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Sample records for high-pressure crystal chemistry

  1. High Pressure Crystal Chemistry of Hydrous Ringwoodite

    NASA Astrophysics Data System (ADS)

    Holl, C. M.; Smyth, J. R.; Frost, D. J.; Jacobsen, S. D.

    2002-12-01

    Single crystals of hydrous Fo90 ringwoodite up to 800 μm in diameter have been synthesized in a multi-anvil press at 1400°C and 20 GPa. The crystals are deep blue in color and contain approximately 0.8 percent H2O by weight as measured by IR spectroscopy. The unit cell parameter of this material has been refined by single-crystal X-ray diffraction at 15 different pressures up to 3.8 GPa. Pressure was determined by refinement of the until cell volume of a standard quartz crystal. Preliminary values for the bulk modulus give a K0 = 172 +/- 9 GPa and K' = 5.1 +/- 1.6 over the range studied. The crystal structure of this material has been refined at six pressures up to 3.8 GPa. Refinements were obtained from an average of 13 unique data with values of Rf < 5%. Preliminary estimates of the polyhedral compressibilities are 1.0x10-2 GPa-1 (K = 100 GPa) for MgVI and 6.3x10-3 GPa-1 (K = 160 GPa) for SiIV. Comparison of the present data with previous results shows a systematic decrease in the bulk modulus of ringwoodite with H content. This decrease is larger than the effect of temperature within the allowable ranges of each so that an increase in H2O content of one percent would have an effect on the bulk modulus equivalent to raising the temperature by 500°C.

  2. Molecular Surface Chemistry by Metal Single Crystals and Nanoparticles from Vacuum to High Pressure.

    SciTech Connect

    Somorjai, Gabor A.; Park, Jeong Y.

    2008-04-05

    Model systems for studying molecular surface chemistry have evolved from single crystal surfaces at low pressure to colloidal nanoparticles at high pressure. Low pressure surface structure studies of platinum single crystals using molecular beam surface scattering and low energy electron diffraction techniques probe the unique activity of defects, steps and kinks at the surface for dissociation reactions (H-H, C-H, C-C, O{double_bond}O bonds). High-pressure investigations of platinum single crystals using sum frequency generation vibrational spectroscopy have revealed the presence and the nature of reaction intermediates. High pressure scanning tunneling microscopy of platinum single crystal surfaces showed adsorbate mobility during a catalytic reaction. Nanoparticle systems are used to determine the role of metal-oxide interfaces, site blocking and the role of surface structures in reactive surface chemistry. The size, shape and composition of nanoparticles play important roles in determining reaction activity and selectivity.

  3. Akimotoite in the Tenham meteorite: Crystal chemistry and high-pressure transformation mechanisms

    NASA Astrophysics Data System (ADS)

    Ferroir, Tristan; Beck, Pierre; Van de Moortèle, Bertrand; Bohn, Marcel; Reynard, Bruno; Simionovici, Alexandre; El Goresy, Ahmed; Gillet, Philippe

    2008-10-01

    The transformation of pyroxene to its high-pressure polymorph akimotoite (MgSiO 3 ilmenite type structure) is documented in the shock-induced melt veins of the L6 Tenham chondrite. Four textural relationships between pyroxene and akimotoite are observed in former pyroxene grains entrained in the shear melt vein and in pyroxene grains attached to the wall of the melt vein. In one of the entrained enstatite grains the transformation to akimotoite is partial. One third of the grain is transformed to a polycrystalline aggregate of akimotoite with a scalloped interface with enstatite. Akimotoite (Fe 0,4Mg 1,24Ca 0.07Na 0,12Al 0,14)(Si 1,963Al 0,037)O 6 is slightly enriched in Ca (CaO = 1.74%), Al and Na with respect to enstatite (CaO = 0.71%). Narrow bands of polycrystalline akimotoite with three crystallographic orientations and a chemical composition similar to the surrounding enstatite intersect the other part of the grain. In a second grain entrained in the shear melt vein, tablets of akimotoite are interwoven with a pyroxene glass with a lower Na and Fe content and a higher Mg content compared to the adjacent akimotoite. This pyroxene glass is probably the product of (Mg,Fe)SiO 3-perovskite amorphization. Polycrystalline akimotoite is also formed at the expense of enstatite at the vein wall of the shear melt vein. In that case akimotoite is also enriched in Ca (CaO = 2.85%) Na (NaO = 1.72%) and Al (Al 2O 3 = 4.14%). All these observations suggest that akimotoite is mainly formed by solid-state transformation of former pyroxenes with subsequent diffusion of calcium, aluminum and sodium from the chondritic melt of the shear melt vein. Finally, the first complete X-ray diffraction pattern of natural akimotoite is presented.

  4. High-pressure synthesis, crystal chemistry and physics of perovskites with small cations at the A site.

    PubMed

    Belik, Alexei A; Yi, Wei

    2014-04-23

    ABO3 perovskites with small cations at the A site (A = Sc(3+), In(3+) and Mn(2+) and B = Al(3+) and transition metals) are reviewed. They extend the corresponding families of perovskites with A(3+) = Y, La-Lu, and Bi and A(2+) = Cd, Ca, Sr and Ba and exhibit the largest structural distortions. As a result of these large distortions, they show, in many cases, distinct structural and magnetic properties. These are manifested in: B-site-ordered monoclinic structures of ScMnO3 and 'InMnO3'; an unusual superstructure of ScRhO3 and InRhO3; antiferromagnetic ground states and multiferroic properties of Sc2NiMnO6 and In2NiMnO6; two magnetic transitions in ScCrO3 and InCrO3 with very close transition temperatures; a Pnma-to-P-1 structural transition and k = (½, 0, ½) magnetic ordering in ScVO3; and incommensurate magnetic ordering of Mn(2+) spins in metallic MnVO3. A large number of simple ScBO3, InBO3 and MnBO3 perovskites has not been synthesized yet, and the number of experimental and theoretical works on each known ScBO3, InBO3 and MnBO3 perovskites counts to only one or two (except for ScAlO3). The synthesis, crystal chemistry and physics of perovskites with small cations at the A site is an emerging field in perovskite science.

  5. Novel chemistry of matter under high pressure

    NASA Astrophysics Data System (ADS)

    Miao, Maosheng

    2015-03-01

    The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry, rooted in the atomic shell structure. Within compounds, Group I elements, for example, invariably assume the +1 oxidation state, and their chemical properties differ completely from those of the p-block elements. These general rules govern our understanding of chemical structures and reactions. Using first principles calculations, we demonstrate that under high pressure, the above doctrines can be broken. We show that both the inner shell electrons and the outer shell empty orbitals of Cs and other elements can involve in chemical reactions. Furthermore, we show that the quantized orbitals of the enclosed interstitial space may play the same role as atomic orbitals, an unprecedented view that led us to a unified theory for the recently observed high-pressure electride phenomenon.

  6. High-pressure crystallography of periodic and aperiodic crystals

    PubMed Central

    Hejny, Clivia; Minkov, Vasily S.

    2015-01-01

    More than five decades have passed since the first single-crystal X-ray diffraction experiments at high pressure were performed. These studies were applied historically to geochemical processes occurring in the Earth and other planets, but high-pressure crystallography has spread across different fields of science including chemistry, physics, biology, materials science and pharmacy. With each passing year, high-pressure studies have become more precise and comprehensive because of the development of instrumentation and software, and the systems investigated have also become more complicated. Starting with crystals of simple minerals and inorganic compounds, the interests of researchers have shifted to complicated metal–organic frameworks, aperiodic crystals and quasicrystals, molecular crystals, and even proteins and viruses. Inspired by contributions to the microsymposium ‘High-Pressure Crystallography of Periodic and Aperiodic Crystals’ presented at the 23rd IUCr Congress and General Assembly, the authors have tried to summarize certain recent results of single-crystal studies of molecular and aperiodic structures under high pressure. While the selected contributions do not cover the whole spectrum of high-pressure research, they demonstrate the broad diversity of novel and fascinating results and may awaken the reader’s interest in this topic. PMID:25866659

  7. Synthetic chemistry with periodic mesostructures at high pressure.

    PubMed

    Mandal, Manik; Landskron, Kai

    2013-11-19

    Over the last two decades, researchers have studied extensively the synthesis of mesostructured materials, which could be useful for drug delivery, catalytic cracking of petroleum, or reinforced plastics, among other applications. However, until very recently researchers used only temperature as a thermodynamic variable for synthesis, completely neglecting pressure. In this Account, we show how pressure can affect the synthetic chemistry of periodic mesoporous structures with desirable effects. In its simplest application, pressure can crystallize the pore walls of periodic mesoporous silicas, which are difficult to crystallize otherwise. The motivation for the synthesis of periodic mesoporous silica materials (with pore sizes from 2 to 50 nm) 20 years ago was to replace the microporous zeolites (which have pore sizes of <2 nm) in petroleum cracking applications, because the larger pore size of mesoporous materials allows for faster transport of larger molecules. However, these mesoporous materials could not replace zeolite materials because they showed lower hydrothermal stability and lower catalytic activity. This reduced performance has been attributed to the amorphous nature of the mesoporous materials' channel walls. To address this problem, we developed the concept of "nanocasting at high pressure". Through this approach, we produced hitherto-unavailable, periodic mesostructured silicas with crystalline pore walls. In nanocasting, we compress a periodic mesostructured composite (e.g. a periodic mesoporous silica with carbon-filled pores) and subsequently heat it to induce the selective crystallization of one of the two phases. We attain the necessary high pressure for synthesis using piston-cylinder and multianvil apparatuses. Using periodic mesostructured silica/carbon nanocomposites as starting material, we have produced periodic mesoporous coesite and periodic mesoporous quartz. The quartz material is highly stable under harsh hydrothermal conditions (800

  8. High pressure chemistry of substituted acetylenes

    SciTech Connect

    Chellappa, Raja; Dattelbaum, Dana; Sheffield, Stephen; Robbins, David

    2011-01-25

    High pressure in situ synchrotron x-ray diffraction experiments were performed on substituted polyacetylenes: tert-butyl acetylene [TBA: (CH{sub 3}){sub 3}-C{triple_bond}CH] and ethynyl trimethylsilane [ETMS: (CH{sub 3}){sub 3}-Si{triple_bond}CH] to investigate pressure-induced chemical reactions. The starting samples were the low temperature crystalline phases which persisted metastably at room temperature and polymerized beyond 11 GPa and 26 GPa for TBA and ETMS respectively. These reaction onset pressures are considerably higher than what we observed in the shockwave studies (6.1 GPa for TBA and 6.6 GPa for ETMS). Interestingly, in the case of ETMS, it was observed with fluid ETMS as starting sample, reacts to form a semi-crystalline polymer (crystalline domains corresponding to the low-T phase) at pressures less than {approx}2 GPa. Further characterization using vibrational spectroscopy is in progress.

  9. High-pressure chemistry of molecular solids: evidences for novel extended phases of carbon dioxide

    SciTech Connect

    Yoo, C S

    1999-07-22

    At high pressures and temperatures, many molecular solids become unstable and transform into denser extended phases. Recently, we have discovered evidences for two novel extended phases of carbon dioxide at high pressures and temperatures: (1) an ionic form of dimeric CO,, C02+C03*- at 8-13 GPa and above 2000 K [I] and (2) a polymeric phase CO,-V above 35 GPa and 1800 K [2,3]. These extended phases can be quenched at room temperature at low pressures, from which their molecular and crystal structures have been determined. These transitions occur to soften highly repulsive intermolecular potentials via delocalization of electrons at high pressures and temperatures. Based on these and other previous results, we conjecture that three fundamental mechanisms of high-pressure chemistry are ionization, polymerization, and metallization, occurring in high-density molecular solids and fluids. [carbon dioxide, polymeric COZ, ionic CO, dimer, high-pressure chemistry, electron delocalization

  10. Crystal structures at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Caldwell, Wendel Alexander

    2000-10-01

    The diamond anvil cell (DAC) is a unique instrument that can generate pressures equivalent to those inside planetary interiors (pressures on the order of 1 million atmospheres) under sustained conditions. When combined with a bright source of collimated x-rays, the DAC can be used to probe the structure of materials in-situ at ultra-high pressures. An understanding of the high-pressure structure of materials is important in determining what types of processes may take place in the Earth at great depths. Motivated by previous studies showing that xenon becomes metallic at pressures above ˜1 megabar (100 GPa), we examined the stable structures and reactivity of xenon at pressures approaching that of the core-mantle boundary in the Earth. Our findings indicate the transformation of xenon from face-centered cubic (fcc) to hexagonal close-packed (hcp) structures is kinetically hindered at room temperature, with the equilibrium fcc--hcp phase boundary at 21 (+/-3) gigapascals, a pressure lower than was previously thought. Additionally, we find no tendency on the part of xenon to form a metal alloy with iron or platinum to at least 100 to 150 gigapascals, making it unlikely that the Earth's core serves as a reservoir for primordial xenon. Measurements of the compressibility of natural (Mg.75,Fe .25)2SiO4 gamma-spinel at pressures of the Earth's transition zone yield a pressure derivative of the bulk modulus K0 ' = 6.3 (+/-0.3). As gamma-spinel is considered to be a dominant mineral phase of the transition-zone of the Earth's mantle (400--670 km depth), the relatively high value of K0' for gamma-spinel may help explain the rapid increase with depth of seismic velocities through the transition zone. The thermodynamics, mechanisms and kinetics of pressure-induced amorphization are not well understood. We report here new studies indicating little or no entropy difference between the crystalline and glassy states of Ca(OH) 2 (portlandite). Additional work on the pressure

  11. High pressure phase transitions in lawsonite at simultaneous high pressure and temperature: A single crystal study

    NASA Astrophysics Data System (ADS)

    O'Bannon, E. F., III; Vennari, C.; Beavers, C. C. G.; Williams, Q. C.

    2015-12-01

    Lawsonite (CaAl2Si2O7(OH)2.H2O) is a hydrous mineral with a high overall water content of ~11.5 wt.%. It is a significant carrier of water in subduction zones to depths greater than ~150 km. The structure of lawsonite has been extensively studied under room temperature, high-pressure conditions. However, simultaneous high-pressure and high-temperature experiments are scarce. We have conducted synchrotron-based simultaneous high-pressure and temperature single crystal experiments on lawsonite up to a maximum pressure of 8.4 GPa at ambient and high temperatures. We used a natural sample of lawsonite from Valley Ford, California (Sonoma County). At room pressure and temperature lawsonite crystallizes in the orthorhombic system with Cmcm symmetry. Room temperature compression indicates that lawsonite remains in the orthorhombic Cmcm space group up to ~9.0 GPa. Our 5.0 GPa crystal structure is similar to the room pressure structure, and shows almost isotropic compression of the crystallographic axes. Unit cell parameters at 5.0 GPa are a- 5.7835(10), b- 8.694(2), and c- 13.009(3). Single-crystal measurements at simultaneous high-pressure and temperature (e.g., >8.0 GPa and ~100 oC) can be indexed to a monoclinic P-centered unit cell. Interestingly, a modest temperature increase of ~100 oC appears to initiate the orthorhombic to monoclinic phase transition at ~0.6-2.4 GPa lower than room temperature compression studies have shown. There is no evidence of dehydration or H atom disorder under these conditions. This suggests that the orthorhombic to monoclinic transition could be kinetically impeded at 298 K, and that monoclinic lawsonite could be the dominant water carrier through much of the depth range of upper mantle subduction processes.

  12. High-pressure cooling of protein crystals without cryoprotectants.

    PubMed

    Kim, Chae Un; Kapfer, Raphael; Gruner, Sol M

    2005-07-01

    Flash-cooling of protein crystals is the best known method to effectively mitigate radiation damage in macromolecular crystallography. To prevent physical damage to crystals upon cooling, suitable cryoprotectants must usually be found, a process that is time-consuming and in some cases unsuccessful. A method is described to cool protein crystals in high-pressure helium gas without the need for penetrative cryoprotectants. The method involves mounting protein crystals from the native mother liquor in a cryoloop with a droplet of oil, pressurizing the crystal to 200 MPa in He gas, cooling the crystal under pressure and then releasing the pressure. The crystal is then removed from the apparatus under liquid nitrogen and handled thereafter like a normal cryocooled crystal. Results are presented from three representative proteins. Dramatic improvement in diffraction quality in terms of resolution and mosaicity was observed in all cases. A mechanism for the pressure cooling is proposed involving high-density amorphous (HDA) ice which is produced at high pressure and is metastable at room pressure and 110 K.

  13. Crystal chemistry of anion-excess ReO3-related phases. III. γ-ZrF4, a high-pressure form of zirconiumtetra fluoride, and a comparison of MX4 structure types.

    PubMed

    Laval, Jean Paul

    2014-08-01

    The crystal structure of the high-pressure (4-8 GPa) form of zirconium tetrafluoride, γ-ZrF4, is based on the association by corner- and edge-sharing of ZrF8 triangulated dodecahedra, forming a three-dimensional framework. It presents some analogies with high-temperature α-ZrF4 but clearly constitutes a new MX4 structure type. The main MX4 ionic structure types, and especially those deriving from the `anion-excess ReO3-type', are compared and it is shown that the TeF4 structure can also be included in this family.

  14. Deformation of Single Crystal Molybdenum at High Pressure

    SciTech Connect

    Bonner, B P; Aracne, C; Farber, D L; Boro, C O; Lassila, D H

    2004-02-24

    Single crystal samples of micron dimensions oriented in the [001] direction were shortened 10 to 40% in uniaxial compression with superposed hydrostatic pressure to begin investigation of how the onset of yielding evolves with pressure. A testing machine based on opposed anvil geometry with precision pneumatic control of the applied force and capability to measure sub micron displacements was developed to produce shape changing deformation at pressure. The experiments extend observations of pressure dependent deformation to {approx}5Gpa at shortening rates of {approx}2*10{sup -4}. Samples have been recovered for post run characterization and analysis to determine if deformation mechanisms are altered by pressure. Experiments under hydrostatic pressure provide insight into the nature of materials under extreme conditions, and also provide a means for altering deformation behavior in a controlled fashion. The approach has a long history demonstrating that pressure enhances ductility in general, and produces enhanced hardening relative to that expected from normal cold work in the BCC metals Mo, Ta and Nb{sup 2}. The pressure hardening is in excess of that predicted from the measured increase in shear modulus at pressure, and therefore is likely due to a dislocation mechanism, such as suppression of kink pair formation or the interaction of forest dislocation cores, and not from lattice resistance. The effect has not been observed in FCC metals, suggesting a fundamental difference between deformation mechanisms at pressure for the two classes. The purpose of this letter is to investigate the origin of pressure hardening with new experiments that extend the pressure range beyond 3 GPa, the upper limit of conventional large sample (1cm{sup 3}) testing methods. Most previous high pressure deformation studies have been on poly crystals, relying on model dependent analysis to infer the maximum deviatoric stress that a deformed sample can support. In one experiment, a

  15. Iron Catalyst Chemistry in High Pressure Carbon Monoxide Nanotube Reactor

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Povitsky, Alexander; Dateo, Christopher; Gokcen, Tahir; Smalley, Richard E.

