid in the melt is sufficiently high, fluid fluxed melting is an efficient mechanism of magma generation. One might expect that the temperature of the infiltrating fluid would have a significant effect on melt productivity, but the results of the calculations show this not to be the case, because a relatively small mass of low molecular weight fluid has a strong effect on the melting point of minerals with much higher molecular weights. The calculations reveal the somewhat

Band Gap Tuning and Defect Tolerance of Atomically Thin Two-Dimensional Organic-Inorganic Halide Perovskites.

PubMed

Pandey, Mohnish; Jacobsen, Karsten W; Thygesen, Kristian S

2016-11-03

Organic-inorganic halide perovskites have proven highly successful for photovoltaics but suffer from low stability, which deteriorates their performance over time. Recent experiments have demonstrated that low dimensional phases of the hybrid perovskites may exhibit improved stability. Here we report first-principles calculations for isolated monolayers of the organometallic halide perovskites (C 4 H 9 NH 3 ) 2 MX 2 Y 2 , where M = Pb, Ge, Sn and X,Y = Cl, Br, I. The band gaps computed using the GLLB-SC functional are found to be in excellent agreement with experimental photoluminescence data for the already synthesized perovskites. Finally, we study the effect of different defects on the band structure. We find that the most common defects only introduce shallow or no states in the band gap, indicating that these atomically thin 2D perovskites are likely to be defect tolerant.

High-pressure melting of molybdenum.

PubMed

Belonoshko, A B; Simak, S I; Kochetov, A E; Johansson, B; Burakovsky, L; Preston, D L

2004-05-14

The melting curve of the body-centered cubic (bcc) phase of Mo has been determined for a wide pressure range using both direct ab initio molecular dynamics simulations of melting as well as a phenomenological theory of melting. These two methods show very good agreement. The simulations are based on density functional theory within the generalized gradient approximation. Our calculated equation of state of bcc Mo is in excellent agreement with experimental data. However, our melting curve is substantially higher than the one determined in diamond anvil cell experiments up to a pressure of 100 GPa. An explanation is suggested for this discrepancy.

Alkali Metal/Salt Thermal-Energy-Storage Systems

NASA Technical Reports Server (NTRS)

Phillips, Wayne W.; Stearns, John W.

1987-01-01

Proposed thermal-energy-storage system based on mixture of alkali metal and one of its halide salts; metal and salt form slurry of two immiscible melts. Use of slurry expected to prevent incrustations of solidified salts on heat-transfer surfaces that occur where salts alone used. Since incrustations impede heat transfer, system performance improved. In system, charging heat-exchanger surface immersed in lower liquid, rich in halide-salt, phase-charge material. Discharging heat exchanger surface immersed in upper liquid, rich in alkali metal.

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

NASA Technical Reports Server (NTRS)

Beckett, J. R.; Stolper, E.

1993-01-01

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

Predicted reentrant melting of dense hydrogen at ultra-high pressures

PubMed Central

Geng, Hua Y.; Wu, Q.

2016-01-01

The phase diagram of hydrogen is one of the most important challenges in high-pressure physics and astrophysics. Especially, the melting of dense hydrogen is complicated by dimer dissociation, metallization and nuclear quantum effect of protons, which together lead to a cold melting of dense hydrogen when above 500 GPa. Nonetheless, the variation of the melting curve at higher pressures is virtually uncharted. Here we report that using ab initio molecular dynamics and path integral simulations based on density functional theory, a new atomic phase is discovered, which gives an uplifting melting curve of dense hydrogen when beyond 2 TPa, and results in a reentrant solid-liquid transition before entering the Wigner crystalline phase of protons. The findings greatly extend the phase diagram of dense hydrogen, and put metallic hydrogen into the group of alkali metals, with its melting curve closely resembling those of lithium and sodium. PMID:27834405

Improved lithium iodide neutron scintillator with Eu 2+ activation: The elimination of Suzuki-Phase precipitates

DOE PAGES

Boatner, Lynn A.; Comer, Eleanor P.; Wright, Gomez W.; ...

2017-02-21

Monovalent alkali halides such as NaI, CsI, and LiI are widely used as inorganic scintillators for radiation detection due to their light yield, the capability for the growth of large single crystals, relatively low cost, and other favorable characteristics. These materials are frequently activated through the addition of small amounts (e.g., a few hundred ppm) of elements such as thallium - or sodium in the case of CsI. The monovalent alkali halide scintillators can also be activated with low concentrations of Eu 2+, however Eu activation has previously not been widely employed due to the non-uniform segregation of the divalentmore » Eu dopant that leads to the formation of unwanted phases during Bridgman or other solidification crystal-growth methods. Specifically, for Eu concentrations near and above ~0.5%, Suzuki Phase precipitates form in the course of the melt-growth process, and these Suzuki Phase particles scatter the scintillation light. This adversely affects the scintillator performance via reduction in the optical transmission of the material, and depending on the crystal thickness and precipitated-particle concentration, this reduction can occur up to the point of opacity. Here we describe a post-growth process for the removal of Suzuki Phase precipitates from single crystals of the neutron scintillator LiI activated with Eu 2+ at concentrations up to and in excess of 3 wt.%, and we correlate the resulting neutron-detection performance with the thermal processing methods used to remove the Suzuki Phase particles. Furthermore, the resulting improved scintillator properties using increased Eu activator levels are applicable to neutron imaging and active interrogation systems, and pulse-height gamma-ray spectroscopy rather than pulse-shape discrimination can be used to discriminate between gamma ray and neutron interaction events.« less

Improved lithium iodide neutron scintillator with Eu2+ activation: The elimination of Suzuki-Phase precipitates

NASA Astrophysics Data System (ADS)

Boatner, L. A.; Comer, E. P.; Wright, G. W.; Ramey, J. O.; Riedel, R. A.; Jellison, G. E.; Kolopus, J. A.

2017-05-01

Monovalent alkali halides such as NaI, CsI, and LiI are widely used as inorganic scintillators for radiation detection due to their light yield, the capability for the growth of large single crystals, relatively low cost, and other favorable characteristics. These materials are frequently activated through the addition of small amounts (e.g., a few hundred ppm) of elements such as thallium - or sodium in the case of CsI. The monovalent alkali halide scintillators can also be activated with low concentrations of Eu2+, however Eu activation has previously not been widely employed due to the non-uniform segregation of the divalent Eu dopant that leads to the formation of unwanted phases during Bridgman or other solidification crystal-growth methods. Specifically, for Eu concentrations near and above 0.5%, Suzuki Phase precipitates form in the course of the melt-growth process, and these Suzuki Phase particles scatter the scintillation light. This adversely affects the scintillator performance via reduction in the optical transmission of the material, and depending on the crystal thickness and precipitated-particle concentration, this reduction can occur up to the point of opacity. Here we describe a post-growth process for the removal of Suzuki Phase precipitates from single crystals of the neutron scintillator LiI activated with Eu2+ at concentrations up to and in excess of 3 wt%, and we correlate the resulting neutron-detection performance with the thermal processing methods used to remove the Suzuki Phase particles. The resulting improved scintillator properties using increased Eu activator levels are applicable to neutron imaging and active interrogation systems, and pulse-height gamma-ray spectroscopy rather than pulse-shape discrimination can be used to discriminate between gamma ray and neutron interaction events.

Coupled phase field, heat conduction, and elastodynamic simulations of kinetic superheating and nanoscale melting of aluminum nanolayer irradiated by picosecond laser.

PubMed

Hwang, Yong Seok; Levitas, Valery I

2015-12-21

An advanced continuum model for nanoscale melting and kinetic superheating of an aluminum nanolayer irradiated by a picosecond laser is formulated. Barrierless nucleation of surface premelting and melting occurs, followed by a propagation of two solid-melt interfaces toward each other and their collision. For a slow heating rate of Q = 0.015 K ps(-1) melting occurs at the equilibrium melting temperature under uniaxial strain conditions T = 898.1 K (i.e., below equilibrium melting temperature Teq = 933.67 K) and corresponding biaxial stresses, which relax during melting. For a high heating rate of Q = 0.99-84 K ps(-1), melting occurs significantly above Teq. Surprisingly, an increase in heating rate leads to temperature reduction at the 3 nm wide moving interfaces due to fast absorption of the heat of fusion. A significant, rapid temperature drop (100-500 K, even below melting temperature) at the very end of melting is revealed, which is caused by the collision of two finite-width interfaces and accelerated melting in about the 5 nm zone. For Q = 25-84 K ps(-1), standing elastic stress waves are observed in a solid with nodal points at the moving solid-melt interfaces, which, however, do not have a profound effect on melting time or temperatures. When surface melting is suppressed, barrierless bulk melting occurs in the entire sample, and elastodynamic effects are more important. Good correspondence with published, experimentally-determined melting time is found for a broad range of heating rates. Similar approaches can be applied to study various phase transformations in different materials and nanostructures under high heating rates.

Removal of phosphorus-rich phase from high-phosphorous iron ore by melt separation at 1573 K in a super-gravity field

NASA Astrophysics Data System (ADS)

Gao, Jin-tao; Guo, Lei; Zhong, Yi-wei; Ren, Hong-ru; Guo, Zhan-cheng

2016-07-01

A new approach of removing the phosphorus-rich phase from high-phosphorous iron ore by melt separation at 1573 K in a super- gravity field was investigated. The iron-slag separation by super-gravity resulted in phosphorus being effectively removed from the iron-rich phase and concentrated as a phosphorus-rich phase at a temperature below the melting point of iron. The samples obtained by super-gravity exhibited obvious layered structures. All the iron grains concentrated at the bottom of the sample along the super-gravity direction, whereas the molten slag concentrated in the upper part of the sample along the opposite direction. Meanwhile, fine apatite crystals collided and grew into larger crystals and concentrated at the slag-iron interface. Consequently, in the case of centrifugation with a gravity coefficient of G = 900, the mass fractions of the slag phase and iron-rich phase were similar to their respective theoretical values. The mass fraction of MFe in the iron-rich phase was as high as 97.77wt% and that of P was decreased to 0.092wt%.

Shock melting method to determine melting curve by molecular dynamics: Cu, Pd, and Al

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

Liu, Zhong-Li, E-mail: zl.liu@163.com; Zhang, Xiu-Lu; Cai, Ling-Cang

A melting simulation method, the shock melting (SM) method, is proposed and proved to be able to determine the melting curves of materials accurately and efficiently. The SM method, which is based on the multi-scale shock technique, determines melting curves by preheating and/or prepressurizing materials before shock. This strategy was extensively verified using both classical and ab initio molecular dynamics (MD). First, the SM method yielded the same satisfactory melting curve of Cu with only 360 atoms using classical MD, compared to the results from the Z-method and the two-phase coexistence method. Then, it also produced a satisfactory melting curvemore » of Pd with only 756 atoms. Finally, the SM method combined with ab initio MD cheaply achieved a good melting curve of Al with only 180 atoms, which agrees well with the experimental data and the calculated results from other methods. It turned out that the SM method is an alternative efficient method for calculating the melting curves of materials.« less

Synthesis of chalcogenide and pnictide crystals in salt melts using a steady-state temperature gradient

NASA Astrophysics Data System (ADS)

Chareev, D. A.; Volkova, O. S.; Geringer, N. V.; Koshelev, A. V.; Nekrasov, A. N.; Osadchii, V. O.; Osadchii, E. G.; Filimonova, O. N.

2016-07-01

Some examples of growing crystals of metals, alloys, chalcogenides, and pnictides in melts of halides of alkali metals and aluminum at a steady-state temperature gradient are described. Transport media are chosen to be salt melts of eutectic composition with the participation of LiCl, NaCl, KCl, RbCl, CsCl, AlCl3, AlBr3, KBr, and KI in a temperature range of 850-150°C. Some crystals have been synthesized only using a conducting contour. This technique of crystal growth is similar to the electrochemical method. In some cases, to exclude mutual influence, some elements have been isolated and forced to migrate to the crystal growth region through independent channels. As a result, crystals of desired quality have been obtained using no special equipment and with sizes sufficient for study under laboratory conditions.

Inhomogeneous degradation in metal halide perovskites

NASA Astrophysics Data System (ADS)

Yang, Rong; Zhang, Li; Cao, Yu; Miao, Yanfeng; Ke, You; Wei, Yingqiang; Guo, Qiang; Wang, Ying; Rong, Zhaohua; Wang, Nana; Li, Renzhi; Wang, Jianpu; Huang, Wei; Gao, Feng

2017-08-01

Although the rapid development of organic-inorganic metal halide perovskite solar cells has led to certified power conversion efficiencies of above 20%, their poor stability remains a major challenge, preventing their practical commercialization. In this paper, we investigate the intrinsic origin of the poor stability in perovskite solar cells by using a confocal fluorescence microscope. We find that the degradation of perovskite films starts from grain boundaries and gradually extend to the center of the grains. Firmly based on our findings, we further demonstrate that the device stability can be significantly enhanced by increasing the grain size of perovskite crystals. Our results have important implications to further enhance the stability of optoelectronic devices based on metal halide perovskites.

Lanthanide-halide based humidity indicators

DOEpatents

Beitz, James V [Hinsdale, IL; Williams, Clayton W [Chicago, IL

2008-01-01

The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

Unraveling halide hydration: A high dilution approach.

PubMed

Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

2014-07-28

The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (ΔG [minus sign in circle symbol]hyd[H+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a ΔG [minus sign in circle symbol]hyd[H] value of -1100 kJ mol(-1) [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl(-), Br(-), and I(-) ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F(-) ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl(-), Br(-), and I(-) ions does not extend beyond the ion first hydration shell, and the structure of water in the F(-) second shell is also substantially unaffected by the ion.

Kinetics of the iodine- and bromine-mediated transport of halide ions: demonstration of an interfacial complexation mechanism.

PubMed Central

Klotz, K H; Benz, R

1993-01-01

Stationary and kinetic experiments were performed on lipid bilayer membranes to study the mechanism of iodine- and bromine-mediated halide transport in detail. The stationary conductance data suggested that four different 1:1 complexes between I2 and Br2 and the halides I- and Br- were responsible for the observed conductance increase by iodine and bromine (I3-, I2Br-, Br2I-, and Br3-). Charge pulse experiments allowed the further elucidation of the transport mechanism. Only two of three exponential voltage relaxations predicted by the Läuger model could be resolved under all experimental conditions. This means that either the heterogeneous complexation reactions kR (association) and kD (dissociation) were too fast to be resolved or that the neutral carriers were always in equilibrium within the membrane. Experiments at different carrier and halide concentrations suggested that the translocation of the neutral carrier is much faster than the other processes involved in carrier-mediated ion transport. The model was modified accordingly. From the charge pulse data at different halide concentrations, the translocation rate constant of the complexed carriers, kAS, the dissociation constant, kD, and the total surface concentration of charged carriers, NAS, could be evaluated from one single charge pulse experiment. The association rate of the complex, kR, could be obtained in some cases from the plot of the stationary conductance data as a function of the halide concentration in the aqueous phase. The translocation rate constant, kAS, of the different complexes is a function of the image force and of the Born charging energy. It increases 5000-fold from Br3- to I3- because of an enlarged ion radius. PMID:8312500

Non-hydrolytic metal oxide films for perovskite halide overcoating and stabilization

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

Martinson, Alex B.; Kim, In Soo

A method of protecting a perovskite halide film from moisture and temperature includes positioning the perovskite halide film in a chamber. The chamber is maintained at a temperature of less than 200 degrees Celsius. An organo-metal compound is inserted into the chamber. A non-hydrolytic oxygen source is subsequently inserted into the chamber. The inserting of the organo-metal compound and subsequent inserting of the non-hydrolytic oxygen source into the chamber is repeated for a predetermined number of cycles. The non-hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a non-hydrolytic metal oxide film on perovskite halide film.more » The non-hydrolytic metal oxide film protects the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius, respectively.« less

Understanding Melt-Memory of Commercial Polyolefins

NASA Astrophysics Data System (ADS)

Alamo, Rufina

Self-nucleation (SN) or controlling self-generated seeds in a polymer melt is an avenue to increase the rate of solidification of semicrystalline polymers of commercial relevance. Self-nuclei are remains in the melt of the segmental self-assembly to form polymer crystallites providing a path to enhance primary crystal nucleation. SN has been extensively studied in homopolymers such as iPP. Recently, a strong memory effect of crystallization has been observed in melts of random ethylene copolymers well above the equilibrium melting temperature. The melt memory is associated with clusters or seeds that remain in the melt from the copolymer's sequence length partitioning. Cooling from progressively lower self-seeded melt temperatures, ethylene copolymers with a broad inter-chain comonomer composition (1 - 15 mol%) display first the expected accelerated crystallization, followed by a decrease in the rate in a range of melt temperatures where narrow copolymers show a continuous acceleration of the rate. This unusual inversion of the crystallization rate was postulated to arise from the onset of liquid-liquid phase separation (LLPS) between comonomer-rich and comonomer-poor components of the broad copolymer. The UCST type phase diagram of these commercial copolymers has been documented via SANS using a blend of components, some deuterated, to reproduce the broad distribution. Furthermore, the components that contribute to LLPS have been identified by the crystallization behavior of molar mass fractions. The influence of long chain branching on the topology of copolymer melts has been analyzed using model 3-arm stars hydrogenated polybutadienes. The effect of melt viscosity on strength of melt memory is also evident when SN data of random ethylene copolymers are compared with those of propylene-ethylene copolymers. The strong dependence of melt viscosity on melt memory, and a critical threshold crystallinity level to observe the effect of melt memory on crystallization

Crystal structures of five 1-alkyl-4-aryl-1,2,4-triazol-1-ium halide salts.

PubMed

Guino-O, Marites A; Talbot, Meghan O; Slitts, Michael M; Pham, Theresa N; Audi, Maya C; Janzen, Daron E

2015-06-01

The asymmetric units for the salts 4-(4-fluoro-phen-yl)-1-isopropyl-1,2,4-triazol-1-ium iodide, C11H13FN3 (+)·I(-), (1), 1-isopropyl-4-(4-methyl-phen-yl)-1,2,4-triazol-1-ium iodide, C12H16N3 (+)·I(-), (2), 1-isopropyl-4-phenyl-1,2,4-triazol-1-ium iodide, C11H14N3 (+)·I(-), (3), and 1-methyl-4-phenyl-1,2,4-triazol-1-ium iodide, C9H10N3 (+)·I(-), (4), contain one cation and one iodide ion, whereas in 1-benzyl-4-phenyl-1,2,4-triazol-1-ium bromide monohydrate, C15H14N3 (+)·Br(-)·H2O, (5), there is an additional single water mol-ecule. There is a predominant C-H⋯X(halide) inter-action for all salts, resulting in a two-dimensional extended sheet network between the triazolium cation and the halide ions. For salts with para-substitution on the aryl ring, there is an additional π-anion inter-action between a triazolium carbon and iodide displayed by the layers. For salts without the para-substitution on the aryl ring, the π-π inter-actions are between the triazolium and aryl rings. The melting points of these salts agree with the predicted substituent inductive effects.

Uranium in granitic magmas: Part 2. Experimental determination of uranium solubility and fluid-melt partition coefficients in the uranium oxide-haplogranite-H 2O-NaX (X = Cl, F) system at 770°C, 2 kbar

NASA Astrophysics Data System (ADS)

Peiffert, Chantal; nguyen-Trung, Chinh; Cuney, Michel

1996-05-01

The solubility of uranium oxide was investigated in both aqueous halide (Cl, F) fluid and granitic melt in equilibrium in the system uranium oxide-haplogranite-H 2O-NaCl (0.1-5.0 molal), NaF (0.1-0.5 molal) at 770°C, 2 kbar, and fO 2 conditions controlled by Ni-NiO, Fe 3O 4-Fe 2O 3, and Cu 2O- CuO buffers. Three distinct uranium oxides UO (2+ x) with x = 0.01 ± 0.01; 0.12 ± 0.02; and 0.28 ± 0.02, respec- tively, were obtained in both chloride and fluoride systems, under the three fO 2 conditions cited above. Changes in the composition of aqueous solutions and silicate melt were observed after the runs. These changes were more pronounced for the fluoride-bearing experiments. Quench pH decreased from 5.9 to 2.1 with increasing chloride molality from 0.085-4.38 molal. For fluoride solutions, the decrease of pH from 5.4 to 3.4 corresponded to the increase of fluoride molality from 0.02-0.23 molal. The U solubility in chloride solutions was in the range 10-967 ppm. For the same molality, fluoride solutions appeared to dissolve up to twenty times more uranium than chloride solutions. The increase of halide molality and oxidation led to increase the U solubility. The U solubility in silicate glasses was in the range 10-1.8 × 10 4 ppm and increased with increasing oxidation and halide concentration. In addition, increasing agpaicity also increased U solubility in the chloride system. This effect was not observed in the fluoride system. The chloride concentration in the silicate melt increased from 100-790 ppm with increasing initial aqueous chloride concentration from 0.1-5.0 m. The fluoride concentration in the silicate melt increased from 2.8 × 10 3 to 1.1 × 10 4 ppm with increasing initial fluoride concentra- tion from 0.1-0.5 m. In the chloride system, the partition coefficient of U (log D)(U) fluid/melt) increased from -1.2-0 with increasing agpaicity from 0.92-1.36, for increasing chloride concentration from 0.085-4.38 molal and for increasing fO 2 from 10 -15

Metal matrix-metal nanoparticle composites with tunable melting temperature and high thermal conductivity for phase-change thermal storage.

PubMed

Liu, Minglu; Ma, Yuanyu; Wu, Hsinwei; Wang, Robert Y

2015-02-24

Phase-change materials (PCMs) are of broad interest for thermal storage and management applications. For energy-dense storage with fast thermal charging/discharging rates, a PCM should have a suitable melting temperature, large enthalpy of fusion, and high thermal conductivity. To simultaneously accomplish these traits, we custom design nanocomposites consisting of phase-change Bi nanoparticles embedded in an Ag matrix. We precisely control nanoparticle size, shape, and volume fraction in the composite by separating the nanoparticle synthesis and nanocomposite formation steps. We demonstrate a 50-100% thermal energy density improvement relative to common organic PCMs with equivalent volume fraction. We also tune the melting temperature from 236-252 °C by varying nanoparticle diameter from 8.1-14.9 nm. Importantly, the silver matrix successfully prevents nanoparticle coalescence, and no melting changes are observed during 100 melt-freeze cycles. The nanocomposite's Ag matrix also leads to very high thermal conductivities. For example, the thermal conductivity of a composite with a 10% volume fraction of 13 nm Bi nanoparticles is 128 ± 23 W/m-K, which is several orders of magnitude higher than typical thermal storage materials. We complement these measurements with calculations using a modified effective medium approximation for nanoscale thermal transport. These calculations predict that the thermal conductivity of composites with 13 nm Bi nanoparticles varies from 142 to 47 W/m-K as the nanoparticle volume fraction changes from 10 to 35%. Larger nanoparticle diameters and/or smaller nanoparticle volume fractions lead to larger thermal conductivities.

Sn–Ag–Cu nanosolders: Melting behavior and phase diagram prediction in the Sn-rich corner of the ternary system

PubMed Central

Roshanghias, Ali; Vrestal, Jan; Yakymovych, Andriy; Richter, Klaus W.; Ipser, Herbert

2015-01-01

Melting temperatures of Sn–Ag–Cu (SAC) alloys in the Sn-rich corner are of interest for lead-free soldering. At the same time, nanoparticle solders with depressed melting temperatures close to the Sn–Pb eutectic temperature have received increasing attention. Recently, the phase stability of nanoparticles has been the subject of plenty of theoretical and empirical investigations. In the present study, SAC nanoparticles of various sizes have been synthesized via chemical reduction and the size dependent melting point depression of these particles has been specified experimentally. The liquidus projection in the Sn-rich corner of the ternary SAC system has also been calculated as a function of particle size, based on the CALPHAD-approach. The calculated melting temperatures were compared with those obtained experimentally and with values reported in the literature, which revealed good agreement. The model also predicts that with decreasing particle size, the eutectic composition shifts towards the Sn-rich corner. PMID:26082567

Order-disorder structural phase transition and magnetocaloric effect in organic-inorganic halide hybrid (C2H5NH3)2CoCl4

NASA Astrophysics Data System (ADS)

Sen, Abhijit; Roy, Soumyabrata; Peter, Sebastian C.; Paul, Arpita; Waghmare, Umesh V.; Sundaresan, A.

2018-02-01

We report a detailed experimental and theoretical investigation of structural, optical, magnetic and magnetothermal properties of single crystals of a new organic-inorganic hybrid (C2H5NH3)2CoCl4. Grown by slow evaporation method at room temperature, the compound crystallizes in centrosymmetric orthorhombic structure (Pnma) which undergoes a reversible phase transition at 235/241 K (cooling/heating) to noncentrosymmetric P212121 space group symmetry associated with order-disorder transformation of carbon atoms of the ammonium cations as well as molecular rearrangement. Electronic absorption spectra of the compound are typical of geometrically distorted [CoCl4]2- tetrahedra having spin-orbit coupling effect. The isolated nature of [CoCl4]2- tetrahedra in the crystal reflect in paramagnetic behaviour of the compound. Interestingly, field induced spin flipping behaviour is observed at low temperature. First principles density functional calculations reveal weak magnetic interaction among cobalt spins with ferromagnetic state being the ground state. The entropy change associated with the spin flipping has been experimentally estimated by magnetic and heat capacity measurements which has a maximum value of 16 J Kg-1 K-1 at 2.5 K under 7 T magnetic field. To the best of our knowledge, this is the first report on magnetocaloric effect observed in an organic-inorganic halide compound. The estimated value is sizable and is comparable to that of well-known transition metal molecular cluster magnets Mn12 or Fe14. The overall findings promise to enlighten new routes to design and constitute multifunctional organic-inorganic halide materials.

Phase field study of surface-induced melting and solidification from a nanovoid: Effect of dimensionless width of void surface and void size

NASA Astrophysics Data System (ADS)

Basak, Anup; Levitas, Valery I.

2018-05-01

The size effect and the effects of a finite-width surface on barrierless transformations between the solid (S), surface melt (SM), and melt (M) from a spherical nanovoid are studied using a phase field approach. Melting (SM → M and S → M) from the nanovoid occurs at temperatures which are significantly greater than the solid-melt equilibrium temperature θe but well below the critical temperature for solid instability. The relationships between the SM and M temperatures and the ratio of the void surface width and width of the solid-melt interface, Δ ¯ , are found for the nanovoids of different sizes. Below a critical ratio Δ¯ * , the melting occurs via SM and the melting temperature slightly reduces with an increase in Δ ¯ . Both S → SM and SM → M transformations have a jump-like character (excluding the case with the sharp void surface), causing small temperature hysteresis. However, the solid melts without SM for Δ ¯>Δ¯ * , and the melting temperature significantly increases with increasing Δ ¯ . The results for a nanovoid are compared with the melting/solidification of a nanoparticle, for which the melting temperatures, in contrast, are much lower than θe. A linear dependency of the melting temperatures with the inverse of the void radius is shown. The present study shows an unexplored way to control the melting from nanovoids by controlling the void size and the width and energy of the surface.