    2001-01-01

    The high-pressure carbon monoxide (HiPco) technique for producing single wall carbon nanotubes (SWNT) is analyzed using a chemical reaction model coupled with properties calculated along streamlines. Streamline properties for mixing jets are calculated by the FLUENT code using the k-e turbulent model for pure carbon monixide. The HiPco process introduces cold iron pentacarbonyl diluted in CO, or alternatively nitrogen, at high pressure, ca. 30 atmospheres into a conical mixing zone. Hot CO is also introduced via three jets at angles with respect to the axis of the reactor. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Cluster reaction rates are from Krestinin, et aI., based on shock tube measurements. Another model is from classical cluster theory given by Girshick's team. The calculations are performed on streamlines that assume that a cold mixture of Fe(CO)5 in CO is introduced along the reactor axis. Then iron forms clusters that catalyze the formation of SWNTs from the Boudouard reaction on Fe-containing clusters by reaction with CO. To simulate the chemical process along streamlines that were calculated by the fluid dynamics code FLUENT, a time history of temperature and dilution are determined along streamlines. Alternative catalyst injection schemes are also evaluated.

  16. Novel charge/discharge method for lead acid battery by high-pressure crystallization

    NASA Astrophysics Data System (ADS)

    Arakawa, Naoko; Maeda, Kouji; Moritoki, Masato; Fukui, Keisuke; Kuramochi, Hidetoshi; Miki, Hideo

    2013-06-01

    The electrical charging and discharging of a battery involves the crystallization of electrolytes or metal oxides on both electrodes. Crystallization technology that can control nucleation, growth, and distribution of solute crystals might be effective for improving battery properties. We performed charge/discharge cycling of a lead acid battery under high pressure. The charging efficiency at high pressure was compared with that at atmospheric pressure. Charging efficiency at high pressure was found to be higher than that at atmospheric pressure under a high charging current. Observation of the positive electrode by scanning electron microscopy revealed that high pressure caused the crystals on the electrode to become extremely fine.

  17. Application of ultra high pressure (UHP) in starch chemistry.

    PubMed

    Kim, Hyun-Seok; Kim, Byung-Yong; Baik, Moo-Yeol

    2012-01-01

    Ultra high pressure (UHP) processing is an attractive non-thermal technique for food treatment and preservation at room temperature, with the potential to achieve interesting functional effects. The majority of UHP process applications in food systems have focused on shelf-life extension associated with non-thermal sterilization and a reduction or increase in enzymatic activity. Only a few studies have investigated modifications of structural characteristics and/or protein functionalities. Despite the rapid expansion of UHP applications in food systems, limited information is available on the effects of UHP on the structural and physicochemical properties of starch and/or its chemical derivatives included in most processed foods as major ingredients or minor additives. Starch and its chemical derivatives are responsible for textural and physical properties of food systems, impacting their end-use quality and/or shelf-life. This article reviews UHP processes for native (unmodified) starch granules and their effects on the physicochemical properties of UHP-treated starch. Furthermore, functional roles of UHP in acid-hydrolysis, hydroxypropylation, acetylation, and cross-linking reactions of starch granules, as well as the physicochemical properties of UHP-assisted starch chemical derivatives, are discussed.

  18. CRYSTAL CHEMISTRY OF HYDROUS MINERALS

    SciTech Connect

    Y. ZHAO; ET AL

    2001-02-01

    Hydrogen has long been appreciated for its role in geological processes of the Earth's crust. However, its role in Earth's deep interior has been neglected in most geophysical thinking. Yet it is now believed that most of our planet's hydrogen may be locked up in high pressure phases of hydrous silicate minerals within the Earth's mantle. This rocky interior (approximately 7/8 of Earth's volume) is conjectured to contain 1-2 orders of magnitude more water than the more obvious oceans (the ''hydrosphere'') and atmosphere. This project is aimed at using the capability of neutron scattering from hydrogen to study the crystal chemistry and stability of hydrogen-bearing minerals at high pressures and temperatures. At the most basic level this is a study of the atomic position and hydrogen bond itself. We have conducted experimental runs on hydrous minerals under high pressure and high temperature conditions. The crystallographic structure of hydrous minerals at extreme conditions and its structural stability, and hydrogen bond at high P-T conditions are the fundamental questions to be addressed. The behavior of the hydrous minerals in the deep interior of the Earth has been discussed.

  19. A New Thermodynamic Model for High Pressure Melts and the Impact on Magma Ocean Crystallization

    NASA Astrophysics Data System (ADS)

    Wolf, A. S.; Bower, D. J.

    2016-12-01

    Terrestrial planet formation is marked by giant impacts that bury tremendous heat deep within growing planets, likely sufficient to have melted the vast majority of the early Earth's mantle [Nakajima & Stevenson, 2015]. Subsequent cooling and crystallization from a (nearly) fully molten initial state is dominated by the thermodynamics of high-pressure silicate melts. Even first order properties like the mantle melting curve are still poorly understood, with strong disagreement between different experimental and theoretical studies [e.g. Stixrude et al. 2009; Fiquet et al. 2010; Andrault et al. 2011]. The relative slopes of the melting curve and the adiabatic melt profile play a primary role in determining the evolutionary path of the magma ocean, with flat vs. highly-curved melting curves causing bottom-up vs. the center-outwards crystallization [Stixrude et al., 2009]. To explore this thermodynamic property and its consequences for magma ocean evolution, we have developed a new high pressure melt equation of state for MgSiO3 and performed magma ocean cooling simulations for each of these end-member scenarios. Currently, the literature has few examples of equation of state (EOS) formulations that are accurate for high pressure melts, thermodynamically self-consistent, and simple yet flexible enough to allow robust determination of the parameters. We have developed a new High Pressure Rosenfeld-Taranzona EOS (RTpress), which extends the original melt-specific Rosenfeld-Taranzona EOS using a limited number of easily understood physically meaningful parameters. We determine a new EOS for MgSiO3 melt to represent a simplified mantle chemistry based on the empirical molecular dynamics simulations of Spera et al. [2011], and show that it compares well with first-principles simulations and shock data [Stixrude et al. 2005; Mosenfelder et al. 2009]. This model is used to explore how the melting curve's degree of curvature strongly affects its thermodynamic consistency with

  20. Crystal Structure and Superconductivity of PH 3 at High Pressures

    DOE PAGES

    Liu, Hanyu; Li, Yinwei; Gao, Guoying; ...

    2016-01-20

    Here, we performed systematic structure search on solid PH3 at high pressures using particle swarm optimization method. Furthermore, at 100-200 GPa, the search led to two structures consisting of P-P bonds that different from these predicted for H2S. Phonon and electron-phonon calculations indicate both structures are dynamically stable and superconductive. Particularly, the estimated critical temperature for the monoclinic (C2/m) phase of 83 K at 200 GPa is in excellent agreement with a recent experimental report.

  1. Combined crystal structure prediction and high-pressure crystallization in rational pharmaceutical polymorph screening

    NASA Astrophysics Data System (ADS)

    Neumann, M. A.; van de Streek, J.; Fabbiani, F. P. A.; Hidber, P.; Grassmann, O.

    2015-07-01

    Organic molecules, such as pharmaceuticals, agro-chemicals and pigments, frequently form several crystal polymorphs with different physicochemical properties. Finding polymorphs has long been a purely experimental game of trial-and-error. Here we utilize in silico polymorph screening in combination with rationally planned crystallization experiments to study the polymorphism of the pharmaceutical compound Dalcetrapib, with 10 torsional degrees of freedom one of the most flexible molecules ever studied computationally. The experimental crystal polymorphs are found at the bottom of the calculated lattice energy landscape, and two predicted structures are identified as candidates for a missing, thermodynamically more stable polymorph. Pressure-dependent stability calculations suggested high pressure as a means to bring these polymorphs into existence. Subsequently, one of them could indeed be crystallized in the 0.02 to 0.50 GPa pressure range and was found to be metastable at ambient pressure, effectively derisking the appearance of a more stable polymorph during late-stage development of Dalcetrapib.

  2. Final Report. IUT No. B560420 with UC Berkeley. Organic Chemistry at High Pressures &Temperatures

    SciTech Connect

    Montgomery, W; Crowhurst, J C; Zaug, J M; Jeanloz, R

    2007-03-20

    We have successfully completed the research outlined in our proposal: Organic Chemistry at High Pressures and Temperatures. We have experimentally determined a phase diagram which documents the phases and reaction regimes of cyanuric acid , H{sub 3}C{sub 3}N{sub 3}O{sub 3} (1,3,5-triazine-2,4,6-trione), from 300 - 750 K and 0 - 8.1 GPa. We utilized a comparatively new technique to study thin samples of cyanuric acid in the diamond anvil cell in order to collect ambient temperature, high pressure FTIR and Raman data as well as the high-pressure, high-temperature data used in the phase diagram. These experiments made use of the CMLS High-pressure lab's diamond anvil facilities as well as the FTIR and Raman systems.

  3. The effect of high-pressure gases on the solubility and crystallization of L-isoleucine

    NASA Astrophysics Data System (ADS)

    Furuta, Satoshi; Rousseau, Ronald W.; Teja, Amyn S.

    1995-02-01

    The effect of dissolved gases on the morphology and purity of L-isoleucine crystals obtained by cooling crystallization from aqueous solutions was studied. The system investigated consisted of L-isoleucine, containing small amounts of L-leucine and L-valine. The presence of high-pressure carbon dioxide, nitrous oxide, and freon-22 caused a decrease in the solubility of the amino acid by about 10%; whereas the solubility remained the same in the presence of high-pressure helium. The morphology of L-isoleucine crystals obtained by cooling crystallization of the solutions remained unchanged with or without the dissolved gases, as did the amount of the impurities present.

  4. High pressure single crystal and powder XRD study for neighborite

    NASA Astrophysics Data System (ADS)

    Liu, H.

    2016-12-01

    After Murakami et al. (2004) identified the post-perovskite (ppv) phase transition in MgSiO3 perovskite (pv) at pressures and temperatures consistent with the onset of Earth's D" layer, lots of post-perovskite type phase transitions were founded in other similar systems. These discoveries provided a better understanding of heterogeneous structures and seismic anisotropy observed in the controversial region of the lower mantle. With previous experimental evidence showing the analogue system of neighborite NaMgF3 will transform from pv to ppv at 30 GPa, we performed high quality single crystal XRD experiment, which led to a more precise structure determination. Using helium as pressure medium, one metastable low symmetric phase before the pv-ppv structure transition was discovered, whose total energy was calculated as well. The comparison between single crystal and powder XRD data will be presented, and potential application will be discussed.

  5. High Pressure Single Crystal Diffraction at PX^2

    PubMed Central

    Zhang, Dongzhou; Dera, Przemyslaw K.; Eng, Peter J.; Stubbs, Joanne E.; Zhang, Jin S.; Prakapenka, Vitali B.; Rivers, Mark L.

    2017-01-01

    In this report we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell (DAC) at the GSECARS 13-BM-C beamline at the Advanced Photon Source. The DAC program at 13-BM-C is part of the Partnership for Extreme Xtallography (PX^2) project. BX-90 type DACs with conical-type diamond anvils and backing plates are recommended for these experiments. The sample chamber should be loaded with noble gas to maintain a hydrostatic pressure environment. The sample is aligned to the rotation center of the diffraction goniometer. The MARCCD area detector is calibrated with a powder diffraction pattern from LaB6. The sample diffraction peaks are analyzed with the ATREX software program, and are then indexed with the RSV software program. RSV is used to refine the UB matrix of the single crystal, and with this information and the peak prediction function, more diffraction peaks can be located. Representative single crystal diffraction data from an omphacite (Ca0.51Na0.48)(Mg0.44Al0.44Fe2+0.14Fe3+0.02)Si2O6 sample were collected. Analysis of the data gave a monoclinic lattice with P2/n space group at 0.35 GPa, and the lattice parameters were found to be: a = 9.496 ±0.006 Å, b = 8.761 ±0.004 Å, c = 5.248 ±0.001 Å, β = 105.06 ±0.03º, α = γ = 90º. PMID:28117811

  6. High Pressure Single Crystal Diffraction at PX^2.

    PubMed

    Zhang, Dongzhou; Dera, Przemyslaw K; Eng, Peter J; Stubbs, Joanne E; Zhang, Jin S; Prakapenka, Vitali B; Rivers, Mark L

    2017-01-16

    In this report we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell (DAC) at the GSECARS 13-BM-C beamline at the Advanced Photon Source. The DAC program at 13-BM-C is part of the Partnership for Extreme Xtallography (PX^2) project. BX-90 type DACs with conical-type diamond anvils and backing plates are recommended for these experiments. The sample chamber should be loaded with noble gas to maintain a hydrostatic pressure environment. The sample is aligned to the rotation center of the diffraction goniometer. The MARCCD area detector is calibrated with a powder diffraction pattern from LaB6. The sample diffraction peaks are analyzed with the ATREX software program, and are then indexed with the RSV software program. RSV is used to refine the UB matrix of the single crystal, and with this information and the peak prediction function, more diffraction peaks can be located. Representative single crystal diffraction data from an omphacite (Ca0.51Na0.48)(Mg0.44Al0.44Fe(2+)0.14Fe(3+)0.02)Si2O6 sample were collected. Analysis of the data gave a monoclinic lattice with P2/n space group at 0.35 GPa, and the lattice parameters were found to be: a = 9.496 ±0.006 Å, b = 8.761 ±0.004 Å, c = 5.248 ±0.001 Å, β = 105.06 ±0.03º, α = γ = 90º.

  7. Photoluminescence changes of C70 nano/submicro-crystals induced by high pressure and high temperature

    PubMed Central

    Liu, Dedi; Liu, Bingbing; Sundqvist, Bertil; Dong, Dapeng; Li, Zhenghua; Liu, Dongping

    2016-01-01

    Hollow C70 nano/submicro-crystals with a fcc lattice structure were treated under various high pressure and high temperature conditions. The energy band structure was visibly changed by the high pressure and high temperature treatment, and the luminescence of the treated C70 nano/submicro-crystals were tuned from the visible to the near infrared range. In-situ high pressure experiments at room temperature indicate that pressure plays a key role in the tuning of the band gap and PL properties in C70 nanocrystals, and temperature plays an important role in the formation of stable intermolecular bonds and thus to define the final red-shift of the PL peaks. The polymeric phases of C70 nanocrystals treated at high pressure and high temperature were identified from their Raman spectra, which showed a change from monomers to a dimer-rich phase and finally to a phase containing larger, disordered C70 oligomers. PMID:27922133

  8. Photoluminescence changes of C70 nano/submicro-crystals induced by high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Liu, Dedi; Liu, Bingbing; Sundqvist, Bertil; Dong, Dapeng; Li, Zhenghua; Liu, Dongping

    2016-12-01

    Hollow C70 nano/submicro-crystals with a fcc lattice structure were treated under various high pressure and high temperature conditions. The energy band structure was visibly changed by the high pressure and high temperature treatment, and the luminescence of the treated C70 nano/submicro-crystals were tuned from the visible to the near infrared range. In-situ high pressure experiments at room temperature indicate that pressure plays a key role in the tuning of the band gap and PL properties in C70 nanocrystals, and temperature plays an important role in the formation of stable intermolecular bonds and thus to define the final red-shift of the PL peaks. The polymeric phases of C70 nanocrystals treated at high pressure and high temperature were identified from their Raman spectra, which showed a change from monomers to a dimer-rich phase and finally to a phase containing larger, disordered C70 oligomers.

  9. Combined crystal structure prediction and high-pressure crystallization in rational pharmaceutical polymorph screening

    PubMed Central

    Neumann, M. A.; van de Streek, J.; Fabbiani, F. P. A.; Hidber, P.; Grassmann, O.

    2015-01-01

    Organic molecules, such as pharmaceuticals, agro-chemicals and pigments, frequently form several crystal polymorphs with different physicochemical properties. Finding polymorphs has long been a purely experimental game of trial-and-error. Here we utilize in silico polymorph screening in combination with rationally planned crystallization experiments to study the polymorphism of the pharmaceutical compound Dalcetrapib, with 10 torsional degrees of freedom one of the most flexible molecules ever studied computationally. The experimental crystal polymorphs are found at the bottom of the calculated lattice energy landscape, and two predicted structures are identified as candidates for a missing, thermodynamically more stable polymorph. Pressure-dependent stability calculations suggested high pressure as a means to bring these polymorphs into existence. Subsequently, one of them could indeed be crystallized in the 0.02 to 0.50 GPa pressure range and was found to be metastable at ambient pressure, effectively derisking the appearance of a more stable polymorph during late-stage development of Dalcetrapib. PMID:26198974

  10. A high pressure optical cell utilizing single crystal cubic zirconia anvil windows

    NASA Astrophysics Data System (ADS)

    Russell, T. P.; Piermarini, G. J.

    1997-04-01

    A high pressure optical cell capable of producing pressures up to 13.2 GPa using gem-cut single crystal cubic zirconia (CZ) anvils was developed. Maximum pressures obtainable were found to depend upon the particular pressure transmitting medium and gasket material employed. The cubic zirconia anvil high pressure cell (CZAC) provides advantages over the diamond anvil cell in optical and infrared spectroscopy while still maintaining a substantial pressure capability. To demonstrate these advantages, microRaman, optical fluorescence, and infrared absorption measurements were made on diamond, ruby, and 1,3,5-trinitrohexahydro-1,3,5-triazine samples, respectively, using the CZAC cell under high pressure conditions.

  11. First visualization of temperature fields in liquids at high pressure using thermochromic liquid crystals

    NASA Astrophysics Data System (ADS)

    Pehl, M.; Werner, F.; Delgado, A.

    A first application of encapsulated thermochromic liquid crystals (TLCs) for visualizing temperature fields in pressurized liquids was studied experimentally. By means of a tempered high-pressure optical cell, investigations were performed in a wide temperature range and at pressures up to 7000bar. The measured calibration curves of isochromes in the pressure/temperature domain as well as photographically documented temperature fields at high pressure are presented and discussed. The results found illustrate that TLCs provide an efficient instrument for investigating thermofluiddynamical processes even at high pressure.

  12. Growth of Sr2CuO3+ δ superconductor single crystals at high pressure

    NASA Astrophysics Data System (ADS)

    Liang, Wen; Liu, QingQing; Liu, Liang; Kakeshita, Teruhisa; Uchida, Shinichi; Jin, ChangQing

    2013-04-01

    We have successfully synthesized Sr2CuO3+ δ single crystals under high pressure and high temperature for the first time. The structure analysis show that this material crystallizes into tetragonal structure isostructural La2CuO4 with single CuO2 plane. The magnetic susceptibility as well as resistance measurements indicates that the bulk superconductivity with the critical transition temperature 37 K is achieved in the crystal.

  13. Single crystal elasticity of majoritic garnet at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Pamato, M. G.; Kurnosov, A.; Boffa Ballaran, T.; Frost, D. J.; Ziberna, L.; Giannini, M.; Trots, D. M.; Tkachev, S. N.; Zhuravlev, K. K.; Prakapenka, V.

    2013-12-01

    Seismological observations are fundamental for understanding the chemistry and structure of the Earth's interior, providing a tangible method for tracing the chemical anomalies caused by the subduction of oceanic lithosphere. The mineral garnet is a dominant component of subducted mid ocean ridge basalts (MORB) in the upper mantle and transition zone and as such can influence its physical-chemical properties. Among garnet minerals, the high pressure structured majoritic garnet, is stable throughout the entire transition zone, being volumetrically the most abundant mineral phase in this region. In order to constrain the seismic appearance and buoyancy of subducting slabs into the Earth's transition zone, the knowledge of the elastic properties and density of majoritic garnet at high pressures and temperatures is of crucial importance. Here, we report for the first time the P-V-T equation of state and Vs and Vp sound velocities of single crystals of majoritic garnet (Mg3.24Al1.53Si3.23O12) simultaneously determined by means of Brillouin spectroscopy and X ray diffraction, up to 30 GPa and 880 K. Measurements were performed on single-crystals synthesized in a multianvil apparatus at 17 GPa and 1900 °C and loaded in a diamond anvil cell with Ne as a pressure transmitting medium. A single crystal of Sm:YAG, whose fluorescence has been calibrated against an absolute pressure determination, was used as a pressure calibrant. In addition, ruby chips were used to accurately derive the temperature inside the cell. A specially designed internal resistive heater was placed around the diamonds for achieving high temperatures. An accurate pressure scale is a major issue in the investigation of physical properties of mantle minerals at the depth and temperature required to understand the Earth's interior. In this study, simultaneous measurements of density and sound velocities at the same conditions, allowed accurate determinations of the absolute pressure. We combine our

  14. Properties of beryl single crystals grown by a high pressure hydrothermal method

    SciTech Connect

    Furusaki, T.; Bando, Y.; Kodaira, K. ); Matsushita, T. )

    1989-08-01

    The authors discuss beryl crystals grown under high pressure hydrothermal condition of 1 GPa. The optimum crystal growth was observed at 600{sup 0}C and from 0.1N NaOH solution. The beryl crystals from 0.1 - 0.3N NaOH solutions incorporated water molecules and alkali cations in the channels of the beryl structure. The crystals showed same refractive indices and density as those of natural emerald crystals. These physical properties were very similar to natural emeralds.

  15. Initial development of a high-pressure crystal growth facility: Center director's discretionary fund

    NASA Technical Reports Server (NTRS)

    Szofran, F. R.; Lehoczky, S. L.; Cobb, S. D.; Gillies, D. C.

    1993-01-01

    A low-cost, flexible, high-pressure (600 psi) system for crystal growth and related thermophysical properties measurements was designed, assembled, and tested. The furnace system includes a magnetically coupled translation mechanism that eliminates the need for a high-pressure mechanical feedthru. The system is currently being used for continuing crystal growth experiments and thermophysical properties measurements on several material systems including Hg(1-x)Cd(x)Te, Hg(1-x)Zn(x)Te, and Hg(1-x)Zn(x)Se.

  16. Single crystal growth of skutterudite CoP 3 under high pressure

    NASA Astrophysics Data System (ADS)

    Lee, C. H.; Kitô, H.; Ihara, H.; Akita, K.; Yanase, N.; Sekine, C.; Shirotani, I.

    2004-03-01

    A new method to grow single crystals of skutterudite compounds is examined. Using a wedge-type, cubic-anvil, high-pressure apparatus, single crystals of CoP3 were grown from stoichiometric melts under a pressure of 3.5 GPa. Powder X-ray diffraction and electron probe microanalysis measurements indicate that the as-grown boules are a single phase of CoP3. The results suggest that CoP3 is a congruent melting compound under high pressure.

  17. Single crystal structure investigations under high-pressure of the mineral cordierite with an improved high-pressure cell

    NASA Astrophysics Data System (ADS)

    Koepke, J.; Schulz, H.

    1986-05-01

    An improved single-crystal high-pressure anvil cell with beryllium-gaskets was used for the investigations of structure and lattice parameters of cordierite which had been heated in an Ar stream at about 1,000° C to remove natural water from its structural channels. The influences of pressure transmitting media were studied by using water as a pressure medium at pressures of 0.3, 0.9, 1.2, and 2.3 GPa and fluorcarbon, a liquid consisting of large molecules, at 2.2 GPa. Water, but not fluorcarbon, is able to enter the channels in the cordierite structure. Large variations in the lattice constants resulted from changing the pressure medium used. A previously supposed discontinuity of the b lattice constant at nearly 0.3 GPa could not be established by the measurements taken so that there is no evidence for a phase transition at this pressure. Possibly the observed tilting of two tetrahedra against each other in this structure could have led to this misinterpretion. When water, but not fluorcarbon, is used as a pressure medium at 2.3 GPa, an additional electron density peak, presumably a water oxygen atom, appears in the channels. The water prevents the channels from shrinking and fixes their width at a value comparable to that of a naturally hydrated cordierite. In one of the silicate-tetrahedra the Si-O bond lengths are compressed almost 1 percent (2.3 GPa). This process may initiate a phase transition at higher pressures.

  18. Crystal Structure of High-Pressure Phases V and VI of Potassium Dihydrogen Phosphate

    NASA Astrophysics Data System (ADS)

    Nakamoto, Yuki; Sakata, Masafumi; Fujihisa, Hiroshi; Shimizu, Katsuya; Deguchi, Kiyoshi

    2012-06-01

    Potassium dihydrogen phosphate KH2PO4 is the most typical hydrogen-bonded ferroelectric. The P--T phase diagram and the existence of high-pressure phases V and VI have already been reported. However, their crystal structures remain unknown. We performed a powder x-ray diffraction experiment under high pressure using synchrotron radiation and analyzed the structures from the obtained data. The structures of phases V and VI were determined to be orthorhombic C2221 and triclinic P\\bar{1}. Their hydrogen positions were predicted by a density functional theory calculation.

  19. The high-pressure behavior of spherocobaltite (CoCO3): a single crystal Raman spectroscopy and XRD study

    NASA Astrophysics Data System (ADS)

    Chariton, Stella; Cerantola, Valerio; Ismailova, Leyla; Bykova, Elena; Bykov, Maxim; Kupenko, Ilya; McCammon, Catherine; Dubrovinsky, Leonid

    2017-06-01

    Magnesite (MgCO3), calcite (CaCO3), dolomite [(Ca, Mg)CO3], and siderite (FeCO3) are among the best-studied carbonate minerals at high pressures and temperatures. Although they all exhibit the calcite-type structure ({R}\\bar{3}{c} ) at ambient conditions, they display very different behavior at mantle pressures. To broaden the knowledge of the high-pressure crystal chemistry of carbonates, we studied spherocobaltite (CoCO3), which contains Co2+ with cation radius in between those of Ca2+ and Mg2+ in calcite and magnesite, respectively. We synthesized single crystals of pure spherocobaltite and studied them using Raman spectroscopy and X-ray diffraction in diamond anvil cells at pressures to over 55 GPa. Based on single crystal diffraction data, we found that the bulk modulus of spherocobaltite is 128 (2) GPa and K' = 4.28 (17). CoCO3 is stable in the calcite-type structure up to at least 56 GPa and 1200 K. At 57 GPa and after laser heating above 2000 K, CoCO3 partially decomposes and forms CoO. In comparison to previously studied carbonates, our results suggest that at lower mantle conditions carbonates can be stable in the calcite-type structure if the radius of the incorporated cation(s) is equal or smaller than that of Co2+ (i.e., 0.745 Å).

  20. Crystal and Electronic Structure of FeSe at High Pressure and Low Temperature

    SciTech Connect

    Kumar, Ravhi S.; Zhang, Yi; Sinogeikin, Stanislav; Xiao, Yuming; Kumar, Sathish; Chow, Paul; Cornelius, Andrew L.; Chen, Changfeng

    2010-10-22

    We have investigated the high-pressure crystal and electronic structures of superconducting FeSe by high-resolution synchrotron powder X-ray diffraction and density functional theory (DFT) calculations at ambient and at low temperatures down to 8 K. Ambient nuclear resonant inelastic X-ray scattering (NRIXS) experiments were performed on FeSe to understand the partial phonon density of states (PDOS) of the high-pressure phases. On the basis of our experimental results and DFT calculations, we demonstrate a pressure-induced distortion of the low-temperature Cmma phase at around 1.6 GPa and the appearance of a high-pressure Pbnm phase. Upon increasing the pressure above 9 GPa, the orthorhombic phase becomes the major phase, and a mixed-phase region exists up to 26 GPa. The pressure-induced structural changes in this system and its connection to T{sub c} enhancement are discussed.

  1. High Pressure Phase Transformations in Heavy Rare Earth Metals and Connections to Actinide Crystal Structures

    SciTech Connect

    Vohra, Yogesh K.; Sangala, Bagvanth Reddy; Stemshorn, Andrew K.; Hope, Kevin M.

    2008-07-01

    High-pressure studies have been performed on heavy rare earth metals Terbium (Tb) to 155 GPa and Holmium (Ho) to 134 GPa in a diamond anvil cell at room temperature. The following crystal structure sequence was observed in both metals hcp {yields} Sm-type {yields} dhcp {yields} distorted fcc (hR-24) {yields} monoclinic (C2/m) with increasing pressure. The last transformation to a low symmetry monoclinic phase is accompanied by a volume collapse of 5 % for Tb at 51 GPa and a volume collapse of 3 % for Ho at 103 GPa. This volume collapse under high pressure is reminiscent of f-shell delocalization in light rare earth metal Cerium (Ce), Praseodymium (Pr), and heavy actinide metals Americium (Am) and Curium (Cm). The orthorhombic Pnma phase that has been reported in Am and Cm after f-shell delocalization is not observed in heavy rare earth metals under high pressures. (authors)

  2. High-pressure structure and elastic properties of tantalum single crystal: First principles investigation

    NASA Astrophysics Data System (ADS)

    Gu, Jian-Bing; Wang, Chen-Ju; Zhang, Wang-Xi; Sun, Bin; Liu, Guo-Qun; Liu, Dan-Dan; Yang, Xiang-Dong

    2016-12-01

    Since knowledge of the structure and elastic properties of Ta at high pressures is critical for addressing the recent controversies regarding the high-pressure stable phase and elastic properties, we perform a systematical study on the high-pressure structure and elastic properties of the cubic Ta by using the first-principles method. Results show that the initial body-centered cubic phase of Ta remains stable even up to 500 GPa and the high-pressure elastic properties are excellently consistent with the available experimental results. Besides, the high-pressure sound velocities of the single- and poly-crystals Ta are also calculated based on the elastic constants, and the predications exhibit good agreement with the existing experimental data. Project supported by the Basic and Frontier Technical Research Project of Henan Province, China (Grant No. 152300410228), the University Innovation Team Project in Henan Province, China (Grant No. 15IRTSTHN004), and the Key Scientific Research Project of Higher Education of Henan Province, China (Grant No. 17A140014).

  3. Fast high-pressure freezing of protein crystals in their mother liquor

    PubMed Central

    Burkhardt, Anja; Warmer, Martin; Panneerselvam, Saravanan; Wagner, Armin; Zouni, Athina; Glöckner, Carina; Reimer, Rudolph; Hohenberg, Heinrich; Meents, Alke

    2012-01-01

    High-pressure freezing (HPF) is a method which allows sample vitrification without cryoprotectants. In the present work, protein crystals were cooled to cryogenic temperatures at a pressure of 210 MPa. In contrast to other HPF methods published to date in the field of cryocrystallography, this protocol involves rapid sample cooling using a standard HPF device. The fast cooling rates allow HPF of protein crystals directly in their mother liquor without the need for cryoprotectants or external reagents. HPF was first attempted with hen egg-white lysozyme and cubic insulin crystals, yielding good to excellent diffraction quality. Non-cryoprotected crystals of the membrane protein photosystem II have been successfully cryocooled for the first time. This indicates that the presented HPF method is well suited to the vitrification of challenging systems with large unit cells and weak crystal contacts. PMID:22505429

  4. High-pressure mechanical instability in close-packed Hooke's-law crystals

    SciTech Connect

    Ladd, A.J.C.; Hoover, W.G.

    1981-01-15

    Lattice dynamics and molecular dynamics are used to study close-packed crystals with pairwise-additive Hooke's-law interparticle potentials. Lattice dynamics describes a mechanical soft-mode instability at high pressure. In two dimensions molecular dynamics reveals that a thermodynamic transition, from the triangular close-packed lattice to the square lattice, occurs before the soft-mode instability density is reached. Similar phenomena occur in the three-dimensional close-packed lattices.

  5. High-pressure hydrogen testing of single crystal superalloys for advanced rocket engine turbopump turbine blades

    NASA Technical Reports Server (NTRS)

    Parr, R. A.; Alter, W. S.; Johnston, M. H.; Strizak, J. P.

    1985-01-01

    A screening program to determine the effects of high pressure hydrogen on selected candidate materials for advanced single crystal turbine blade applications is examined. The alloys chosen for the investigation are CM SX-2, CM SX-4C, Rene N-4, and PWA1480. Testing is carried out in hydrogen and helium at 34 MPa and room temperature, with both notched and unnotched single crystal specimens. Results show a significant variation in susceptibility to Hydrogen Environment Embrittlement (HEE) among the four alloys and a marked difference in fracture topography between hydrogen and helium environment specimens.

  6. High-pressure hydrogen testing of single crystal superalloys for advanced rocket engine turbopump turbine blades

    NASA Technical Reports Server (NTRS)

    Alter, W. S.; Parr, R. A.; Johnston, M. H.; Strizak, J. P.

    1984-01-01

    A screening program to determine the effects of high pressure hydrogen on selected candidate materials for advanced single crystal turbine blade applications is examined. The alloys chosen for the investigation are CM SX-2, CM SX-4C, Rene N-4, and PWA1480. Testing is carried out in hydrogen and helium at 34 MPa and room temperature, with both notched and unnotched single crystal specimens. Results show a significant variation in susceptibility to Hydrogen Environment Embrittlement (HEE) among the four alloys and a marked difference in fracture topography between hydrogen and helium environment specimens.

  7. Low temperature amorphization and superconductivity in FeSe single crystals at high pressures

    SciTech Connect

    Stemshorn, Andrew K.; Tsoi, Georgiy; Vohra, Yogesh K.; Sinogeiken, Stanislav; Wu, Phillip M.; Huang, Yilin; Rao, Sistla M.; Wu, Maw-Kuen; Yeh, Kuo W.; Weir, Samuel T.

    2010-08-04

    In this study, we report low temperature x-ray diffraction studies combined with electrical resistance measurements on single crystals of iron-based layered superconductor FeSe to a temperature of 10 K and a pressure of 44 GPa. The low temperature high pressure x-ray diffraction studies were performed using a synchrotron source and superconductivity at high pressure was studied using designer diamond anvils. At ambient temperature, the FeSe sample shows a phase transformation from a PbO-type tetragonal phase to a NiAs-type hexagonal phase at 10 {+-} 2 GPa. On cooling, a structural distortion from a PbO-type tetragonal phase to an orthorhombic Cmma phase is observed below 100 K. At a low temperature of 10 K, compression of the orthorhombic Cmma phase results in a gradual transformation to an amorphous phase above 15 GPa. The transformation to the amorphous phase is completed by 40 GPa at 10 K. A loss of superconductivity is observed in the amorphous phase and a dramatic change in the temperature behavior of electrical resistance indicates formation of a semiconducting state at high pressures and low temperatures. The formation of the amorphous phase is attributed to a kinetic hindrance to the growth of a hexagonal NiAs phase under high pressures and low temperatures.

  8. Radiation and Turbulence-Chemistry-Soot-Radiation Interactions in a High-Pressure Turbulent Spray Flame

    NASA Astrophysics Data System (ADS)

    Ferreyro, S.; Paul, C.; Sircar, A.; Imren, A.; Haworth, D. C.; Roy, S.; Modest, M. F.

    2016-11-01

    Simulations are performed of a transient high-pressure turbulent n-dodecane spray flame under engine-relevant conditions. An unsteady RANS formulation is used, with detailed chemistry, a two-equation soot model, various radiation heat transfer models, and a particle-based transported composition probability density function (PDF) method to account for composition and temperature. The PDF model results are compared with those from a locally well-stirred reactor (WSR) model to quantify the effects of turbulence-chemistry-soot-radiation interactions. Computed liquid and vapor penetration versus time, ignition delay, and flame lift-off are in good agreement with experiment, and relatively small differences are seen between the WSR and PDF models for these global quantities. Computed soot levels and spatial distributions from the WSR and PDF models show large differences, with PDF results being in better agreement with experimental measurements. A photon Monte Carlo method with line-by-line spectral resolution is used to compute the spectral intensity distribution of the radiation reachingthe wall. This provides new insight into the relative importance of molecular gas radiation versus soot radiation, and the importance of unresolved turbulent fluctuations on radiative heat transfer.

  9. High-pressure photodissociation of water as a tool for hydrogen synthesis and fundamental chemistry

    PubMed Central

    Ceppatelli, Matteo; Bini, Roberto; Schettino, Vincenzo

    2009-01-01

    High-pressure methods have been demonstrated to be efficient in providing new routes for the synthesis of materials of technological interest. In several molecular compounds, the drastic pressure conditions required for spontaneous transformations have been lowered to the kilobar range by photoactivation of the reactions. At these pressures, the syntheses are accessible to large-volume applications and are of interest to bioscience, space, and environmental chemistry. Here, we show that the short-lived hydroxyl radicals, produced in the photodissociation of water molecules by near-UV radiation at room temperature and pressures of a few tenths of a gigapascal (GPa), can be successfully used to trigger chemical reactions in mixtures of water with carbon monoxide or nitrogen. The detection of molecular hydrogen among the reaction products is of particular relevance. Besides the implications in fundamental chemistry, the mild pressure and irradiation conditions, the efficiency of the process, and the nature of the reactant and product molecules suggest applications in synthesis. PMID:19581572

  10. Coherent diffraction imaging of nanoscale strain evolution in a single crystal under high pressure

    PubMed Central

    Yang, Wenge; Huang, Xiaojing; Harder, Ross; Clark, Jesse N.; Robinson, Ian K.; Mao, Ho-kwang

    2013-01-01

    The evolution of morphology and internal strain under high pressure fundamentally alters the physical property, structural stability, phase transition and deformation mechanism of materials. Until now, only averaged strain distributions have been studied. Bragg coherent X-ray diffraction imaging is highly sensitive to the internal strain distribution of individual crystals but requires coherent illumination, which can be compromised by the complex high-pressure sample environment. Here we report the successful de-convolution of these effects with the recently developed mutual coherent function method to reveal the three-dimensional strain distribution inside a 400 nm gold single crystal during compression within a diamond-anvil cell. The three-dimensional morphology and evolution of the strain under pressures up to 6.4 GPa were obtained with better than 30 nm spatial resolution. In addition to providing a new approach for high-pressure nanotechnology and rheology studies, we draw fundamental conclusions about the origin of the anomalous compressibility of nanocrystals. PMID:23575684

  11. High-Pressure High-Temperature Phase Diagram of the Organic Crystal Paracetamol

    NASA Astrophysics Data System (ADS)

    Smith, Spencer; Montgomery, Jeffrey; Vohra, Yogesh

    High-pressure high-temperature (HPHT) Raman spectroscopy studies have been performed on the organic crystal paracetamol in a diamond anvil cell utilizing boron-doped diamond as heating anvil. The HPHT data obtained from boron-doped diamond heater is cross-checked with data obtained using a standard block heater diamond anvil cell. Isobaric measurements were conducted at pressures up to 8.5 GPa and temperature up to 520 K in a number of different experiments. Solid state phase transitions from monoclinic Form I --> orthorhombic Form II were observed at various pressures and temperatures as well as transitions from Form II --> unknown Form IV. The melting temperature for paracetamol was observed to increase with increasing pressures to 8.5 GPa. Our previous angle dispersive x-ray diffraction studies at the Advanced Photon Source has confirmed the existence of two unknown crystal structures Form IV and Form V of paracetamol at high pressure and ambient temperature. The phase transformation from Form II to Form IV occurs at ~8.5 GPa and from Form IV to Form V occurs at ~11 GPa at ambient temperature. Our new data is combined with the previous ambient temperature high-pressure Raman and X- ray diffraction data to create the first HPHT phase diagram of paracetamol. Doe-NNSA Carnegie DOE Alliance Center (CDAC) under Grant Number DE-NA0002006.