Molecular dynamics simulations of the melting curve of NiAl alloy under pressure

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

Zhang, Wenjin; Peng, Yufeng; Liu, Zhongli, E-mail: zhongliliu@yeah.net

2014-05-15

The melting curve of B2-NiAl alloy under pressure has been investigated using molecular dynamics technique and the embedded atom method (EAM) potential. The melting temperatures were determined with two approaches, the one-phase and the two-phase methods. The first one simulates a homogeneous melting, while the second one involves a heterogeneous melting of materials. Both approaches reduce the superheating effectively and their results are close to each other at the applied pressures. By fitting the well-known Simon equation to our melting data, we yielded the melting curves for NiAl: 1783(1 + P/9.801){sup 0.298} (one-phase approach), 1850(1 + P/12.806){sup 0.357} (two-phase approach).more » The good agreement of the resulting equation of states and the zero-pressure melting point (calc., 1850 ± 25 K, exp., 1911 K) with experiment proved the correctness of these results. These melting data complemented the absence of experimental high-pressure melting of NiAl. To check the transferability of this EAM potential, we have also predicted the melting curves of pure nickel and pure aluminum. Results show the calculated melting point of Nickel agrees well with experiment at zero pressure, while the melting point of aluminum is slightly higher than experiment.« less

Melt Segregation and Tidal Heating at Io

NASA Astrophysics Data System (ADS)

Rajendar, A.; Dufek, J.; Roberts, J. H.; Paty, C. S.

2011-12-01

Recent evidence of melt beneath Io's surface (Khurana et al., 2010) and repeated observation of volcanic activity and features consistent with volcanic activity at the surface (e.g. Veeder et al, 1994; Rathbun et al., 2004; Lopes-Gautier et al., 1999; Smith et al., 1979) has raised further questions about the structure of the Galilean moon and the processes that shape it. In this study we examine the thermal state, melt fraction, and multiphase dynamics of melt segregation within Io's interior. Using a coupled multiphase dynamics and tidal heating model we explore the location, spatial extent, and temporal residence times of melt in Io's subsurface, as well as response to orbital parameters. In a thermally evolving body subject to tidal forcing, in which melt production and migration takes place, feedback can occur with respect to the physical and thermal properties. We explore this feedback to produce a thermal model of Io, taking into account the rate of tidal heating and fluid motion within the interior. First, a layered model of the internal structure is assumed. The equations of motion for forced oscillations in a layered spherical body are then solved using the propagator matrix method (Sabadini and Vermeesen, 2004) to obtain the displacements and strains due to tidal motion (Roberts and Nimmo, 2008). From this, the radial distribution of tidal heat generation within Io is calculated. This radial heating profile is then used as input for a multi-phase fluid model in order to obtain an estimate of the radial temperature distribution and thus the material properties and melt fractions. In the multiphase model individual phases (melt and solid residue) separately conserve mass, momentum and enthalpy (Dufek and Bachmann, 2010) allowing us to explore melt segregation phenomena. Enthalpy closure is provided by the MELTS (Ghiorso and Sack, 1995) thermodynamics algorithm, which is called at each point in space. This accounts for the partitioning between latent and

The Microwave Properties of Simulated Melting Precipitation Particles: Sensitivity to Initial Melting

NASA Technical Reports Server (NTRS)

Johnson, B. T.; Olson, W. S.; Skofronick-Jackson, G.

2016-01-01

A simplified approach is presented for assessing the microwave response to the initial melting of realistically shaped ice particles. This paper is divided into two parts: (1) a description of the Single Particle Melting Model (SPMM), a heuristic melting simulation for ice-phase precipitation particles of any shape or size (SPMM is applied to two simulated aggregate snow particles, simulating melting up to 0.15 melt fraction by mass), and (2) the computation of the single-particle microwave scattering and extinction properties of these hydrometeors, using the discrete dipole approximation (via DDSCAT), at the following selected frequencies: 13.4, 35.6, and 94.0GHz for radar applications and 89, 165.0, and 183.31GHz for radiometer applications. These selected frequencies are consistent with current microwave remote-sensing platforms, such as CloudSat and the Global Precipitation Measurement (GPM) mission. Comparisons with calculations using variable-density spheres indicate significant deviations in scattering and extinction properties throughout the initial range of melting (liquid volume fractions less than 0.15). Integration of the single-particle properties over an exponential particle size distribution provides additional insight into idealized radar reflectivity and passive microwave brightness temperature sensitivity to variations in size/mass, shape, melt fraction, and particle orientation.

10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

Code of Federal Regulations, 2010 CFR

2010-01-01

... is produced by radiation of metal halides and their products of dissociation, possibly in combination... electromagnetic ballast that starts a pulse-start metal halide lamp with high voltage pulses, where lamps shall be...

Crystal-melt interface mobility in bcc Fe: Linking molecular dynamics to phase-field and phase-field crystal modeling

NASA Astrophysics Data System (ADS)

Guerdane, M.; Berghoff, M.

2018-04-01

By combining molecular dynamics (MD) simulations with phase-field (PF) and phase-field crystal (PFC) modeling we study collision-controlled growth kinetics from the melt for pure Fe. The MD/PF comparison shows, on the one hand, that the PF model can be properly designed to reproduce quantitatively different aspects of the growth kinetics and anisotropy of planar and curved solid-liquid interfaces. On the other hand, this comparison demonstrates the ability of classical MD simulations to predict morphology and dynamics of moving curved interfaces up to a length scale of about 0.15 μ m . After mapping the MD model to the PF one, the latter permits to analyze the separate contribution of different anisotropies to the interface morphology. The MD/PFC agreement regarding the growth anisotropy and morphology extends the trend already observed for the here used PFC model in describing structural and elastic properties of bcc Fe.

Exhaustive thin-layer cyclic voltammetry for absolute multianalyte halide detection.

PubMed

Cuartero, Maria; Crespo, Gastón A; Ghahraman Afshar, Majid; Bakker, Eric

2014-11-18

Water analysis is one of the greatest challenges in the field of environmental analysis. In particular, seawater analysis is often difficult because a large amount of NaCl may mask the determination of other ions, i.e., nutrients, halides, and carbonate species. We demonstrate here the use of thin-layer samples controlled by cyclic voltammetry to analyze water samples for chloride, bromide, and iodide. The fabrication of a microfluidic electrochemical cell based on a Ag/AgX wire (working electrode) inserted into a tubular Nafion membrane is described, which confines the sample solution layer to less than 15 μm. By increasing the applied potential, halide ions present in the thin-layer sample (X(-)) are electrodeposited on the working electrode as AgX, while their respective counterions are transported across the perm-selective membrane to an outer solution. Thin-layer cyclic voltammetry allows us to obtain separated peaks in mixed samples of these three halides, finding a linear relationship between the halide concentration and the corresponding peak area from about 10(-5) to 0.1 M for bromide and iodide and from 10(-4) to 0.6 M for chloride. This technique was successfully applied for the halide analysis in tap, mineral, and river water as well as seawater. The proposed methodology is absolute and potentially calibration-free, as evidenced by an observed 2.5% RSD cell to cell reproducibility and independence from the operating temperature.

Ab initio molecular dynamics study of high-pressure melting of beryllium oxide

PubMed Central

Li, Dafang; Zhang, Ping; Yan, Jun

2014-01-01

We investigate, through first-principles molecular dynamics simulations, the high-pressure melting of BeO in the range 0 ≤ p ≤ 100 GPa. The wurtzite (WZ), zinc blend (ZB), and rocksalt (RS) phases of BeO are considered. It is shown that below 40 GPa, the melting temperature for the WZ phase is higher than that for the ZB and RS phases. When the pressure is beyond 66 GPa, the melting temperature for the RS phase is the highest one, in consistent with the previously reported phase diagram calculated within the quasiharmonic approximation. We find that in the medium pressure range between 40 to 66 GPa, the ZB melting data are very close to those of RS, which results from the fact that the ZB structure first transforms to RS phase before melting. The ZB-RS-liquid phase transitions have been observed directly during the molecular dynamics runs and confirmed using the pair correlation functions analysis. In addition, we propose the melting curve of BeO in the form Tm = 2696.05 (1 + P/24.67)0.42, the zero-pressure value of 2696.05 K falling into the experimental data range of 2693 ~ 2853 K. PMID:24759594

Vaporisation and thermal decomposition of dialkylimidazolium halide ion ionic liquids.

PubMed

Lovelock, Kevin R J; Armstrong, James P; Licence, Peter; Jones, Robert G

2014-01-28

Vaporisation and liquid phase thermal decomposition, TD, of two halide ion ionic liquids, 1-octyl-3-methylimidazolium chloride, [C8C1Im]Cl, and 1-octyl-3-methylimidazolium iodide, [C8C1Im]I, are investigated using temperature programmed desorption (TPD) line of sight mass spectrometry (LOSMS) at ultra-high vacuum (UHV). The ability to use MS to distinguish between vaporisation and TD allows the thermodynamics/kinetics of both vaporisation and TD to be investigated within the same experiments. Vaporisation of both halide ion ionic liquids is demonstrated. For both [C8C1Im]Cl and [C8C1Im]I the vapour is shown to be composed of neutral ion pairs (NIPs). The enthalpy of vaporisation at temperature T, ΔvapHT, was experimentally determined as ΔvapH455 = 151 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH480 = 149 ± 8 kJ mol(-1) for [C8C1Im]I. Extrapolation of ΔvapHT to the reference temperature, 298 K, gave ΔvapH298 = 166 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH298 = 167 ± 8 kJ mol(-1) for [C8C1Im]I, higher than most ΔvapH298 values measured to date for other [C8C1Im](+)-containing ionic liquids. In addition, predictions of ΔvapH298 for other halide ion ionic liquids are made. Liquid phase TD is shown to proceed via nucleophilic substitution to give two sets of products: 1-octylimidazole and methylhalide, and 1-methylimidazole and 1-octylhalide. The activation energy of TD at a temperature T, Ea,TD,T, is measured for the nucleophilic substitution of [C8C1Im]I to give methyliodide; Ea,TD,480 = 136 ± 15 kJ mol(-1). Ea,TD,T is measured for the nucleophilic substitution of [C8C1Im]Cl to give methylchloride; Ea,TD,455 = 132 ± 10 kJ mol(-1). The fact that ΔvapHT and Ea,TD,T are the same (within error) for both ionic liquids is commented upon, and conclusions are drawn as to the thermal stability of these ionic liquids.

Thallous halide materials for use in cryogenic applications

NASA Technical Reports Server (NTRS)

Lawless, William N. (Inventor)

1981-01-01

Thallous halides, either alone or in combination with other ceramic materials, are used in cryogenic applications such as heat exchange material for the regenerator section of a closed-cycle cryogenic refrigeration section, as stabilizing coatings for superconducting wires, and as dielectric insulating materials. The thallous halides possess unusually large specific heats at low temperatures, have large thermal conductivities, are nonmagnetic, and are nonconductors of electricity. They can be formed into a variety of shapes such as spheres, bars, rods, or the like and can be coated onto substrates.

New silver-halide-sensitized gelatin material: the influence of bleaches on holograms

NASA Astrophysics Data System (ADS)

Zhang, Weiping; Pang, Lin; Guo, Lurong

1996-12-01

A new high-resolution-silver-halide (HRSH-II) material was produced, which has proper initial hardness for fabricating silver halide sensitized gelatin (SHSG) holograms. That would avoid high noise by seeking the gelatin in hot water. With different alkali halide component in B solution and its concentration (the ratio B/A), experiments were presented about bleaching effect with R-10 on processing for SHSG derived from this new material. High diffraction efficiency, as high as 81%, was achieved. Some of the observations are discussed.

Lattice dynamics and the nature of structural transitions in organolead halide perovskites

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

Comin, Riccardo; Crawford, Michael K.; Said, Ayman H.

Organolead halide perovskites are a family of hybrid organic-inorganic compounds whose remarkable optoelectronic properties have been under intensive scrutiny in recent years. Here we use inelastic x-ray scattering to study low-energy lattice excitations in single crystals of methylammonium lead iodide and bromide perovskites. Our findings confirm the displacive nature of the cubic-to-tetragonal phase transition, which is further shown, using neutron and x-ray diffraction, to be close to a tricritical point. Lastly, we detect quasistatic symmetry-breaking nanodomains persisting well into the high-temperature cubic phase, possibly stabilized by local defects. These findings reveal key structural properties of these materials, and also bearmore » important implications for carrier dynamics across an extended temperature range relevant for photovoltaic applications.« less

Melt spinning study

NASA Technical Reports Server (NTRS)

Workman, Gary L.; Rathz, Thomas

1993-01-01

Containerless processing of materials provides an excellent opportunity to study nucleation phenomena and produce unique materials, primarily through the formation of metastable phases and deep undercoolings. Deep undercoolings can be readily achieved in falling drops of molten material. Extended solute solubilities and greatly refined microstructures can also be obtained in containerless processing experiments. The Drop Tube Facility at Marshall Space Flight Center has played an important role in enhancing that area of research. Previous experiments performed in the Drop Tube with refractory metals has shown very interesting microstructural changes associated with deep undercoolings. It is apparent also that the microstructure of the deep undercooled species may be changing due to the release of the latent heat of fusion during recalescence. For scientific purposes, it is important to be able to differentiate between the microstructures of the two types of metallic species. A review of the literature shows that although significant advances have been made with respect to the engineering aspects of rapid solidification phenomena, there is still much to be learned in terms of understanding the basic phenomena. The two major ways in which rapid solidification processing provides improved structures and hence improved properties are: (1) production of refined structures such as fine dendrites and eutectics, and (2) production of new alloy compositions, microstructures, and phases through extended solid solubility, new phase reaction sequences, and the formation of metallic-glass microstructures. The objective of this work has been to determine the optimal methodology required to extract this excess energy without affecting the thermo-physical parameters of the under-cooled melt. In normal containerless processing experiments recalescence occurs as the melt returns toward the melting point in order to solidify. A new type of experiment is sought in which the resultant

Secondary Confinement of Water Observed in Eutectic Melting of Aqueous Salt Systems in Nanopores.

PubMed

Meissner, Jens; Prause, Albert; Findenegg, Gerhard H

2016-05-19

Freezing and melting of aqueous solutions of alkali halides confined in the cylindrical nanopores of MCM-41 and SBA-15 silica was probed by differential scanning calorimetry (DSC). We find that the confinement-induced shift of the eutectic temperature in the pores can be significantly greater than the shift of the melting temperature of pure water. Greatest shifts of the eutectic temperature are found for salts that crystallize as oligohydrates at the eutectic point. This behavior is explained by the larger fraction of pore volume occupied by salt hydrates as compared to anhydrous salts, on the assumption that precipitated salt constitutes an additional confinement for ice/water in the pores. A model based on this secondary confinement effect gives a good representation of the experimental data. Salt-specific secondary confinement may play a role in a variety of fields, from salt-impregnated advanced adsorbents and catalysts to the thermal weathering of building materials.

The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Beckett, J. R.; Stolper, E.

1994-01-01

Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that

Using Pre-Melted Phase Change Material to Keep Payloads in Space Warm for Hours without Power

NASA Technical Reports Server (NTRS)

Choi, Michael

2013-01-01

Adding phase change material (PCM) to a mission payload can maintain its temperature above the cold survival limit, without power, for several hours in space. For the International Space Station, PCM is melted by heaters just prior to the payload translation to the worksite when power is available. When power is cut off during the six-hour translation, the PCM releases its latent heat to make up the heat loss from the radiator(s) to space. For the interplanetary Probe, PCM is melted by heaters just prior to separation from the orbiter when power is available from the orbiter power system. After the Probe separates from the orbiter, the PCM releases its latent heat to make up the heat loss from the Probe exterior to space. Paraffin wax is a good PCM candidate.

Effect of Halide Composition on the Photochemical Stability of Perovskite Photovoltaic Materials.

PubMed

Misra, Ravi K; Ciammaruchi, Laura; Aharon, Sigalit; Mogilyansky, Dmitry; Etgar, Lioz; Visoly-Fisher, Iris; Katz, Eugene A

2016-09-22

The photochemical stability of encapsulated films of mixed halide perovskites with a range of MAPb(I 1-x Br x ) 3 (MA=methylammonium) compositions (solid solutions) was investigated under accelerated stressing using concentrated sunlight. The relevance of accelerated testing to standard operational conditions of solar cells was confirmed by comparison to degradation experiments under outdoor sunlight exposure. We found that MAPbBr 3 films exhibited no degradation, while MAPbI 3 and mixed halide MAPb(I 1-x Br x ) 3 films decomposed yielding crystallization of inorganic PbI 2 accompanied by degradation of the perovskite solar light absorption, with faster absorption degradation in mixed halide films. The crystal coherence length was found to correlate with the stability of the films. We postulate that the introduction of Br into the mixed halide solid solution stressed its structure and induced more structural defects and/or grain boundaries compared to pure halide perovskites, which might be responsible for the accelerated degradation. Hence, the cause for accelerated degradation may be the increased defect density rather than the chemical composition of the perovskite materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies

DOE PAGES

Guo, Peijun; Xia, Yi; Gong, Jue; ...

2017-09-28

Solution-processable metal-halide perovskites (MHPs) offer great promise for efficient light harvesting and emitting devices due to their long carrier lifetime and superior carrier transport characteristics. Ferroelectric effects, a hallmark of traditional oxide perovskites, was proposed to be a mechanism to suppress carrier recombination and enhance charge transport in MHPs, but the existence and influence of such polar order is still of considerable debate. Here we performed transient reflection measurements on single crystals of both inorganic and organic-inorganic (hybrid) MHPs over a range of temperatures, and demonstrate significant phonon softening in the cubic phases close to the cubic-to-tetragonal phase transition temperatures.more » Such phonon softening indicates the formation of polar domains, which grow in size upon cooling and can persist in the low-temperature tetragonal and orthorhombic phases. Our results link the extraordinary electronic properties of MHPs to the spontaneous polarizations which can contribute to more efficient charge separation and characteristics of an indirect bandgap.« less

Ultrafast time-resolved spectroscopy of lead halide perovskite films

NASA Astrophysics Data System (ADS)

Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

2015-09-01

Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

DOE PAGES

Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; ...

2016-03-01

Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ionsmore » prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.« less

Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

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

Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou

Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ionsmore » prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.« less

Lanthanide doped strontium-barium cesium halide scintillators

DOEpatents

Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

2015-06-09

The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

A benchmark initiative on mantle convection with melting and melt segregation

NASA Astrophysics Data System (ADS)

Schmeling, Harro; Dannberg, Juliane; Dohmen, Janik; Kalousova, Klara; Maurice, Maxim; Noack, Lena; Plesa, Ana; Soucek, Ondrej; Spiegelman, Marc; Thieulot, Cedric; Tosi, Nicola; Wallner, Herbert

2016-04-01

In recent years a number of mantle convection models have been developed which include partial melting within the asthenosphere, estimation of melt volumes, as well as melt extraction with and without redistribution at the surface or within the lithosphere. All these approaches use various simplifying modelling assumptions whose effects on the dynamics of convection including the feedback on melting have not been explored in sufficient detail. To better assess the significance of such assumptions and to provide test cases for the modelling community we carry out a benchmark comparison. The reference model is taken from the mantle convection benchmark, cases 1a to 1c (Blankenbach et al., 1989), assuming a square box with free slip boundary conditions, the Boussinesq approximation, constant viscosity and Rayleigh numbers of 104 to 10^6. Melting is modelled using a simplified binary solid solution with linearly depth dependent solidus and liquidus temperatures, as well as a solidus temperature depending linearly on depletion. Starting from a plume free initial temperature condition (to avoid melting at the onset time) five cases are investigated: Case 1 includes melting, but without thermal or dynamic feedback on the convection flow. This case provides a total melt generation rate (qm) in a steady state. Case 2 is identical to case 1 except that latent heat is switched on. Case 3 includes batch melting, melt buoyancy (melt Rayleigh number Rm) and depletion buoyancy, but no melt percolation. Output quantities are the Nusselt number (Nu), root mean square velocity (vrms), the maximum and the total melt volume and qm approaching a statistical steady state. Case 4 includes two-phase flow, i.e. melt percolation, assuming a constant shear and bulk viscosity of the matrix and various melt retention numbers (Rt). These cases are carried out using the Compaction Boussinseq Approximation (Schmeling, 2000) or the full compaction formulation. For cases 1 - 3 very good agreement

Using Pre-melted Phase Change Material to Keep Payload Warm without Power for Hours in Space

NASA Technical Reports Server (NTRS)

Choi, Michael K.

2012-01-01

During a payload transition from the transport vehicle to its worksite on the International Space Station (ISS), the payload is unpowered for up to 6 hours. Its radiator(s) will continue to radiate heat to space. It is necessary to make up the heat loss to maintain the payload temperature above the cold survival limit. Typically an interplanetary Probe has no power generation system. It relies on its battery to provide limited power for the Communication and Data Handling (C&DH) subsystem during cruise, and heater power is unavailable. It is necessary to maintain the C&DH temperature above the minimum operating limit. This paper presents a novel thermal design concept that utilizes phase change material (PCM) to store thermal energy by melting it before the payload or interplanetary Probe is unpowered. For the ISS, the PCM is melted by heaters just prior to the payload transition from the transport vehicle to its worksite. For an interplanetary Probe, the PCM is melted by heaters just prior to separation from the orbiter. The PCM releases thermal energy to keep the payload warm for several hours after power is cut off.

Ultrafast studies of shock-induced melting and phase transitions at LCLS

NASA Astrophysics Data System (ADS)

McMahon, Malcolm

The study of shock-induced phase transitions, which is vital to the understanding of material response to rapid pressure changes, dates back to the 1950s, when Bankcroft et al reported a transition in iron. Since then, many transitions have been reported in a wide range of materials, but, due to the lack of sufficiently bright x-ray sources, the structural details of these new phases has been notably lacking. While the development of nanosecond in situ x-ray diffraction has meant that lattice-level studies of such phenomena have become possible, including studies of the phase transition reported 60 years ago in iron, the quality of the diffraction data from such studies is noticeably poorer than that obtained from statically-compressed samples on synchrotrons. The advent of x-ray free electron lasers (XFELs), such as the LCLS, has resulted in an unprecedented improvement in the quality of diffraction data that can be obtained from shock-compressed matter. Here I describe the results from three recent experiment at the LCLS that looked at the solid-solid and solid-liquid phase transitions in Sb, Bi and Sc using single 50 fs x-ray exposures. The results provide new insight into the structural changes and melting induced by shock compression. This work is supported by EPSRC under Grant No. EP/J017051/1. Use of the LCLS, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.

Preliminary results of sulfide melt/silicate wetting experiments in a partially melted ordinary chondrite

NASA Technical Reports Server (NTRS)

Jurewicz, Stephen R.; Jones, John H.

1994-01-01

Recently, mechanisms for core formation in planetary bodies have received considerable attention. Most current theories emphasize the need for large degrees of silicate partial melting to facilitate the coalescence and sinking of sulfide-metal liquid blebs through a low strength semi-crystalline silicate mush. This scenario is based upon observations that sulfide-metal liquid tends to form circular blebs in partially molten meteorites during laboratory experiments. However, recent experimental work by Herpfer and Larimer indicates that some sulfide-Fe liquids have wetting angles at and slightly below 60 deg in an olivine aggregate, implying an interconnected melt structure at any melt fraction. Such melt interconnectivity provides a means for gravitational compaction and extraction of the majority of a sulfide liquid phase in small planetary bodies without invoking large degrees of silicate partial melting. Because of the important ramifications of these results, we conducted a series of experiments using H-chondrite starting material in order to evaluate sulfide-liquid/silicate wetting behavior in a more complex natural system.

10 CFR Appendix B to Subpart S to... - Certification Report for Metal Halide Lamp Ballasts

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 3 2011-01-01 2011-01-01 false Certification Report for Metal Halide Lamp Ballasts B... PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures Pt. 431, Subpt. S, App. B Appendix B to Subpart S to Part 431—Certification Report for Metal Halide Lamp Ballasts...

Fluorescent Properties of Manganese Halide Benzothiazole Inorganic-Organic Hybrids.

PubMed

Yu, Hui; Mei, YingXuan; Wei, ZhenHong; Mei, GuangQuan; Cai, Hu

2016-11-01

The reaction of manganese (II) halides MnX 2 and benzothiazole (btz) in the concentrated acids HX (X = Cl, Br) at 80 °C resulted in the formation of two inorganic-organic hybrid complexes: [(btz) 2 (MnX 4 )]·2H 2 O (X = Cl, 1; X = Br, 2). Both compounds showed green luminescence and exhibited moderate quantum yields of 43.17 % for 1 and 26.18 % for 2, which were directly originated from the tetrahedral coordination of Mn 2+ ion. Two organic - inorganic hybrids [(btz) 2 (MnX 4 )]·2H 2 O based on MnCl 2 , benzothiazole and halide acids emitted green light with the moderate quantum efficiencies when excited by 365 nm light. Graphical abstract Two organic-inorganic hybrids [(btz) 2 (MnX 4 )]·2H 2 O based on MnCl 2 , benzothiazole and halide acids emitted green light with the moderate quantum efficiencies when excited by 365 nm light.

Crystal structures of five 1-alkyl-4-aryl-1,2,4-triazol-1-ium halide salts

PubMed Central

Guino-o, Marites A.; Talbot, Meghan O.; Slitts, Michael M.; Pham, Theresa N.; Audi, Maya C.; Janzen, Daron E.

2015-01-01

The asymmetric units for the salts 4-(4-fluoro­phen­yl)-1-isopropyl-1,2,4-triazol-1-ium iodide, C11H13FN3 +·I−, (1), 1-isopropyl-4-(4-methyl­phen­yl)-1,2,4-triazol-1-ium iodide, C12H16N3 +·I−, (2), 1-isopropyl-4-phenyl-1,2,4-triazol-1-ium iodide, C11H14N3 +·I−, (3), and 1-methyl-4-phenyl-1,2,4-triazol-1-ium iodide, C9H10N3 +·I−, (4), contain one cation and one iodide ion, whereas in 1-benzyl-4-phenyl-1,2,4-triazol-1-ium bromide monohydrate, C15H14N3 +·Br−·H2O, (5), there is an additional single water mol­ecule. There is a predominant C—H⋯X(halide) inter­action for all salts, resulting in a two-dimensional extended sheet network between the triazolium cation and the halide ions. For salts with para-substitution on the aryl ring, there is an additional π–anion inter­action between a triazolium carbon and iodide displayed by the layers. For salts without the para-substitution on the aryl ring, the π–π inter­actions are between the triazolium and aryl rings. The melting points of these salts agree with the predicted substituent inductive effects. PMID:26090137

Oceanic slab melting and mantle metasomatism.

PubMed

Scaillet, B; Prouteau, G

2001-01-01

Modern plate tectonic brings down oceanic crust along subduction zones where it either dehydrates or melts. Those hydrous fluids or melts migrate into the overlying mantle wedge trigerring its melting which produces arc magmas and thus additional continental crust. Nowadays, melting seems to be restricted to cases of young (< 50 Ma) subducted plates. Slab melts are silicic and strongly sodic (trondhjemitic). They are produced at low temperatures (< 1000 degrees C) and under water excess conditions. Their interaction with mantle peridotite produces hydrous metasomatic phases such as amphibole and phlogopite that can be more or less sodium rich. Upon interaction the slab melt becomes less silicic (dacitic to andesitic), and Mg, Ni and Cr richer. Virtually all exposed slab melts display geochemical evidence of ingestion of mantle material. Modern slab melts are thus unlike Archean Trondhjemite-Tonalite-Granodiorite rocks (TTG), which suggests that both types of magmas were generated via different petrogenetic pathways which may imply an Archean tectonic model of crust production different from that of the present-day, subduction-related, one.