  12. The preparation of BP single crystals by high pressure flux method

    NASA Technical Reports Server (NTRS)

    Kumashiro, Y.; Misawa, S.; Gonda, S.

    1984-01-01

    Single crystals of BP, a III-V compound semiconductor, were obtained by the high pressure flux method. Cu3P and Ni12P5 powders were used as the flux, and mixed with BP powder. Two kinds of mixtures were prepared: (1) 1.8g (BP) + 35 G (Cu3P) and (2) 1.7 g (BP) + 25 g (Ni12P5). They were compressed into pellets, heated at 1300 C for 24 h in an induction furnace under a pressure of 1 MPa using Ar-P2 gas, and slowly cooled to room temperature. In case (1), BP single crystals grew along the (III) plane, and in case (2) they grew as an aggregate of crystallites. The cathodoluminescence spectra of the synthetic BP crystals showed peaks near 680 nm (1.82 eV) for case (1), and 500 nm (2.47 eV) for case (2). By using the high pressure flux method conventional sized crystals were obtained in a relatively short time.

  13. High-pressure high-temperature phase diagram of organic crystal paracetamol.

    PubMed

    Smith, Spencer J; Montgomery, Jeffrey M; Vohra, Yogesh K

    2016-01-27

    High-pressure high-temperature (HPHT) Raman spectroscopy studies have been performed on the organic crystal paracetamol in a diamond anvil cell utilizing boron-doped heating diamond anvil. Isobaric measurements were conducted at pressures up to 8.5 GPa and temperature up to 520 K in five different experiments. Solid state phase transitions from monoclinic Form I  →  orthorhombic Form II were observed at various pressures and temperatures as well as transitions from Form II  →  unknown Form IV. The melting temperature for paracetamol was observed to increase with increasing pressures to 8.5 GPa. This new data is combined with previous ambient temperature high-pressure Raman and x-ray diffraction data to create the first HPHT phase diagram of paracetamol.

  14. Infrared study of α–SiO{sub 2} single crystal under high pressure

    SciTech Connect

    Pellicer-Porres, J. Segura, A.; Santamaría-Pérez, D.

    2016-02-07

    We have measured high pressure α-quartz reflectance spectra in the mid infrared. We used single crystals, taking full profit of polarization. The quality of the spectra allows fitting the reflectance spectra. We have characterized the pressure evolution of E and A{sub 2} modes with increased precision, even in the spectral regions where they overlap. In addition, we have determined the TO-LO splitting of each mode. Some of the A{sub 2} modes show dramatic pressure variations of the LO-TO splitting, which cannot be explained only by changes in length and ionicity of individual bonds, requiring a new mechanism. We suggest that rotation of the SiO{sub 4} tetrahedra plays a fundamental role. We have also determined the evolution of the electronic dielectric constant under high pressure. We find that its pressure increment is mainly a volume effect, although the small increase in birefringence points to secondary changes associated to the electronic resonances.

  15. High-pressure high-temperature phase diagram of organic crystal paracetamol

    NASA Astrophysics Data System (ADS)

    Smith, Spencer J.; Montgomery, Jeffrey M.; Vohra, Yogesh K.

    2016-01-01

    High-pressure high-temperature (HPHT) Raman spectroscopy studies have been performed on the organic crystal paracetamol in a diamond anvil cell utilizing boron-doped heating diamond anvil. Isobaric measurements were conducted at pressures up to 8.5 GPa and temperature up to 520 K in five different experiments. Solid state phase transitions from monoclinic Form I  →  orthorhombic Form II were observed at various pressures and temperatures as well as transitions from Form II  →  unknown Form IV. The melting temperature for paracetamol was observed to increase with increasing pressures to 8.5 GPa. This new data is combined with previous ambient temperature high-pressure Raman and x-ray diffraction data to create the first HPHT phase diagram of paracetamol.

  16. High-pressure high-temperature phase diagram of organic crystal paracetamol

    SciTech Connect

    Smith, Spencer J.; Montgomery, Jeffrey M.; Vohra, Yogesh K.

    2016-01-06

    High-pressure high-temperature (HPHT) Raman spectroscopy studies have been performed on the organic crystal paracetamol in a diamond anvil cell utilizing boron-doped heating diamond anvil. Isobaric measurements were conducted at pressures up to 8.5 GPa and temperature up to 520 K in five different experiments. Solid state phase transitions from monoclinic Form I → orthorhombic Form II were observed at various pressures and temperatures as well as transitions from Form II → unknown Form IV. The melting temperature for paracetamol was observed to increase with increasing pressures to 8.5 GPa. As a result, this new data is combined with previous ambient temperature high-pressure Raman and X- ray diffraction data to create the first HPHT phase diagram of paracetamol.

  17. High-pressure high-temperature phase diagram of organic crystal paracetamol

    DOE PAGES

    Smith, Spencer J.; Montgomery, Jeffrey M.; Vohra, Yogesh K.

    2016-01-06

    High-pressure high-temperature (HPHT) Raman spectroscopy studies have been performed on the organic crystal paracetamol in a diamond anvil cell utilizing boron-doped heating diamond anvil. Isobaric measurements were conducted at pressures up to 8.5 GPa and temperature up to 520 K in five different experiments. Solid state phase transitions from monoclinic Form I → orthorhombic Form II were observed at various pressures and temperatures as well as transitions from Form II → unknown Form IV. The melting temperature for paracetamol was observed to increase with increasing pressures to 8.5 GPa. As a result, this new data is combined with previous ambientmore » temperature high-pressure Raman and X- ray diffraction data to create the first HPHT phase diagram of paracetamol.« less

  18. High-Pressure Crystal Structure, Lattice Vibrations, and Band Structure of BiSbO4.

    PubMed

    Errandonea, Daniel; Muñoz, Alfonso; Rodríguez-Hernández, Placida; Gomis, Oscar; Achary, S Nagabhusan; Popescu, Catalin; Patwe, Sadeque J; Tyagi, Avesh K

    2016-05-16

    The high-pressure crystal structure, lattice-vibrations, and electronic band structure of BiSbO4 were studied by ab initio simulations. We also performed Raman spectroscopy, infrared spectroscopy, and diffuse-reflectance measurements, as well as synchrotron powder X-ray diffraction. High-pressure X-ray diffraction measurements show that the crystal structure of BiSbO4 remains stable up to at least 70 GPa, unlike other known MTO4-type ternary oxides. These experiments also give information on the pressure dependence of the unit-cell parameters. Calculations properly describe the crystal structure of BiSbO4 and the changes induced by pressure on it. They also predict a possible high-pressure phase. A room-temperature pressure-volume equation of state is determined, and the effect of pressure on the coordination polyhedron of Bi and Sb is discussed. Raman- and infrared-active phonons were measured and calculated. In particular, calculations provide assignments for all the vibrational modes as well as their pressure dependence. In addition, the band structure and electronic density of states under pressure were also calculated. The calculations combined with the optical measurements allow us to conclude that BiSbO4 is an indirect-gap semiconductor, with an electronic band gap of 2.9(1) eV. Finally, the isothermal compressibility tensor for BiSbO4 is given at 1.8 GPa. The experimental (theoretical) data revealed that the direction of maximum compressibility is in the (0 1 0) plane at ∼33° (38°) to the c-axis and 47° (42°) to the a-axis. The reliability of the reported results is supported by the consistency between experiments and calculations.

  19. [The high-pressure chemistry, barophysiological chemistry, comparative enzymology of cholinesterase the 100th anniversary from the birth of A. P. Brestkin].

    PubMed

    Rozengart, E V

    2012-01-01

    There are exposed the main landmarks of the scientific biography of Professor Aleksandr Pavlovich Brestkin, connected with his investigations in the field of chemistry of high pressures, physiological chemistry of caisson disease, kinetics of esterase catalysis, and in comparative enzymology of cholinesterases.

  20. Effect of high pressure microfluidization on the crystallization behavior of palm stearin - palm olein blends.

    PubMed

    Han, Lijuan; Li, Lin; Li, Bing; Zhao, Lei; Liu, Guoqin; Liu, Xinqi; Wang, Xuede

    2014-04-24

    Moderate and high microfluidization pressures (60 and 120 MPa) and different treatment times (once and twice) were used to investigate the effect of high-pressure microfluidization (HPM) treatment on the crystallization behavior and physical properties of binary mixtures of palm stearin (PS) and palm olein (PO). The polarized light microscopy (PLM), texture analyzer, X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques were applied to analyze the changes in crystal network structure, hardness, polymorphism and thermal property of the control and treated blends. PLM results showed that HPM caused significant reductions in maximum crystal diameter in all treated blends, and thus led to changes in the crystal network structure, and finally caused higher hardness in than the control blends. The XRD study demonstrated that HPM altered crystalline polymorphism. The HPM-treated blends showed a predominance of the more stable β' form, which is of more interest for food applications, while the control blend had more α- and β-form. This result was further confirmed by DSC observations. These changes in crystallization behavior indicated that HPM treatment was more likely to modify the crystallization processes and nucleation mechanisms.

  1. Reduction of lattice disorder in protein crystals by high-pressure cryocooling.

    PubMed

    Huang, Qingqiu; Gruner, Sol M; Kim, Chae Un; Mao, Yuxin; Wu, Xiaochun; Szebenyi, Doletha M E

    2016-02-01

    High-pressure cryocooling (HPC) has been developed as a technique for reducing the damage that frequently occurs when macromolecular crystals are cryocooled at ambient pressure. Crystals are typically pressurized at around 200 MPa and then cooled to liquid nitrogen temperature under pressure; this process reduces the need for penetrating cryoprotectants, as well as the damage due to cryocooling, but does not improve the diffraction quality of the as-grown crystals. Here it is reported that HPC using a pressure above 300 MPa can reduce lattice disorder, in the form of high mosaicity and/or nonmerohedral twinning, in crystals of three different proteins, namely human glutaminase C, the GTP pyrophosphokinase YjbM and the uncharacterized protein lpg1496. Pressure lower than 250 MPa does not induce this transformation, even with a prolonged pressurization time. These results indicate that HPC at elevated pressures can be a useful tool for improving crystal packing and hence the quality of the diffraction data collected from pressurized crystals.

  2. Reduction of lattice disorder in protein crystals by high-pressure cryocooling

    PubMed Central

    Huang, Qingqiu; Gruner, Sol M.; Kim, Chae Un; Mao, Yuxin; Wu, Xiaochun; Szebenyi, Doletha M. E.

    2016-01-01

    High-pressure cryocooling (HPC) has been developed as a technique for reducing the damage that frequently occurs when macromolecular crystals are cryocooled at ambient pressure. Crystals are typically pressurized at around 200 MPa and then cooled to liquid nitrogen temperature under pressure; this process reduces the need for penetrating cryoprotectants, as well as the damage due to cryocooling, but does not improve the diffraction quality of the as-grown crystals. Here it is reported that HPC using a pressure above 300 MPa can reduce lattice disorder, in the form of high mosaicity and/or nonmerohedral twinning, in crystals of three different proteins, namely human glutaminase C, the GTP pyrophosphokinase YjbM and the uncharacterized protein lpg1496. Pressure lower than 250 MPa does not induce this transformation, even with a prolonged pressurization time. These results indicate that HPC at elevated pressures can be a useful tool for improving crystal packing and hence the quality of the diffraction data collected from pressurized crystals. PMID:26937238

  3. High-pressure crystal structures of an insensitive energetic crystal: 1,1-diamino-2,2-dinitroethene

    SciTech Connect

    Dreger, Zbigniew A.; Stash, Adam I.; Yu, Zhi -Gang; Chen, Yu -Sheng; Tao, Yuchuan; Gupta, Yogendra M.

    2015-12-03

    Understanding the insensitivity/stability of insensitive high explosive crystals requires detailed structural information at high pressures and high temperatures of interest. Synchrotron single crystal x-ray diffraction experiments were used to determine the high-pressure structures of 1,1-diamino-2,2-dinitroethene (FOX-7), a prototypical insensitive high explosive. The phase transition around 4.5 GPa was investigated and the structures were determined at 4.27 GPa (α’-phase) and 5.9 GPa (ε-phase). The α’-phase (monoclinic, P21/n), structurally indistinguishable from the ambient α-phase, transforms to the new ε-phase (triclinic, P1). The most notable features of the ε-phase, compared to the α’-phase, are: formation of planar layers and flattening of molecules. Density functional theory (DFT-D2) calculations complemented the experimental results. Furthermore, the results presented here are important for understanding the molecular and crystalline attributes governing the high-pressure insensitivity/stability of insensitive high explosive crystals.

  4. High-pressure crystal structures of an insensitive energetic crystal: 1,1-diamino-2,2-dinitroethene

    DOE PAGES

    Dreger, Zbigniew A.; Stash, Adam I.; Yu, Zhi -Gang; ...

    2015-12-03

    Understanding the insensitivity/stability of insensitive high explosive crystals requires detailed structural information at high pressures and high temperatures of interest. Synchrotron single crystal x-ray diffraction experiments were used to determine the high-pressure structures of 1,1-diamino-2,2-dinitroethene (FOX-7), a prototypical insensitive high explosive. The phase transition around 4.5 GPa was investigated and the structures were determined at 4.27 GPa (α’-phase) and 5.9 GPa (ε-phase). The α’-phase (monoclinic, P21/n), structurally indistinguishable from the ambient α-phase, transforms to the new ε-phase (triclinic, P1). The most notable features of the ε-phase, compared to the α’-phase, are: formation of planar layers and flattening of molecules. Densitymore » functional theory (DFT-D2) calculations complemented the experimental results. Furthermore, the results presented here are important for understanding the molecular and crystalline attributes governing the high-pressure insensitivity/stability of insensitive high explosive crystals.« less

  5. High-pressure single-crystal synchrotron diffraction study of MnGe and related compounds

    NASA Astrophysics Data System (ADS)

    Valkovskiy, G. A.; Yashina, E. G.; Dyadkin, V. A.; Tsvyashchenko, A. V.; Fomicheva, L. N.; Bykov, M.; Bykova, E.; Dubrovinsky, L.; Chernyshov, D. Yu; Grigoriev, S. V.

    2017-03-01

    Single crystal synchrotron diffraction for pressures up to 50 GPa has revealed an essential difference in structural properties and compressibility of MnGe compared with Mn1-x Co x Ge and Mn1-x Fe x Ge solid solutions. A negative thermal expansion has been observed for MnGe at low-temperatures and high-pressures. The single crystal refinement has shown a discontinuous change of the atomic coordinates and Mn-Ge interatomic distances of MnGe in contrast to Mn0.1Co0.9Ge. These peculiarities of MnGe are likely to be associated with high-spin-low-spin transition. The relation between anisotropy of the coordination of Mn-atom and its magnetic moment is discussed.

  6. CRISTAPRESS: An optical cell for structure development in high-pressure crystallization

    NASA Astrophysics Data System (ADS)

    Boyer, S. A. E.; Fournier, F. E. J.; Gandin, Ch.-A.; Haudin, J.-M.

    2014-01-01

    An original optical high-pressure cell, named CRISTAPRESS, has been especially designed to investigate phase transitions of complex liquids, i.e., polymers, polymer blends, nano-composites, etc. The design of the cell is based on the optical properties of morphological entities through in situ light depolarizing microscopic observations. Pressure up to 200 MPa with a fine temperature control up to 300 °C can be applied. A striking advantage of this cell is the possibility to select the pressure transmitting medium that can be water, silicone oil, a fluid in the supercritical state, etc. The potential of the novel technique was demonstrated by carrying out time-resolved measurements during polymer crystallization induced by water pressure. These preliminary experimental investigations permit to discriminate the role of the barometric and thermal histories on the kinetics of polymer growth, as well as on the subsequent morphologies. It should lead to new reliable crystallization kinetics models.

  7. High-pressure crystal structures and superconductivity of Stannane (SnH4).

    PubMed

    Gao, Guoying; Oganov, Artem R; Li, Peifang; Li, Zhenwei; Wang, Hui; Cui, Tian; Ma, Yanming; Bergara, Aitor; Lyakhov, Andriy O; Iitaka, Toshiaki; Zou, Guangtian

    2010-01-26

    There is great interest in the exploration of hydrogen-rich compounds upon strong compression where they can become superconductors. Stannane (SnH(4)) has been proposed to be a potential high-temperature superconductor under pressure, but its high-pressure crystal structures, fundamental for the understanding of superconductivity, remain unsolved. Using an ab initio evolutionary algorithm for crystal structure prediction, we propose the existence of two unique high-pressure metallic phases having space groups Ama2 and P6(3)/mmc, which both contain hexagonal layers of Sn atoms and semimolecular (perhydride) H(2) units. Enthalpy calculations reveal that the Ama2 and P6(3)/mmc structures are stable at 96-180 GPa and above 180 GPa, respectively, while below 96 GPa SnH(4) is unstable with respect to elemental decomposition. The application of the Allen-Dynes modified McMillan equation reveals high superconducting temperatures of 15-22 K for the Ama2 phase at 120 GPa and 52-62 K for the P6(3)/mmc phase at 200 GPa.

  8. Energy efficient engine high-pressure turbine single crystal vane and blade fabrication technology report

    NASA Technical Reports Server (NTRS)

    Giamei, A. F.; Salkeld, R. W.; Hayes, C. W.

    1981-01-01

    The objective of the High-Pressure Turbine Fabrication Program was to demonstrate the application and feasibility of Pratt & Whitney Aircraft-developed two-piece, single crystal casting and bonding technology on the turbine blade and vane configurations required for the high-pressure turbine in the Energy Efficient Engine. During the first phase of the program, casting feasibility was demonstrated. Several blade and vane halves were made for the bonding trials, plus solid blades and vanes were successfully cast for materials evaluation tests. Specimens exhibited the required microstructure and chemical composition. Bonding feasibility was demonstrated in the second phase of the effort. Bonding yields of 75 percent for the vane and 30 percent for the blade were achieved, and methods for improving these yield percentages were identified. A bond process was established for PWA 1480 single crystal material which incorporated a transient liquid phase interlayer. Bond properties were substantiated and sensitivities determined. Tooling die materials were identified, and an advanced differential thermal expansion tooling concept was incorporated into the bond process.