Improved catalytic properties of halohydrin dehalogenase by modification of the halide-binding site.

PubMed

Tang, Lixia; Torres Pazmiño, Daniel E; Fraaije, Marco W; de Jong, René M; Dijkstra, Bauke W; Janssen, Dick B

2005-05-03

Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the dehalogenation of vicinal haloalcohols by an intramolecular substitution reaction, resulting in the formation of the corresponding epoxide, a halide ion, and a proton. Halide release is rate-limiting during the catalytic cycle of the conversion of (R)-p-nitro-2-bromo-1-phenylethanol by the enzyme. The recent elucidation of the X-ray structure of HheC showed that hydrogen bonds between the OH group of Tyr187 and between the Odelta1 atom of Asn176 and Nepsilon1 atom of Trp249 could play a role in stabilizing the conformation of the halide-binding site. The possibility that these hydrogen bonds are important for halide binding and release was studied using site-directed mutagenesis. Steady-state kinetic studies revealed that mutant Y187F, which has lost both hydrogen bonds, has a higher catalytic activity (k(cat)) with two of the three tested substrates compared to the wild-type enzyme. Mutant W249F also shows an enhanced k(cat) value with these two substrates, as well as a remarkable increase in enantiopreference for (R)-p-nitro-2-bromo-1-phenylethanol. In case of a mutation at position 176 (N176A and N176D), a 1000-fold lower catalytic efficiency (k(cat)/K(m)) was obtained, which is mainly due to an increase of the K(m) value of the enzyme. Pre-steady-state kinetic studies showed that a burst of product formation precedes the steady state, indicating that halide release is still rate-limiting for mutants Y187F and W249F. Stopped-flow fluorescence experiments revealed that the rate of halide release is 5.6-fold higher for the Y187F mutant than for the wild-type enzyme and even higher for the W249F enzyme. Taken together, these results show that the disruption of two hydrogen bonds around the halide-binding site increases the rate of halide release and can enhance the overall catalytic activity of HheC.

Material transport in laser-heated diamond anvil cell melting experiments

NASA Technical Reports Server (NTRS)

Campbell, Andrew J.; Heinz, Dion L.; Davis, Andrew M.

1992-01-01

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

MELTS_Excel: A Microsoft Excel-based MELTS interface for research and teaching of magma properties and evolution

NASA Astrophysics Data System (ADS)

Gualda, Guilherme A. R.; Ghiorso, Mark S.

2015-01-01

thermodynamic modeling software MELTS is a powerful tool for investigating crystallization and melting in natural magmatic systems. Rhyolite-MELTS is a recalibration of MELTS that better captures the evolution of silicic magmas in the upper crust. The current interface of rhyolite-MELTS, while flexible, can be somewhat cumbersome for the novice. We present a new interface that uses web services consumed by a VBA backend in Microsoft Excel©. The interface is contained within a macro-enabled workbook, where the user can insert the model input information and initiate computations that are executed on a central server at OFM Research. Results of simple calculations are shown immediately within the interface itself. It is also possible to combine a sequence of calculations into an evolutionary path; the user can input starting and ending temperatures and pressures, temperature and pressure steps, and the prevailing oxidation conditions. The program shows partial updates at every step of the computations; at the conclusion of the calculations, a series of data sheets and diagrams are created in a separate workbook, which can be saved independently of the interface. Additionally, the user can specify a grid of temperatures and pressures and calculate a phase diagram showing the conditions at which different phases are present. The interface can be used to apply the rhyolite-MELTS geobarometer. We demonstrate applications of the interface using an example early-erupted Bishop Tuff composition. The interface is simple to use and flexible, but it requires an internet connection. The interface is distributed for free from http://melts.ofm-research.org.

Melting of anisotropic colloidal crystals in two dimensions

NASA Astrophysics Data System (ADS)

Eisenmann, C.; Keim, P.; Gasser, U.; Maret, G.

2004-09-01

The crystal structure and melting transition of two-dimensional colloids interacting via an anisotropic magnetic dipole-dipole potential are studied. Anisotropy is achieved by tilting the external magnetic field inducing the dipole moments of the colloidal particles away from the direction perpendicular to the particle plane. We find a centred rectangular lattice and a two-step melting similar to the phase transitions of the corresponding isotropic crystals via a quasi-hexatic phase. The latter is broadened compared to the hexatic phase for isotropic interaction potential due to strengthening of orientational order.

White-Light Emission from Layered Halide Perovskites.

PubMed

Smith, Matthew D; Karunadasa, Hemamala I

2018-03-20

exciton couples strongly to the lattice, creating transient elastic lattice distortions that can be viewed as "excited-state defects". These deformations stabilize the exciton affording a broad emission with a large Stokes shift. Although material defects very likely contribute to the emission width, our mechanistic studies suggest that the emission mostly arises from the bulk material. Ultrafast spectroscopic measurements support self-trapping, with new, transient, electronic states appearing upon photoexcitation. Importantly, the broad emission appears common to layered Pb-Br and Pb-Cl perovskites, albeit with a strong temperature dependence. Although the emission is attributed to light-induced defects, it still reflects changes in the crystal structure. We find that greater out-of-plane octahedral tilting increases the propensity for the broad emission, enabling synthetic control over the broad emission. Many of these perovskites have color rendering abilities that exceed commercial requirements and mixing halides affords both "warm" and "cold" white light. The most efficient white-light-emitting perovskite has a quantum efficiency of 9%. Improving this value will make these phosphors attractive for solid-state lighting, particularly as large-area coatings that can be deposited inexpensively. The emission mechanism can also be extended to other low-dimensional systems. We hope this Account aids in expanding the phase space of white-light emitters and controlling their exciton dynamics by the synthetic, spectroscopic, theoretical, and engineering communities.

Molecular dynamics study of the melting curve of NiTi alloy under pressure

NASA Astrophysics Data System (ADS)

Zeng, Zhao-Yi; Hu, Cui-E.; Cai, Ling-Cang; Chen, Xiang-Rong; Jing, Fu-Qian

2011-02-01

The melting curve of NiTi alloy was predicted by using molecular dynamics simulations combining with the embedded atom model potential. The calculated thermal equation of state consists well with our previous results obtained from quasiharmonic Debye approximation. Fitting the well-known Simon form to our Tm data yields the melting curves for NiTi: 1850(1 + P/21.938)0.328 (for one-phase method) and 1575(1 + P/7.476)0.305 (for two-phase method). The two-phase simulations can effectively eliminate the superheating in one-phase simulations. At 1 bar, the melting temperature of NiTi is 1575 ± 25 K and the corresponding melting slope is 64 K/GPa.

Vibration-Resistant Support for Halide Lamps

NASA Technical Reports Server (NTRS)

Kiss, J.

1987-01-01

Lamp envelope protected against breakage. Old and new mounts for halide arc lamp sealed in housing with parabolic refector and quartz window. New version supports lamp with compliant garters instead of rigid brazed joint at top and dimensionally unstable finger stock at bottom.

Diffusive loss of argon in response to melt vein formation in polygenetic impact melt breccias

NASA Astrophysics Data System (ADS)

Mercer, Cameron M.; Hodges, Kip V.

2017-08-01

Many planetary surfaces in the solar system have experienced prolonged bombardment. With each impact, new rocks can be assembled that incorporate freshly generated impact melts with fragments of older rocks. Some breccias can become polygenetic, containing multiple generations of impact melt products, and can potentially provide important insights into the extensive bombardment history of a region. However, the amount of chronological information that can be extracted from such samples depends on how well the mineral isotopic systems of geochronometers can preserve the ages of individual melt generations without being disturbed by younger events. We model the thermal evolution of impact melt veins and the resulting loss of Ar from K-bearing phases common in impact melt breccias to assess the potential for preserving the 40Ar/39Ar ages of individual melt generations. Our model results demonstrate that millimeter-scale, clast-free melt veins cause significant heating of adjacent host rock minerals and can cause detectable Ar loss in contact zones that are generally thinner than, and at most about the same thickness as, the vein width. The incorporation of cold clasts in melt veins reduces the magnitudes of heating and Ar loss in the host rocks, and Ar loss can be virtually undetectable for sufficiently clast-rich veins. Quantitative evidence of the timing of impacts, as measured with the 40Ar/39Ar method, can be preserved in polygenetic impact melt breccias, particularly for those containing millimeter-scale bodies of clast-bearing melt products.

Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix

PubMed Central

2015-01-01

In recent years, organometal halide perovskite materials have attracted significant research interest in the field of optoelectronics. Here, we introduce a simple and low-temperature route for the formation of self-assembled perovskite nanocrystals in a solid organic matrix. We demonstrate that the size and photoluminescence peak of the perovskite nanocrystals can be tuned by varying the concentration of perovskite in the matrix material. The physical origin of the blue shift of the perovskite nanocrystals’ emission compared to its bulk phase is also discussed. PMID:25949773

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

NASA Technical Reports Server (NTRS)

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

1979-01-01

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

Melting in Superheated Silicon Films Under Pulsed-Laser Irradiation

NASA Astrophysics Data System (ADS)

Wang, Jin Jimmy

This thesis examines melting in superheated silicon films in contact with SiO2 under pulsed laser irradiation. An excimer-laser pulse was employed to induce heating of the film by irradiating the film through the transparent fused-quartz substrate such that most of the beam energy was deposited near the bottom Si-SiO2 interface. Melting dynamics were probed via in situ transient reflectance measurements. The temperature profile was estimated computationally by incorporating temperature- and phase-dependent physical parameters and the time-dependent intensity profile of the incident excimer-laser beam obtained from the experiments. The results indicate that a significant degree of superheating occurred in the subsurface region of the film. Surface-initiated melting was observed in spite of the internal heating scheme, which resulted in the film being substantially hotter at and near the bottom Si-SiO2 interface. By considering that the surface melts at the equilibrium melting point, the solid-phase-only heat-flow analysis estimates that the bottom Si-SiO2 interface can be superheated by at least 220 K during excimer-laser irradiation. It was found that at higher laser fluences (i.e., at higher temperatures), melting can be triggered internally. At heating rates of 1010 K/s, melting was observed to initiate at or near the (100)-oriented Si-SiO2 interface at temperatures estimated to be over 300 K above the equilibrium melting point. Based on theoretical considerations, it was deduced that melting in the superheated solid initiated via a nucleation and growth process. Nucleation rates were estimated from the experimental data using Johnson-Mehl-Avrami-Kolmogorov (JMAK) analysis. Interpretation of the results using classical nucleation theory suggests that nucleation of the liquid phase occurred via the heterogeneous mechanism along the Si-SiO2 interface.

Melting of Simple Solids and the Elementary Excitations of the Communal Entropy

NASA Astrophysics Data System (ADS)

Bongiorno, Angelo

2010-03-01

The melting phase transition of simple solids is addressed through the use of atomistic computer simulations. Three transition metals (Ni, Au, and Pt) and a semiconductor (Si) are considered in this study. Iso-enthalpic molecular dynamics simulations are used to compute caloric curves across the solid-to-liquid phase transition of a periodic crystalline system, to construct the free energy function of the solid and liquid phases, and thus to derive the thermodynamical limit of the melting point, latent heat and entropy of fusion of the material. The computational strategy used in this study yields accurate estimates of melting parameters, it consents to determine the superheating and supercooling temperature limits, and it gives access to the atomistic mechanisms mediating the melting process. In particular, it is found that the melting phase transition in simple solids is driven by exchange steps involving a few atoms and preserving the crystalline structure. These self-diffusion phenomena correspond to the elementary excitations of the communal entropy and, as their rate depends on the local material cohesivity, they mediate both the homogeneous and non-homogeneous melting process in simple solids.

Effect of Cation Rotation on Charge Dynamics in Hybrid Lead Halide Perovskites

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

Gélvez-Rueda, María C.; Cao, Duyen H.; Patwardhan, Sameer

Organic-inorganic hybrid halide perovskites are a promising class of materials for photovoltaic application with reported power efficiencies over similar to 22%. However, not much is known about the influence of the organic dipole rotation and phase transitions on charge carrier dynamics. Here, we report substantial changes in mobility and lifetime of charge carriers in CH 3NH 3PbI 3 after the low-temperature tetragonal (beta) to orthorhombic (gamma) phase transition. By using microwave conductivity measurements, we observed that the mobility and lifetime of ionized charge carriers increase as the temperature decreases and a sudden increment is seen after the beta-gamma phase transition.more » For CH 3NH 3PbI 3, the mobility and the half-lifetime increase by a factor of 36 compared with the values before the beta-gamma phase transition. We attribute the considerable change in the dynamics at low temperature to the decrease of the inherent dynamic disorder of the organic cation (CH 3NH 3+) inside the perovskite crystal structure.« less

Method for producing hydrocarbon fuels from heavy polynuclear hydrocarbons by use of molten metal halide catalyst

DOEpatents

Gorin, Everett

1979-01-01

In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst, thereafter separating at least a substantial portion of the carbonaceous material associated with the reaction mixture from the spent molten metal halide and thereafter regenerating the metal halide catalyst, an improvement comprising contacting the spent molten metal halide catalyst after removal of a major portion of the carbonaceous material therefrom with an additional quantity of hydrogen is disclosed.

Evolution of the East Philippine Arc: experimental constraints on magmatic phase relations and adakitic melt formation

NASA Astrophysics Data System (ADS)

Coldwell, B.; Adam, J.; Rushmer, T.; MacPherson, C. G.

2011-10-01

Piston-cylinder experiments on a Pleistocene adakite from Mindanao in the Philippines have been used to establish near-liquidus and sub-liquidus phase relationships relevant to conditions in the East Philippines subduction zone. The experimental starting material belongs to a consanguineous suite of adakitic andesites. Experiments were conducted at pressures from 0.5 to 2 GPa and temperatures from 950 to 1,150°C. With 5 wt. % of dissolved H2O in the starting mix, garnet, clinopyroxene and orthopyroxene are liquidus phases at pressures above 1.5 GPa, whereas clinopyroxene and orthopyroxene are liquidus (or near-liquidus) phases at pressures <1.5 GPa. Although amphibole is not a liquidus phase under any of the conditions examined, it is stable under sub-liquidus conditions at temperature ≤1,050°C and pressures up to 1.5 GPa. When combined with petrographic observations and bulk rock chemical data for the Mindanao adakites, these findings are consistent with polybaric fractionation that initially involved garnet (at pressures >1.5 GPa) and subsequently involved the lower pressure fractionation of amphibole, plagioclase and subordinate clinopyroxene. Thus, the distinctive Y and HREE depletions of the andesitic adakites (which distinguish them from associated non-adakitic andesites) must be established relatively early in the fractionation process. Our experiments show that this early fractionation must have occurred at pressures >1.5 GPa and, thus, deeper than the Mindanao Moho. Published thermal models of the Philippine Sea Plate preclude a direct origin by melting of the subducting ocean crust. Thus, our results favour a model whereby basaltic arc melt underwent high-pressure crystal fractionation while stalled beneath immature arc lithosphere. This produced residual magma of adakitic character which underwent further fractionation at relatively low (i.e. crustal) pressures before being erupted.

Maximizing and stabilizing luminescence from halide perovskites with potassium passivation

NASA Astrophysics Data System (ADS)

Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania; Stavrakas, Camille; Philippe, Bertrand; Richter, Johannes M.; Alsari, Mejd; Booker, Edward P.; Hutter, Eline M.; Pearson, Andrew J.; Lilliu, Samuele; Savenije, Tom J.; Rensmo, Håkan; Divitini, Giorgio; Ducati, Caterina; Friend, Richard H.; Stranks, Samuel D.

2018-03-01

Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield—a quantity that must be maximized to obtain high efficiency—remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can

Maximizing and stabilizing luminescence from halide perovskites with potassium passivation.

PubMed

Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania; Stavrakas, Camille; Philippe, Bertrand; Richter, Johannes M; Alsari, Mejd; Booker, Edward P; Hutter, Eline M; Pearson, Andrew J; Lilliu, Samuele; Savenije, Tom J; Rensmo, Håkan; Divitini, Giorgio; Ducati, Caterina; Friend, Richard H; Stranks, Samuel D

2018-03-21

Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield-a quantity that must be maximized to obtain high efficiency-remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can approach

Mineralogy and Microstructures of Shock-Induced Melt Veins in Chondrites

NASA Technical Reports Server (NTRS)

Sharp, Thomas G.

2000-01-01

The applicability of phase equilibrium data to the interpretation of shock-induced melt veins can only be tested by a detailed study of melt- vein mineralogy to see how high-pressure assemblages vary as a function of shock conditions inferred from other indicators. We have used transmission electron microscopy (TEM), analytical electron microscopy (AEM), scanning electron microscopy (SEM), electron microprobe analysis (EMA) and optical petrography to characterize the mineralogy, microstructures, and compositions of melt veins and associated high-pressure minerals in shocked chondrites and SNC meteorites. In the processes, we have gained a better understanding of what melt veining can tell us about shock conditions and we have discovered new mineral phases in chondritic and SNC meteorites.

A metastable liquid melted from a crystalline solid under decompression

NASA Astrophysics Data System (ADS)

Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; Kono, Yoshio; Park, Changyong; Kenney-Benson, Curtis; Shen, Guoyin

2017-01-01

A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid-solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. The decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure-temperature region similar to where the supercooled liquid Bi is observed. Akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought.

A metastable liquid melted from a crystalline solid under decompression

PubMed Central

Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; Kono, Yoshio; Park, Changyong; Kenney-Benson, Curtis; Shen, Guoyin

2017-01-01

A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid–solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. The decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure–temperature region similar to where the supercooled liquid Bi is observed. Akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought. PMID:28112152

Refined global methyl halide budgets with respect to rapeseed (Brassica napus) by life-cycle measurements

NASA Astrophysics Data System (ADS)

Jiao, Y.; Acdan, J.; Xu, R.; Deventer, M. J.; Rhew, R. C.

2017-12-01

A precise quantification of global methyl halide budgets is needed to evaluate the ozone depletion potential of these compounds and to predict future changes of stratospheric ozone. However, the global budgets of methyl halides are not balanced between currently identified and quantified sources and sinks. Our study re-evaluated the methyl bromide budget from global cultivated rapeseed (Brassica napus) through life-cycle flux measurements both in the greenhouse and in the field, yielding a methyl bromide emission rate that scales globally to 1.0 - 1.2 Gg yr-1. While this indicates a globally significant source, it is much smaller than the previously widely cited value of 5 - 6 Gg yr-1(Mead et al., 2008), even taking into account the near tripling of annual global yield of rapeseed since the previous evaluation was conducted. Our study also evaluated the methyl chloride and methyl iodide emission levels from rapeseed, yielding emission rates that scale to 5.4 Gg yr-1 for methyl chloride and 1.8 Gg yr-1 of methyl iodide. The concentrations of the methyl donor SAM (S-adenosyl methionine) and the resultant product SAH (S-Adenosyl-L-homocysteine) were also analyzed to explore their role in biogenic methyl halide formation. Halide gradient incubations showed that the magnitude of methyl halide emissions from rapeseed is highly correlated to soil halide levels, thus raising the concern that the heterogeneity of soil halide contents geographically should be considered when extrapolating to global budget.

B-Site Metal Cation Exchange in Halide Perovskites

DOE PAGES

Eperon, Giles E.; Ginger, David S.

2017-05-02

Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

B-Site Metal Cation Exchange in Halide Perovskites

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

Eperon, Giles E.; Ginger, David S.

Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

The Role of CO2 on Silica Undersaturated Melt Structure: Implication for Melt Physical Properties

NASA Astrophysics Data System (ADS)

Scaillet, B.; Morizet, Y.; Paris, M.; Gaillard, F.

2012-12-01

Silica undersaturated melts such as nephelinite and melilitite are very peculiar magmatic materials. Their occurrence on the Earth surface is often associated with carbonatites melts. These low-silica melts can dissolve a large quantity of CO2 issued from mantle fluid metasomatism. However, the melt structure, the way CO2 dissolves into these melts and the effect of different alkalis element are poorly constrained. We present preliminary experimental results on the melt structure of synthetic nephelinite (NBO/T = 1.25) and Ca-melilitite (NBO/T = 2.50) synthesized in the NKCMAS system and equilibrated at high-pressure (200-300 MPa), high-temperature (1250°C) with an excess C-O-H fluid phase. The nephelinite glasses were synthesized with varying K2O / K2O+Na2O (0-10 mol.% K2O) ratio so as to investigate the differential effect of those two cations. All experiments were conducted under oxidizing conditions (ΔNNO+5) resulting in binary fluid phase composition with CO2 and H2O species. The silicate melt structure, CO2 solubility and speciation were investigated using Micro-Raman and Solid State NMR spectroscopies for 13C, 1H, 29Si, 27Al and 23Na nuclei. The replacement of Na by K does not change the nephelinite melt structure for volatile-free sample suggesting that the basicity of these glasses is not dramatically affected by the presence of mixed alkali. Within 5 mol.% K2O, the CO2 solubility (measured in relative to Raman signature of the melt structure) is only slightly affected with an increasing CO2 solubility with increasing K2O content. As a function of pressure, we observe an increase in CO2 solubility consistent with previous studies. The 13C NMR investigation of the CO2 speciation show three different carbonates environments for CO2 in nephelinite melts attributed to non-network carbonates: 1) 170 ppm shift assigned to NBO-carb. Na or K; 2) 169 ppm assigned to NBO-carb. Ca; and 3) 165 ppm assigned to isolated Na+..CO32- carbonates. As K2O is increased into

Measuring the expressed abundance of the three phases of water with an imaging spectrometer over melting snow

NASA Astrophysics Data System (ADS)

Green, Robert O.; Painter, Thomas H.; Roberts, Dar A.; Dozier, Jeff

2006-10-01

From imaging spectrometer data, we simultaneously estimate the abundance of the three phases of water in an environment that includes melting snow, basing the analysis on the spectral shift in the absorption coefficient between water vapor, liquid water, and ice at 940, 980, and 1030 nm respectively. We apply a spectral fitting algorithm that measures the expressed abundance of the three phases of water to a data set acquired by the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) over Mount Rainier, Washington, on 14 June 1996. Precipitable water vapor varies from 1 mm over the summit of Mount Rainier to 10 mm over the lower valleys to the northwest. Equivalent path absorption of liquid water varies from 0 to 13 mm, with the zero values over rocky areas and high-elevation snow and the high values associated with liquid water held in vegetation canopies and in melting snow. Ice abundance varies from 0 to 30 mm equivalent path absorption in the snow- and glacier-covered portions of Mount Rainier. The water and ice abundances are related to the amount of liquid water and the sizes of the ice grains in the near-surface layer. Precision of the estimates, calculated over locally homogeneous areas, indicates an uncertainty of better than 1.5% for all three phases, except for liquid water in vegetation, where an optimally homogeneous site was not found. The analysis supports new strategies for hydrological research and applications as imaging spectrometers become more available.

Sm5(Fe,Ti)17 melt-spun ribbons with high coercivity

NASA Astrophysics Data System (ADS)

Saito, Tetsuji; Horita, Toru

2018-05-01

It has previously been reported that annealing of amorphous Sm5Fe17 melt-spun ribbon resulted in the formation of the Sm5Fe17 phase and the resultant Sm5Fe17 melt-spun ribbon exhibited a high coercivity. However, the annealing condition of the amorphous Sm5Fe17 melt-spun ribbon was somewhat critical and it was not easy to obtain Sm5Fe17 grains with high coercivity. In the present study, it was found that the small substitution of Ti for Fe in the Sm5Fe17 melt-spun ribbon stabilized the Sm5Fe17 phase. Annealed Sm5Fe16.7Ti0.3 melt-spun ribbon consisted of small and homogeneous Sm5(Fe,Ti)17 grains and exhibited a higher coercivity than the annealed Sm5Fe17 melt-spun ribbon.

Fractionation of Cl/Br during fluid phase separation in magmatic-hydrothermal fluids

NASA Astrophysics Data System (ADS)

Seo, Jung Hun; Zajacz, Zoltán

2016-06-01

Brine and vapor inclusions were synthesized to study Cl/Br fractionation during magmatic-hydrothermal fluid phase separation at 900 °C and pressures of 90, 120, and 150 MPa in Li/Na/K halide salt-H2O systems. Laser ablation ICP-MS microanalysis of high-density brine inclusions show an elevated Cl/Br ratio compared to the coexisting low-density vapor inclusions. The degree of Cl/Br fractionation between vapor and brine is significantly dependent on the identity of the alkali metal in the system: stronger vapor partitioning of Br occurs in the Li halide-H2O system compared to the systems of K and Na halide-H2O. The effect of the identity of alkali-metals in the system is stronger compared to the effect of vapor-brine density contrast. We infer that competition between alkali-halide and alkali-OH complexes in high-temperature fluids might cause the Cl/Br fractionation, consistent with the observed molar imbalances of alkali metals compared to halides in the analyzed brine inclusions. Our experiments show that the identity of alkali metals controls the degrees of Cl/Br fractionation between the separating aqueous fluid phases at 900 °C, and suggest that a significant variability in the Cl/Br ratios of magmatic fluids can arise in Li-rich systems.

Heterogeneously entrapped, vapor-rich melt inclusions record pre-eruptive magmatic volatile contents

NASA Astrophysics Data System (ADS)

Steele-MacInnis, Matthew; Esposito, Rosario; Moore, Lowell R.; Hartley, Margaret E.

2017-04-01

Silicate melt inclusions (MI) commonly provide the best record of pre-eruptive H2O and CO2 contents of subvolcanic melts, but the concentrations of CO2 and H2O in the melt (glass) phase within MI can be modified by partitioning into a vapor bubble after trapping. Melt inclusions may also enclose vapor bubbles together with the melt (i.e., heterogeneous entrapment), affecting the bulk volatile composition of the MI, and its post-entrapment evolution. In this study, we use numerical modeling to examine the systematics of post-entrapment volatile evolution within MI containing various proportions of trapped vapor from zero to 95 volume percent. Modeling indicates that inclusions that trap only a vapor-saturated melt exhibit significant decrease in CO2 and moderate increase in H2O concentrations in the melt upon nucleation and growth of a vapor bubble. In contrast, inclusions that trap melt plus vapor exhibit subdued CO2 depletion at equivalent conditions. In the extreme case of inclusions that trap mostly the vapor phase (i.e., CO2-H2O fluid inclusions containing trapped melt), degassing of CO2 from the melt is negligible. In the latter scenario, the large fraction of vapor enclosed in the MI during trapping essentially serves as a buffer, preventing post-entrapment modification of volatile concentrations in the melt. Hence, the glass phase within such heterogeneously entrapped, vapor-rich MI records the volatile concentrations of the melt at the time of trapping. These numerical modeling results suggest that heterogeneously entrapped MI containing large vapor bubbles represent amenable samples for constraining pre-eruptive volatile concentrations of subvolcanic melts.

First-principles melting of gallium clusters down to nine atoms: structural and electronic contributions to melting.