  9. High-pressure crystal structures and superconductivity of Stannane (SnH4)

    PubMed Central

    Gao, Guoying; Oganov, Artem R.; Li, Peifang; Li, Zhenwei; Wang, Hui; Cui, Tian; Ma, Yanming; Bergara, Aitor; Lyakhov, Andriy O.; Iitaka, Toshiaki; Zou, Guangtian

    2010-01-01

    There is great interest in the exploration of hydrogen-rich compounds upon strong compression where they can become superconductors. Stannane (SnH4) has been proposed to be a potential high-temperature superconductor under pressure, but its high-pressure crystal structures, fundamental for the understanding of superconductivity, remain unsolved. Using an ab initio evolutionary algorithm for crystal structure prediction, we propose the existence of two unique high-pressure metallic phases having space groups Ama2 and P63/mmc, which both contain hexagonal layers of Sn atoms and semimolecular (perhydride) H2 units. Enthalpy calculations reveal that the Ama2 and P63/mmc structures are stable at 96–180 GPa and above 180 GPa, respectively, while below 96 GPa SnH4 is unstable with respect to elemental decomposition. The application of the Allen-Dynes modified McMillan equation reveals high superconducting temperatures of 15–22 K for the Ama2 phase at 120 GPa and 52–62 K for the P63/mmc phase at 200 GPa. PMID:20080576

  10. High pressure chemistry in the H2-SiH4 system

    SciTech Connect

    Wang, S.

    2010-02-24

    Understanding the behavior of hydrogen-rich systems at extreme conditions has significance to both condensed matter physics, where it may provide insight into the metallization and superconductivity of element one, and also to applied research areas, where it can provide guidance for designing improved hydrogen storage materials for transportation applications. Here we report the high-pressure study of the SiH{sub 4}-H{sub 2} binary system up to 6.5 GPa at 300 K in a diamond anvil cell. Raman measurements indicate significant intermolecular interactions between H{sub 2} and SiH{sub 4}. We found that the H{sub 2} vibron frequency is softened by the presence of SiH{sub 4} by as much as 40 cm{sup -1} for the fluid with 50 mol% H{sub 2} compared with pure H{sub 2} fluid at the same pressures. In contrast, the Si-H stretching modes of SiH{sub 4} shift to higher frequency in the mixed fluid compared with pure SiH{sub 4}. Pressure-induced solidification of the H{sub 2}-SiH{sub 4} fluid shows a binary eutectic point at 72({+-}2) mol% H{sub 2} and 6.1({+-}0.1) GPa, above which the fluid crystallizes into a mixture of two nearly end-member solids. Neither solid has a pure end-member composition, with the silane-rich solid containing 0.5-1.5 mol% H{sub 2} and the hydrogen-rich solid containing 0.5-1 mol% SiH{sub 4}. These two crystalline phases can be regarded as doped hydrogen-dominant compounds. We were able to superpressurize the sample by 0.2-0.4 GPa above the eutectic before complete crystallization, indicating extended metastability.

  11. Crystal growth, complex phase diagram and high pressure studies of layer compound PdBi2

    NASA Astrophysics Data System (ADS)

    Zhao, Kui; Zhu, Xiyu; Lv, Bing; Xue, Yuyi; Chu, Paul

    2013-03-01

    Among the different Pd-Bi Alloys, β-PdBi2, which is crystallized in a layered tetragonal (I4/mmm) structure, has been identified as a superconductor with transition temperature at ~ 5.4K. Band structure calculation indicates that the interlayer Bi-Bi bonds are weak but not negligible, which implies the 3D bonding character of this compound. In order to enhance or weaken the interlayer bonding and ultimately increase the Tc in this system, high pressure measurement, isovalent chemical substitution of Bi with Sb, and chemical intercalation using transition metal Cu and alkali metal Na, are applied to the system. Meanwhile, aliovalent chemical substitution on the Bi site by Pb is also carried out. The magnetic, electrical, and calorimetric properties of these compounds are determined at ambient pressure and compared. The detailed high pressure results and the complete phase diagram of chemical substitution and intercalation will be presented and discussed. Work in Houston is supported in part by US AFOSR, the State of Texas, T. L. L. Temple Foundation and John and Rebecca Moores Endowment.

  12. High-pressure crystal growth and electromagnetic properties of 5d double-perovskite Ca₃OsO₆

    SciTech Connect

    Feng, Hai Luke; Shi, Youguo; Guo, Yanfeng; Li, Jun; Sato, Akira; Sun, Ying; Wang, Xia; Yu, Shan; Sathish, Clastin I.; Yamaura, Kazunari

    2013-05-01

    Single crystals of the osmium-containing compound Ca₃OsO₆ have been successfully grown under high-pressure conditions, for the first time. The crystal structure of Ca₃OsO₆ atoms being fully ordered at the perovskite B-site. The electromagnetic analysis shows that the crystal exhibits a semiconductor-like behavior below 300 K and undergoes an antiferromagnetic transition at 50 K. - Graphical Abstract: Schematic image of crystal structure of Ca₃OsO₆ as determined by X-ray diffraction, where the gray and black octahedrons are occupied by Ca and Os, respectively. Top inset reveals an optic image of a typical Ca₃OsO₆ single crystal. Highlights: • Single crystals of Ca₃OsO₆ have been successfully grown under high-pressure. • Ca₃OsO₆ crystalizes into an ordered double-perovskite structure. • The Ca₃OsO₆ undergoes an antiferromagnetic transition at 50 K.

  13. Dynamic High Pressure Study of Chemistry and Physics of Molecular Materials

    NASA Astrophysics Data System (ADS)

    Jezowski, Sebastian Ryszard

    Both temperature and pressure control and influence the packing of molecules in crystalline phases. Our molecular simulations indicate that at ambient pressure, the cubic polymorph of tetracyanoethylene, TCNE, is the energetically stable form up to ˜ 160 K. The observed transition from the cubic to the monoclinic polymorph occurs however only at temperatures above ˜ 318 K due to the large transition barrier. The temperature-induced phase transition in TCNE studied with high-resolution IR spectroscopy is explained in terms of the increased vibrational entropy in the crystals of the monoclinic polymorph. Based upon the inverted design of the Merril-Bassett Diamond Anvil Cell, an improved, second generation dynamic Diamond Anvil Cell was developed. Based on the fluorescence of ruby crystals, we were able to demonstrate that the pressure variation range can be further increased at least up to 7 kbar and that the dynamic pressure compression of up to 1400 GPa/s can be achieved. A new class of mechanophoric system, bis-anthracene, BA, and its photoisomer, PI, is shown to respond reversibly to a mild, static pressure induced by a Diamond Anvil Cell as well as to shear deformation based on absorption spectroscopic measurements. The forward reaction occurs upon illumination with light while the back-reaction may be accelerated upon heating or mechanical stress, coupled to a rehybridization on four equivalent carbon atoms. It is an intriguing result as high pressure stabilizes the photodimerized species in related systems. Our molecular volume simulations ruled out significant differences in the volumes between bis-anthracene and its photoisomer. Kinetic absorption measurements at several different pressures reveal a negative volume of activation in the exothermic back-reaction at room temperature. Through a series of temperature-dependent kinetic measurements it is shown that the barrier of activation for the back-reaction is reduced by more than an order of magnitude at

  14. Single Crystal Preparation for High-Pressure Experiments in the Diamond Anvil Cell

    SciTech Connect

    Aracne, C; Farber, D; Benterou, J; Occelli, F; Krisch, M; Antonangeli, D; Requardt, H; Fiquet, G

    2003-07-01

    Most research conducted in diamond anvil cells (DAC) is performed on polycrystalline samples. While data from polycrystalline samples are sufficient for determining the bulk properties, high-pressure experiments on single crystals allow for measurements on a range of tensor properties such as: thermal and electrical conductivity; magnetic susceptibility; elasticity; and plasticity. However, in order to achieve pressures above 1 Mbar in a DAC, single crystal samples must be <50 m in diameter and <15 m thick while maintaining a high degree of crystallinity. Thus, we have developed new procedures for producing extremely high-quality micro single crystal samples from commercially available material. Our sample preparation steps include cutting, classical metallographic polishing, and laser ablation. The key to our new process is the preservation of crystallinity during cutting and thinning. We have been successful in maintaining orientation, along with an extremely high degree of crystallinity in completed metal samples. To date, we have analyzed cobalt and molybdenum samples with both white-light interferometry and synchrotron x-ray diffraction, and are in the process of extending these methods to other metals and ceramics.

  15. Effects of hydrogen on diamond single crystal synthesized under high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Li, Yong; Jia, Xiaopeng; Song, Mousheng; Ma, Hong-An; Zhou, Zhenxiang; Fang, Chao; Wang, Fangbiao; Chen, Ning; Wang, Ying

    2015-09-01

    In this paper, diamond single crystals doped with LiH and boron additives were synthesized in Fe64Ni36-C system under high pressure and high temperature. Under the fixed pressure condition, we found that the synthesis temperature increased slightly after the addition of LiH in the synthesis system. The {100}-orientated surface morphology was investigated by scanning electron microscopy (SEM). The nitrogen concentration in the obtained diamond was analyzed and evaluated using Fourier transmission infrared spectroscopy (FTIR). Furthermore, the electrical properties of Ib-type and boron-doped diamond before and after hydrogenation using Hall effect measurement, which suggested that the conductivity of diamond co-doped with hydrogen and boron was obviously enhanced than that of boron-doped diamond.

  16. Template-directed high-pressure growth of single-crystal wires within microstructured optical fibers

    NASA Astrophysics Data System (ADS)

    Jackson, Bryan R.

    Microstructured optical fibers (MOFs) have received considerable recent interest due to their novel optical guiding properties and interesting structural design. The structure of these fibers possess capillary holes extending axially within the fiber cladding, which also presents the opportunity for material infusion and the potential for multifunctional optoelectronic devices. Several devices have been realized using gases and liquids in as-drawn fibers, but there are few examples of solid-state material infusion into the capillaries and only one in as-drawn fibers. The research presented in this thesis represents the first demonstration of template-directed, single-crystal wire growth using high-pressure gas. It is also the first demonstration of this type within an extreme aspect-ratio silica capillary fiber, which could lead to a number of technologically innovative developments. Single-crystal silicon wires were grown within silica capillary MOFs using the well-known vapor-liquid-solid (VLS) technique. VLS requires the presence of a metal catalyst, which has a low eutectic temperature with silicon. Gold serves this purpose well and was deposited by a technique created in our laboratory called laser-assisted supercritical fluid deposition (LASCFD). The single-crystal wires were analyzed using optical microscopy and Raman spectroscopy while still encased in the MOF. Femtosecond laser micromachining and buffered-oxide etching were used to remove the single-crystal microwire for analysis by scanning electron microscopy and focused-ion-beam (FIB) milling was used to prepare samples for transmission electron microscopy. The FIB thinned microwires exhibited both <111> and <112> growth directions, which is consistent with previous reports. A number of processing and experimental conditions including temperature, pressure, and gold deposition are examined for their impact on growth of long, single-crystal microwires.

  17. Size and location of ice crystals in pork frozen by high-pressure-assisted freezing as compared to classical methods.

    PubMed

    Martino, M N; Otero, L; Sanz, P D; Zaritzky, N E

    1998-11-01

    In high-pressure-assisted freezing, samples are cooled under pressure (200 MPa) to - 20 °C without ice formation then pressure is released (0.1 MPa) and the high super-cooling reached (approx. 20 °C), promotes uniform and rapid ice nucleation. The size and location of ice crystals in large meat pieces (Longissimus dorsi pork muscle) as a result of high-pressure-assisted freezing were compared to those obtained by air-blast and liquid N(2). Samples from the surface and centre of the frozen muscle were histologically analysed using an indirect technique (isothermal-freeze fixation). Air-blast and cryogenic fluid freezing, having thermal gradients, showed non-uniform ice crystal distributions. High-pressure-assisted frozen samples, both at the surface and at the central zones, showed similar, small-sized ice crystals. This technique is particularly useful for freezing large pieces of food when uniform ice crystal sizes are required.

  18. Effects of catalyst height on diamond crystal morphology under high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Ya-Dong, Li; Xiao-Peng, Jia; Bing-Min, Yan; Ning, Chen; Chao, Fang; Yong, Li; Hong-An, Ma

    2016-04-01

    The effect of the catalyst height on the morphology of diamond crystal is investigated by means of temperature gradient growth (TGG) under high pressure and high temperature (HPHT) conditions with using a Ni-based catalyst in this article. The experimental results show that the morphology of diamond changes from an octahedral shape to a cub-octahedral shape as the catalyst height rises. Moreover, the finite element method (FEM) is used to simulate the temperature field of the melted catalyst/solvent. The results show that the temperature at the location of the seed diamond continues to decrease with the increase of catalyst height, which is conducive to changing the morphology of diamond. This work provides a new way to change the diamond crystal morphology. Project supported by the National Natural Science Foundation of China (Grant No. 51172089), the Program for New Century Excellent Talents in University, the Natural Science Foundation of Guizhou Provincial Education Department (Grant No. KY[2013]183), and the Collaborative Fund of Science and Technology Office of Guizhou Province, China (Grant No. LH[2015]7232).

  19. Exploring charge density analysis in crystals at high pressure: data collection, data analysis and advanced modelling.

    PubMed

    Casati, Nicola; Genoni, Alessandro; Meyer, Benjamin; Krawczuk, Anna; Macchi, Piero

    2017-08-01

    The possibility to determine electron-density distribution in crystals has been an enormous breakthrough, stimulated by a favourable combination of equipment for X-ray and neutron diffraction at low temperature, by the development of simplified, though accurate, electron-density models refined from the experimental data and by the progress in charge density analysis often in combination with theoretical work. Many years after the first successful charge density determination and analysis, scientists face new challenges, for example: (i) determination of the finer details of the electron-density distribution in the atomic cores, (ii) simultaneous refinement of electron charge and spin density or (iii) measuring crystals under perturbation. In this context, the possibility of obtaining experimental charge density at high pressure has recently been demonstrated [Casati et al. (2016). Nat. Commun. 7, 10901]. This paper reports on the necessities and pitfalls of this new challenge, focusing on the species syn-1,6:8,13-biscarbonyl[14]annulene. The experimental requirements, the expected data quality and data corrections are discussed in detail, including warnings about possible shortcomings. At the same time, new modelling techniques are proposed, which could enable specific information to be extracted, from the limited and less accurate observations, like the degree of localization of double bonds, which is fundamental to the scientific case under examination.

  20. Structural and spectroscopical study of crystals of 1,3,4-oxadiazole derivatives at high pressure

    NASA Astrophysics Data System (ADS)

    Franco González, Olga

    2002-07-01

    In recent years the search for new materials of technological interest has given new impulses to the study of organic compounds. Organic substances possess a great number of advantages such as the possibility to adjust their properties for a given purpose by different chemical and physical techniques in the preparation process. Oxadiazole derivatives are interesting due to their use as material for light emitting diodes (LED) as well as scintillators. The physical properties of a solid depend on its structure. Different structures induce different intra- and intermolecular interactions. An advantageous method to modify the intra- as well as the intermolecular interactions of a given substance is the application of high pressure. Furthermore, using this method the chemical features of the compound are not influenced. We have investigated the influence of high pressure and high temperature on the super-molecular structure of several oxadiazole derivatives in crystalline state. From the results of this investigation an equation of state for these crystals was determined. Furthermore, the spectroscopical features of these materials under high pressure were characterized. Die Suche nach neuen Materialien von technischem Interesse hat in den letzten Jahren neue Antriebe zu der Untersuchung organischer Verbindungen gegeben. Organische Substanzen haben viele Vorteile wie z.B. die Möglichkeit, ihre Eigenschaften durch verschiedene chemische und physikalische Techniken im Herstellung-Prozess für ein bestimmtes Ziel zu modifizieren. Oxadiazolverbindungen sind interessant aufgrund ihrer Nutzung als Material für Licht emittierende Dioden und Scintillatoren. Die physikalischen Eigenschaften eines Festkörpers hängen von seiner Struktur ab. Unterschiedliche Strukturen entwickeln unterschiedliche intra- und intermolekülare Wechselwirkungen. Eine ausgezeichnete Weise, um sowohl die intra- als auch die intermolekularen Wechselwirkungen eines bestimmtes Stoffes zu beeinflussen

  1. Comparison of melting and crystallization behaviors of polylactide under high-pressure CO2, N2, and He

    NASA Astrophysics Data System (ADS)

    Nofar, M.; Tabatabaei, A.; Ameli, A.; Park, C. B.

    2014-05-01

    This study investigated the melting and crystallization behaviors of polylactide (PLA) under high-pressure CO2, N2, and helium (He) using a high-pressure differential scanning calorimeter. The results showed that the PLA's melting temperature was depressed only in contact with pressurized CO2 where at high CO2 pressures the lubricating gas molecules induced more imperfect melt and cold crystals during the cooling and heating cycles, respectively. PLA's melt crystallization was analyzed during nonisothermal processes. Despite the effect of dissolved CO2 that expedited the PLA's crystallization rate, N2 showed almost a neutral impact on the PLA's crystallization kinetics. Because of the lower solubility, N2 gas content dissolved in the PLA had a diminutive plasticization effect, and thereby it could only counterbalance its negative hydraulic pressure effect. Moreover, as the helium pressure increased, the PLA's final crystallinity was reduced due to the dominant effect of helium's hydraulic pressure.

  2. Crystal structures of (Mg1-x,Fe(x))SiO3 postperovskite at high pressures.

    PubMed

    Yamanaka, Takamitsu; Hirose, Kei; Mao, Wendy L; Meng, Yue; Ganesh, P; Shulenburger, Luke; Shen, Guoyin; Hemley, Russell J

    2012-01-24

    X-ray diffraction experiments on postperovskite (ppv) with compositions (Mg(0.9)Fe(0.1))SiO(3) and (Mg(0.6)Fe(0.4))SiO(3) at Earth core-mantle boundary pressures reveal different crystal structures. The former adopts the CaIrO(3)-type structure with space group Cmcm, whereas the latter crystallizes in a structure with the Pmcm (Pmma) space group. The latter has a significantly higher density (ρ = 6.119(1) g/cm(3)) than the former (ρ = 5.694(8) g/cm(3)) due to both the larger amount of iron and the smaller ionic radius of Fe(2+) as a result of an electronic spin transition observed by X-ray emission spectroscopy (XES). The smaller ionic radius for low-spin compared to high-spin Fe(2+) also leads to an ordered cation distribution in the M1 and M2 crystallographic sites of the higher density ppv structure. Rietveld structure refinement indicates that approximately 70% of the total Fe(2+) in that phase occupies the M2 site. XES results indicate a loss of 70% of the unpaired electronic spins consistent with a low spin M2 site and high spin M1 site. First-principles calculations of the magnetic ordering confirm that Pmcm with a two-site model is energetically more favorable at high pressure, and predict that the ordered structure is anisotropic in its electrical and elastic properties. These results suggest that interpretations of seismic structure in the deep mantle need to treat a broader range of mineral structures than previously considered.

  3. Evolution of crystal and electronic structures of magnesium dicarbide at high pressure

    PubMed Central

    Wang, Dashuai; Yan, Yan; Zhou, Dan; Liu, Yanhui

    2015-01-01

    Carbon-based compounds exhibit unexpected structures and electronic behavior at high pressure arising from various bonding features of carbon (e.g., sp, sp2 and sp3 C-C bonds). Here we report evolution of crystal structures of MgC2 in a wide pressure range of 0–200 GPa as predicted through ab-initio calculations in combination with an unbiased swarm structure search. Three pressure-induced structural transformations are unraveled, following the phase sequence of ambient-pressure P42/mnm (α-phase) → Cmcm (β-phase) → C2m (γ-phase) → EuGe2-type P-3m1 (δ-phase), where significant C-C bonding modifications from C-C dimer to quasi 1-dimensionzigzag chain, to polymerized ribbon and then to winkled quasi 2- dimension graphite sheet are evident. The predicted β- and γ-phases with sp2 C-C hybridization are metals, while the δ- phase characterized by a sp3C-C hybridization is a narrow-gap semiconductor with a band gap of 0.667 eV. Strong electron-phonon couplings in the compressed β- and γ- phases arepredicted with β-phase showing a high superconducting critical temperature of 11.2 K. The current results indicate that pressure is effective in tuning the crystal and electronic structures of MgC2, which is expected to have impact on physical properties for potential applications. PMID:26634906

  4. Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

    SciTech Connect

    Yamaura, Kazunari

    2016-04-15

    High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

  5. High pressure solid state chemistry of C-N-H and Ti-N systems

    NASA Astrophysics Data System (ADS)

    Salamat, N.

    This thesis presents the use of molecular precursors for the synthesis of solid-state materials through the application of extreme conditions. The main tool for the exploration of these materials was the diamond anvil cell which generated static pressures of up to 85 GPa. Combined with the use of high power lasers, it provides a powerful and efficient technique for high-pressure high- temperature synthesis of solid-state materials. The work presented here is an investigation into the synthesis and recovery of new materials within two solid-state systems, C-N-H and Ti-N-O. Crystallographic analysis of these systems is a challenging process, made more difficult by their relatively light elemental composition and the use of the diamond anvil cell. In both cases a systematic experimental and analytical strategy was adopted to enable the extraction of the best data possible, both qualitatively and statistically. Two C-N-H systems were investigated: C2N3H and C6N9H3.HCl. Synchrotron X-ray diffraction and Raman scattering data are reported for the new dense tetrahedrally bonded phase C2N3H with a defective wurtzite structure. This is synthesised by laser heating from an organic precursor, dicyandiamide, C2N4H4 at high-pressure in a diamond anvil cell. This work confirms the structure deduced in previous work from electron diffraction experiments on samples recovered to ambient conditions. The graphitic layered compound C6N9H3.HCl was subjected to pressures up to 70 GPa in a diamond anvil cell and its structural behaviour was examined using synchrotron X-ray diffraction. The use of laser heating experiments revealed the synthesis of a new carbon nitride phase which is recoverable to ambient conditions. The second group of systems explored was those based on Ti-O-N. Amorphous or nano-crystalline precursors were used to attempt the synthesis of Ti3N4. The high-pressure and temperature behaviour of these materials was examined using synchrotron X-ray diffraction and Raman

  6. Chemical Pressure-Driven Incommensurability in CaPd5: Clues to High-Pressure Chemistry Offered by Complex Intermetallics.

    PubMed

    Kilduff, Brandon J; Fredrickson, Daniel C

    2016-07-05

    While composition and pressure are generally considered orthogonal parameters in the synthesis and optimization of solid state materials, their distinctness is blurred by the concept of chemical pressure (CP): microscopic pressure arising from lattice constraints rather than an externally applied force. In this article, we describe the first cycle of an iterative theoretical/experimental investigation into this connection. We begin by theoretically probing the ability of physical pressure to promote structural transitions in CaCu5-type phases that are driven by CP in other systems. Our results point to the instability of the reported CaCu5-type CaPd5 phase to such a transition even at ambient pressure, suggesting that new structural chemistry should arise at only modest pressures. We thus attempted to synthesize CaPd5 as a starting material for high-pressure experiments. However, rather than obtaining the expected CaCu5-type phase, we encountered crystals of an incommensurately modulated variant CaPd5+q/2, whose composition is related to its satellite spacing, q = qbbasic* with q ≈ 0.44. Its structure was solved and refined in the (3 + 1)D superspace group Cmcm(0β0)s00, revealing CaCu5-type slabs separated by distorted Pd hexagonal nets with an incommensurate periodicity. DFT-CP analysis on a commensurate model for CaPd5+q/2 indicates that the new Pd nets serve to relieve intense negative CPs that the Ca atoms would experience in a CaCu5-type CaPd5 phase but suffer from a desire to contract relative to the rest of the structure. In this way, both the Pd layer substitution and incommensurability in CaPd5+q/2 are anticipated by the CP schemes of simpler model systems, with CP quadrupoles tracing the paths of the favorable atomic motions. This picture offers predictions for how elemental substitution and physical pressure should affect these structural motifs, which could be applicable to the magnetic phase Zr2Co11 whose previously proposed structures show close

  7. High-pressure single-crystal elasticity measurements of Al-Fe-bridgmanite

    NASA Astrophysics Data System (ADS)

    Kurnosov, Alexander; Marquardt, Hauke; Frost, Dan; Boffa-Ballaran, Tiziana; Ziberna, luca

    2017-04-01

    The chemical composition of Earth's lower mantle can be constrained by combining seismological observations with mineral physics elasticity measurements. However, the lack of laboratory data for Earth's most abundant mineral (Mg,Fe,Al)(Al,Fe,Si)O3 bridgmanite has hampered any conclusive result. Here, we report single-crystal elasticity measurements on Al-Fe-bearing bridgmanite (Mg0.9Fe0.1Si0.9Al0.1)O3 to pressures above 40 GPa. The experimetns were conducted using in-situ high-pressure Brillouin spectroscopy and x-ray diffraction combined with advanced sample preparation that allows for the simultaneous loading of two single-crystals with different crystallographic orientations. Our measurements show that the elastic behavior of Fe-Al-bearing bridgmanite is markedly different from the behavior of the MgSiO3 endmember reported previously. Values and uncertainties of K0, K0', G0 and G0' as well as the elastic constants Cij and absolute pressure values for all experimental points were derived using a global fit of all our experimental data, combining the usually employed Christoffel equation that relates elastic constants and density to direction-dependent acoustic wave velocities with the finite strain formalism. We employ our data to model seismic wave velocities in the top portion of the lower mantle, assuming a pyrolitic mantle composition and accounting for depth-dependent changes in iron partitioning between bridgmanite and ferropericlase. We find excellent agreement between our mineral physics predictions and the seismic Preliminary Reference Earth Model down to at least 1200 km depth, indicating chemical homogeneity of the upper and shallow lower mantle. A high Fe3+/Fe2+ ratio of about 2 in shallow lower mantle bridgmanite is required to match seismic data, implying the presence of metallic iron in an isochemical mantle. Our calculated velocities are in increasingly poor agreement with those of the lower mantle at depths >1200 km, possibly indicating a

  8. A high-pressure cryocooling method for protein crystals and biological samples with reduced background X-ray scatter

    PubMed Central

    Kim, Chae Un; Wierman, Jennifer L.; Gillilan, Richard; Lima, Enju; Gruner, Sol M.

    2013-01-01

    High-pressure cryocooling has been developed as an alternative method for cryopreservation of macromolecular crystals and successfully applied for various technical and scientific studies. The method requires the preservation of crystal hydration as the crystal is pressurized with dry helium gas. Previously, crystal hydration was maintained either by coating crystals with a mineral oil or by enclosing crystals in a capillary which was filled with crystallization mother liquor. These methods are not well suited to weakly diffracting crystals because of the relatively high background scattering from the hydrating materials. Here, an alternative method of crystal hydration, called capillary shielding, is described. The specimen is kept hydrated via vapor diffusion in a shielding capillary while it is being pressure cryocooled. After cryocooling, the shielding capillary is removed to reduce background X-ray scattering. It is shown that, compared to previous crystal-hydration methods, the new hydration method produces superior crystal diffraction with little sign of crystal damage. Using the new method, a weakly diffracting protein crystal may be properly pressure cryo­cooled with little or no addition of external cryoprotectants, and significantly reduced background scattering can be observed from the resulting sample. Beyond the applications for macromolecular crystallography, it is shown that the method has great potential for the preparation of noncrystalline hydrated biological samples for coherent diffraction imaging with future X-ray sources. PMID:23396891

  9. Single-crystal CVD diamonds as small-angle X-ray scattering windows for high-pressure research.

    PubMed

    Wang, Suntao; Meng, Yu-Fei; Ando, Nozomi; Tate, Mark; Krasnicki, Szczesny; Yan, Chih-Shiue; Liang, Qi; Lai, Joseph; Mao, Ho-Kwang; Gruner, Sol M; Hemley, Russell J

    2012-06-01

    Small-angle X-ray scattering (SAXS) was performed on single-crystal chemical vapor deposition (CVD) diamonds with low nitrogen concentrations, which were fabricated by microwave plasma-assisted chemical vapor deposition at high growth rates. High optical quality undoped 500 µm-thick single-crystal CVD diamonds grown without intentional nitrogen addition proved to be excellent as windows on SAXS cells, yielding parasitic scattering no more intense than a 7.5 µm-thick Kapton film. A single-crystal CVD diamond window was successfully used in a high-pressure SAXS cell.

  10. Thermoset recycling via high-pressure high-temperature sintering: Revisiting the effect of interchange chemistry

    NASA Astrophysics Data System (ADS)

    Morin, Jeremy Edward

    In 1844 Charles Goodyear obtained U.S. Patent #3,633 for his "Gum Elastic Composition". In a published circular, which describes his patent for the sulfur vulcanization of gum elastic composition, he stated: "No degree of heat, without blaze, can melt it (rubber)... It resists the most powerful chemical reagents. Aquafortis (nitric acid), sulphuric acid, essential and common oils, turpentine and other solvents... ..." Goodyear's sulfur vulcanization of rubber fueled much of the industrial revolution and made transportation possible, as it exists today. In doing so, Goodyear created one of the most difficult materials to recycle. Rubber will not melt, dissolve, or lend itself to the usual methods of chemical decomposition. Ironically, Goodyear recognized this problem and in 1853 he patented the process of adding ground rubber to virgin material, now currently known as regrind blending. Today, scrap tires represent one of the most serious sources of pollution in the world. Studies estimate that there are roughly 2 billion scrap tires in U.S. landfills and more are being added at a rate of over 273 million tires per year. Current methods of recycling waste tires are crude, ineffective, and use rubber powder as a low cost filler instead of a new rubber. The groundwork for a very simple and effective method of producing high-quality rubber goods using 100% scrap rubber was discovered in 1944 by A. V. Tobolsky et al. This application, however, was not recognized until recently in our laboratory. The process as studied to date represents a method of creating quality, high-value added rubber goods with nothing other than heat and pressure. High pressure is required to obtain a void-free compaction of the rubber particles by forcing all of the free surfaces into intimate contact. High temperature then activates the chemical rearrangement, scission, and reformation of the chemical bonds thus providing new bridges between the once fractured interfaces. This occurs both within

  11. High pressure single-crystal micro X-ray diffraction analysis with GSE_ADA/RSV software

    NASA Astrophysics Data System (ADS)

    Dera, Przemyslaw; Zhuravlev, Kirill; Prakapenka, Vitali; Rivers, Mark L.; Finkelstein, Gregory J.; Grubor-Urosevic, Ognjen; Tschauner, Oliver; Clark, Simon M.; Downs, Robert T.

    2013-08-01

    GSE_ADA/RSV is a free software package for custom analysis of single-crystal micro X-ray diffraction (SCμXRD) data, developed with particular emphasis on data from samples enclosed in diamond anvil cells and subject to high pressure conditions. The package has been in extensive use at the high pressure beamlines of Advanced Photon Source (APS), Argonne National Laboratory and Advanced Light Source (ALS), Lawrence Berkeley National Laboratory. The software is optimized for processing of wide-rotation images and includes a variety of peak intensity corrections and peak filtering features, which are custom-designed to make processing of high pressure SCμXRD easier and more reliable.

  12. High-pressure chemistry of hydrogen in metals: in situ study of iron hydride.

    PubMed

    Badding, J V; Hemley, R J; Mao, H K

    1991-07-26

    Optical observations and x-ray diffraction measurements of the reaction between iron and hydrogen at high pressure to form iron hydride are described. The reaction is associated with a sudden pressure-induced expansion at 3.5 gigapascals of iron samples immersed in fluid hydrogen. Synchrotron x-ray diffraction measurements carried out to 62 gigapascals demonstrate that iron hydride has a double hexagonal close-packed structure, a cell volume up to 17% larger than pure iron, and a stoichiometry close to FeH. These results greatly extend the pressure range over which the technologically important iron-hydrogen phase diagram has been characterized and have implications for problems ranging from hydrogen degradation and embrittlement of ferrous metals to the presence of hydrogen in Earth's metallic core.

  13. One-step green synthesis of cuprous oxide crystals with truncated octahedra shapes via a high pressure flux approach

    SciTech Connect

    Li Benxian; Wang Xiaofeng; Xia Dandan; Chu Qingxin; Liu Xiaoyang; Lu Fengguo; Zhao Xudong

    2011-08-15

    Cuprous oxide (Cu{sub 2}O) was synthesized via reactions between cupric oxide (CuO) and copper metal (Cu) at a low temperature of 300 deg. C. This progress is green, environmentally friendly and energy efficient. Cu{sub 2}O crystals with truncated octahedra morphology were grown under high pressure using sodium hydroxide (NaOH) and potassium hydroxide (KOH) with a molar ratio of 1:1 as a flux. The growth mechanism of Cu{sub 2}O polyhedral microcrystals are proposed and discussed. - Graphical Abstract: The Cu{sub 2}O crystals with truncated octahedral shape were one-step synthesized in high yield via high pressure flux method for the first time, which is green and environmentally friendly. The mechanisms of synthesis and crystal growth were discussed in this paper. Highlights: > Cuprous oxide was one-step green synthesized by high pressure flux method. > The approach was based on the reverse dismutation reactions between cupric oxide and copper metal. > This progress is green, environmentally friendly and energy efficient. > The synthesized Cu2O crystals were of truncated octahedra morphology.

  14. High-pressure behavior of natural single-crystal epidote and clinozoisite up to 40 GPa

    NASA Astrophysics Data System (ADS)

    Qin, Fei; Wu, Xiang; Wang, Ying; Fan, Dawei; Qin, Shan; Yang, Ke; Townsend, Joshua P.; Jacobsen, Steven D.

    2016-10-01

    The comparative compressibility and high-pressure stability of a natural epidote (0.79 Fe-total per formula unit, Fetot pfu) and clinozoisite (0.40 Fetot pfu) were investigated by single-crystal X-ray diffraction and Raman spectroscopy. The lattice parameters of both phases exhibit continuous compression behavior up to 30 GPa without evidence of phase transformation. Pressure-volume data for both phases were fitted to a third-order Birch-Murnaghan equation of state with V 0 = 461.1(1) Å3, K 0 = 115(2) GPa, and K0' = 3.7(2) for epidote and V 0 = 457.8(1) Å3, K 0 = 142(3) GPa, and K0' = 5.2(4) for clinozoisite. In both epidote and clinozoisite, the b-axis is the stiffest direction, and the ratios of axial compressibility are 1.19:1.00:1.15 for epidote and 1.82:1.00:1.19 for clinozoisite. Whereas the compressibility of the a-axis is nearly the same for both phases, the b- and c-axes of the epidote are about 1.5 times more compressible than in clinozoisite, consistent with epidote having a lower bulk modulus. Raman spectra collected up to 40.4 GPa also show no indication of phase transformation and were used to obtain mode Grüneisen parameters ( γ i) for Si-O vibrations, which were found to be 0.5-0.8, typical for hydrous silicate minerals. The average pressure coefficient of Raman frequency shifts for M-O modes in epidote, 2.61(6) cm-1/GPa, is larger than found for clinozoisite, 2.40(6) cm-1/GPa, mainly due to the different compressibility of FeO6 and AlO6 octahedra in M3 sites. Epidote and clinozoisite contain about 2 wt% H2O are thus potentially important carriers of water in subducted slabs.

  15. High-pressure floating-zone growth of perovskite nickelate LaNiO3 single crystals

    DOE PAGES

    Zhang, Junjie; Zheng, Hong; Ren, Yang; ...

    2017-04-07

    We report the first single crystal growth of the correlated metal LaNiO3 using a high-pressure optical-image floating zone furnace. The crystals were studied using single crystal/powder X-ray diffraction, resistivity, specific heat, and magnetic susceptibility. The availability of bulk LaNiO3 crystals will (i) promote deep understanding in this correlated material, including the mechanism of enhanced paramagnetic susceptibility, and (ii) provide rich opportunities as a substrate for thin film growth such as important ferroelectric and/or multiferroic materials. As a result, this study demonstrates the power of high pO2 single crystal growth of nickelate perovskites and correlated electron oxides more generally.

  16. High-pressure studies on Tc and crystal structure of iron chalcogenide superconductors

    PubMed Central

    Takahashi, Hiroki; Tomita, Takahiro; Takahashi, Hiroyuki; Mizuguchi, Yoshikazu; Takano, Yoshihiko; Nakano, Satoshi; Matsubayashi, Kazuyuki; Uwatoko, Yoshiya

    2012-01-01

    The superconducting transition temperature, Tc, in iron-based solids can be enhanced by applied pressure: Tc increases from 8 to 37 K for the 11-type FeSe when the pressure is raised from 0 to 4 GPa. High-pressure studies can elucidate the mechanism of superconductivity in such novel materials. In this paper, we present a high-pressure study of Fe(Se1−xTex) and Fe(Se1−xSx). In the case of Fe(Se1−xTex), the maximum Tc under high pressure did not exceed the Tc of FeSe, which can be attributed to the structural transition to the monoclinic phase. For Fe(Se1−xSx) (0 < x < 0.3), Tc exhibited a significant increase with pressure; however, the maximum Tc under high pressure did not exceed the Tc of FeSe. This may be due to the disorder induced by substituting S for Se, which is similar to the pressure effect on Tc for the 1111-type superconductor Ca(Fe1−xCox)AsF. The Tc of Fe(Se1−xSx) showed a complex behavior below 1 GPa, first decreasing and then increasing with increasing pressure. From high-pressure x-ray diffraction measurements, the Tc (P) curve was correlated with the local structural parameter. PMID:27877519

  17. Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Povitsky, Alexander; Dateo, Christopher; Gokcen, Tahir; Willis, Peter A.; Smalley, Richard E.