PubMed

Steenbergen, Krista G; Gaston, Nicola

2013-10-07

First-principles Born-Oppenheimer molecular dynamics simulations of small gallium clusters, including parallel tempering, probe the distinction between cluster and molecule in the size range of 7-12 atoms. In contrast to the larger sizes, dynamic measures of structural change at finite temperature demonstrate that Ga7 and Ga8 do not melt, suggesting a size limit to melting in gallium exists at 9 atoms. Analysis of electronic structure further supports this size limit, additionally demonstrating that a covalent nature cannot be identified for clusters larger than the gallium dimer. Ga9, Ga10 and Ga11 melt at greater-than-bulk temperatures, with no evident covalent character. As Ga12 represents the first small gallium cluster to melt at a lower-than-bulk temperature, we examine the structural properties of each cluster at finite temperature in order to probe both the origins of greater-than-bulk melting, as well as the significant differences in melting temperatures induced by a single atom addition. Size-sensitive melting temperatures can be explained by both energetic and entropic differences between the solid and liquid phases for each cluster. We show that the lower-than-bulk melting temperature of the 12-atom cluster can be attributed to persistent pair bonding, reminiscent of the pairing observed in α-gallium. This result supports the attribution of greater-than-bulk melting in gallium clusters to the anomalously low melting temperature of the bulk, due to its dimeric structure.

The Additive Coloration of Alkali Halides

ERIC Educational Resources Information Center

Jirgal, G. H.; and others

1969-01-01

Describes the construction and use of an inexpensive, vacuum furnace designed to produce F-centers in alkali halide crystals by additive coloration. The method described avoids corrosion or contamination during the coloration process. Examination of the resultant crystals is discussed and several experiments using additively colored crystals are…

Real-time phase evolution of Selective Laser Melted (SLM) Inconel 718 with temperature through synchrotron X-rays

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

Sarley, Brooke A.; Manero, Albert; Cotelo, Jose

2017-01-01

Selective laser melting (SLM) is an additive manufacturing process that uses laser scanning to achieve melting and solidification of a metal powder bed. This process, when applied to develop high temperature material systems, holds great promise for more efficient manufacturing of turbine components that withstand extreme temperatures, heat fluxes, and high mechanical stresses associated with engine environments. These extreme operational conditions demand stringent tolerances and an understanding of the material evolution under thermal loading. This work presents a real-time approach to elucidating the evolution of precipitate phases in SLM Inconel 718 (IN718) under high temperatures using high-energy synchrotron x-ray diffraction.more » Four representative samples (taken along variable build height) were studied in room temperature conditions. Two samples were studied as-processed (samples 1 and 4) and two samples after different thermal treatments (samples 2 and 3). The as-processed samples were found to contain greater amounts of weakening phase, δ. Precipitation hardening of Sample 2 reduced the detectable volume of δ, while also promoting growth of γ00 in the γ matrix. Inversely, solution treatment of Sample 3 produced an overall decrease in precipitate phases. High-temperature, in-situ synchrotron scans during ramp-up, hold, and cool down of two different thermal cycles show the development of precipitate phases. Sample 1 was held at 870°C and subsequently ramped up to 1100°C, during which the high temperature instability of strengthening precipitate, γ00, was seen. γ00 dissolution occurred after 15 minutes at 870°C and was followed by an increase of δ-phase. Sample 4 was held at 800°C and exhibited growth of γ00 after 20 minutes at this temperature. These experiments use in-situ observations to understand the intrinsic thermal effect of the SLM process and the use of heat treatment to manipulate the phase composition of SLM IN718.« less

Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors.

PubMed

Pedesseau, Laurent; Sapori, Daniel; Traore, Boubacar; Robles, Roberto; Fang, Hong-Hua; Loi, Maria Antonietta; Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe; Neukirch, Amanda; Tretiak, Sergei; Mohite, Aditya D; Katan, Claudine; Even, Jacky; Kepenekian, Mikaël

2016-11-22

Layered halide hybrid organic-inorganic perovskites (HOP) have been the subject of intense investigation before the rise of three-dimensional (3D) HOP and their impressive performance in solar cells. Recently, layered HOP have also been proposed as attractive alternatives for photostable solar cells and revisited for light-emitting devices. In this review, we combine classical solid-state physics concepts with simulation tools based on density functional theory to overview the main features of the optoelectronic properties of layered HOP. A detailed comparison between layered and 3D HOP is performed to highlight differences and similarities. In the same way as the cubic phase was established for 3D HOP, here we introduce the tetragonal phase with D 4h symmetry as the reference phase for 2D monolayered HOP. It allows for detailed analysis of the spin-orbit coupling effects and structural transitions with corresponding electronic band folding. We further investigate the effects of octahedral tilting on the band gap, loss of inversion symmetry and possible Rashba effect, quantum confinement, and dielectric confinement related to the organic barrier, up to excitonic properties. Altogether, this paper aims to provide an interpretive and predictive framework for 3D and 2D layered HOP optoelectronic properties.

Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution

DOE PAGES

Doane, Tennyson L.; Ryan, Kayla L.; Pathade, Laxmikant; ...

2016-05-05

The ability of cesium lead halide (CsPbX 3; X = Cl –, Br –, I –) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. Also, the exchange of CsPbI 3 with Cl – or Br – causes a significant blue-shift in absorption and photoluminescence, whereas reacting I – with CsPbBr 3 causesmore » a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. Finally, the merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites.« less

Water freezing and ice melting

DOE PAGES

Malolepsza, Edyta; Keyes, Tom

2015-10-12

The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to freezing of liquid water, and melting of hexagonal and cubic ice. It is confirmed that coexisting states are well sampled. The statistical temperature as a function of enthalpy, T S(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice↔liquid and cubicmore » ice↔liquid, with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. As a result, pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice.« less

Bication lead iodide 2D perovskite component to stabilize inorganic α-CsPbI3 perovskite phase for high-efficiency solar cells

PubMed Central

Zhang, Taiyang; Dar, M. Ibrahim; Li, Ge; Xu, Feng; Guo, Nanjie; Grätzel, Michael; Zhao, Yixin

2017-01-01

Among various all-inorganic halide perovskites exhibiting better stability than organic-inorganic halide perovskites, α-CsPbI3 with the most suitable band gap for tandem solar cell application faces an issue of phase instability under ambient conditions. We discovered that a small amount of two-dimensional (2D) EDAPbI4 perovskite containing the ethylenediamine (EDA) cation stabilizes the α-CsPbI3 to avoid the undesirable formation of the nonperovskite δ phase. Moreover, not only the 2D perovskite of EDAPbI4 facilitate the formation of α-CsPbI3 perovskite films exhibiting high phase stability at room temperature for months and at 100°C for >150 hours but also the α-CsPbI3 perovskite solar cells (PSCs) display highly reproducible efficiency of 11.8%, a record for all-inorganic lead halide PSCs. Therefore, using the bication EDA presents a novel and promising strategy to design all-inorganic lead halide PSCs with high performance and reliability. PMID:28975149

Phonon Speed, Not Scattering, Differentiates Thermal Transport in Lead Halide Perovskites.

PubMed

Elbaz, Giselle A; Ong, Wee-Liat; Doud, Evan A; Kim, Philip; Paley, Daniel W; Roy, Xavier; Malen, Jonathan A

2017-09-13

Thermal management plays a critical role in the design of solid state materials for energy conversion. Lead halide perovskites have emerged as promising candidates for photovoltaic, thermoelectric, and optoelectronic applications, but their thermal properties are still poorly understood. Here, we report on the thermal conductivity, elastic modulus, and sound speed of a series of lead halide perovskites MAPbX 3 (X = Cl, Br, I), CsPbBr 3 , and FAPbBr 3 (MA = methylammonium, FA = formamidinium). Using frequency domain thermoreflectance, we find that the room temperature thermal conductivities of single crystal lead halide perovskites range from 0.34 to 0.73 W/m·K and scale with sound speed. These results indicate that regardless of composition, thermal transport arises from acoustic phonons having similar mean free path distributions. A modified Callaway model with Born von Karmen-based acoustic phonon dispersion predicts that at least ∼70% of thermal conductivity results from phonons having mean free paths shorter than 100 nm, regardless of whether resonant scattering is invoked. Hence, nanostructures or crystal grains with dimensions smaller than 100 nm will appreciably reduce thermal transport. These results are important design considerations to optimize future lead halide perovskite-based photovoltaic, optoelectronic, and thermoelectric devices.

Shape Evolution and Single Particle Luminescence of Organometal Halide Perovskite Nanocrystals

DOE PAGES

Zhu, Feng; Men, Long; Guo, Yijun; ...

2015-02-09

Organometallic halide perovskites CH 3NH 3PbX 3 (X = I, Br, Cl) have quickly become one of the most promising semiconductors for solar cells, with photovoltaics made of these materials reaching power conversion efficiencies of near 20%. Improving our ability to harness the full potential of organometal halide perovskites will require more controllable syntheses that permit a detailed understanding of their fundamental chemistry and photophysics. In our manuscript, we systematically synthesize CH 3NH 3PbX 3 (X = I, Br) nanocrystals with different morphologies (dots, rods, plates or sheets) by using different solvents and capping ligands. CH 3NH 3PbX 3 nanowiresmore » and nanorods capped with octylammonium halides show relatively higher photoluminescence (PL) quantum yields and long PL lifetimes. CH 3NH 3PbI 3 nanowires monitored at the single particle level show shape-correlated PL emission across whole particles, with little photobleaching observed and very few off periods. Our work highlights the potential of low-dimensional organometal halide perovskite semiconductors in constructing new porous and nanostructured solar cell architectures, as well as in applying these materials to other fields such as light-emitting devices and single particle imaging and tracking.« less

Evaluation of melting point of UO 2 by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Arima, Tatsumi; Idemitsu, Kazuya; Inagaki, Yaohiro; Tsujita, Yuichi; Kinoshita, Motoyasu; Yakub, Eugene

2009-06-01

The melting point of UO 2 has been evaluated by molecular dynamics simulation (MD) in terms of interatomic potential, pressure and Schottky defect concentration. The Born-Mayer-Huggins potentials with or without a Morse potential were explored in the present study. Two-phase simulation whose supercell at the initial state consisted of solid and liquid phases gave the melting point comparable to the experimental data using the potential proposed by Yakub. The heat of fusion was determined by the difference in enthalpy at the melting point. In addition, MD calculations showed that the melting point increased with pressure applied to the system. Thus, the Clausius-Clapeyron equation was verified. Furthermore, MD calculations clarified that an addition of Schottky defects, which generated the local disorder in the UO 2 crystal, lowered the melting point.

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

NASA Astrophysics Data System (ADS)

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

2001-12-01

Sulphide inclusions have been identified in olivine phenocrysts (and in one case in a spinel phenocryst) in primitive volcanic rocks from mid- ocean ridges, subduction-related island arcs and backarc basins. These inclusions represent droplets of an immiscible sulphide melt and are trapped by olivine crystals growing from silicate melts. Sulphide melt is usually trapped as separate inclusions, however combined inclusions of sulphide and silicate melts have also been observed. Sulphide inclusions have rounded shapes and vary in size from several up to 100 microns in diameter. At room temperature sulphide inclusions consist of several phases. These phases are formed as a result of crystallisation of the sulphide melt after it was trapped. Crystallisation occurs due to decreasing temperature in the magma chamber after trapping and/or when magma ascents from the magma chamber during eruptions. In all studied sulphides three different phases can be identified: a high- Fe, low-Ni, low-Cu phase; a high-Fe, high-Ni, low-Cu phase; and high-Fe, low-Ni, high-Cu phase. Low-Cu phases appear to be monomineralic, whereas the high-Cu phase is usually composed of a fine intergrowth of high- and low-Cu phases, resembling the quench 'spinifex' structure. Fe, Ni and Cu are the major elements in all sulphides studied. The amount of Ni decreases with decreasing forsterite content of the host olivine phenocryst, which is an index of the degree of silicate magma fractionation. Since Ni content of the silicate magma is decreasing during fractionation, this indicates either that the immiscible sulfide melt remains in equilibrium with the silicate melt continuously changing its composition during fractionation, or that the sulfide melt is continuously separated from the silicate melt during fractionation, with later formed droplets having lower Ni content due to the lower Ni content of the evolved, stronger fractionated silicate melt. Trace element contents of the sulfide inclusions have

Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

PubMed

You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

2017-02-03

A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

Copper/amino acid catalyzed cross-couplings of aryl and vinyl halides with nucleophiles.

PubMed

Ma, Dawei; Cai, Qian

2008-11-18

Copper-assisted Ullmann-type coupling reactions are valuable transformations for organic synthesis. Researchers have extensively applied these reactions in both academic and industrial settings. However, two important issues, the high reaction temperatures (normally above 150 degrees C) and the stoichiometric amounts of copper necessary, have greatly limited the reaction scope. To solve these problems, we and other groups have recently explored the use of special ligands to promote these coupling reactions. We first showed that the structure of alpha-amino acids can accelerate Cu-assisted Ullmann reactions, leading to the coupling reactions of aryl halides and alpha-amino acids at 80-90 degrees C. In response to these encouraging results, we also discovered that an l-proline ligand facilitated the following transformations: (1) coupling of aryl halides with primary amines, cyclic secondary amines, and N-containing heterocycles at 40-90 degrees C; (2) coupling of aryl halides with sulfinic acid salts at 80-95 degrees C; (3) azidation of aryl halides and vinyl halides with sodium azide at 40-95 degrees C; (4) coupling of aryl halides with activated methylene compounds at 25-50 degrees C. In addition, we found that N,N-dimethylglycine as a ligand facilitated Cu-catalyzed biaryl ether formation at 90 degrees C. Moreover, Sonogashira reactions worked in the absence of palladium and phosphine ligands, forming enamides from vinyl halides and amides at temperatures ranging from ambient temperature up to 80 degrees C. Furthermore, we discovered that an ortho-amide group can accelerate some Ullmann-type reactions. This functional group in combination with other ligand effects allowed for aryl amination or biaryl ether formation at ambient temperature. The coupling between aryl halides and activated methylene compounds even proceeded at -45 degrees C to enantioselectively form a quaternary carbon center. Taking advantage of these results, we developed several novel approaches

THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER: A COMPARATIVE STUDY OF TWO INSTRUMENTS

EPA Science Inventory

Total organic halide (TOX) analyzers are commonly used to measure the amount of dissolved halogenated organic byproducts in disinfected waters. ecause of the lack of information on the identity of disinfection byproducts, rigorous testing of the dissolved organic halide (DOX) pro...

The Role of Garnet Pyroxenite in High-Fe Mantle Melt Generation: High Pressure Melting Experiments

NASA Astrophysics Data System (ADS)

Tuff, J.; Takahashi, E.; Gibson, S.

2004-12-01

Evidence for the existence of heterogeneous or 'marble cake' convecting mantle1 is provided recently by rare, high MgO ( ˜ 15 wt.%) primitive magmas with anomalously high abundances of FeO* ( ˜ 13.5 to 16 wt. %2,3; where FeO* = total Fe as FeO). These high-Fe mantle melts show a limited occurrence in the initial stage of magmatism in large igneous provinces (e.g. Deccan, Ethiopia and Paraná-Etendeka) and some have incompatible trace-element and radiogenic-isotopic ratios (Sr, Nd and Pb) that resemble those of ocean-island basalts. This suggests that they are predominantly derived from the convecting mantle2. The ferropicrites are mildly- to sub-alkaline and have low contents of Al2O3 (< 10 wt.%) and heavy rare-earth elements (e.g. Lu < 0.18ppm) that are consistent with the increased stability of garnet, due to the high FeO* content in the ferropicrite mantle source. It has been proposed that the source of the high FeO* may be garnet-pyroxenite streaks derived from subducted mafic oceanic crust2. We have undertaken melting experiments between 1 atmosphere and 7 GPa in order to determine the anhydrous phase relations of an uncontaminated ferropicrite lava from the base of the Early-Cretaceous Paraná-Etendeka continental flood-basalt province. The sample has high contents of MgO ( ˜ 14.9 wt.%), FeO* (14.9 wt.%) and NiO (0.07 wt.%). Olivine phenocrysts have maximum Fo contents of 85 and are in equilibrium with the host rock, assuming a Kd of 0.32 and we believe that the sample is representative of a primary Fe-rich mantle plume derived melt. In total, 75 experimental runs were carried out. Melting phase relations as well as compositions and modal proportions of all coexisting phases were successfully determined in 60 run products. Phase relations indicate that the ferropicrite melt was generated either at ˜ 2.2 GPa from an olivine-pyroxene residue or ˜ 5 GPa from a garnet-pyroxene residue. A low bulk-rock Al2O3 content (9 wt.%) and high [Gd/Yb]n ratio (3.1) are

Effect of Low-Melting Metals (Pb, Bi, Cd, In) on the Structure, Phase Composition, and Properties of Casting Al-5% Si-4% Cu Alloy

NASA Astrophysics Data System (ADS)

Yakovleva, A. O.; Belov, N. A.; Bazlova, T. A.; Shkalei, I. V.

2018-01-01

The effect of low-melting metals (Pb, Bi, Cd, In) on the structure, phase composition, and properties of the Al-5% Si-4% Cu alloy was studied using calculations. Polythermal sections have been reported, which show that the considered systems are characterized by the presence of liquid regions and monotectic reactions. The effect of low-melting metals on the microstructure and hardening of base alloy in the cast and heat-treated states has been studied.

Phase Diagram of HgTe -ZnTe Pseudobinary and Density, Heat Capacity, and Enthalphy of Mixing of Hg(sub 1-x)Zn(sub x)Te Pseudobinary Melts

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Sha, Yi-Gao; Mazuruk, K.; Lehoczky, S. L.

1996-01-01

In this article, the solidus temperatures of the Hg(sub 1-x) Zn(sub x)Te pseudobinary phase diagram for several compositions in the low x region were measured by differential thermal analysis and the HgTe-ZnTe pseudobinary phase diagram was constructed. The densities of two HgZnTe melts, x = 0.10 and 0.16, were determined by an in situ pycnometric technique in a transparent furnace over, respectively, 110 and 50 C ranges of temperature. The thermodynamic properties of the melts, such as the heat capacity and enthalpy of mixing, were calculated for temperatures between the liquidus and 1500 C by assuming an associated solution model for the liquid phase.

A metastable liquid melted from a crystalline solid under decompression

DOE PAGES

Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; ...

2017-01-23

A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid–solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. Themore » decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure–temperature region similar to where the supercooled liquid Bi is observed. Finally, akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought.« less

Melt structure and self-nucleation of ethylene copolymers

NASA Astrophysics Data System (ADS)

Alamo, Rufina G.

A strong memory effect of crystallization has been observed in melts of random ethylene copolymers well above the equilibrium melting temperature. These studies have been carried out by DSC, x-ray, TEM and optical microscopy on a large number of model, narrow, and broad copolymers with different comonomer types and contents. Melt memory is correlated with self-seeds that increase the crystallization rate of ethylene copolymers. The seeds are associated with molten ethylene sequences from the initial crystals that remain in close proximity and lower the nucleation barrier. Diffusion of all sequences to a randomized melt state is a slow process, restricted by topological chain constraints (loops, knots, and other entanglements) that build in the intercrystalline region during crystallization. Self-seeds dissolve above a critical melt temperature that demarcates homogeneity of the copolymer melt. There is a critical threshold level of crystallinity to observe the effect of melt memory on crystallization rate, thus supporting the correlation between melt memory and the change in melt structure during copolymer crystallization. Unlike binary blends, commercial ethylene-1-alkene copolymers with a range in inter-chain comonomer composition between 1 and about 15 mol % display an inversion of the crystallization rate in a range of melt temperatures where narrow copolymers show a continuous acceleration of the rate. With decreasing the initial melt temperature, broadly distributed copolymers show enhanced crystallization followed by a decrease of crystallization rate. The inversion demarcates the onset of liquid-liquid phase separation (LLPS) and a reduction of self-nuclei due to the strong thermodynamic drive for molecular segregation inside the binodal. The strong effect of melt memory on crystallization rate can be used to identify liquid-liquid phase separation in broadly distributed copolymers, and offers strategies to control the state of copolymer melts in ways of

Environmental Effects on the Photophysics of Organic-Inorganic Halide Perovskites.

PubMed

Galisteo-López, Juan F; Anaya, M; Calvo, M E; Míguez, H

2015-06-18

The photophysical properties of films of organic-inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials.

Environmental Effects on the Photophysics of Organic–Inorganic Halide Perovskites

PubMed Central

2015-01-01

The photophysical properties of films of organic–inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials. PMID:26266592

Advancement on Lead-Free Organic-Inorganic Halide Perovskite Solar Cells: A Review.

PubMed

Sani, Faruk; Shafie, Suhaidi; Lim, Hong Ngee; Musa, Abubakar Ohinoyi

2018-06-14

Remarkable attention has been committed to the recently discovered cost effective and solution processable lead-free organic-inorganic halide perovskite solar cells. Recent studies have reported that, within five years, the reported efficiency has reached 9.0%, which makes them an extremely promising and fast developing candidate to compete with conventional lead-based perovskite solar cells. The major challenge associated with the conventional perovskite solar cells is the toxic nature of lead (Pb) used in the active layer of perovskite material. If lead continues to be used in fabricating solar cells, negative health impacts will result in the environment due to the toxicity of lead. Alternatively, lead free perovskite solar cells could give a safe way by substituting low-cost, abundant and non toxic material. This review focuses on formability of lead-free organic-inorganic halide perovskite, alternative metal cations candidates to replace lead (Pb), and possible substitutions of organic cations, as well as halide anions in the lead-free organic-inorganic halide perovskite architecture. Furthermore, the review gives highlights on the impact of organic cations, metal cations and inorganic anions on stability and the overall performance of lead free perovskite solar cells.

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.

CO2-rich phonolitic melt and carbonatite immiscibility in melt inclusions in nephelinite (Hanang volcano, North Tanzanian Divergence, East African Rift).

NASA Astrophysics Data System (ADS)

Baudouin, C.; Parat, F.

2016-12-01

Hanang is the southern volcano of the East branch of the East African Rift and represents volcanic activity at early stage rifting (0.9 Ma). Lavas are highly alkaline Mg-poor nephelinites (Mg#=24.4-35.2) with cpx, garnet, nepheline, titanite, and apatite and result from fractional crystallisation of primary melilitite magmas (Parat et al. AGU2016). In this study, we investigate glassy melt inclusions at the rim of nepheline phenocrysts to constrain the late stage of nephelinite evolution and the behaviour of volatiles (CO2, H2O, S, F, Cl) during magma storage and ascent. The melt inclusions have a green silicate glass, a microcrystalline carbonate phase and a shrinkage bubble free of gas phase (Raman analyses) suggesting that carbonatite-silicate liquid immiscibility (85:15) occurred during nephelinite differentiation. The silicate glasses have trachytic composition (Na+K/Al=1.6-7.2, SiO2=54-65.5 wt%) with high CO2 (0.43 wt% CO2, SIMS analyses), sulfur (0.21-0.92 wt% S) and halogens (0.28-0.84 wt% Cl; 0.35-2.54 wt% F) content and very low H2O content (<0.1wt%, Raman analyses). The carbonate phase is an anhydrous Ca-Na±S,K- carbonate with 33 wt% CaO, 20 wt% Na2O, 3 wt% K2O, and 3 wt% S. The pre-immiscible silicate liquid (e.g. silicate melt + carbonatite) in equilibrium with nepheline and cpx phenocrysts has CO2-rich phonolitic composition (Na+K/Al=6.2-6.9) with 6 ± 1.5 wt% CO2 at pressure of 700-1100 MPa. The entrapped melt in nepheline corresponds to evolved interstitial silicate melt after crystallisation of cpx (16.7%), nepheline (40%) garnet (6.5%) and apatite (1.7%) from Mg-nephelinite magma. The immiscibility process leading to glassy silicate melt and microcrystalline carbonatitic melt occurred in closed system during rapid ascent at crustal level at 200-230 MPa. The absence of gas phase in shrinkage bubble in melt inclusions suggests CO2-undersaturated conditions during quenching. The absence of carbonatite lavas at Hanang volcano is then explained by

Metal halides vapor lasers with inner reactor and small active volume.

NASA Astrophysics Data System (ADS)

Shiyanov, D. V.; Sukhanov, V. B.; Evtushenko, G. S.

2018-04-01

Investigation of the energy characteristics of copper, manganese, lead halide vapor lasers with inner reactor and small active volume 90 cm3 was made. The optimal operating pulse repetition rates, temperatures, and buffer gas pressure for gas discharge tubes with internal and external electrodes are determined. Under identical pump conditions, such systems are not inferior in their characteristics to standard metal halide vapor lasers. It is shown that the use of a zeolite halogen generator provides lifetime laser operation.

Melting phase relation of nominally anhydrous, carbonated pelitic-eclogite at 2.5-3.0 GPa and deep cycling of sedimentary carbon

NASA Astrophysics Data System (ADS)

Tsuno, Kyusei; Dasgupta, Rajdeep

2011-05-01

We have experimentally investigated melting phase relation of a nominally anhydrous, carbonated pelitic eclogite (HPLC1) at 2.5 and 3.0 GPa at 900-1,350°C in order to constrain the cycling of sedimentary carbon in subduction zones. The starting composition HPLC1 (with 5 wt% bulk CO2) is a model composition, on a water-free basis, and is aimed to represent a mixture of 10 wt% pelagic carbonate unit and 90 wt% hemipelagic mud unit that enter the Central American trench. Sub-solidus assemblage comprises clinopyroxene + garnet + K-feldspar + quartz/coesite + rutile + calcio-ankerite/ankeritess. Solidus temperature is at 900-950°C at 2.5 GPa and at 900-1,000°C at 3.0 GPa, and the near-solidus melt is K-rich granitic. Crystalline carbonates persist only 50-100°C above the solidus and at temperatures above carbonate breakdown, carbon exists in the form of dissolved CO2 in silica-rich melts and as a vapor phase. The rhyodacitic to dacitic partial melt evolves from a K-rich composition at near-solidus condition to K-poor, and Na- and Ca-rich composition with increasing temperature. The low breakdown temperatures of crystalline carbonate in our study compared to those of recent studies on carbonated basaltic eclogite and peridotite owes to Fe-enrichment of carbonates in pelitic lithologies. However, the conditions of carbonate release in our study still remain higher than the modern depth-temperature trajectories of slab-mantle interface at sub-arc depths, suggesting that the release of sedimentary carbonates is unlikely in modern subduction zones. One possible scenario of carbonate release in modern subduction zones is the detachment and advection of sedimentary piles to hotter mantle wedge and consequent dissolution of carbonate in rhyodacitic partial melt. In the Paleo-NeoProterozoic Earth, on the other hand, the hotter slab-surface temperatures at subduction zones likely caused efficient liberation of carbon from subducting sedimentary carbonates. Deeply subducted

Melting of Boltzmann particles in different 2D trapping potential

NASA Astrophysics Data System (ADS)

Bhattacharya, Dyuti; Filinov, Alexei; Ghosal, Amit; Bonitz, Michael

2015-03-01

We analyze the quantum melting of two dimensional Wigner solid in several confined geometries and compare them with corresponding thermal melting in a purely classical system. Our results show that the geometry play little role in deciding the crossover quantum parameter nX, as the effects from boundary is well screened by the quantum zero point motion. The unique phase diagram in the plane of thermal and quantum fluctuations determined from independent melting criteria separates out the Wigner molecule ``phase'' from the classical and quantum ``liquids''. An intriguing signature of weakening liquidity with increasing temperature T have been found in the extreme quantum regime (n). This crossover is associated with production of defects, just like in case of thermal melting, though the role of them in determining the mechanism of the crossover appears different. Our study will help comprehending melting in a variety of experimental realization of confined system - from quantum dots to complex plasma.

Single-Track Melt-Pool Measurements and Microstructures in Inconel 625

NASA Astrophysics Data System (ADS)

Ghosh, Supriyo; Ma, Li; Levine, Lyle E.; Ricker, Richard E.; Stoudt, Mark R.; Heigel, Jarred C.; Guyer, Jonathan E.

2018-06-01

We use single-track laser melting experiments and simulations on Inconel 625 to estimate the dimensions and microstructure of the resulting melt pool. Our work is based on a design-of-experiments approach which uses multiple laser power and scan speed combinations. Single-track experiments generated melt pools of certain dimensions that showed reasonable agreement with our finite-element calculations. Phase-field simulations were used to predict the size and segregation of the cellular microstructure that formed along the melt-pool boundaries for the solidification conditions that changed as a function of melt-pool dimensions.

Single-Track Melt-Pool Measurements and Microstructures in Inconel 625

NASA Astrophysics Data System (ADS)

Ghosh, Supriyo; Ma, Li; Levine, Lyle E.; Ricker, Richard E.; Stoudt, Mark R.; Heigel, Jarred C.; Guyer, Jonathan E.

2018-02-01

We use single-track laser melting experiments and simulations on Inconel 625 to estimate the dimensions and microstructure of the resulting melt pool. Our work is based on a design-of-experiments approach which uses multiple laser power and scan speed combinations. Single-track experiments generated melt pools of certain dimensions that showed reasonable agreement with our finite-element calculations. Phase-field simulations were used to predict the size and segregation of the cellular microstructure that formed along the melt-pool boundaries for the solidification conditions that changed as a function of melt-pool dimensions.

Chiral Alkyl Halides: Underexplored Motifs in Medicine

PubMed Central

Gál, Bálint; Bucher, Cyril; Burns, Noah Z.

2016-01-01

While alkyl halides are valuable intermediates in synthetic organic chemistry, their use as bioactive motifs in drug discovery and medicinal chemistry is rare in comparison. This is likely attributable to the common misconception that these compounds are merely non-specific alkylators in biological systems. A number of chlorinated compounds in the pharmaceutical and food industries, as well as a growing number of halogenated marine natural products showing unique bioactivity, illustrate the role that chiral alkyl halides can play in drug discovery. Through a series of case studies, we demonstrate in this review that these motifs can indeed be stable under physiological conditions, and that halogenation can enhance bioactivity through both steric and electronic effects. Our hope is that, by placing such compounds in the minds of the chemical community, they may gain more traction in drug discovery and inspire more synthetic chemists to develop methods for selective halogenation. PMID:27827902

Alkali Halide FLIR Lens Development

DTIC Science & Technology

1981-10-01

in the atmosphere. The main emphasis in this 3 report has been development of protective coatings for potassium bromide lenses. The most favorable...placed onto the bottom electrode. Pieces of single-crystalline potassium chloride of approximately the same thickness as coated alkali halide samples...none of the samples appeared to be degraded by the high humidity associated with the exposure. 2. UNITS TESTED Four coated potassium bromide lenses

Olivine-hosted melt inclusions record efficient mixing of mantle melts in continental flood basalt provinces

NASA Astrophysics Data System (ADS)

Jennings, E. S.; Gibson, S. A.; Maclennan, J.; Heinonen, J. S.

2017-12-01

Primitive melt inclusions trapped in various minerals found in global ridge settings have been shown to record highly variable magmatic compositions. Mantle melting is expected to be near-fractional, producing a wide range of melt compositions that must accumulate and mix in crustal magma chambers. In primitive rocks, the melt inclusion variability observed in major, trace and isotope geochemistry is consistent to the first order with partial melting of variably depleted mantle, and indicate that the host phases began to crystallise prior to the completion of melt aggregation and mixing. We present new major and trace element data from a large number of rehomogenised olivine-hosted melt inclusions from the Cretaceous Paraná-Etendeka and Jurassic Karoo continental flood basalt (CFB) provinces [1]. We show that the major element chemistry of the melt inclusions can be severely disrupted by the rehomogenisation process and, as a consequence, their initial compositions cannot easily be back-calculated. However, despite the age of the samples, the trace element geochemistry of the melt inclusions is well-preserved. Despite coming from near-liquidus olivines from primitive picrites and ferropicrites, the inclusions are remarkably homogeneous; none of the anticipated variability in incompatible trace element compositions is observed. When considered alongside literature data, it appears that variability in primitive melts - as recorded by melt inclusions - is low in CFBs and OIBs relative to ridge settings, e.g. Iceland. We suggest that the tectonic setting imposes a control on the mixing of mantle melts: hot, plume-derived melts generated beneath relatively thick lithosphere may be prone to efficient mixing, perhaps due to their low viscosity, long transport pathways, and/or a superliquidus emplacement temperature [1]. This interpretation is supported by the almost non-existent variability of olivine-hosted inclusions from ferropicrite samples: these magmas represents

Rock Melt Borehole Sealing System, Final Technical Report for SBIR Phase I Grant No. DE-SC0011888

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

Osnes, John D.; Vining, Cody A.; Nopola, Jay R.

providing the required heat generation, container materials that can withstand the anticipated temperatures, and a system capable of providing power to the heater. Evaluating the feasibility of performing field-scale experiments resulted in the following major findings: • The Sanford Underground Research Facility (SURF) has been identified as a host site for field testing of prototype heaters. The technical and logistical requirements for performing the rock melt tests can be met by using or expanding the existing infrastructure at SURF with on-site personnel and contractors. • In situ hydraulic conductivity test using packers can test the effectiveness of the rock melt seal, while a mine back performed from a lower level can further evaluate the recrystallized melt. • Preliminary costing indicates that a field-scale melting experiment at SURF is feasible within a Phase II Small Business Innovation Research budget while allowing sufficient budget for refining the heater design, coordinating the test program, and interpreting the results. Application of Research The rock melt sealing concept has the potential to reduce uncertainty associated with the long-term storage of nuclear waste. Preliminary efforts of this study defined the requirements of a downhole heater system capable of melting rock and indicated that developing such a system is feasible using available technology. The next logical step is designing and manufacturing prototype heaters. Concurrent with prototype development is coordinating robust field-scale experiments that are capable of validating the design for marketing to potential users.« less

The role of the "Casimir force analogue" at the microscopic processes of crystallization and melting

NASA Astrophysics Data System (ADS)

Chuvildeev, V. N.; Semenycheva, A. V.

2016-10-01

Melting (crystallization), a phase transition from a crystalline solid to a liquid state, is a common phenomenon in nature. We suggest a new factor, "the Casimir force analogue", to describe mechanisms of melting and crystallization. The Casimir force analogue is a force occurring between the surfaces of solid and liquid phases of metals caused by different energy density of phonons of these phases. It explains abrupt changes in geometry and thermodynamic parameters at a melting point. "The Casimir force analogue" helps to estimate latent melting heat and to gain an insight into a solid-liquid transition problem.

Polarization Switching and Light-Enhanced Piezoelectricity in Lead Halide Perovskites.

PubMed

Coll, Mariona; Gomez, Andrés; Mas-Marza, Elena; Almora, Osbel; Garcia-Belmonte, Germà; Campoy-Quiles, Mariano; Bisquert, Juan

2015-04-16

We investigate the ferroelectric properties of photovoltaic methylammonium lead halide CH3NH3PbI3 perovskite using piezoelectric force microscopy (PFM) and macroscopic polarization methods. The electric polarization is clearly observed by amplitude and phase hysteresis loops. However, the polarization loop decreases as the frequency is lowered, persisting for a short time only, in the one second regime, indicating that CH3NH3PbI3 does not exhibit permanent polarization at room temperature. This result is confirmed by macroscopic polarization measurement based on a standard capacitive method. We have observed a strong increase of piezoelectric response under illumination, consistent with the previously reported giant photoinduced dielectric constant at low frequencies. We speculate that an intrinsic charge transfer photoinduced dipole in the perovskite cage may lie at the origin of this effect.

P- T phase relations of silicic, alkaline, aluminous liquids: new results and applications to mantle melting and metasomatism

NASA Astrophysics Data System (ADS)

Draper, David S.; Green, Trevor H.

1999-07-01

We report new experimental results obtained under nominally anhydrous conditions at 1.0-1.5 GPa on a synthetic melt whose composition is typical of extreme-composition xenolith glasses. These results demonstrate that part of this extreme compositional range is in equilibrium with a lherzolitic assemblage (olivine, orthopyroxene, and clinopyroxene on the liquidus), extending our earlier findings [D.S. Draper, T.H. Green P- T phase relations of silicic, alkaline, aluminous mantle-xenolith glasses under anhydrous and C-O-H fluid-saturated conditions, J. Petrol. 38 (1997) 1187-1224] showing saturation with harzburgite minerals (olivine and orthopyroxene on the liquidus). The new results strengthen the view that such liquids can readily coexist with upper mantle rocks. Our results also bear on the current debate regarding the nature of low-degree mantle melts between proponents of the diamond-aggregate technique [who argue for comparatively silica- and alkali-rich low-degree melts; e.g., M.B. Baker, M.M. Hirschmann, M.S. Ghiorso, E.M. Stolper, Compositions of near-solidus peridotite melts from experiments and thermodynamic calculations, Nature 375 (1995) 308-311; M.B. Baker, M.M. Hirschmann, L.E. Wasylenki, E.M. Stolper, M.S. Ghiorso, Quest for low-degree mantle melts, Nature 381 (1996) 286] and those favoring the sandwich technique [who question the value of the diamond-aggregate work and argue that near-solidus melts must be nepheline- and olivine-normative; T.J. Falloon, D.H. Green, H.St.C. O'Neill, C.G. Ballhaus, Quest for low-degree mantle melts, Nature 381 (1996) 285; T.J. Falloon, D.H. Green, H.St.C. O'Neill, W.O. Hibberson, Experimental tests of low degree peridotite partial melt compositions: implications for the nature of anhydrous near-solidus peridotite melts at 1 GPa, Earth Planet. Sci. Lett. 152 (1997) 149-162]. Our results support aspects of both views. The sandwich-technique view is supported, for example, because all our liquids coexisting with mantle

Nucleation and growth of metal nanocrystals during electrocrystallization in melts

NASA Astrophysics Data System (ADS)

Isaev, V. A.; Grishenkova, O. V.; Semerikova, O. L.; Kosov, A. V.; Zaykov, Yu. P.

2016-08-01

The initial stages of electrocrystallization in melts are considered. The nucleation and growth rates of metal nanocrystals during electrodeposition are calculated. The diffusion coefficients in the size space in the Fokker-Planck equation, which describes phase formation, are found. The method of calculating the number of nanoclusters formed on an electrode has been proposed. The concentration dependence of the phase formation under potentiostatic and galvanostatic electrodeposition conditions in melts is considered.

Rheology and microstructure of filled polymer melts

NASA Astrophysics Data System (ADS)

Anderson, Benjamin John

The states of particle dispersion in polymer nanocomposite melts are studied through rheological characterization of nanocomposite melt mechanical properties and small angle X-ray scattering measurement of the particle microstructure. The particle microstructure probed with scattering is related to bulk flow mechanics to determine the origin of slow dynamics in these complex dispersions: whether a gel or glass transition or a slowing down of dispersing phase dynamics. These studies were conducted to understand polymer mediated particle-particle interactions and potential particle-polymer phase separation. The phase behavior of the dispersion will be governed by enthalpic and entropic contributions. A variety of phases are expected: homogeneous fluid, phase separated, or non-equilibrium gel. The effects of dispersion control parameters, namely particle volume fraction, polymer molecular weight, and polymer-particle surface affinity, on the phase behavior of 44 nm silica dispersions are studied in low molecular weight polyethylene oxide (PEO), polyethylene oxide dimethylether (PEODME), and polytetrahydrofuran (PTHF). Scattering measurements of the particle second virial coefficient in PEO melts indicates repulsive particles by a value slightly greater than unity. In PEO nanocomposites, dispersion dynamics slow down witnessed by a plateau in the elastic modulus as the particle separation approaches the length scale of the polymer radius of gyration. As the polymer molecular weight is increased, the transition shifts to lower particle volume fractions. Below polymer entanglement, the slow dynamics mimics that of a colloidal glass by the appearance of two relaxation times in the viscous modulus that display power law scaling with volume fraction. Above entanglement, the slow dynamics is qualitatively different resembling the behavior of a gelled suspension yet lacking any sign of scattering from particle agglomerates. As polymer molecular weight is increased at a fixed

Broad Wavelength Tunable Robust Lasing from Single-Crystal Nanowires of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I).

PubMed

Fu, Yongping; Zhu, Haiming; Stoumpos, Constantinos C; Ding, Qi; Wang, Jue; Kanatzidis, Mercouri G; Zhu, Xiaoyang; Jin, Song

2016-08-23

Lead halide perovskite nanowires (NWs) are emerging as a class of inexpensive semiconductors with broad bandgap tunability for optoelectronics, such as tunable NW lasers. Despite exciting progress, the current organic-inorganic hybrid perovskite NW lasers suffer from limited tunable wavelength range and poor material stability. Herein, we report facile solution growth of single-crystal NWs of inorganic perovskite CsPbX3 (X = Br, Cl) and their alloys [CsPb(Br,Cl)3] and a low-temperature vapor-phase halide exchange method to convert CsPbBr3 NWs into perovskite phase CsPb(Br,I)3 alloys and metastable CsPbI3 with well-preserved perovskite crystal lattice and NW morphology. These single crystalline NWs with smooth end facets and subwavelength dimensions are ideal Fabry-Perot cavities for NW lasers. Optically pumped tunable lasing across the entire visible spectrum (420-710 nm) is demonstrated at room temperature from these NWs with low lasing thresholds and high-quality factors. Such highly efficient lasing similar to what can be achieved with organic-inorganic hybrid perovskites indicates that organic cation is not essential for light emission application from these lead halide perovskite materials. Furthermore, the CsPbBr3 NW lasers show stable lasing emission with no measurable degradation after at least 8 h or 7.2 × 10(9) laser shots under continuous illumination, which are substantially more robust than their organic-inorganic counterparts. The Cs-based perovskites offer a stable material platform for tunable NW lasers and other nanoscale optoelectronic devices.

Shape and Symmetry Determine Two-Dimensional Melting Transitions of Hard Regular Polygons

NASA Astrophysics Data System (ADS)

Anderson, Joshua A.; Antonaglia, James; Millan, Jaime A.; Engel, Michael; Glotzer, Sharon C.

2017-04-01

The melting transition of two-dimensional systems is a fundamental problem in condensed matter and statistical physics that has advanced significantly through the application of computational resources and algorithms. Two-dimensional systems present the opportunity for novel phases and phase transition scenarios not observed in 3D systems, but these phases depend sensitively on the system and, thus, predicting how any given 2D system will behave remains a challenge. Here, we report a comprehensive simulation study of the phase behavior near the melting transition of all hard regular polygons with 3 ≤n ≤14 vertices using massively parallel Monte Carlo simulations of up to 1 ×106 particles. By investigating this family of shapes, we show that the melting transition depends upon both particle shape and symmetry considerations, which together can predict which of three different melting scenarios will occur for a given n . We show that systems of polygons with as few as seven edges behave like hard disks; they melt continuously from a solid to a hexatic fluid and then undergo a first-order transition from the hexatic phase to the isotropic fluid phase. We show that this behavior, which holds for all 7 ≤n ≤14 , arises from weak entropic forces among the particles. Strong directional entropic forces align polygons with fewer than seven edges and impose local order in the fluid. These forces can enhance or suppress the discontinuous character of the transition depending on whether the local order in the fluid is compatible with the local order in the solid. As a result, systems of triangles, squares, and hexagons exhibit a Kosterlitz-Thouless-Halperin-Nelson-Young (KTHNY) predicted continuous transition between isotropic fluid and triatic, tetratic, and hexatic phases, respectively, and a continuous transition from the appropriate x -atic to the solid. In particular, we find that systems of hexagons display continuous two-step KTHNY melting. In contrast, due to

Laser Direct Write Synthesis of Lead Halide Perovskites

DOE PAGES

Chou, Stanley S.; Swartzentruber, Brian S.; Janish, Matthew T.; ...

2016-09-05

Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. In this study, we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We also demonstrate arbitrary pattern formation of crystalline CH 3NH 3PbBr 3 on a range of substrates and fabricate and characterize a microscale photodetectormore » using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices.« less

Laser Direct Write Synthesis of Lead Halide Perovskites

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

Chou, Stanley S.; Swartzentruber, Brian S.; Janish, Matthew T.

Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. In this study, we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We also demonstrate arbitrary pattern formation of crystalline CH 3NH 3PbBr 3 on a range of substrates and fabricate and characterize a microscale photodetectormore » using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices.« less

The distribution of H2O between silicate melt and nominally anhydrous peridotite and the onset of hydrous melting in the deep upper mantle

NASA Astrophysics Data System (ADS)

Novella, Davide; Frost, Daniel J.; Hauri, Erik H.; Bureau, Helene; Raepsaet, Caroline; Roberge, Mathilde

2014-08-01

The partitioning of H2O between a mantle peridotite assemblage and low degree hydrous melt has been investigated at 6 GPa (corresponding to ∼180 km depth) at a temperature of 1400 °C. Peridotite mineral phases were analysed from 6 melting experiments performed in a natural chemical system. The experiments contained ∼80 wt% of a low degree hydrous melt that was obtained through a series of experiments where the melt composition was iteratively adjusted until saturation with the appropriate peridotite assemblage was achieved. The melt is fluid-undersaturated at the conditions of the experiment. Ion microprobe measurements of the mineral phases indicate olivine H2O concentrations of 434±61 ppm wt and average clinopyroxene (cpx) concentrations of 1268±173 ppm wt H2O. Orthopyroxene (opx) and garnet contain 700±46 ppm wt and 347±83 ppm wt H2O, respectively. The H2O content of the hydrous melts was determined by mass balance to be 11±0.5 wt% H2O. H2O partition coefficients between minerals and melt (DH2Omin/melt=XH2Omin/XH2Omelt) are 0.0040±0.0006 for olivine, 0.0064±0.0004 for opx, 0.0115±0.0016 for cpx and 0.0032±0.0008 for garnet. Using the determined H2O partition coefficients the onset and extent of melting at conditions equivalent to 180 km below mid-ocean ridges was determined as a function of mantle H2O content. Current estimates for the H2O content of the depleted mantle (50-200 ppm wt H2O) are insufficient to induce mantle melting at this depth, which requires ∼700 ppm wt H2O to produce 0.1% melting and 1600 ppm wt H2O for 1% melting, along an adiabat with a potential temperature of 1327 °C. Melting can occur at these conditions within the mantle source of ocean island basalts, which are estimated to contain up to 900 ppm wt H2O. If adiabatic temperatures are 200 °C higher within such plume related sources, then melt fractions of over 1% can be reached at 180 km depth. In addition, a model for the distribution of H2O between peridotite mineral

Changes in Carbon Isotope Composition of Methyl Halides Resulting from Biological and Chemical Degradation

NASA Astrophysics Data System (ADS)

Baesman, S. M.; Miller, L. G.; Oremland, R. S.

2003-12-01

Methyl bromide (MeBr), methyl chloride (MeCl) and methyl iodide (MeI) are reactive trace gases that are produced and released to the atmosphere at the Earths surface. These methyl halides have the potential to influence ozone levels in the stratosphere. Current estimates of the relative contributions of natural and anthropogenic sources of these methyl halides are the subject of considerable debate. In addition, there is uncertainty in the magnitude of some of the largest sinks for these compounds. Hence, the atmospheric budgets of MeBr, MeCl and MeI, while uncertain at present, may be better constrained using stable isotope ratio (13C/12C) mass balances of sources and sinks. Our work has focused on characterizing the effects upon δ 13C values of methyl halides released after reactions which discriminate in favor of 12C during removal processes. Previously, we determined very large fractionations of carbon isotopes by pure cultures of soil bacteria. Further, we have documented large fractionations (kinetic isotope effects or KIEs) of methyl halides in live soils. In the case of MeBr and MeI, substantial fractionation also occurred in heat-killed soil, suggesting that chemical degradation resulted in a shift in the stable isotopic composition. At elevated concentrations, for instance during agricultural soil fumigations, the δ 13C value of MeBr or MeI released from soil can be determined by flux measurements or soil profiles. However, more information is needed regarding the processes responsible for isotope fractionation to be able to extrapolate to areas where the concentration is low or direct measurement is not otherwise possible. We report here on measurements of the fractionation of carbon isotopes in methyl halides during degradation by chemical processes that are likely to occur in soil or seawater. These processes include aqueous hydrolysis and halide exchange and the methylation of organic matter using humic acid as the model methyl acceptor. Results are

Thermodynamics of freezing and melting

PubMed Central

Pedersen, Ulf R.; Costigliola, Lorenzo; Bailey, Nicholas P.; Schrøder, Thomas B.; Dyre, Jeppe C.

2016-01-01

Although the freezing of liquids and melting of crystals are fundamental for many areas of the sciences, even simple properties like the temperature–pressure relation along the melting line cannot be predicted today. Here we present a theory in which properties of the coexisting crystal and liquid phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio), and the liquid's diffusion constant and viscosity. The framework developed, which applies for the sizable class of systems characterized by hidden scale invariance, is validated by computer simulations of the standard 12-6 Lennard-Jones system. PMID:27530064

Method for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock in the presence of a molten metal halide catalyst

DOEpatents

Gorin, Everett

1981-01-01

A method for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock to produce lighter hydrocarbon fuels by contacting the feedstock with hydrogen in the presence of a molten metal halide catalyst, the method comprising: mixing the feedstock with a heavy naphtha fraction which has an initial boiling point from about 100.degree. to about 160.degree. C. with a boiling point difference between the initial boiling point and the final boiling point of no more than about 50.degree. C. to produce a mixture; thereafter contacting the mixture with partially spent molten metal halide and hydrogen under temperature and pressure conditions so that the temperature is near the critical temperature of the heavy naphtha fraction; separating at least a portion of the heavy naphtha fraction and lighter hydrocarbon fuels from the partially spent molten metal halide, unreacted feedstock and reaction products; thereafter contacting the partially spent molten metal halide, unreacted feedstock and reaction products with hydrogen and fresh molten metal halide in a hydrocracking zone to produce additional lighter hydrocarbon fuels and separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide.

Non-halide sediments from the Loule diapir salt mine: characterization and environmental significance

NASA Astrophysics Data System (ADS)

Ribeiro, Carlos; Terrinha, Pedro; Andrade, Alexandre; Fonseca, Bruno; Caetano, Miguel; Neres, Marta; Font, Eric; Mirão, José; Dias, Cristina; Rosado, Lúcia; Maurer, Anne-France; Manhita, Ana

2017-04-01

The sedimentary record of the Mesozoic Algarve Basin (south Portugal) spans from the Triassic to the Lower Cretaceous. Following the initial phase of Pangaea breakup and the related continental sedimentation during the Triassic, the sedimentation evolved through transitional (Triassic-Jurassic transition) to marine (Jurassic) environments. During the Hettangian a thick sequence of evaporites deposited in the basin. Most of the occurrences of these deposits have undetermined volumes, due to the post depositional diapiric movements. At the central Algarve, under the town of Loulé, a salt wall of up to > 1 km across, > 3 km in length and > 2 km in height has been exploited for the chemical industry (Loulé Diapir - LD). Most of the sediments that constitute LD are halides (> 99% halite), the exception being a package of non-halide sediments, constituted by carbonates (dolomite and magnesite) and sulphates (anhydrite) in various proportions with a maximum thickness of 3 meters. This package has a distinctive mesoscopic aspect of three layers of approximately the same thickness, different colours and primary sedimentary structures: black-brow-grey, from bottom to top. The sediments of this package were studied with a multidisciplinary approach aiming their mineralogical and chemical characterization, the determination of the organic matter content and origin, as well as the characterization and understanding of the chemical processes that occurred during the emplacement and compression of the LD: (i) X-ray diffraction for the determination of the mineral phases present and semi-quantification using the RIR-Reference Intensity Ratio method; (ii) micro analysis of the mineralogical samples by Scanning Electron Microscopy coupled to Energy Dispersive Spectroscopy; (iii) REE content determination by ICP-MS; (iv) determination of the carbon content by CHN Elemental analysis; (v) determination of the organic matter content by elemental analysis and their composition by

SHSG processing for three-wavelength HOEs recording in silver halide materials

NASA Astrophysics Data System (ADS)

Kim, Jong Man; Choi, Yoon S.; Bjelkhagen, Hans I.; Phillips, Nicholas J.

2002-06-01

The recording and processing technique for color HOEs in ultrafine-grain panchromatic silver halide emulsions is presented. It is possible to obtain high diffraction efficiency employing the silver halide sensitized gelatin (SHSG) process. SHSG holograms are similar to holograms recorded in dichromated gelatin (DCG). The drawback of DCG is its low sensitivity and limited spectral response. Panchromatic silver halide materials from Slavich can be processed in such a way that the final holograms have properties like a DCG hologram. The processing method or microvoid technique has been optimized for three laser- wavelength recordings in Slavich PFG-03C emulsion. For example, applying this new processing technique high- efficiency white holographic reflectors can be manufactured. The technique is also suitable for producing efficiency color display holograms. In particular, masters for mass production of color holograms or color HOEs can be performed by contact-copying into photopolymer materials because the reconstruction wavelengths are identical to the recording wavelengths.

Electrolytic Generation of Nano-Scale Carbon Phases with Framework Structures in Molten Salts on Metal Cathodes

NASA Astrophysics Data System (ADS)

Novoselova, Inessa A.; Oliinyk, Nikolai F.; Voronina, Anastasiya B.; Volkov, Sergei V.

2008-08-01

An electrochemical study of mechanisms of electrodeposition of carbon solid phases from halide melts (Na,K|Cl; Na,K,Cs|Cl), saturated with carbon dioxide under an excessive pressure of up to 1.5 MPa, has been carried out in the temperature range 550 - 850 °C by cyclic voltammetry. It has been found that the cathode process occurs in three steps at sweep rates of less than 0.1 Vs-1, and its electrochemical-chemical-electrochemical (ECE) mechanism is suggested. It has furthermore been found that cathodic deposits contain nano-sized carbon particles of different forms and structure: blocks of amorphous carbon, crystalline graphite, carbon nanotubes (CNT), and nanofibres. The outer diameter of the tubes is 5 - 250 nm, and the internal diameter is 2 - 140 nm. A correlation between the product structure and yield against electrolysis conditions and regimes has been established.

Frequency dispersion of sound propagation in Rouse polymer melts via generalized dynamic random phase approximation.

PubMed

Erukhimovich, I Ya; Kudryavtsev, Ya V

2003-08-01

An extended generalization of the dynamic random phase approximation (DRPA) for L-component polymer systems is presented. Unlike the original version of the DRPA, which relates the (LxL) matrices of the collective density-density time correlation functions and the corresponding susceptibilities of concentrated polymer systems to those of the tracer macromolecules and so-called broken-links system (BLS), our generalized DRPA solves this problem for the (5xL) x (5xL) matrices of the coupled susceptibilities and time correlation functions of the component number, kinetic energy and flux densities. The presented technique is used to study propagation of sound and dynamic form-factor in disentangled (Rouse) monodisperse homopolymer melt. The calculated ultrasonic velocity and absorption coefficient reveal substantial frequency dispersion. The relaxation time tau is proportional to the degree of polymerization N, which is N times less than the Rouse time and evidences strong dynamic screening because of interchain interaction. We discuss also some peculiarities of the Brillouin scattering in polymer melts. Besides, a new convenient expression for the dynamic structure function of the single Rouse chain in (q,p) representation is found.