    2003-01-01

    The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

  18. Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Povitsky, Alexander; Dateo, Christopher; Gokcen, Tahir; Willis, Peter A.; Smalley, Richard E.

    2003-01-01

    The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

  19. Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

    NASA Astrophysics Data System (ADS)

    Yamaura, Kazunari

    2016-04-01

    High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO3, LiOsO3, and Na2OsO4, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal-insulator transition in NaOsO3, a ferroelectric-like transition in LiOsO3, and high-temperature ferrimagnetism driven by a local structural distortion in Ca2FeOsO6 may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices.

  20. Crystallization of diamond from a silicate melt of kimberlite composition in high-pressure and high-temperature experiments

    SciTech Connect

    Arima, Makoto; Nakayama, Kazuhiro ); Akaishi, Minoru; Yamaoka, Shinobu; Kanda, Hisao )

    1993-11-01

    In high-pressure and high-temperature experiments (1800-2200[degrees]C and 7.0-7.7 GPa), diamond crystallized and grew in a volatile-rich silicate melt of kimberlite composition. This diamond has well-developed [111] faces, and its morphologic characteristics resemble those of natural diamond but differ from those of synthetic diamond grown from metallic solvent-catalysts. The kimberlite melt has a strong solvent-catalytic effect on diamond formation, supporting the view that some natural diamonds crystallized from volatile-rich melts in the upper mantle. 19 refs., 3 figs., 1 tab.

  1. High-pressure and high-temperature characteristics of a Fabry-Perot interferometer based on photonic crystal fiber.

    PubMed

    Wu, Chuang; Fu, H Y; Qureshi, Khurram Karim; Guan, Bai-Ou; Tam, H Y

    2011-02-01

    A fiber-optic Fabry-Perot interferometer was constructed by splicing a short length of photonic crystal fiber to a standard single-mode fiber. The photonic crystal fiber functions as a Fabry-Perot cavity and serves as a direct sensing probe without any additional components. Its pressure and temperature responses in the range of 0-40 MPa and 25°C-700°C were experimentally studied. The proposed sensor is easy to fabricate, potentially low-cost, and compact in size, which makes it very attractive for high-pressure and high-temperature sensing applications.

  2. Influence of annealing treatment on as-grown Ib-type diamond crystal at a high temperature and high pressure

    NASA Astrophysics Data System (ADS)

    Huang, Guo-Feng; Yin, Ji-Wen; Bai, Hong-Bo; Hu, Yi-Ga; Kai, Li; Jing, Jing; Ma, Hong-An; Jia, Xiao-Peng

    2012-10-01

    In this paper, we report on the influence of annealing treatment on as-grown Ib-type diamond crystal under high pressure and high temperature in a china-type cubic anvil high-pressure apparatus. Experiments are carried out at a pressure of 7.0 GPa and temperatures ranging from 1700 °C to 1900 °C for 1 h. Annealing treatment of the diamond crystal shows that the aggregation rate constant of nitrogen atoms in the as-grown Ib-type diamond crystal strongly depends on diamond morphology and annealing temperature. The aggregation rate constant of nitrogen remarkably increases with the increase of annealing temperature and its value in octahedral diamond is much higher than that in cubic diamond annealed at the same temperature. The colour of octahedral diamond crystal is obviously reduced from yellow to nearly colorless after annealing treatment for 1 h at 1900 °C, which is induced by nitrogen aggregation in a diamond lattice. The extent of nitrogen aggregation in an annealed diamond could approach approximately 98% indicated from the infrared absorption spectra. The micro-Raman spectrum reveals that the annealing treatment can improve the crystalline quality of Ib-type diamond characterized by a half width at full maximum at first order Raman peak, and therefore the annealed diamond crystals exhibit nearly the same properties as the natural IaA-type diamond stones of high quality in the Raman measurements.

  3. Electronic structure of ytterbium-implanted GaN at ambient and high pressure: experimental and crystal field studies.

    PubMed

    Kaminska, A; Ma, C-G; Brik, M G; Kozanecki, A; Boćkowski, M; Alves, E; Suchocki, A

    2012-03-07

    The results of high-pressure low-temperature optical measurements in a diamond-anvil cell of bulk gallium nitride crystals implanted with ytterbium are reported in combination with crystal field calculations of the Yb(3+) energy levels. Crystal field analysis of splitting of the (2)F(7/2) and (2)F(5/2) states has been performed, with the aim of assigning all features of the experimental luminescence spectra. A thorough analysis of the pressure behavior of the Yb(3+) luminescence lines in GaN allowed the determination of the ambient-pressure positions and pressure dependence of the Yb(3+) energy levels in the trigonal crystal field as well as the pressure-induced changes of the spin-orbit coupling coefficient.

  4. FAST TRACK COMMUNICATION: Single crystals of superconducting SmFeAsO1-xFy grown at high pressure

    NASA Astrophysics Data System (ADS)

    Zhigadlo, N. D.; Katrych, S.; Bukowski, Z.; Weyeneth, S.; Puzniak, R.; Karpinski, J.

    2008-08-01

    Single crystals of SmFeAsO1-xFy of a size up to 120 × 100 µm2 have been grown from NaCl/KCl flux at a pressure of 30 kbar and temperature of 1350-1450 °C using the cubic anvil high-pressure technique. The superconducting transition temperature of the obtained single crystals varies between 45 and 53 K. Obtained crystals are characterized by a full diamagnetic response in low magnetic fields and by a high critical current density in high magnetic fields. Structural refinement has been performed on the single crystal. Differential thermal analysis investigations at 1 bar Ar pressure show decomposition of SmFeAsO1-xFy at 1302 °C.

  5. High Pressure Crystallization of Mafic Magma: Field Observations, Compositional Measurements and Computer Modeling

    NASA Astrophysics Data System (ADS)

    Tracy, R. J.

    2009-05-01

    The Cortlandt Complex is a small early Silurian composite, mafic to ultramafic, anorogenic deep crustal pluton about 60 km N of New York City in which most rocks in the six mapped plutonic phases have resulted from either fractionation or contamination or both. Bender et al (AJS-1984) estimated Cortlandt parental composition as an alkalic gabbro based on the nature of early plutons. The youngest and easternmost pluton consists largely of concentrically layered pyroxenites and olivine pyroxenites (with subequal modal proportions of opx and cpx, and only minor ol) and it appears to have had a different parental magma. Samples collected through a series of layers reflecting a few hundred meters of stratigraphy in layered pyroxenites indicate wide variation in F/FM (0.18 to 0.3) and both Al and Ti contents of pyroxenes are unusually high (cpx - Al2O3 from 6-7 wt percent and TiO2 from 1.0 - 1.5 wt percent; opx - Al2O3 from 3.8 - 5.7 wt percent and TiO2 from 0.2 to 0.7 wt percent). All pyroxenes show significant exsolution of ilm lamellae. Crystallization pressure has been well constrained by thermobarometry of metapelites in the thermal aureole at roughly 0.8 GPa, making this a very unusual example of very high P cumulate formation. Several magma compositions were tested as suitable parents by running computer simulations using MELTS (Ghiorso and Sack, 1995, CMP; Asimow and Ghiorso, 1998, Am. Min.). These MELTS runs quickly eliminated the proposed alkalic gabbro parent - it did not crystallize opx at any P. In this preliminary modeling, the most suitable parental magma for the cumulates was a picritic Karoo basalt (SiO2 - 46.9, TiO2 - 1.6, Al2O3 - 9.3, FeO - 12.2, MgO - 15.9, CaO - 9.1; Na2O - 1.3, K2O - 0.6, P2O5 - 0.2). MELTS runs at 8 kbar and FMQ showed a close approximation to both mineral proportions and mineral chemistry of the Cortlandt samples. The initial liquidus phase was opx at 1421C, ol at 1407C (L 4.4percent crystallized), spl at 1301C (L 19.7 percent

  6. A high-pressure plug flow reactor for combustion chemistry investigations

    NASA Astrophysics Data System (ADS)

    Lu, Zhewen; Cochet, Julien; Leplat, Nicolas; Yang, Yi; Brear, Michael J.

    2017-10-01

    A plug flow reactor (PFR) is built for investigating the oxidation chemistry of fuels at up to 50 bar and 1000 K. These conditions include those corresponding to the low temperature combustion (i.e. the autoignition) that commonly occurs in internal combustion engines. Turbulent flow that approximates ideal, plug flow conditions is established in a quartz tube reactor. The reacting mixture is highly diluted by excess air to reduce the reaction rates for kinetic investigations. A novel mixer design is used to achieve fast mixing of the preheated air and fuel vapour at the reactor entrance, reducing the issue of reaction initialization in kinetic modelling. A water-cooled probe moves along the reactor extracting gases for further analysis. Measurement of the sampled gas temperature uses an extended form of a three-thermocouple method that corrects for radiative heat losses from the thermocouples to the enclosed PFR environment. Investigation of the PFR’s operation is first conducted using non-reacting flows, and then with isooctane oxidation at 900 K and 10 bar. Mixing of the non-reacting temperature and species fields is shown to be rapid. The measured fuel consumption and CO formation are then closely reproduced by kinetic modelling using an extensively validated iso-octane mechanism from the literature and the corrected gas temperature. Together, these results demonstrate the PFR’s utility for chemical kinetic investigations.

  7. High-resolution X-ray crystal structure of bovine H-protein using the high-pressure cryocooling method

    PubMed Central

    Higashiura, Akifumi; Ohta, Kazunori; Masaki, Mika; Sato, Masaru; Inaka, Koji; Tanaka, Hiroaki; Nakagawa, Atsushi

    2013-01-01

    Recently, many technical improvements in macromolecular X-ray crystallography have increased the number of structures deposited in the Protein Data Bank and improved the resolution limit of protein structures. Almost all high-resolution structures have been determined using a synchrotron radiation source in conjunction with cryocooling techniques, which are required in order to minimize radiation damage. However, optimization of cryoprotectant conditions is a time-consuming and difficult step. To overcome this problem, the high-pressure cryocooling method was developed (Kim et al., 2005 ▶) and successfully applied to many protein-structure analyses. In this report, using the high-pressure cryocooling method, the X-ray crystal structure of bovine H-protein was determined at 0.86 Å resolution. Structural comparisons between high- and ambient-pressure cryocooled crystals at ultra-high resolution illustrate the versatility of this technique. This is the first ultra-high-resolution X-ray structure obtained using the high-pressure cryocooling method. PMID:24121354

  8. The Effect of Iron and Aluminium Incorporation on the Single-Crystal Elasticity of Bridgmanite at High Pressure.

    NASA Astrophysics Data System (ADS)

    Kurnosov, A.; Marquardt, H.; Boffa Ballaran, T.; Frost, D. J.

    2015-12-01

    MgSiO3 bridgmanite constitutes about 70% by volume of the Earth's lower mantle and likely governs the physical behavior of this region. Chemical substitutions in MgSiO3 bridgmanite involving Al and Fe may explain seismic velocity anomalies observed in the Earth's lower mantle [1-3]. However, the effects of these substitutions on the anisotropic elastic properties of bridgmanite at high pressure and temperature are still experimentally unconstrained. Here, we present data of internally consistent measurements of the single-crystal elastic properties of Mg0.88Fe0.12Si0.09Al0.11O3 bridgmanite at high-pressures. Two differently oriented single-crystals of brigmanite have been double-side polished and cut as two semi-disks using a FEI Scios Focused Ion Beam (FIB) machine [4]. Two semi-disks, one for each of the crystallographic orientations, were loaded together in the pressure chamber of a diamond anvil cell with helium as a pressure-transmitting medium. Simultaneous measurements of density and sound velocities have been made on both crystals at high pressures using single-crystal X-ray diffraction and Brillouin spectroscopy in order to obtain self-consistent data, which do not depend on a secondary pressure scale. The Brillouin data at each pressure were fitted for both crystals simultaneously in order to reduce correlations among the elastic constants Cij. Our approach allows determining the single-crystal elastic properties of bridgmanite as a function of pressure, derived independently of a secondary pressure. We will use our results for Al-Fe-bearing bridgmanite to discuss the effects of chemical substitution on the high-pressure elasticity of bridgmanite and implications for the interpretation of seismic heterogeneities in Earth's lower mantle. [1] Ni et al. (2005), Geophys. J. Int. 161, 283-294. [2] Masters et al. (2000), AGU Monograph Series, 117, 63-87. [3] Garnero et al. (2005), The Geological Society of America Special Paper, 430, 79-101. [4] Marquardt et al

  9. Crystal structure and stability of Tl2CO3 at high pressures

    PubMed Central

    Grzechnik, A.; Friese, K.

    2010-01-01

    The crystal structure of dithallium carbonate, Tl2CO3 (C2/m, Z = 4), was investigated at pressures of up to 7.4 GPa using single-crystal X-ray diffraction in a diamond anvil cell. It is stable to at least 5.82 GPa. All atoms except for one of the O atoms lie on crystallographic mirror planes. At higher pressures, the material undergoes a phase transition that destroys the single crystal. PMID:20203393

  10. Improved resistance to wear and fatigue fracture in high pressure crystallized vitamin E-containing ultra-high molecular weight polyethylene

    PubMed Central

    Oral, Ebru; Beckos, Christine A. Godleski; Lozynsky, Andrew J.; Malhi, Arnaz S.; Muratoglu, Orhun K.

    2013-01-01

    Higher crystallinity and extended chain morphology are induced in ultra-high molecular weight polyethylene (UHMWPE) in the hexagonal phase at temperatures and pressures above the triple point, resulting in improved mechanical properties. In this study, we report the effects of the presence of a plasticizing agent, namely vitamin E (α-tocopherol), in UHMWPE during high pressure crystallization. We found that this new vitamin E-blended and high pressure crystallized UHMWPE (VEHPE) has improved fatigue strength and wear resistance compared to virgin high pressure crystallized (HP) UHMWPE. This suggested different mechanisms of wear reduction and fatigue crack propagation resistance in UHMWPE. PMID:19135247

  11. Improved resistance to wear and fatigue fracture in high pressure crystallized vitamin E-containing ultra-high molecular weight polyethylene.

    PubMed

    Oral, Ebru; Godleski Beckos, Christine A; Lozynsky, Andrew J; Malhi, Arnaz S; Muratoglu, Orhun K

    2009-04-01

    Higher crystallinity and extended chain morphology are induced in ultra-high molecular weight polyethylene (UHMWPE) in the hexagonal phase at temperatures and pressures above the triple point, resulting in improved mechanical properties. In this study, we report the effects of the presence of a plasticizing agent, namely vitamin E (alpha-tocopherol), in UHMWPE during high pressure crystallization. We found that this new vitamin E-blended and high pressure crystallized UHMWPE (VEHPE) has improved fatigue strength and wear resistance compared to virgin high pressure crystallized (HP) UHMWPE. This suggested different mechanisms of wear reduction and fatigue crack propagation resistance in UHMWPE.

  12. Crystal Structure and Superconductivity of PH 3 at High Pressures

    SciTech Connect

    Liu, Hanyu; Li, Yinwei; Gao, Guoying; Tse, John S.; Naumov, Ivan I.

    2016-01-20

    Here, we performed systematic structure search on solid PH3 at high pressures using particle swarm optimization method. Furthermore, at 100-200 GPa, the search led to two structures consisting of P-P bonds that different from these predicted for H2S. Phonon and electron-phonon calculations indicate both structures are dynamically stable and superconductive. Particularly, the estimated critical temperature for the monoclinic (C2/m) phase of 83 K at 200 GPa is in excellent agreement with a recent experimental report.

  13. High pressure transformation of single-crystal graphite to form molecular carbon onions

    NASA Astrophysics Data System (ADS)

    Blank, V. D.; Denisov, V. N.; Kirichenko, A. N.; Kulnitskiy, B. A.; Martushov, S. Yu; Mavrin, B. N.; Perezhogin, I. A.

    2007-08-01

    Carbon onions were formed in graphite in the diamond anvil high pressure cell under axial pressure combined with shear deformation at room temperature. The onions were ranging in size from 1-2 nm to 1-2 µm and HREM studies have shown that the amount of their concentric shells tended to increase with pressure and deformation growth. Raman spectra were taken from large-size onions. Narrow bands found between 1400 and 1550 cm-1 correspond to fullerene-related carbon materials. The splitting of the pentagonal pinch mode 1446-1489 cm-1 is considered to be connected with the formation of heptagons.

  14. Nonstoichiometry and luminescent properties of ZnSe crystals grown from the melt at high pressures

    NASA Astrophysics Data System (ADS)

    Khanh, Tran; Mozhevitina, Elena; Khomyakov, Andrew; Avetisov, Roman; Davydov, Albert; Chegnov, Vladimir; Antonov, Vladimir; Kobeleva, Svetlana; Zhavoronkov, Nikolai; Avetissov, Igor

    2017-01-01

    50 mm diameter ZnSe crystals have been grown from the melt by a vertical Bridgman technique at 100 atm argon pressure in a graphite crucible. 3D impurities concentration and nonstoichiometry mappings of the grown crystals have been defined by ICP-MS and a direct physic-chemical method, correspondingly. Photoluminescence mapping of the analyzed crystal has been done. It was found out that along the crystal height the nonstoichiometry changed from Se excess over stoichiometrical composition in the cone (bottom) part to Zn excess in the tail (upper) part passing through the stoichiometrical composition in the cylindrical part of the crystal. Metal impurities concentrated in the upper part of the crystal. The gas-forming impurities (H, C, O, N, F) had stochastic distribution but Cl impurity concentrated in the crystal peripheral part (near the crucible walls). It was found out that the as-grown crystal had a single wide PL peal with maximum of 583 nm. A proposal about complex structure luminescent center based on Cl dopant an overstoichiometric Se has been made.

  15. Effect of crystallization water on the structural and electrical properties of CuWO{sub 4} under high pressure

    SciTech Connect

    Wang, Li; Yan, Jiejuan; Liu, Cailong; Liu, Xizhe; Han, Yonghao E-mail: cc060109@qq.com; Gao, Chunxiao E-mail: cc060109@qq.com; Ke, Feng; Wang, Qinglin; Li, Yanchun; Ma, Yanzhang

    2015-11-16

    The effect of crystallization water on the structural and electrical properties of CuWO{sub 4} under high pressure has been investigated by in situ X-ray diffraction and alternating current impedance spectra measurements. The crystallization water was found to be a key role in modulating the structural stability of CuWO{sub 4} at high pressures. The anhydrous CuWO{sub 4} undergoes two pressure-induced structural transitions at 8.8 and 18.5 GPa, respectively, while CuWO{sub 4}·2H{sub 2}O keeps its original structure up to 40.5 GPa. Besides, the crystallization water makes the electrical transport behavior of anhydrous CuWO{sub 4} and CuWO{sub 4}·2H{sub 2}O quite different. The charge carrier transportation is always isotropic in CuWO{sub 4}·2H{sub 2}O, but anisotropic in the triclinic and the third phase of anhydrous CuWO{sub 4}. The grain resistance of CuWO{sub 4}·2H{sub 2}O is always larger than that of anhydrous CuWO{sub 4} in the entire pressure range. By analyzing the relaxation response, we found that the large number of hydrogen bonds can soften the grain characteristic frequency of CuWO{sub 4}·2H{sub 2}O over CuWO{sub 4} by one order of magnitude.