Alkali Halide Microstructured Optical Fiber for X-Ray Detection

NASA Technical Reports Server (NTRS)

DeHaven, S. L.; Wincheski, R. A.; Albin, S.

2014-01-01

Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

Simple calculation of ab initio melting curves: Application to aluminum.

PubMed

Robert, Grégory; Legrand, Philippe; Arnault, Philippe; Desbiens, Nicolas; Clérouin, Jean

2015-03-01

We present a simple, fast, and promising method to compute the melting curves of materials with ab initio molecular dynamics. It is based on the two-phase thermodynamic model of Lin et al [J. Chem. Phys. 119, 11792 (2003)] and its improved version given by Desjarlais [Phys. Rev. E 88, 062145 (2013)]. In this model, the velocity autocorrelation function is utilized to calculate the contribution of the nuclei motion to the entropy of the solid and liquid phases. It is then possible to find the thermodynamic conditions of equal Gibbs free energy between these phases, defining the melting curve. The first benchmark on the face-centered cubic melting curve of aluminum from 0 to 300 GPa demonstrates how to obtain an accuracy of 5%-10%, comparable to the most sophisticated methods, for a much lower computational cost.

Nanotexturing of surfaces to reduce melting point.

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

Garcia, Ernest J.; Zubia, David; Mireles, Jose

2011-11-01

This investigation examined the use of nano-patterned structures on Silicon-on-Insulator (SOI) material to reduce the bulk material melting point (1414 C). It has been found that sharp-tipped and other similar structures have a propensity to move to the lower energy states of spherical structures and as a result exhibit lower melting points than the bulk material. Such a reduction of the melting point would offer a number of interesting opportunities for bonding in microsystems packaging applications. Nano patterning process capabilities were developed to create the required structures for the investigation. One of the technical challenges of the project was understandingmore » and creating the specialized conditions required to observe the melting and reshaping phenomena. Through systematic experimentation and review of the literature these conditions were determined and used to conduct phase change experiments. Melting temperatures as low as 1030 C were observed.« less

Silver-halide photographic materials based on nanoporous glasses

NASA Astrophysics Data System (ADS)

Andreeva, O. V.; Obyknovennaya, I. E.; Gavrilyuk, E. R.; Paramonov, A. A.; Kushnarenko, A. P.

2005-12-01

This paper discusses the results of an investigation of the recording of composite nanoporous photographic materials with a photosensitive composite made from silver halide in gelatin, developed and created at S. I. Vavilov State Optical Institute.

Study of formation mechanism of incipient melting in thixo-cast Al–Si–Cu–Mg alloys

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

Du, Kang, E-mail: du126kang@126.com; Zhu, Qiang, E-mail: zhu.qiang@grinm.com; Li, Daquan, E-mail: lidaquan@grinm.com

Mechanical properties of thixo-cast Al–Si–Cu–Mg alloys can be enhanced by T61 heat treatment. Copper and magnesium atoms in aluminum matrix can form homogeneously distributed precipitations after solution and aging treatment which harden the alloys. However, microsegregation of these alloying elements could form numerous tiny multi-compound phases during solidification. These phases could cause incipient melting defects in subsequent heat treatment process and degrade the macro-mechanical properties of productions. This study is to present heterogeneous distribution of Cu, Si, and Mg elements and formation of incipient melting defects (pores). In this study, incipient melting pores that occurred during solution treatment at variousmore » temperatures, even lower than common melting points of various intermetallic phases, were identified, in terms of a method of investigating the same surface area in the samples before and after solution treatment in a vacuum environment. The results also show that the incipient melting mostly originates at the clusters with fine intermetallic particles while also some at the edge of block-like Al{sub 2}Cu. The fine particles were determined being Al{sub 2}Cu, Al{sub 5}Cu{sub 2}Mg{sub 8}Si{sub 6} and Al{sub 8}Mg{sub 3}FeSi{sub 2}. Tendency of the incipient melting decreases with decreases of the width of the clusters. The formation mechanism of incipient melting pores in solution treatment process was discussed using both the Fick law and the LSW theory. Finally, a criterion of solution treatment to avoid incipient melting pores for the thixo-cast alloys is proposed. - Highlights: • In-situ comparison technique was used to analysis the change of eutectic phases. • The ralationship between eutectic phase size and incipient melting was studied. • Teat treatment criterion for higher incipient melting resistance was proposed.« less

Occurrence of silicate melt, carbonate-rich melt and fluid during medium pressure anatexis of metapelitic gneisses (Oberpfalz, Bavaria) revealed by melt and fluid inclusions study

NASA Astrophysics Data System (ADS)

Ferrero, Silvio; O'Brien, Patrick; Hecht, Lutz; Wunder, Bernd

2014-05-01

In the last decades our understanding of partial melting processes in the lower crust profited from the investigation of fluid inclusions (Touret et al., 2009) and more recently of anatectic melt inclusions (Cesare et al., 2011) within enclaves and high-grade terranes. The latter finding allowed us to directly analyse the original anatectic melt (Ferrero et al., 2012; Bartoli et al., 2013) preserved within peritectic phases, i.e. mainly garnet, but also ilmenite and spinel, before fractionation, mixing and contamination processes took place. Furthermore, the occurrence of primary fluid inclusions (FI) and anatectic melt inclusions (MI) within enclaves allowed the characterization of the COH fluid present during anatexis under fluid+melt immiscibility conditions (Ferrero et al., 2014). Primary crystallized MI, or "nanogranites", and FI have been identified to occur as clusters in garnet from stromatic migmatites (Zeilengneise) from Oberpfalz, Eastern Bavaria (Moldanubian Zone). During the late Carboniferous, these Grt+Bt+Sill+Crd+Spl metapelitic gneisses underwent HT/MP metamorphism, followed by a HT/LP event (Tanner & Behrmann, 1995). Nanogranites, ≤20 µm in size, consist of Qtz+Bt+Wm+Ab±Ap, and show abundant nanoporosity, localized in the quartz. Fluid inclusions are smaller, generally ≤10 µm, and contain CO2+N2+CH4 plus siderite, pyrophillite and cristobalite, mineral phases not observed in the surrounding rock or as mineral inclusion in garnet. Polycrystalline inclusions containing Cc+Wm+Opx±Qz, commonly ≤10 µm in diameter, occur in the same cluster with MI and FI. Microstructural features, negative-crystal shape and the well-developed crystalline faces of calcite within inclusions suggest that they may result from the crystallization of a carbonate-rich melt. The lack of arrays of carbonate-bearing MI, verified by cathodoluminiscence investigation, supports their primary nature, i.e. they formed during garnet growth. This would suggest the occurrence

THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER: AN INTERLABORATORY COMPARATIVE STUDY OF TWO METHODS

EPA Science Inventory

Total organic halide (TOX) analyzers are commonly used to measure the amount of dissolved halogenated organic byproducts in disinfected waters. Because of the lack of information on the identity of disinfection byproducts, rigorous testing of the dissolved organic halide (DOX) pr...

Two-Dimensional Materials for Halide Perovskite-Based Optoelectronic Devices.

PubMed

Chen, Shan; Shi, Gaoquan

2017-06-01

Halide perovskites have high light absorption coefficients, long charge carrier diffusion lengths, intense photoluminescence, and slow rates of non-radiative charge recombination. Thus, they are attractive photoactive materials for developing high-performance optoelectronic devices. These devices are also cheap and easy to be fabricated. To realize the optimal performances of halide perovskite-based optoelectronic devices (HPODs), perovskite photoactive layers should work effectively with other functional materials such as electrodes, interfacial layers and encapsulating films. Conventional two-dimensional (2D) materials are promising candidates for this purpose because of their unique structures and/or interesting optoelectronic properties. Here, we comprehensively summarize the recent advancements in the applications of conventional 2D materials for halide perovskite-based photodetectors, solar cells and light-emitting diodes. The examples of these 2D materials are graphene and its derivatives, mono- and few-layer transition metal dichalcogenides (TMDs), graphdiyne and metal nanosheets, etc. The research related to 2D nanostructured perovskites and 2D Ruddlesden-Popper perovskites as efficient and stable photoactive layers is also outlined. The syntheses, functions and working mechanisms of relevant 2D materials are introduced, and the challenges to achieving practical applications of HPODs using 2D materials are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unraveling the Stepwise Melting of an Ionic Liquid.

PubMed

Lima, Thamires A; Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C

2017-05-04

Differential scanning calorimetry, X-ray diffraction, and Raman spectroscopy were used to reveal the premelting events precursors of melting of the ionic liquid triethylsulfonium bis(trifluoromethanesufonyl)imide, [S 222 ][NTf 2 ]. On heating the crystalline phase of [S 222 ][NTf 2 ], melting occurs along a sequence of at least three steps. First, the crystalline long-range order breaks down, but local order is retained. The second step is characterized by conformational freedom of the ethyl chains of cations related to premelting of nonpolar domains, and the complete melting finally occurs when anions acquire conformational freedom. This work provides a microscopic view on the mechanism of melting of [S 222 ][NTf 2 ] in line with the picture of melting taking place as a sequence of structural changes. The results of this work shed light on the understanding of the complex melting process of ionic liquids.

Lattice dynamics and the nature of structural transitions in organolead halide perovskites

DOE PAGES

Comin, Riccardo; Crawford, Michael K.; Said, Ayman H.; ...

2016-09-09

Organolead halide perovskites are a family of hybrid organic-inorganic compounds whose remark- able optoelectronic properties have been under intensive scrutiny in recent years. Here we use inelastic X-ray scattering to study low-energy lattice excitations in single crystals of methylammonium lead iodide and bromide perovskites. Our ndings conrm the displacive nature of the cubic-to- tetragonal phase transition, which is further shown, using neutron and x-ray diraction, to be close to a tricritical point. The experimental sound speed, around 100-200 m/s, suggests that electron- phonon scattering is likely a limiting factor for further improvements in carrier mobility. Lastly, we detect quasistatic symmetry-breakingmore » nanodomains persisting well into the high-temperature cubic phase, possibly stabilized by local defects. These ndings reveal key structural properties of these materials, but also bear important implications for carrier dynamics across an extended temperature range relevant for photovoltaic applications.« less

Lattice dynamics and the nature of structural transitions in organolead halide perovskites

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

Comin, Riccardo; Crawford, Michael K.; Said, Ayman H.

Organolead halide perovskites are a family of hybrid organic-inorganic compounds whose remark- able optoelectronic properties have been under intensive scrutiny in recent years. Here we use inelastic X-ray scattering to study low-energy lattice excitations in single crystals of methylammonium lead iodide and bromide perovskites. Our ndings conrm the displacive nature of the cubic-to- tetragonal phase transition, which is further shown, using neutron and x-ray diraction, to be close to a tricritical point. The experimental sound speed, around 100-200 m/s, suggests that electron- phonon scattering is likely a limiting factor for further improvements in carrier mobility. Lastly, we detect quasistatic symmetry-breakingmore » nanodomains persisting well into the high-temperature cubic phase, possibly stabilized by local defects. These ndings reveal key structural properties of these materials, but also bear important implications for carrier dynamics across an extended temperature range relevant for photovoltaic applications.« less

Permeability and 3-Dimensional Melt Distribution in Partially Molten Rocks

NASA Astrophysics Data System (ADS)

Zhu, Wen-Lu; Gaetani, Glenn; Fusseis, Florian

2010-05-01

Quantitative knowledge of the distribution of small amounts of silicate melt in peridotite and of its influence on permeability are critical to our understanding of melt migration and segregation processes in the upper mantle, as well as interpretations of the geochemical and geophysical observations at ocean ridges. For a system containing a single solid phase of isotropic interfacial energy, chemical and mechanical equilibrium requires a constant mean curvature of solid-melt interfaces and a single dihedral angle. Under these conditions, a simple power-law relationship between permeability, grain size and melt fraction, has been derived [e.g., von Bargen and Waff, 1986]. However, microstructural observations on texturally equilibrated, partially molten rocks reveal that the melt distribution is more complex than predicted by the isotropic model. Several factors, such as non-hydrostatic stress, anisotropic interfacial energy, or the presence of a second solid phase, will alter the power-law relationship. Better estimates for the permeability of partially molten rock require an accurate assessment of 3-dimensional melt distribution at the grain-scale. Existing studies of melt distribution, carried out on 2-D slices through experimental charges, have produced divergent models for melt distribution at small melt fractions. While some studies conclude that small amounts of melt are distributed primarily along 3-grain junctions [e.g., Wark et al., 2003], others predict an important role for melt distribution along grain boundaries at low melt fractions [e.g., Faul 1997]. Using X-ray synchrotron microtomography, we have carried out the first high quality non-destructive imaging of 3-dimensional melt distribution in experimentally equilibrated olivine-basalt aggregates [Zhu et al., 2009]. Microtomographic images of melt distribution were obtained on 1 mm cylindrical cores with melt fractions of 0.2, 0.1, and 0.02, at a spatial resolution of 0.7 microns. Textual

3D Compressible Melt Transport with Adaptive Mesh Refinement

NASA Astrophysics Data System (ADS)

Dannberg, Juliane; Heister, Timo

2015-04-01

Melt generation and migration have been the subject of numerous investigations, but their typical time and length-scales are vastly different from mantle convection, which makes it difficult to study these processes in a unified framework. The equations that describe coupled Stokes-Darcy flow have been derived a long time ago and they have been successfully implemented and applied in numerical models (Keller et al., 2013). However, modelling magma dynamics poses the challenge of highly non-linear and spatially variable material properties, in particular the viscosity. Applying adaptive mesh refinement to this type of problems is particularly advantageous, as the resolution can be increased in mesh cells where melt is present and viscosity gradients are high, whereas a lower resolution is sufficient in regions without melt. In addition, previous models neglect the compressibility of both the solid and the fluid phase. However, experiments have shown that the melt density change from the depth of melt generation to the surface leads to a volume increase of up to 20%. Considering these volume changes in both phases also ensures self-consistency of models that strive to link melt generation to processes in the deeper mantle, where the compressibility of the solid phase becomes more important. We describe our extension of the finite-element mantle convection code ASPECT (Kronbichler et al., 2012) that allows for solving additional equations describing the behaviour of silicate melt percolating through and interacting with a viscously deforming host rock. We use the original compressible formulation of the McKenzie equations, augmented by an equation for the conservation of energy. This approach includes both melt migration and melt generation with the accompanying latent heat effects. We evaluate the functionality and potential of this method using a series of simple model setups and benchmarks, comparing results of the compressible and incompressible formulation and

The role of the “Casimir force analogue” at the microscopic processes of crystallization and melting

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

Chuvildeev, V.N., E-mail: chuvildeev@gmail.com; Semenycheva, A.V., E-mail: avsemenycheva@gmail.com

Melting (crystallization), a phase transition from a crystalline solid to a liquid state, is a common phenomenon in nature. We suggest a new factor, “the Casimir force analogue”, to describe mechanisms of melting and crystallization. The Casimir force analogue is a force occurring between the surfaces of solid and liquid phases of metals caused by different energy density of phonons of these phases. It explains abrupt changes in geometry and thermodynamic parameters at a melting point. “The Casimir force analogue” helps to estimate latent melting heat and to gain an insight into a solid–liquid transition problem.

Electron detachment energies in high-symmetry alkali halide solvated-electron anions

NASA Astrophysics Data System (ADS)

Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

2003-07-01

We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

Melting of the Abrikosov flux lattice in anisotropic superconductors

NASA Technical Reports Server (NTRS)

Beck, R. G.; Farrell, D. E.; Rice, J. P.; Ginsberg, D. M.; Kogan, V. G.

1992-01-01

It has been proposed that the Abrikosov flux lattice in high-Tc superconductors is melted over a significant fraction of the phase diagram. A thermodynamic argument is provided which establishes that the angular dependence of the melting temperature is controlled by the superconducting mass anisotropy. Using a low-frequency torsional-oscillator technique, this relationship has been tested in untwinned single-crystal YBa2Cu3O(7-delta). The results offer decisive support for the melting proposal.

Method For Synthesizing Extremely High-Temperature Melting Materials

DOEpatents

Saboungi, Marie-Louise; Glorieux, Benoit

2005-11-22

The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as borides, carbides and transition-metal, lanthanide and actinide oxides, using an Aerodynamic Levitator and a laser. The object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce, without the use of containers, allowing the manipulation of the phase (amorphous/crystalline/metastable) and permitting changes of the environment such as different gaseous compositions.

Method for synthesizing extremely high-temperature melting materials

DOEpatents

Saboungi, Marie-Louise; Glorieux, Benoit

2007-11-06

The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as carbides and transition-metal, lanthanide and actinide oxides, using an aerodynamic levitator and a laser. The object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce, without the use of containers, allowing the manipulation of the phase (amorphous/crystalline/metastable) and permitting changes of the environment such as different gaseous compositions.

Method for Synthesizing Extremeley High Temperature Melting Materials

DOEpatents

Saboungi, Marie-Louise and Glorieux, Benoit

2005-11-22

The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as borides, carbides and transition-metal, lanthanide and actinide oxides, using an Aerodynamic Levitator and a laser. The object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce, without the use of containers, allowing the manipulation of the phase (amorphous/crystalline/metastable) and permitting changes of the environment such as different gaseous compositions.

Remarkably Enhancing Green-Excitation Efficiency for Solar Energy Utilization: Red Phosphors Ba2ZnS3:Eu2+, X- Co-Doped Halide Ions (X = Cl, Br, I).

PubMed

Luo, Tingting; Du, Yun; Qiu, Zhongxian; Li, Yanmei; Wang, Xiaofang; Zhou, Wenli; Zhang, Jilin; Yu, Liping; Lian, Shixun

2017-05-15

Eu 2+ -activated Ba 2 ZnS 3 has been reported as a red phosphor with a broad emission band peaking at 650 nm under blue excitation for white-LED. In this study, Ba 2 ZnS 3 :Eu 2+ , X - (X = F, Cl, Br, I) phosphors doped with halide ions were prepared by traditional high-temperature solid-state reaction. Phase identification of powders was performed by X-ray powder diffraction analysis, confirming the existence of single-phase Ba 2 ZnS 3 crystals without dopant. The corresponding excitation spectra showed an additional broad band in the green region peaking at 550 nm when the phosphor was halogenated except by the smallest F - . It was proved that the green-excitation efficiency successively strengthened from Cl - , to Br - , to I - , which suggested larger halide ions made a greater contribution to the further splitting of the t 2g energy level of the doped Eu 2+ ions in the host Ba 2 ZnS 3 , and the optimized formula Ba 1.995 ZnS 2.82 :Eu 2+ 0.005 , I - 0.18 showed a potential application in solar spectral conversion for agricultural greenhouse and solar cell. Defect chemistry theory and crystal field theory provided insights into the key role of halide ions in enhancing green-excitation efficiency.

High-pressure melting of MgSiO3.

PubMed

Belonoshko, A B; Skorodumova, N V; Rosengren, A; Ahuja, R; Johansson, B; Burakovsky, L; Preston, D L

2005-05-20

The melting curve of MgSiO(3) perovskite has been determined by means of ab initio molecular dynamics complemented by effective pair potentials, and a new phenomenological model of melting. Using first principles ground state calculations, we find that the MgSiO(3) perovskite phase transforms into post perovskite at pressures above 100 GPa, in agreement with recent theoretical and experimental studies. We find that the melting curve of MgSiO(3), being very steep at pressures below 60 GPa, rapidly flattens on increasing pressure. The experimental controversy on the melting of the MgSiO(3) perovskite at high pressures is resolved, confirming the data by Zerr and Boehler.

A Two-Dimensional Liquid Structure Explains the Elevated Melting Temperatures of Gallium Nanoclusters.

PubMed

Steenbergen, Krista G; Gaston, Nicola

2016-01-13

Melting in finite-sized materials differs in two ways from the solid-liquid phase transition in bulk systems. First, there is an inherent scaling of the melting temperature below that of the bulk, known as melting point depression. Second, at small sizes changes in melting temperature become nonmonotonic and show a size-dependence that is sensitive to the structure of the particle. Melting temperatures that exceed those of the bulk material have been shown to occur for a very limited range of nanoclusters, including gallium, but have still never been ascribed a convincing physical explanation. Here, we analyze the structure of the liquid phase in gallium clusters based on molecular dynamics simulations that reproduce the greater-than-bulk melting behavior observed in experiments. We observe persistent nonspherical shape distortion indicating a stabilization of the surface, which invalidates the paradigm of melting point depression. This shape distortion suggests that the surface acts as a constraint on the liquid state that lowers its entropy relative to that of the bulk liquid and thus raises the melting temperature.

Synthesis of Cesium Lead Halide Perovskite Nanocrystals in a Droplet-Based Microfluidic Platform: Fast Parametric Space Mapping.

PubMed

Lignos, Ioannis; Stavrakis, Stavros; Nedelcu, Georgian; Protesescu, Loredana; deMello, Andrew J; Kovalenko, Maksym V

2016-03-09

Prior to this work, fully inorganic nanocrystals of cesium lead halide perovskite (CsPbX3, X = Br, I, Cl and Cl/Br and Br/I mixed halide systems), exhibiting bright and tunable photoluminescence, have been synthesized using conventional batch (flask-based) reactions. Unfortunately, our understanding of the parameters governing the formation of these nanocrystals is still very limited due to extremely fast reaction kinetics and multiple variables involved in ion-metathesis-based synthesis of such multinary halide systems. Herein, we report the use of a droplet-based microfluidic platform for the synthesis of CsPbX3 nanocrystals. The combination of online photoluminescence and absorption measurements and the fast mixing of reagents within such a platform allows the rigorous and rapid mapping of the reaction parameters, including molar ratios of Cs, Pb, and halide precursors, reaction temperatures, and reaction times. This translates into enormous savings in reagent usage and screening times when compared to analogous batch synthetic approaches. The early-stage insight into the mechanism of nucleation of metal halide nanocrystals suggests similarities with multinary metal chalcogenide systems, albeit with much faster reaction kinetics in the case of halides. Furthermore, we show that microfluidics-optimized synthesis parameters are also directly transferrable to the conventional flask-based reaction.

Evidence for melt partitioning between olivine and orthopyroxene in partially molten harzburgite

NASA Astrophysics Data System (ADS)

Miller, K.; Zhu, W.; Montesi, L. G.; Le Roux, V.; Gaetani, G. A.

2013-12-01

During melting at mid-ocean ridges, melt is driven into an equilibrium, minimum-energy configuration by surface energy gradients between solid-solid and solid-liquid phase boundaries. Such a configuration, where melt is mostly restricted to three and four-grain junctions, acts as a porous medium through which melt can percolate to the surface. For a monomineralic system, melt is distributed evenly among all grains. However, in mineralogical heterogeneous systems, melt partitions unevenly between the various solid phases to minimize the total energy of the system. In a ocean ridge melting environment, where olivine is often juxtaposed against orthopyroxene (opx), lithologic partitioning is expected to turn olivine-rich regions into high-permeability conduits, through which melt can be quickly extracted, drastically increasing the permeability of the mantle [Zhu and Hirth, 2003]. Lithologic partitioning has been demonstrated in experiments using analogue systems [Watson, 1999]; however, to date, no experiment has confirmed its existence in partially molten mantle systems. We present experimental results that determine the degree of melt partitioning between olivine and opx in partially molten harzburgites. Samples were prepared from a powdered mixture of oxides and carbonates and then hot-pressed in a solid-media piston-cylinder apparatus at 1350°C and 1.5GPa [Zhu et al., 2011] to achieve an 82/18 vol. % ratio of olivine to opx. Prior to hot-pressing, basalt was added to the powdered mixtures in various proportions to test for lithologic partitioning across a range of melt fractions. Three-dimensional, 700nm-resolution images of our samples were obtained using synchrotron X-ray microtomography on the 2BM station of the Advanced Photon Source at Argonne National Labs. Image data were filtered using an anisotropic diffusion filter to enhance phase contrast and then segmented to produce binary representations of each phase. In order to quantitatively demonstrate

Effects of halide ions on photodegradation of sulfonamide antibiotics: Formation of halogenated intermediates.

PubMed

Li, Yingjie; Qiao, Xianliang; Zhang, Ya-Nan; Zhou, Chengzhi; Xie, Huaijun; Chen, Jingwen

2016-10-01

The occurrence of sulfonamide antibiotics (SAs) in estuarine waters urges insights into their environmental fate for ecological risk assessment. Although many studies focused on the photochemical behavior of SAs, yet the effects of halide ions relevant to estuarine and marine environments on their photodegradation have been poorly understood. Here, we investigated the effects of halide ions on the photodegradation of SAs with sulfapyridine, sulfamethazine, and sulfamethoxazole as representative compounds. Results showed that halide ions did not significantly impact the photodegradation of sulfapyridine and sulfamethoxazole, while they significantly promoted the photodegradation of sulfamethazine. Further experiments found that ionic strength applied with NaClO4 significantly enhanced the photodegradation of the SAs, which was attributed to the decreased quenching rate constant of the triplet-excited SAs ((3)SA(∗)). Compared with ionic strength, specific Cl(-) effects retarded the photodegradation of the SAs. Our study found that triplet-excited sulfamethazine can oxidize halide ions to produce halogen radicals, subsequently leading to the halogenation of sulfamethazine, which was confirmed by the identification of both chlorinated and brominated intermediates. These results indicate that halide ions play an important role in the photochemical behavior of some SAs in estuarine waters and seawater. The occurrence of halogenation for certain organic pollutants can be predicted by comparing the oxidation potentials of triplet-excited contaminants with those of halogen radicals. Our findings are helpful in understanding the photochemical behavior and assessing the ecological risks of SAs and other organic pollutants in estuarine and marine environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations.

PubMed

Sum, Tze Chien; Mathews, Nripan; Xing, Guichuan; Lim, Swee Sien; Chong, Wee Kiang; Giovanni, David; Dewi, Herlina Arianita

2016-02-16

Lead halide perovskite solar cells are presently the forerunner among the third generation solution-processed photovoltaic technologies. With efficiencies exceeding 20% and low production costs, they are prime candidates for commercialization. Critical insights into their light harvesting, charge transport, and loss mechanisms have been gained through time-resolved optical probes such as femtosecond transient absorption spectroscopy (fs-TAS), transient photoluminescence spectroscopy, and time-resolved terahertz spectroscopy. Specifically, the discoveries of long balanced electron-hole diffusion lengths and gain properties in halide perovskites underpin their significant roles in uncovering structure-function relations and providing essential feedback for materials development and device optimization. In particular, fs-TAS is becoming increasingly popular in perovskite characterization studies, with commercial one-box pump-probe systems readily available as part of a researcher's toolkit. Although TAS is a powerful probe in the study of charge dynamics and recombination mechanisms, its instrumentation and data interpretation can be daunting even for experienced researchers. This issue is exacerbated by the sensitive nature of halide perovskites where the kinetics are especially susceptible to pump fluence, sample preparation and handling and even degradation effects that could lead to disparate conclusions. Nonetheless, with end-users having a clear understanding of TAS's capabilities, subtleties, and limitations, cutting-edge work with deep insights can still be performed using commercial setups as has been the trend for ubiquitous spectroscopy instruments like absorption, fluorescence, and transient photoluminescence spectrometers. Herein, we will first briefly examine the photophysical processes in lead halide perovskites, highlighting their novel properties. Next, we proceed to give a succinct overview of the fundamentals of pump-probe spectroscopy in relation

Methyl halide fluxes from tropical plants under controlled radiation and temperature regimes

NASA Astrophysics Data System (ADS)

Blei, Emanuel; Yokouchi, Yoko; Saito, Takuya; Nozoe, Susumu

2015-04-01

Methyl halides (CH3Cl, CH3Br, CH3I) contribute significantly to the halogen burden of the atmosphere and have the potential to influence the stratospheric ozone layer through their catalytic effect in the Chapman cycle. As such they have been studied over the years, and many plants and biota have been examined for their potential to act as a source of these gases. One of the potentially largest terrestrial sources identified was tropical vegetation such as tropical ferns and Dipterocarp trees. Most of these studies concentrated on the identification and quantification of such fluxes rather than their characteristics and often the chambers used in these studies were either opaque or only partially transparent to the full solar spectrum. Therefore it is not certain to which degree emissions of methyl halides are innate to the plants and how much they might vary due to radiation or temperature conditions inside the enclosures. In a separate development it had been proposed that UV-radiation could cause live plant materials to be become emitters of methane even under non-anoxic conditions. As methane is chemically very similar to methyl halides and had been proposed to be produced from methyl-groups ubiquitously found in plant cell material there is a relatively good chance that such a production mechanism would also apply to methyl halides. To test whether radiation can affect elevated emissions of methyl halides from plant materials and to distinguish this from temperature effects caused by heat build-up in chambers a set of controlled laboratory chamber enclosures under various radiation and temperature regimes was conducted on four different tropical plant species (Magnolia grandiflora, Cinnamonum camphora, Cyathea lepifera, Angiopteris lygodiifolia), the latter two of which had previously been identified as strong methyl halide emitters. Abscised leaf samples of these species were subjected to radiation treatments such UV-B, UV-A and broad spectrum radiation

Melting behavior of SnI4 reexamined

NASA Astrophysics Data System (ADS)

Fuchizaki, Kazuhiro

2013-12-01

The low-pressure crystalline phase of a molecular crystal, SnI4, has a rising melting curve that breaks abruptly at around 1.5 GPa, beyond which it becomes almost flat, with a slight maximum at about 3 GPa. Although the overall aspect of this melting curve can be captured by the Kumari-Dass-Kechin equation, the values for the parameters involved in the equation were definitely different from those predicted on the basis of the Clapeyron-Clausius relationship. On the other hand, the accuracy of our experimental data prevented us from judging whether the parameters are derivable from the Lindemann melting law, as shown independently by Kumari and Dass, and by Kechin. The Kraut-Kennedy and Magalinskii-Zubov relationships seem to be valid in the low-pressure region where the melting curve is rising. The breakdown of these relationships suggests a qualitative change in the intermolecular interaction upon compression, thereby making the melting behavior unusual.

Lanthanum halide scintillators for time-of-flight 3-D pet

DOEpatents

Karp, Joel S [Glenside, PA; Surti, Suleman [Philadelphia, PA

2008-06-03

A Lanthanum Halide scintillator (for example LaCl.sub.3 and LaBr.sub.3) with fast decay time and good timing resolution, as well as high light output and good energy resolution, is used in the design of a PET scanner. The PET scanner includes a cavity for accepting a patient and a plurality of PET detector modules arranged in an approximately cylindrical configuration about the cavity. Each PET detector includes a Lanthanum Halide scintillator having a plurality of Lanthanum Halide crystals, a light guide, and a plurality of photomultiplier tubes arranged respectively peripherally around the cavity. The good timing resolution enables a time-of-flight (TOF) PET scanner to be developed that exhibits a reduction in noise propagation during image reconstruction and a gain in the signal-to-noise ratio. Such a PET scanner includes a time stamp circuit that records the time of receipt of gamma rays by respective PET detectors and provides timing data outputs that are provided to a processor that, in turn, calculates time-of-flight (TOF) of gamma rays through a patient in the cavity and uses the TOF of gamma rays in the reconstruction of images of the patient.

Depth profile of halide anions under highly charged biological membrane

NASA Astrophysics Data System (ADS)

Sung, Woongmo; Wang, Wenjie; Lee, Jonggwan; Vaknin, David; Kim, Doseok

2015-03-01

Halide ion (Cl- and I-) distribution under a cationic Langmuir monolayer consisting of 1,2-dipalmitoyl-3 trimethylammonium-propane (DPTAP) molecules was investigated by vibrational sum-frequency generation (VSFG) and X-ray spectroscopy. From VSFG spectra, it was observed that large halide anions (I-) screen surface charge more efficiently so that interfacial water alignment becomes more randomized. On the other hand, number density of ions directly measured by X-ray fluorescence spectroscopy at grazing incidence angle reveals that the ion densities within 6 ~ 8 nm are the same for both I- and Cl-. Since the observed ion densities in both cases are almost equal to the charge density of the DPTAP monolayer, we propose that larger halide anions are attracted closer to the surface making direct binding with the charged headgroups of the molecules in the monolayer, accomplishing charge neutrality in short distance. This direct adsorption of anions also disturbs the monolayer structure both in terms of the conformation of alkyl chains and the vertical configuration of the monolayer, with iodine having the stronger effect. Our study shows that the length scale that ions neutralize a charged interface varies significantly and specifically even between monovalent ions.

Influence of Halide Solutions on Collagen Networks: Measurements of Physical Properties by Atomic Force Microscopy

PubMed Central

Kempe, André; Lackner, Maximilian

2016-01-01

The influence of aqueous halide solutions on collagen coatings was tested. The effects on resistance against indentation/penetration on adhesion forces were measured by atomic force microscopy (AFM) and the change of Young's modulus of the coating was derived. Comparative measurements over time were conducted with halide solutions of various concentrations. Physical properties of the mesh-like coating generally showed large variability. Starting with a compact set of physical properties, data disperse after minutes. A trend of increase in elasticity and permeability was found for all halide solutions. These changes were largest in NaI, displaying a logical trend with ion size. However a correlation with concentration was not measured. Adhesion properties were found to be independent of mechanical properties. The paper also presents practical experience for AFM measurements of soft tissue under liquids, particularly related to data evaluation. The weakening in physical strength found after exposure to halide solutions may be interpreted as widening of the network structure or change in the chemical properties in part of the collagen fibres (swelling). In order to design customized surface coatings at optimized conditions also for medical applications, halide solutions might be used as agents with little impact on the safety of patients. PMID:27721994

Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

DOEpatents

Rohrmann, Charles A.

1978-01-01

A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

Alkali halide microstructured optical fiber for X-ray detection

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

DeHaven, S. L., E-mail: stanton.l.dehaven@nasa.gov, E-mail: russel.a.wincheski@nasa.gov; Wincheski, R. A., E-mail: stanton.l.dehaven@nasa.gov, E-mail: russel.a.wincheski@nasa.gov; Albin, S., E-mail: salbin@nsu.edu

Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. Themore » results and associated materials difference are discussed.« less

Microstructures define melting of molybdenum at high pressures

NASA Astrophysics Data System (ADS)

Hrubiak, Rostislav; Meng, Yue; Shen, Guoyin

2017-03-01

High-pressure melting anchors the phase diagram of a material, revealing the effect of pressure on the breakdown of the ordering of atoms in the solid. An important case is molybdenum, which has long been speculated to undergo an exceptionally steep increase in melting temperature when compressed. On the other hand, previous experiments showed nearly constant melting temperature as a function of pressure, in large discrepancy with theoretical expectations. Here we report a high-slope melting curve in molybdenum by synchrotron X-ray diffraction analysis of crystalline microstructures, generated by heating and subsequently rapidly quenching samples in a laser-heated diamond anvil cell. Distinct microstructural changes, observed at pressures up to 130 gigapascals, appear exclusively after melting, thus offering a reliable melting criterion. In addition, our study reveals a previously unsuspected transition in molybdenum at high pressure and high temperature, which yields highly textured body-centred cubic nanograins above a transition temperature.

Microstructures define melting of molybdenum at high pressures

PubMed Central

Hrubiak, Rostislav; Meng, Yue; Shen, Guoyin

2017-01-01

High-pressure melting anchors the phase diagram of a material, revealing the effect of pressure on the breakdown of the ordering of atoms in the solid. An important case is molybdenum, which has long been speculated to undergo an exceptionally steep increase in melting temperature when compressed. On the other hand, previous experiments showed nearly constant melting temperature as a function of pressure, in large discrepancy with theoretical expectations. Here we report a high-slope melting curve in molybdenum by synchrotron X-ray diffraction analysis of crystalline microstructures, generated by heating and subsequently rapidly quenching samples in a laser-heated diamond anvil cell. Distinct microstructural changes, observed at pressures up to 130 gigapascals, appear exclusively after melting, thus offering a reliable melting criterion. In addition, our study reveals a previously unsuspected transition in molybdenum at high pressure and high temperature, which yields highly textured body-centred cubic nanograins above a transition temperature. PMID:28248309

High-Efficiency Flexible Solar Cells Based on Organometal Halide Perovskites.

PubMed

Wang, Yuming; Bai, Sai; Cheng, Lu; Wang, Nana; Wang, Jianpu; Gao, Feng; Huang, Wei

2016-06-01

Flexible and light-weight solar cells are important because they not only supply power to wearable and portable devices, but also reduce the transportation and installation cost of solar panels. High-efficiency organometal halide perovskite solar cells can be fabricated by a low-temperature solution process, and hence are promising for flexible-solar-cell applications. Here, the development of perovskite solar cells is briefly discussed, followed by the merits of organometal halide perovskites as promising candidates as high-efficiency, flexible, and light-weight photovoltaic materials. Afterward, recent developments of flexible solar cells based on perovskites are reviewed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pathway from subducting slab to surface for melt and fluids beneath Mount Rainier.

PubMed

McGary, R Shane; Evans, Rob L; Wannamaker, Philip E; Elsenbeck, Jimmy; Rondenay, Stéphane

2014-07-17

Convergent margin volcanism originates with partial melting, primarily of the upper mantle, into which the subducting slab descends. Melting of this material can occur in one of two ways. The flow induced in the mantle by the slab can result in upwelling and melting through adiabatic decompression. Alternatively, fluids released from the descending slab through dehydration reactions can migrate into the hot mantle wedge, inducing melting by lowering the solidus temperature. The two mechanisms are not mutually exclusive. In either case, the buoyant melts make their way towards the surface to reside in the crust or to be extruded as lava. Here we use magnetotelluric data collected across the central state of Washington, USA, to image the complete pathway for the fluid-melt phase. By incorporating constraints from a collocated seismic study into the magnetotelluric inversion process, we obtain superior constraints on the fluids and melt in a subduction setting. Specifically, we are able to identify and connect fluid release at or near the top of the slab, migration of fluids into the overlying mantle wedge, melting in the wedge, and transport of the melt/fluid phase to a reservoir in the crust beneath Mt Rainier.

Pathway from subducting slab to surface for melt and fluids beneath Mount Rainier

NASA Astrophysics Data System (ADS)

McGary, R. Shane; Evans, Rob L.; Wannamaker, Philip E.; Elsenbeck, Jimmy; Rondenay, Stéphane

2014-07-01

Convergent margin volcanism originates with partial melting, primarily of the upper mantle, into which the subducting slab descends. Melting of this material can occur in one of two ways. The flow induced in the mantle by the slab can result in upwelling and melting through adiabatic decompression. Alternatively, fluids released from the descending slab through dehydration reactions can migrate into the hot mantle wedge, inducing melting by lowering the solidus temperature. The two mechanisms are not mutually exclusive. In either case, the buoyant melts make their way towards the surface to reside in the crust or to be extruded as lava. Here we use magnetotelluric data collected across the central state of Washington, USA, to image the complete pathway for the fluid-melt phase. By incorporating constraints from a collocated seismic study into the magnetotelluric inversion process, we obtain superior constraints on the fluids and melt in a subduction setting. Specifically, we are able to identify and connect fluid release at or near the top of the slab, migration of fluids into the overlying mantle wedge, melting in the wedge, and transport of the melt/fluid phase to a reservoir in the crust beneath Mt Rainier.

Adsorption of molecular additive onto lead halide perovskite surfaces: A computational study on Lewis base thiophene additive passivation

NASA Astrophysics Data System (ADS)

Zhang, Lei; Yu, Fengxi; Chen, Lihong; Li, Jingfa

2018-06-01

Organic additives, such as the Lewis base thiophene, have been successfully applied to passivate halide perovskite surfaces, improving the stability and properties of perovskite devices based on CH3NH3PbI3. Yet, the detailed nanostructure of the perovskite surface passivated by additives and the mechanisms of such passivation are not well understood. This study presents a nanoscopic view on the interfacial structure of an additive/perovskite interface, consisting of a Lewis base thiophene molecular additive and a lead halide perovskite surface substrate, providing insights on the mechanisms that molecular additives can passivate the halide perovskite surfaces and enhance the perovskite-based device performance. Molecular dynamics study on the interactions between water molecules and the perovskite surfaces passivated by the investigated additive reveal the effectiveness of employing the molecular additives to improve the stability of the halide perovskite materials. The additive/perovskite surface system is further probed via molecular engineering the perovskite surfaces. This study reveals the nanoscopic structure-property relationships of the halide perovskite surface passivated by molecular additives, which helps the fundamental understanding of the surface/interface engineering strategies for the development of halide perovskite based devices.

Size-Dependent Melting Behavior of Colloidal In, Sn, and Bi Nanocrystals

PubMed Central

Liu, Minglu; Wang, Robert Y.

2015-01-01

Colloidal nanocrystals are a technologically important class of nanostructures whose phase change properties have been largely unexplored. Here we report on the melting behavior of In, Sn, and Bi nanocrystals dispersed in a polymer matrix. This polymer matrix prevents the nanocrystals from coalescing with one another and enables previously unaccessed observations on the melting behavior of colloidal nanocrystals. We measure the melting temperature, melting enthalpy, and melting entropy of colloidal nanocrystals with diameters of approximately 10 to 20 nm. All of these properties decrease as nanocrystal size decreases, although the depression rate for melting temperature is comparatively slower than that of melting enthalpy and melting entropy. We also observe an elevated melting temperature during the initial melt-freeze cycle that we attribute to surface stabilization from the organic ligands on the nanocrystal surface. Broad endothermic melting valleys and very large supercoolings in our calorimetry data suggest that colloidal nanocrystals exhibit a significant amount of surface pre-melting and low heterogeneous nucleation probabilities during freezing. PMID:26573146

Non-Potassic Melts In CMAS-CO2-H2O-K2O Model Peridotite

NASA Astrophysics Data System (ADS)

Buisman, I.; Walter, M. J.; Keshav, S.

2009-12-01

Volatile mediated model systems have been fundamental in shaping our knowledge about the way we view melting phase relations of peridotite at various depths in the Earth. Volatiles not only affect the melting temperatures, but the resulting liquids are, in some case, dramatically different than those witnessed in melting of dry peridotite. For example, the influence of CO2 and H2O on the melting phase relations of model peridotite shows a remarkable decrease in the solidus temperatures when compared to the dry peridotite (Gudfinnsson and Presnall, 2005). These model systems illustrate a gradational change above the solidus from carbonatites to kimberlites over several hundreds of degrees. Group-II kimberlites are ultrapotassic rocks with high water content where the mineral phlogopite is abundant. To get a better understanding of the melting phase relations related to carbonatitic and kimberlitic magmas, K2O was added to the system CMAS-CO2-H2O. In these systems, fluid and melt can co-exist in P-T space. However, from past studies, it is also known that in hydrous systems, both the fluid and melt will become indistinguishable from one another creating a singularity (second critical endpoint). Starting from the solidus located in six components (Keshav and Gudfinnsson, AGU abstract, 2009), with seven phases, melting phase relations in CMAS-CO2-H2O-K2O involving, fo-opx-cpx-garnet-carbonate-melt-fluid, are divariant. Fluid was recognized with the observation of large cavities seen in exposed capsules. Moreover, the presence of bright, needle-like grains found in large cavities in backscattered images implies the presence of solute in the fluid phase. Significantly, liquids on this divariant region have about 1000 ppm K2O, and so is the case with accompanying cpx. Hence, with this non-interesting amount of K2O in the mentioned phases, fluid must have all the potassium. At 30 kbar/1100C, with fo-opx-cpx-garnet-carbonate-phlogopite-melt-fluid, the melting phase

The microdopant effects of surfactant elements on structure-phase transitions during the rapid quenched crystallization of Fe-C-based melts

NASA Astrophysics Data System (ADS)

Polukhin, V. A.; Belyakova, R. M.; Rigmant, L. K.

2008-02-01

The nature of microdopant effects of surfactant Te and H2 reagents on structure-phase transitions in rapidly quenched and crystallized eutectic Fe-C-based melts were studied by experimental and computer methods. On the base of results of statistic-geometrical analysis the new information about the structure changes in multi-scaling systems -from meso- to nano-ones were obtained.

75 FR 5544 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures: Public...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-02-03

...-2009-BT-STD-0018] RIN 1904-AC00 Energy Conservation Program: Energy Conservation Standards for Metal... certain metal halide lamp fixtures. This document announces that the period for submitting comments on the... identify the Framework Document for energy conservation standards for metal halide lamp fixtures and...

An observational and thermodynamic investigation of carbonate partial melting

NASA Astrophysics Data System (ADS)

Floess, David; Baumgartner, Lukas P.; Vonlanthen, Pierre

2015-01-01

Melting experiments available in the literature show that carbonates and pelites melt at similar conditions in the crust. While partial melting of pelitic rocks is common and well-documented, reports of partial melting in carbonates are rare and ambiguous, mainly because of intensive recrystallization and the resulting lack of criteria for unequivocal identification of melting. Here we present microstructural, textural, and geochemical evidence for partial melting of calcareous dolomite marbles in the contact aureole of the Tertiary Adamello Batholith. Petrographic observations and X-ray micro-computed tomography (X-ray μCT) show that calcite crystallized either in cm- to dm-scale melt pockets, or as an interstitial phase forming an interconnected network between dolomite grains. Calcite-dolomite thermometry yields a temperature of at least 670 °C, which is well above the minimum melting temperature of ∼600 °C reported for the CaO-MgO-CO2-H2O system. Rare-earth element (REE) partition coefficients (KDcc/do) range between 9-35 for adjacent calcite-dolomite pairs. These KD values are 3-10 times higher than equilibrium values between dolomite and calcite reported in the literature. They suggest partitioning of incompatible elements into a melt phase. The δ18O and δ13C isotopic values of calcite and dolomite support this interpretation. Crystallographic orientations measured by electron backscattered diffraction (EBSD) show a clustering of c-axes for dolomite and interstitial calcite normal to the foliation plane, a typical feature for compressional deformation, whereas calcite crystallized in pockets shows a strong clustering of c-axes parallel to the pocket walls, suggesting that it crystallized after deformation had stopped. All this together suggests the formation of partial melts in these carbonates. A Schreinemaker analysis of the experimental data for a CO2-H2O fluid-saturated system indeed predicts formation of calcite-rich melt between 650-880 °C, in

Melting and Freezing of Metal Clusters

NASA Astrophysics Data System (ADS)

Aguado, Andrés; Jarrold, Martin F.

2011-05-01

Recent developments allow heat capacities to be measured for size-selected clusters isolated in the gas phase. For clusters with tens to hundreds of atoms, the heat capacities determined as a function of temperature usually have a single peak attributed to a melting transition. The melting temperatures and latent heats show large size-dependent fluctuations. In some cases, the melting temperatures change by hundreds of degrees with the addition of a single atom. Theory has played a critical role in understanding the origin of the size-dependent fluctuations, and in understanding the properties of the liquid-like and solid-like states. In some cases, the heat capacities have extra features (an additional peak or a dip) that reveal a more complex behavior than simple melting. In this article we provide a description of the methods used to measure the heat capacities and provide an overview of the experimental and theoretical results obtained for sodium and aluminum clusters.

Polar-solvent-free colloidal synthesis of highly luminescent alkylammonium lead halide perovskite nanocrystals

NASA Astrophysics Data System (ADS)

Vybornyi, Oleh; Yakunin, Sergii; Kovalenko, Maksym V.

2016-03-01

A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2.A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2. Electronic supplementary information (ESI) available: Materials and methods, additional figures. See DOI: 10.1039/c5nr06890h

Random pinning elucidates the nature of melting transition in two-dimensional core-softened potential system

NASA Astrophysics Data System (ADS)

Tsiok, E. N.; Fomin, Y. D.; Ryzhov, V. N.

2018-01-01

Despite about forty years of investigations, the nature of the melting transition in two dimensions is not completely clear. In the framework of the most popular Berezinskii-Kosterlitz-Thouless-Halperin-Nelson-Young (BKTHNY) theory, 2D systems melt through two continuous Berezinskii-Kosterlitz-Thouless (BKT) transitions with intermediate hexatic phase. The conventional first-order transition is also possible. On the other hand, recently on the basis of computer simulations the new melting scenario was proposed with continuous BKT type solid-hexatic transition and first order hexatic-liquid transition. However, in the simulations the hexatic phase is extremely narrow that makes its study difficult. In the present paper, we propose to apply the random pinning to investigate the hexatic phase in more detail. The results of molecular dynamics simulations of two dimensional system having core-softened potentials with narrow repulsive step which is similar to the soft disk system are outlined. The system has a small fraction of pinned particles giving quenched disorder. Random pinning widens the hexatic phase without changing the melting scenario and gives the possibility to study the behavior of the diffusivity and order parameters in the vicinity of the melting transition and inside the hexatic phase.

Steric engineering of metal-halide perovskites with tunable optical band gaps

NASA Astrophysics Data System (ADS)

Filip, Marina R.; Eperon, Giles E.; Snaith, Henry J.; Giustino, Feliciano

2014-12-01

Owing to their high energy-conversion efficiency and inexpensive fabrication routes, solar cells based on metal-organic halide perovskites have rapidly gained prominence as a disruptive technology. An attractive feature of perovskite absorbers is the possibility of tailoring their properties by changing the elemental composition through the chemical precursors. In this context, rational in silico design represents a powerful tool for mapping the vast materials landscape and accelerating discovery. Here we show that the optical band gap of metal-halide perovskites, a key design parameter for solar cells, strongly correlates with a simple structural feature, the largest metal-halide-metal bond angle. Using this descriptor we suggest continuous tunability of the optical gap from the mid-infrared to the visible. Precise band gap engineering is achieved by controlling the bond angles through the steric size of the molecular cation. On the basis of these design principles we predict novel low-gap perovskites for optimum photovoltaic efficiency, and we demonstrate the concept of band gap modulation by synthesising and characterising novel mixed-cation perovskites.

Tailoring Oxygen Sensitivity with Halide Substitution in Difluoroboron Dibenzoylmethane Polylactide Materials

PubMed Central

DeRosa, Christopher A.; Kerr, Caroline; Fan, Ziyi; Kolpaczynska, Milena; Mathew, Alexander S.; Evans, Ruffin E.; Zhang, Guoqing; Fraser, Cassandra L.

2015-01-01

The dual-emissive properties of solid-state difluoroboron β-diketonate-poly(lactic acid) (BF2bdkPLA) materials have been utilized for biological oxygen sensing. In this work, BF2dbm(X)PLA materials were synthesized, where X = H, F, Cl, Br, and I. The effects of changing the halide substituent and PLA polymer chain length on the optical properties in dilute CH2Cl2 solutions and solid-state polymer films were studied. These luminescent materials show fluorescence, phosphorescence, and lifetime tunability on the basis of molecular weight, as well as lifetime modulation via the halide substituent. Short BF2dbm(Br)PLA (6.0 kDa) and both short and long BF2dbm(I)PLA polymers (6.0 or 20.3 kDa) have fluorescence and intense phosphorescence ideal for ratiometric oxygen sensing. The lighter halide-dye polymers with hydrogen, fluorine, and chlorine substitution have longer phosphorescence lifetimes and can be utilized as ultrasensitive oxygen sensors. Photostability was also analyzed for the polymer films. PMID:26480236

2D halide perovskite-based van der Waals heterostructures: contact evaluation and performance modulation

NASA Astrophysics Data System (ADS)

Guo, Yaguang; Saidi, Wissam A.; Wang, Qian

2017-09-01

Halide perovskites and van der Waals (vdW) heterostructures are both of current interest owing to their novel properties and potential applications in nano-devices. Here, we show the great potential of 2D halide perovskite sheets (C4H9NH3)2PbX4 (X  =  Cl, Br and I) that were synthesized recently (Dou et al 2015 Science 349 1518-21) as the channel materials contacting with graphene and other 2D metallic sheets to form van der Waals heterostructures for field effect transistor (FET). Based on state-of-the-art theoretical simulations, we show that the intrinsic properties of the 2D halide perovskites are preserved in the heterojunction, which is different from the conventional contact with metal surfaces. The 2D halide perovskites form a p-type Schottky barrier (Φh) contact with graphene, where tunneling barrier exists, and a negative band bending occurs at the lateral interface. We demonstrate that the Schottky barrier can be turned from p-type to n-type by doping graphene with nitrogen atoms, and a low-Φh or an Ohmic contact can be realized by doping graphene with boron atoms or replacing graphene with other high-work-function 2D metallic sheets such as ZT-MoS2, ZT-MoSe2 and H-NbS2. This study not only predicts a 2D halide perovskite-based FETs, but also enhances the understanding of tuning Schottky barrier height in device applications.

Transformation of sintered CsPbBr 3 nanocrystals to cubic CsPbI 3 and gradient CsPbBr xI 3–x through halide exchange

DOE PAGES

Hoffman, Jacob B.; Schleper, A. Lennart; Kamat, Prashant V.

2016-06-20

All-inorganic cesium lead halide (CsPbX 3, X = Br –, I –) perovskites could potentially provide comparable photovoltaic performance with enhanced stability compared to organic–inorganic lead halide species. However, small-bandgap cubic CsPbI3 has been difficult to study due to challenges forming CsPbI 3 in the cubic phase. Here, a low-temperature procedure to form cubic CsPbI 3 has been developed through a halide exchange reaction using films of sintered CsPbBr 3 nanocrystals. The reaction was found to be strongly dependent upon temperature, featuring an Arrhenius relationship. Additionally, film thickness played a significant role in determining internal film structure at intermediate reactionmore » times. Thin films (50 nm) showed only a small distribution of CsPbBr xI 3–x species, while thicker films (350 nm) exhibited much broader distributions. Furthermore, internal film structure was ordered, featuring a compositional gradient within film. Transient absorption spectroscopy showed the influence of halide exchange on the excited state of the material. In thicker films, charge carriers were rapidly transferred to iodide-rich regions near the film surface within the first several picoseconds after excitation. Furthermore, this ultrafast vectorial charge-transfer process illustrates the potential of utilizing compositional gradients to direct charge flow in perovskite-based photovoltaics.« less

Containerless Processing: Fabrication of Advanced Functional Materials from Undercooled Oxide Melt

NASA Astrophysics Data System (ADS)

Kumar, M. S. Vijaya; Ishikawa, Takehiko; Yoda, Shinichi; Kuribayashi, Kazuhiko

2012-07-01

Materials science in Microgravity condition is one of newly established cutting edge science field. After the effort of space development and space utilization, microgravity of space environment has been considered as one of novel tools for materials science because it assures containerless levitation. Containerless processing is a promising technique to explore the technologically important materials using rapid solidification of an undercooled melt. Recently, rare-earth ferrites and manganites have attracted great interest towards their wide applications in the field of electronic industry. Among these new hexagonal phases with a space group of P6 _{3}cm are technologically important materials because of multiferroic characteristics, i.e., the coexistence of ferroelectricity and magnetism in one compound. In the present study, containerless solidification of the R-Fe-O, and R-Mn-O melts were carried out to fabricate multiferroics under the controlled Po _{2}. Containerless processing is a promising technique to explore the new materials using rapid solidification of an undercooled melt because it provides large undercooling prior to nucleation. In order to undercool the melt deeply below the melting temperature under a precisely controlled oxygen partial pressure, an aerodynamic levitator (ADL) combined with ZrO _{2} oxygen sensor was designed. A spherical RFeO _{3} and RMnO _{3} sample was levitated by an ADL and completely melted by a CO _{2} laser in an atmosphere with predetermined Po _{2}.The surface temperature of the levitated droplet was monitored by a two-color pyrometer. Then, the droplet was cooled by turning off the CO _{2} laser. The XRD results of the rapidly solidified LuFeO _{3} and LuMnO _{3} samples at Po _{2} of 1x10 ^{5} Pa confirms the existence of the hexagonal metastable LuFeO _{3} phase. On the other hand, orthorhombic RFeO _{3} (R=Yb, Er, Y and Dy)and hexagonal RMnO _{3} (R=Ho-Lu)phases were identified. The cross-sectioned scanning

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

Sodium-metal halide and sodium-air batteries.

PubMed

Ha, Seongmin; Kim, Jae-Kwang; Choi, Aram; Kim, Youngsik; Lee, Kyu Tae

2014-07-21

Impressive developments have been made in the past a few years toward the establishment of Na-ion batteries as next-generation energy-storage devices and replacements for Li-ion batteries. Na-based cells have attracted increasing attention owing to low production costs due to abundant sodium resources. However, applications of Na-ion batteries are limited to large-scale energy-storage systems because of their lower energy density compared to Li-ion batteries and their potential safety problems. Recently, Na-metal cells such as Na-metal halide and Na-air batteries have been considered to be promising for use in electric vehicles owing to good safety and high energy density, although less attention is focused on Na-metal cells than on Na-ion cells. This Minireview provides an overview of the fundamentals and recent progress in the fields of Na-metal halide and Na-air batteries, with the aim of providing a better understanding of new electrochemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of halide ions on the electrochemical behaviour of iron in alkali solutions

NASA Astrophysics Data System (ADS)

Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

2008-02-01

Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

Abiotic Formation of Methyl Halides in the Terrestrial Environment

NASA Astrophysics Data System (ADS)

Keppler, F.

2011-12-01

Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

High-Pressure Study of Perovskite-Like Organometal Halide: Band-Gap Narrowing and Structural Evolution of [NH 3 -(CH 2 ) 4 -NH 3 ]CuCl 4

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

Li, Qian; Li, Shourui; Wang, Kai

Searching for nontoxic and stable perovskite-like alternatives to lead-based halide perovskites for photovoltaic application is one urgent issue in photoelectricity science. Such exploration inevitably requires an effective method to accurately control both the crystalline and electronic structures. This work applies high pressure to narrow the band gap of perovskite-like organometal halide, [NH 3-(CH 2) 4-NH 3]CuCl 4 (DABCuCl4), through the crystalline-structure tuning. The band gap keeps decreasing below ~12 GPa, involving the shrinkage and distortion of CuCl 4 2–. Inorganic distortion determines both band-gap narrowing and phase transition between 6.4 and 10.5 GPa, and organic chains function as the springmore » cushion, evidenced by the structural transition at ~0.8 GPa. The supporting function of organic chains protects DABCuCl 4 from phase transition and amorphization, which also contributes to the sustaining band-gap narrowing. This work combines crystal structure and macroscopic property together and offers new strategies for the further design and synthesis of hybrid perovskite-like alternatives.« less

ELECTROLYTIC PROCESS FOR PRODUCING METALS

DOEpatents

Kopelman, B.; Holden, R.B.

1961-06-01

A method is described for reducing beryllium halides to beryllium. The beryllfum halide fs placed in an eutectic mixture of alkali halides and alkaline earth halides. The constituents of this eutectic bath are so chosen that it has a melting point less than the boiling point of mercury, which acts as a cathode for the system. The beryllium metal is then deposited in the mercury upon electrolysis.

Anion binding by bambus[6]uril probed in the gas phase and in solution.

PubMed

Révész, Agnes; Schröder, Detlef; Svec, Jan; Wimmerová, Michaela; Sindelar, Vladimir

2011-10-20

Electrospray ionization mass spectrometry (ESI-MS) is used to probe the binding of small anions to the macrocycle of bambus[6]uril. For the halide ions, the experimental patterns suggest F(-) < Cl(-) < Br(-) < I(-), which is consistent with the order of anion binding found in the condensed phase. Parallel equilibrium studies in the condensed phase establish the association constants of halide anions and bambus[6]uril in mixed solvents. A detailed analysis of the mass spectrometric data is used to shed light on the correlations between the binding constants in the condensed phase and the ion abundances observed using ESI-MS. From the analysis it becomes apparent that ESI-MS can indeed represent the situation in solution to some extent, but the sampling in the gas-phase experiment is not 1:1 compared to that in solution.

Partial melting of metagreywackes, Part II. Compositions of minerals and melts

NASA Astrophysics Data System (ADS)

Montel, Jean-Marc; Vielzeuf, Daniel

A series of experiments on the fluid-absent melting of a quartz-rich aluminous metagreywacke has been carried out. In this paper, we report the chemical composition of the phases present in the experimental charges as determined by electron microprobe. This analytical work includes biotite, plagioclase, orthopyroxene, garnet, cordierite, hercynite, staurolite, gedrite, oxide, and glass, over the range 100-1000MPa, 780-1025°C. Biotites are Na- and Mg-rich, with Ti contents increasing with temperature. The compositions of plagioclase range from An17 to An35, with a significant orthoclase component, and are always different from the starting minerals. At high temperature, plagioclase crystals correspond to ternary feldspars with Or contents in the range 11-20 mol%. Garnets are almandine pyrope grossular spessartine solid solutions, with a regular and significant increase of the grossular content with pressure. All glasses are silicic (SiO2=67.6-74.4 wt%), peraluminous, and leucocratic (FeO+MgO=0.9-2.9 wt%), with a bulk composition close to that of peraluminous leucogranites, even for degrees of melting as high as 60 vol.%. With increasing pressure, SiO2 contents decrease while K2O increases. At any pressure, the melt compositions are more potassic than the water-saturated granitic minima. The H2O contents estimated by mass balance are in the range 2.5-5.6 wt%. These values are higher than those predicted by thermodynamic models. Modal compositions were estimated by mass balance calculations and by image processing of the SEM photographs. The positions of the 20 to 70% isotects (curves of equal proportion of melt) have been located in the pressure-temperature space between 100MPa and 1000MPa. With increasing pressure, the isotects shift toward lower temperature between 100 and 200MPa, then bend back toward higher temperature. The melting interval increases with pressure; the difference in temperature between the 20% and the 70% isotects is 40°C at 100MPa, and 150�

Melting of iron determined by X-ray absorption spectroscopy to 100 GPa

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

Aquilanti, Giuliana; Trapananti, Angela; Karandikar, Amol

2015-09-14

There is a long-standing controversy over the melting curve of Fe at high pressure as determined from static laser heated diamond anvil cell and dynamic compression studies. X-ray absorption spectroscopy measurements are used here as a criterion to detect melting under pressure. Confronted with a diversity of obtained melting curves, this technique, used at such pressure and temperature conditions, is eligible to be at the forefront to probe Earth's deep interior. Furthermore, the experiment reported here holds promise for addressing important issues related to the structure and phase diagram of compressed melts, such as the existence of structural complexity (polyamorphism)more » in the liquid phase or the extent of icosahedral ordering whose investigation has been limited until now to ambient conditions.« less

Lipid melting and cuticular permeability: new insights into an old problem.

PubMed

Gibbs, Allen G.

2002-04-01

The idea that the physical properties of cuticular lipids affect cuticular permeability goes back over 65 years. This proposal has achieved textbook status, despite controversy and the general lack of direct supporting evidence. Recent work supports the standard model, in which lipid melting results in increased cuticular permeability. Surprisingly, although all species studied to date can synthesize lipids that remain in a solid state at environmental temperatures, partial melting often occurs due to the deposition of lipids with low melting points. This will tend to increase water loss; the benefits may include better dispersal of lipids or other compounds across the cuticle or improved communication via cuticular pheromones. In addition, insects with high melting-point lipids are not necessarily less permeable at low temperatures. One likely reason is variation in lipid properties within the cuticle. Surface lipids differ from one region to another, and biophysical studies of model mixtures suggest the occurrence of phase separation between melted and solid lipid fractions. Lipid phase separation may have important implications for insect water balance and chemical communication.

Dehydration and melting experiments constrain the fate of subducted sediments

NASA Astrophysics Data System (ADS)

Johnson, Marie C.; Plank, Terry

1999-12-01

Geochemical tracers demonstrate that elements are cycled from subducted sediments into the arc melting regime at subduction zones, although the transfer mechanism is poorly understood. Are key elements (Th, Be, Rb) lost during sediment dehydration or is sediment melting required? To investigate this question, we conducted phase equilibria and trace element partitioning experiments on a pelagic red clay for conditions appropriate to the slab beneath arc volcanoes (2-4 GPa, 600°-1000°C). Using both piston cylinders and multianvils, we determined the solidus, phase stabilities, and major element compositions of coexisting phases. The solidus (H2O + Cl fluid-saturated) was located at 775 +/- 25°C at 2 GPa, 810 +/- 15°C at 3 GPa, and 1025 +/- 25°C at 4 GPa with noevidence for complete miscibility between melt and fluid. This sediment composition produces a profusion of phases both above and below the solidus: garnet, jadeitic pyroxene, alkali-rich amphibole, phengite, biotite, magnetite, coesite, kyanite, apatite, zircon, Cl-rich fluids, and peraluminous to peralkaline granitic melts. At 2 GPa the phengite dehydration solidus is at 800°-825°C, while biotite breaks down between 850° and 900°C. To explore trace element partitioning across the solidus at 2 GPa, we used diamonds to trap fluids and melts. Both the bulk sediment residues and diamond traps were analyzed postexperiment by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) for 40 elements for which we calculated bulk partition coefficients (D = Csolid/Cfluid). Below the solidus, Rb, Sr, Ba, and Pb showed the greatest mobility (D ~ 0.5-1.0), while at the solidus, Th and Be became notably partitioned into the melt (D values changing from >2.0 to <1.0). K and Rb D values fall below 1.0 when the micas breakdown. Only at the solidus do Th and Rb attain similar partition coefficients, a condition required by arc data. Taken together, the

Dehydration and melting experiments constrain the fate of subducted sediments

NASA Astrophysics Data System (ADS)

Johnson, Marie C.; Plank, Terry

2000-12-01

Geochemical tracers demonstrate that elements are cycled from subducted sediments into the arc melting regime at subduction zones, although the transfer mechanism is poorly understood. Are key elements (Th, Be, Rb) lost during sediment dehydration or is sediment melting required? To investigate this question, we conducted phase equilibria and trace element partitioning experiments on a pelagic red clay for conditions appropriate to the slab beneath arc volcanoes (2-4 GPa, 600°-1000°C). Using both piston cylinders and multianvils, we determined the solidus, phase stabilities, and major element compositions of coexisting phases. The solidus (H2O + Cl fluid-saturated) was located at 775 ± 25°C at 2 GPa, 810 ± 15°C at 3 GPa, and 1025 ± 25°C at 4 GPa with noevidence for complete miscibility between melt and fluid. This sediment composition produces a profusion of phases both above and below the solidus: garnet, jadeitic pyroxene, alkali-rich amphibole, phengite, biotite, magnetite, coesite, kyanite, apatite, zircon, Cl-rich fluids, and peraluminous to peralkaline granitic melts. At 2 GPa the phengite dehydration solidus is at 800°-825°C, while biotite breaks down between 850° and 900°C. To explore trace element partitioning across the solidus at 2 GPa, we used diamonds to trap fluids and melts. Both the bulk sediment residues and diamond traps were analyzed postexperiment by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) for 40 elements for which we calculated bulk partition coefficients (D = Csolid/Cfluid). Below the solidus, Rb, Sr, Ba, and Pb showed the greatest mobility (D ˜ 0.5-1.0), while at the solidus, Th and Be became notably partitioned into the melt (D values changing from >2.0 to <1.0). K and Rb D values fall below 1.0 when the micas breakdown. Only at the solidus do Th and Rb attain similar partition coefficients, a condition required by arc data. Taken together, the

Picosecond pulse radiolysis of direct and indirect radiolytic effects in highly concentrated halide aqueous solutions.

PubMed

Balcerzyk, Anna; Schmidhammer, Uli; El Omar, Abdel Karim; Jeunesse, Pierre; Larbre, Jean-Philippe; Mostafavi, Mehran

2011-08-25

Recently we measured the amount of the single product, Br(3)(-), of steady-state radiolysis of highly concentrated Br(-) aqueous solutions, and we showed the effect of the direct ionization of Br(-) on the yield of Br(3)(-). Here, we report the first picosecond pulse-probe radiolysis measurements of ionization of highly concentrated Br(-) and Cl(-) aqueous solutions to describe the oxidation mechanism of the halide anions. The transient absorption spectra are reported from 350 to 750 nm on the picosecond range for halide solutions at different concentrations. In the highly concentrated halide solutions, we observed that, due to the presence of Na(+), the absorption band of the solvated electron is shifted to shorter wavelengths, but its decay, taking place during the spur reactions, is not affected within the first 4 ns. The kinetic measurements in the UV reveal the direct ionization of halide ions. The analysis of pulse-probe measurements show that after the electron pulse, the main reactions in solutions containing 1 M of Cl(-) and 2 M of Br(-) are the formation of ClOH(-•) and BrOH(-•), respectively. In contrast, in highly concentrated halide solutions, containing 5 M of Cl(-) and 6 M of Br(-), mainly Cl(2)(-•) and Br(2)(-•) are formed within the electron pulse without formation of ClOH(-•) and BrOH(-•). The results suggest that, not only Br(-) and Cl(-) are directly ionized into Br(•) and Cl(•) by the electron pulse, the halide atoms can also be rapidly generated through the reactions initiated by excitation and ionization of water, such as the prompt oxidation by the hole, H(2)O(+•), generated in the coordination sphere of the anion. © 2011 American Chemical Society

Kinetic theory for DNA melting with vibrational entropy

NASA Astrophysics Data System (ADS)

Sensale, Sebastian; Peng, Zhangli; Chang, Hsueh-Chia

2017-10-01

By treating DNA as a vibrating nonlinear lattice, an activated kinetic theory for DNA melting is developed to capture the breakage of the hydrogen bonds and subsequent softening of torsional and bending vibration modes. With a coarse-grained lattice model, we identify a key bending mode with GHz frequency that replaces the hydrogen vibration modes as the dominant out-of-phase phonon vibration at the transition state. By associating its bending modulus to a universal in-phase bending vibration modulus at equilibrium, we can hence estimate the entropic change in the out-of-phase vibration from near-equilibrium all-atom simulations. This and estimates of torsional and bending entropy changes lead to the first predictive and sequence-dependent theory with good quantitative agreement with experimental data for the activation energy of melting of short DNA molecules without intermediate hairpin structures.

Melt-growth dynamics in CdTe crystals

DOE PAGES

Zhou, X. W.; Ward, D. K.; Wong, B. M.; ...

2012-06-01

We use a new, quantum-mechanics-based bond-order potential (BOP) to reveal melt growth dynamics and fine scale defect formation mechanisms in CdTe crystals. Previous molecular dynamics simulations of semiconductors have shown qualitatively incorrect behavior due to the lack of an interatomic potential capable of predicting both crystalline growth and property trends of many transitional structures encountered during the melt → crystal transformation. Here, we demonstrate successful molecular dynamics simulations of melt growth in CdTe using a BOP that significantly improves over other potentials on property trends of different phases. Our simulations result in a detailed understanding of defect formation during themore » melt growth process. Equally important, we show that the new BOP enables defect formation mechanisms to be studied at a scale level comparable to empirical molecular dynamics simulation methods with a fidelity level approaching quantum-mechanical methods.« less

Methyl halide production associated with kelp

NASA Technical Reports Server (NTRS)

Dastoor, Minoo N.; Manley, Steven L.

1985-01-01

Methyl halides (MeX) are important trace constituents of the atmosphere because they, mostly MeCl, have a major impact on the atmospheric ozone layer. Also, MeCl may account for 5 pct. of the total Cl budget and MeI may have a central role in the biogeochemical cycling of iodine. High MeI concentrations were found in seawater from kelp beds and it has been suggested that MeI is produced by kelps and that MeI and MeBr along with numerous other halocarbons were released by non-kelp marine macroalgae. The objective was to determine if kelps (and other seaweeds) are sources of MeX and to assess their contribution to the estimated global source strength (EGSS) of MeX. Although the production of MeX appears to be associated with kelp, microbes involved with kelp degradation also produce MeX. Microbial MeX production may be of global significance. The microbial MeX production potential, assuming annual kelp production equals kelp degradation and 100 pct. conversion of kelp halides to MeX, is approx. 2 x the EGSS. This is not achieved but indicates that microbial production of MeX may be of global significance.

Lasing from lead halide perovskite semiconductor microcavity system.

PubMed

Wang, Jun; Da, Peimei; Zhang, Zhe; Luo, Song; Liao, Liming; Sun, Zeyuan; Shen, Xuechu; Wu, Shiwei; Zheng, Gengfeng; Chen, Zhanghai

2018-06-07

Organic-inorganic halide perovskite semiconductors are ideal gain media for fabricating laser and photonic devices due to high absorption, photoluminescence (PL) efficiency and low nonradiative recombination losses. Herein, organic-inorganic halide perovskite CH3NH3PbI3 is embedded in the Fabry-Perot (FP) microcavity, and a wavelength-tunable excitonic lasing with a threshold of 12.9 μJ cm-2 and the spectral coherence of 0.76 nm are realized. The lasing threshold decreases and the spectral coherence enhances as the temperature decreases; these results are ascribed to the suppression of exciton irradiative recombination caused by thermal fluctuation. Moreover, both lasing and light emission below threshold from the perovskite microcavity (PM) system demonstrate a redshift with the decreasing temperature. These results provide a feasible platform based on the PM system for the study of light-matter interaction for quantum optics and the development of optoelectronic devices such as polariton lasers.

Nanostructure of propylammonium nitrate in the presence of poly(ethylene oxide) and halide salts

NASA Astrophysics Data System (ADS)

Stefanovic, Ryan; Webber, Grant B.; Page, Alister J.

2018-05-01

Nanoscale structure of protic ionic liquids is critical to their utility as molecular electrochemical solvents since it determines the capacity to dissolve salts and polymers such as poly(ethylene oxide) (PEO). Here we use quantum chemical molecular dynamics simulations to investigate the impact of dissolved halide anions on the nanostructure of an archetypal nanostructured protic ionic liquid, propylammonium nitrate (PAN), and how this impacts the solvation of a model PEO polymer. At the molecular level, PAN is nanostructured, consisting of charged/polar and uncharged/nonpolar domains. The charged domain consists of the cation/anion charge groups, and is formed by their electrostatic interaction. This domain solvophobically excludes the propyl chains on the cation, which form a distinct, self-assembled nonpolar domain within the liquid. Our simulations demonstrate that the addition of Cl- and Br- anions to PAN disrupts the structure within the PAN charged domain due to competition between nitrate and halide anions for the ammonium charge centre. This disruption increases with halide concentration (up to 10 mol. %). However, at these concentrations, halide addition has little effect on the structure of the PAN nonpolar domain. Addition of PEO to pure PAN also disrupts the structure within the charged domain of the liquid due to hydrogen bonding between the charge groups and the terminal PEO hydroxyl groups. There is little other association between the PEO structure and the surrounding ionic liquid solvent, with strong PEO self-interaction yielding a compact, coiled polymer morphology. Halide addition results in greater association between the ionic liquid charge centres and the ethylene oxide components of the PEO structure, resulting in reduced conformational flexibility, compared to that observed in pure PAN. Similarly, PEO self-interactions increase in the presence of Cl- and Br- anions, compared to PAN, indicating that the addition of halide salts to PAN

Resonant halide perovskite nanoparticles

NASA Astrophysics Data System (ADS)

Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

2017-09-01

The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

Numerical simulation of viscoelastic layer rearrangement in polymer melts using OpenFOAM®

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

Köpplmayr, Thomas, E-mail: tkoepplmayr@gmail.com; Mayrhofer, Elias

In addition to their shear-thinning behavior, polymer melts are characterized by first and second normal stress differences, which cause secondary motions. Polymer coextrusion processes involve viscoelastic two-phase flows that influence layer formation. Using polymer melts with different pigmentation makes visible the layers deformed by second normal stress differences. We used a new solver for the OpenFOAM CFD toolbox which handles viscoelastic two-phase flows. A derivative of the volume-of-fluid (VoF) methodology was employed to describe the interface. Different types of polymer melt, such as polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) were investigated. In a coextrusion process, the less viscousmore » phase usually tends to encapsulate the more viscous one. However, the different viscoelastic properties of the melts also influence interface deformation. The materials were characterized by small-amplitude oscillatory-shear rheometry, and a multimode Giesekus model was used to fit shear viscosity, storage and loss modulus. Our simulations also took interfacial tension into account. Experimental observations and corresponding numerical simulations were found to be in good accordance.« less

Magnetic properties of single-phase MnBi grown from MnBi{sub 49} melt

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

Xiao, X. F.; Si, P. Z., E-mail: pzsi@cjlu.edu.cn; Feng, H.

2014-05-07

The single-phase NiAs-type MnBi, embedded in Bi matrix, was grown from homogeneous MnBi{sub 49} melt at low temperatures to prevent the formation of Mn{sub 1.08}Bi. An abrupt magnetization change was observed at ∼240 K. The origin of this change was ascribed to the movement of the Mn atoms between the regular sites and the interstitial sites in the MnBi lattices. The splitting of the x-ray photoelectron lines of MnBi indicates the presence of two binding states of Mn atoms, one of which was ascribed to interstitial Mn atoms. A large coercivity up to 1.79 T at 400 K was observed in the as-grownmore » bulk isotropic MnBi alloys.« less

The geometry and volume of melt beneath Ethiopia

NASA Astrophysics Data System (ADS)

Kendall, J. M.; Hammond, J. O. S.

2016-12-01

A range of seismic measurements can be used to map melt distribution in the crust and uppermost mantle. These include seismic P- and S-wave velocities derived from surface- and body-wave tomography, Vp/Vs ratios obtained from receiver functions, and estimates of seismic anisotropy and attenuation. The most obvious melt parameter that seismic data might be sensitive to is volume fraction. However, such data are more sensitive to the aspect ratio of melt inclusions, which is controlled by the melt wetting angle or in other words the shape of the melt inclusion. To better understand this we perform numerical modelling, varying the shape and amount of melt, to show how various seismic phases are effected by melt. To consider the effects on seismic anisotropy we assume that the melt can be stored in pockets of melt that are either horizontally or vertically aligned (e.g., sills versus dykes). We then consider a range of seismic observations from the rifting environment of Ethiopia. Recent studies of P- and S-wave tomography, Rayleigh and Love waves, and Pn or wide angle P-wave refractions provide provide complimentary constraints on melt volume, orientation and inclusion aspect ratio. Furthermore, receiver functions and shear-wave splitting in body waves show strong anisotropy in this region and can be used to constrain the strike of vertically-aligned partial melt. We show that melt in the mantle beneath Ethiopia is likely stored in low aspect ratio disk-like inclusions, suggesting melt is not in textural equilibrium. We estimate that 2-7% vertically aligned melt is stored beneath the Main Ethiopian Rift, >6% horizontally and vertically aligned melt is stored beneath the Afar-region of the Red Sea Rift and 1-6% horizontally aligned melt is stored beneath the Danakil microplate. This supports ideas of strong shear-derived segregation of melt in narrow parts of the rift and large volumes of melt beneath Afar.

Gas-Phase Interaction of Anions with Polyisobutylenes: Collision-Induced Dissociation Study and Quantum Chemical Modeling.

PubMed

Nagy, Lajos; Kuki, Ákos; Deák, György; Purgel, Mihály; Vékony, Ádám; Zsuga, Miklós; Kéki, Sándor

2016-09-01

The gas-phase interaction of anions including fluoride, chloride, bromide, iodide, ethyl sulfate, chlorate, and nitrate with polyisobutylene (PIB) derivatives was studied using collision-induced dissociation (CID). The gas-phase adducts of anions with PIBs ([PIB + anion](-)) were generated from the electrosprayed solution of PIBs in the presence of the corresponding anions. The so-formed adducts subjected to CID showed a loss of anion at different characteristic collision energies, thus allowing the study of the strength of interaction between the anions and nonpolar PIBs having different end-groups. The values of characteristic collision energies (the energy needed to obtain 50% fragmentation) obtained by CID experiments correlated linearly with the binding enthalpies between the anion and PIB, as determined by density functional theory calculations. In the case of halide ions, the critical energies for dissociation, that is, the binding enthalpies for [PIB + anion](-) adducts, increased in the order of I(-) < Br(-) < Cl(-) < F(-). Furthermore, it was found that the binding enthalpies for the adducts formed with halide ions decreased approximately with the square radius of the halide ion, suggesting that the strength of interaction is mainly determined by the "surface" charge density of the halide ion. In addition, the characteristic collision energy versus the number of isobutylene units revealed a linear dependence.

Probing the growth and melting pathways of a decagonal quasicrystal in real-time

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

Han, Insung; Xiao, Xianghui; Shahani, Ashwin J.

How does a quasicrystal grow? Despite the decades of research that have been dedicated to this area of study, it remains one of the fundamental puzzles in the field of crystal growth. Although there has been no lack of theoretical studies on quasicrystal growth, there have been very few experimental investigations with which to test their various hypotheses. In particular, evidence of the in situ and three-dimensional (3D) growth of a quasicrystal from a parent liquid phase is lacking. To fill-in-the-gaps in our understanding of the solidification and melting pathways of quasicrystals, we performed synchrotron-based X-ray imaging experiments on amore » decagonal phase with composition of Al-15at%Ni-15at%Co. High-flux X-ray tomography enabled us to observe both growth and melting morphologies of the 3D quasicrystal at temperature. We determined that there is no time-reversal symmetry upon growth and melting of the decagonal quasicrystal. While quasicrystal growth is predominantly dominated by the attachment kinetics of atomic clusters in the liquid phase, melting is instead barrier-less and limited by buoyancy-driven convection. These experimental results provide the much-needed benchmark data that can be used to validate simulations of phase transformations involving this unique phase of matter.« less