  16. Equation of state and stability of metal crystals at high pressure by DFT calculations

    NASA Astrophysics Data System (ADS)

    Minakov, Dmitry; Levashov, Pavel

    2013-06-01

    In this work we present ab initio equation-of-state calculations for crystals of some metals. Density functional theory at finite temperature (VASP code) is used to obatin the properties of electrons; lattice is simulated in quasi-harmonic approximation at non-zero temperature of electrons. Anharmonic effects are taken into account by the thermal expansion of a crystal. All calculations were performed for aluminum, copper and gold. We compare our results with available shock-wave data in crystal phase, including isentropic expansion. The melting curves are calculated by different criteria; the effect of different temperatures of electrons and ions is taken into account. Also we determine thermodynamic and kinetic boundaries of stability of crystals. Our calculations demonstrate that ab initio approaches can be used to theoretically reconstruct thermodynamically complete EOS of metallic crystals. This work was supported by RFBR grant 12-08-31475 mol a.

  17. High-pressure polymorphs of ZnCO3: Evolutionary crystal structure prediction

    PubMed Central

    Bouibes, A.; Zaoui, A.

    2014-01-01

    The high-pressure behavior of zinc carbonate ZnCO3 has been investigated using universal structure prediction method together with the density functional theory. In order to explore all possible structures under pressure, separate calculations at high pressure are done here with increasing number of formula units in the unit cell. Two pressures induced phase transitions were considered. The first one occurs at 78 GPa and the second one at 121 GPa. The most stable ZnCO3 at ambient condition corresponds to the space group R-3c (phase I), which is in favorable agreement with experiment. The structure with C2/m space group (phase II) becomes stable between 78 GPa and 121 GPa. Finally, the structure with the space group P212121 (phase III) becomes the most stable when the pressure achieves 121 GPa. Some mechanical properties of R-3c structure were –additionally- calculated and compared with the experimental and previous theoretical data. The resulting behaviors support our findings and confirm the obtained phase transition. Besides, from the analysis of the electronic charge density it comes that at 78 GPa, new bond between oxygen and zinc is formed, what is likely the main cause behind the phase transition. PMID:24894072

  18. High-Pressure Freezing, Crystal Structure Studies and Si-CF3 Bond Polarizability of Trimethyl(trifluoromethyl)silane (Postprint)

    DTIC Science & Technology

    2008-11-01

    Base, 10 E. Saturn Boulevard, Building 8451, CA 93524, USA A R T I C L E I N F O Article history: Received 8 May 2008 Received in revised form 14 July ...2008 Accepted 15 July 2008 Available online 29 July 2008 Keywords: Ruppert reagent High pressure X-rays Crystal structure Intermolecular interactions...Group Met. Chem. 24 (2001) 315–350. [8] K. Klatte , D. Christen, I. Merke, W. Stahl, H. Oberhammer, J. Phys. Chem. A 109 (2005) 8438–8442. [9] H

  19. Electrical resistance relaxation induced by high pressure in single crystals of YBa2Cu3O7-δ

    NASA Astrophysics Data System (ADS)

    Khadzhai, G. Ya.; Vovk, R. V.; Vovk, N. R.

    2013-06-01

    An effect of high hydrostatic pressure on the electrical resistance in the ab-plane of single crystals of YBa2Cu3O7-δ with oxygen deficiency is investigated. It is found that the temperature dependence of the electrical resistance is determined by the fluctuation conductivity near Tc and by the scattering of electrons by phonons in a normal state. A high pressure causes the redistribution of labile oxygen, increasing a phase separation. The depressuriazation is accompanied by relaxation processes in both the phonon and the electronic subsystems, the characteristic times of which are significantly different from each other.

  20. Morphology of diamond crystals grown in magnesium-based systems at high temperatures and high pressures

    NASA Astrophysics Data System (ADS)

    Khokhryakov, Alexander F.; Sokol, Alexander G.; Borzdov, Yuri M.; Palyanov, Yuri N.

    2015-09-01

    A series of experiments on diamond growth in the Mg45Cu55-C, Mg50Ni50-C, Mg50Cu25Ni25-C, Mg50Ag25Ni25-C and Mg25Cu25Ni50-C systems at a pressure of 6.3 GPa in the temperature range of 1550-1650 °C was conducted. The morphology of diamond crystals and the features of their growth were studied. The {111} and {100} faces, with the cube faces playing the dominant role, were found to be the plane-faced forms of diamond crystal growth. If the magnesium content in the system is 45-50 at%, crystal growth occurs in the regime of inhibition of the {100} faces with the formation of antiskeletal crystals. In case of a constant intensity of the face inhibition up to its complete growing out, the quasi-faces of trapezohedron {311} are formed with striations in the [110] direction. The inhibition of face growth and formation of antiskeletal crystals are related to oxygen inflow from the cell parts and are accompanied by crystallization of magnesium oxide on the diamond surface. A reduction in the magnesium content in the system from 50 to 25 at% or an increase in the temperature leads to the cessation of {100} face inhibition and promotes growth of plane-faced crystals.

  1. Structural and vibrational properties of single crystals of Scandia, Sc{sub 2}O{sub 3} under high pressure

    SciTech Connect

    Ovsyannikov, Sergey V. E-mail: sergey2503@gmail.com; Wenz, Michelle D.; Pakhomova, Anna S.; Dubrovinsky, Leonid; Bykova, Elena; Bykov, Maxim; Glazyrin, Konstantin; Liermann, Hanns-Peter

    2015-10-28

    We report the results of single-crystal X-ray diffraction and Raman spectroscopy studies of scandium oxide, Sc{sub 2}O{sub 3}, at ambient temperature under high pressure up to 55 and 28 GPa, respectively. Both X-ray diffraction and Raman studies indicated a phase transition from the cubic bixbyite phase (so-called C-Res phase) to a monoclinic C2/m phase (so-called B-Res phase) at pressures around 25–28 GPa. The transition was accompanied by a significant volumetric drop by ∼6.7%. In addition, the Raman spectroscopy detected a minor crossover around 10–12 GPa, which manifested in the appearance of new and disappearance of some Raman modes, as well as in softening of one Raman mode. We found the bulk modulus values of the both C-Res and B-Res phases as B{sub 0} = 198.2(3) and 171.2(1) GPa (for fixed B′ = 4), respectively. Thus, the denser high-pressure lattice of Sc{sub 2}O{sub 3} is much softer than the original lattice. We discuss possible mechanisms that might be responsible for the pronounced elastic softening in the monoclinic high-pressure phase in this “simple” oxide with an ultra-wide band gap.

  2. The Crystal Structure and Behavior of Fenamic Acid-Acridine Complex Under High Pressure.

    PubMed

    Jerzykiewicz, Lucjan; Sroka, Adam; Majerz, Irena

    2016-12-01

    The crystal structure of fenamic acid-acridine complex is determined by X-ray diffraction. The strong OHN hydrogen bond linking the complex components and other interactions responsible for packing of the molecules into a crystal are investigated within the Quantum Theory of Atom in Molecule theory. The crystal structure is compared with the structure optimized at B3LYP/6-311++G** level and with the theoretical structures optimized under systematically changed pressure. Analysis of the lattice constants, hydrogen bond lengths, and angles of the inter- and intramolecular hydrogen bond under compression is performed. The structural transformation observed at 5 GPa is connected with a change in the intermolecular OHN hydrogen bond. The proton shifts to acceptor and a new interaction in the crystal appears.

  3. High-Pressure Effects on the Electronic Structure of Anthracene Single Crystals: Role of Nonhydrostaticity

    SciTech Connect

    Dreger, Zbigniew A.; Balasubramaniam, E.; Gupta, Yogendra M.; Joly, Alan G.

    2009-02-26

    Optical spectroscopy methods were used to examine the effect of nonhydrostaticity on the electronic structure of anthracene single crystals compressed statically to 9 GPa. Two pressure-transmitting media, nitrogen (hydrostatic) and water (nonhydrostatic above ~ 5.5 GPa), were utilized. It was found that nonhydrostatic compression generates several new features both in the absorption and fluorescence spectra: (i) formation of new absorption and fluorescence bands, (ii) deviations in pressure shift of fluorescence peaks, (iii) extensive broadening of vibrational peaks, and (iv) irreversible changes in the spectra shape upon pressure unloading. Furthermore, the time-resolved fluorescence decay curves measured at the wavelength corresponding to the new fluorescence band show clear initial increase. These new features are accompanied by inhomogeneous color changes and macroscopic lines on the (001) plane of the crystal. All of the changes are discussed and correlated with microscopic transformations in the crystal. It is demonstrated that nonhydrostatic compression in anthracene crystal introduces inelastic changes in the form of dislocations along [110] and [1 10 ] directions. These dislocations lead to the development of dimeric structures and, consequently, to various changes in the electronic response of the compressed anthracene crystal.

  4. Crystal Chemistry of Melanite Garnet

    NASA Technical Reports Server (NTRS)

    Nguyen, Dawn Marie

    1999-01-01

    This original project resulted in a detailed crystal chemical data map of a titanium rich garnet (melanite) suite that originates from the Crowsnest Volcanics of Alberta Canada. Garnet is typically present during the partial melting of the earth's mantle to produce basalt. Prior studies conducted at Youngstown State University have yielded questions as to the crystal structure of the melanite. In the Studies conducted at Youngstown State University, through the use of single crystal x-ray diffraction, the c-axis appears to be distorted creating a tetragonal crystal instead of the typical cubic crystal of garnets. The micro probe was used on the same suite of titanium rich garnets as used in the single crystal x-ray diffraction. The combination of the single crystal x-ray research and the detailed microprobe research will allow us to determine the exact crystal chemical structure of the melanite garnet. The crystal chemical data was gathered through the utilization of the SX100 Electron Probe Micro Analyzer. Determination of the exact chemical nature may prove useful in modeling the ultramafic source rock responsible for the formation of the titanium rich lunar basalts.

  5. High Pressure Single Crystal Diffraction at PX2

    SciTech Connect

    Zhang, Dongzhou; Dera, Przemyslaw K.; Eng, Peter J.; Stubbs, Joanne E.; Zhang, Jin S.; Prakapenka, Vitali B.; Rivers, Mark L.

    2017-01-01

    In this report, we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell at the GSECARS 13-BM-C beamline at the Advanced Photon Source. ATREX and RSV programs are used to analyze the data.

  6. High-Pressure Synthesis and Crystal Structure of Ce4B14O27

    PubMed Central

    Hinteregger, Ernst; Perfler, Lukas; Huppertz, Hubert

    2013-01-01

    Ce4B14O27 was synthesized under conditions of 2.6 GPa and 750 °C in a Walker-type multianvil apparatus. The crystal structure was determined on the basis of single-crystal X-ray diffraction data, collected at room temperature, revealing that Ce4B14O27 is isotypic to La4B14O27. Ce4B14O27 crystallizes monoclinically with four formula units in the space group C2/c (No. 15) and the lattice parameters a = 1117.8(2), b = 640.9(2), c = 2531.7(5) pm, and β = 100.2(1)°. The three-dimensional boron-oxygen framework consists of [BO4]5– tetrahedra and trigonal-planar [BO3]3– groups. The structure contains two crystallographically different cerium ions. Furthermore, Raman spectroscopy was performed on single crystals of Ce4B14O27. PMID:25995523

  7. Rediscovering the Crystal Chemistry of Borides.

    PubMed

    Akopov, Georgiy; Yeung, Michael T; Kaner, Richard B

    2017-03-21

    For decades, borides have been primarily studied as crystallographic oddities. With such a wide variety of structures (a quick survey of the Inorganic Crystal Structure Database counts 1253 entries for binary boron compounds!), it is surprising that the applications of borides have been quite limited despite a great deal of fundamental research. If anything, the rich crystal chemistry found in borides could well provide the right tool for almost any application. The interplay between metals and the boron results in even more varied material's properties, many of which can be tuned via chemistry. Thus, the aim of this review is to reintroduce to the scientific community the developments in boride crystal chemistry over the past 60 years. We tie structures to material properties, and furthermore, elaborate on convenient synthetic routes toward preparing borides.

  8. High-pressure high-temperature crystal growth of equiatomic rare earth stannides RENiSn and REPdSn

    SciTech Connect

    Heymann, Gunter; Heying, Birgit; Rodewald, Ute Ch.; Janka, Oliver; Huppertz, Hubert; Pöttgen, Rainer

    2016-04-15

    The two series of equiatomic rare earth (RE) stannides RENiSn and REPdSn were systematically studied with respect to high-pressure modifications. The normal-pressure (NP) low-temperature (LT) modifications were synthesized by arc-melting and subsequently treated under high-pressure (P{sub max}=11.5 GPa) and high-temperature (T{sub max}=1570 K) conditions in a Walker-type multi-anvil press. The pressure and temperature conditions were systematically varied in order to improve the crystallization conditions. The new ZrNiAl-type high-pressure modifications HP-RENiSn (RE=Sc, Y, La, Gd–Lu) and HP-REPdSn (RE=Y, Sm–Dy) were obtained in 80 mg quantities, several of them in X-ray pure form. Some of the REPdSn stannides with the heavy rare earth elements show high-temperature (HT) modifications. The structures of HP-ScNiSn, HP-GdNiSn, HP-DyNiSn (both ZrNiAl-type), NP-YbNiSn, and HT-ErPdSn (both TiNiSi-type) were refined from single crystal diffractometer data, indicating full ordering of the transition metal and tin sites. TiNiSi-type NP-EuPdSn transforms to MgZn{sub 2}-type HP-EuPdSn: P6{sub 3}/mmc, a=588.5(2), c=917.0(3) pm, wR2=0.0769, 211 F{sup 2} values, 11 variables. The structure refinement indicated statistical occupancy of the palladium and tin sites on the tetrahedral network. The X-ray pure high-pressure phases were studied with respect to their magnetic properties. HP-YPdSn is a Pauli paramagnet. The susceptibility data of HP-TbNiSn, HP-DyNiSn, HP-GdPdSn, and HP-TbPdSn show experimental magnetic moments close to the free ion values of RE{sup 3+} and antiferromagnetic ordering at low temperature with the highest Néel temperature of 15.8 K for HP-TbPdSn. HP-SmPdSn shows the typical Van Vleck type behavior along with antiferromagnetic ordering at T{sub N}=5.1 K. HP-EuPdSn shows divalent europium and antiferromagnetic ordering at 8.9 K followed by a spin reorientation at 5.7 K. - Graphical abstract: Packing of the polyhedra in the high-pressure phase of Eu

  9. Crystal Structures and Mechanical Properties of Ca₂C at High Pressure.

    PubMed

    Wei, Qun; Zhang, Quan; Zhang, Meiguang

    2016-07-14

    Recently, a new high-pressure semiconductor phase of Ca₂C (space group Pnma) was successfully synthesized, it has a low-pressure metallic phase (space group C2/m). In this paper, a systematic investigation of the pressure-induced phase transition of Ca₂C is studied on the basis of first-principles calculations. The calculated enthalpy reveals that the phase transition which transforms from C2/m-Ca₂C to Pnma-Ca₂C occurs at 7.8 GPa, and it is a first-order phase transition with a volume drop of 26.7%. The calculated elastic constants show that C2/m-Ca₂C is mechanically unstable above 6.4 GPa, indicating that the structural phase transition is due to mechanical instability. Both of the two phases exhibit the elastic anisotropy. The semiconductivity of Pnma-Ca₂C and the metallicity of C2/m-Ca₂C have been demonstrated by the electronic band structure calculations. The quasi-direct band gap of Pnma-Ca₂C at 0 GPa is 0.86 eV. Furthermore, the detailed analysis of the total and partial density of states is performed to show the specific contribution to the Fermi level.

  10. Preparation and characterization of single crystal samples for high-pressure experiments

    SciTech Connect

    Farber, D; Antonangeli, D; Aracne, C; Benterou, J

    2005-10-26

    To date, most research utilizing the diamond anvil cell (DAC) has been conducted with polycrystalline samples, thus the results are limited to addressing average bulk properties. However, experiments on single crystals can yield data on a range of orientation dependent properties such as thermal and electrical conductivity, magnetic susceptibility, elasticity and plasticity. Here we report new procedures to produce extremely high-quality metallic single crystal samples of size compatible with DAC experiments in the Mbar range. So far, we have produced samples of zinc, Al{sub 2}O{sub 3}, cobalt, molybdenum and cerium, and have evaluated the quality of the finished samples with white-light interferometry, synchrotron x-ray diffraction and inelastic x-ray scattering.

  11. Use of a miniature diamond-anvil cell in high-pressure single-crystal neutron Laue diffraction

    PubMed Central

    Binns, Jack; Kamenev, Konstantin V.; McIntyre, Garry J.; Moggach, Stephen A.; Parsons, Simon

    2016-01-01

    The first high-pressure neutron diffraction study in a miniature diamond-anvil cell of a single crystal of size typical for X-ray diffraction is reported. This is made possible by modern Laue diffraction using a large solid-angle image-plate detector. An unexpected finding is that even reflections whose diffracted beams pass through the cell body are reliably observed, albeit with some attenuation. The cell body does limit the range of usable incident angles, but the crystallographic completeness for a high-symmetry unit cell is only slightly less than for a data collection without the cell. Data collections for two sizes of hexamine single crystals, with and without the pressure cell, and at 300 and 150 K, show that sample size and temperature are the most important factors that influence data quality. Despite the smaller crystal size and dominant parasitic scattering from the diamond-anvil cell, the data collected allow a full anisotropic refinement of hexamine with bond lengths and angles that agree with literature data within experimental error. This technique is shown to be suitable for low-symmetry crystals, and in these cases the transmission of diffracted beams through the cell body results in much higher completeness values than are possible with X-rays. The way is now open for joint X-ray and neutron studies on the same sample under identical conditions. PMID:27158503

  12. Use of a miniature diamond-anvil cell in high-pressure single-crystal neutron Laue diffraction.

    PubMed

    Binns, Jack; Kamenev, Konstantin V; McIntyre, Garry J; Moggach, Stephen A; Parsons, Simon

    2016-05-01

    The first high-pressure neutron diffraction study in a miniature diamond-anvil cell of a single crystal of size typical for X-ray diffraction is reported. This is made possible by modern Laue diffraction using a large solid-angle image-plate detector. An unexpected finding is that even reflections whose diffracted beams pass through the cell body are reliably observed, albeit with some attenuation. The cell body does limit the range of usable incident angles, but the crystallographic completeness for a high-symmetry unit cell is only slightly less than for a data collection without the cell. Data collections for two sizes of hexamine single crystals, with and without the pressure cell, and at 300 and 150 K, show that sample size and temperature are the most important factors that influence data quality. Despite the smaller crystal size and dominant parasitic scattering from the diamond-anvil cell, the data collected allow a full anisotropic refinement of hexamine with bond lengths and angles that agree with literature data within experimental error. This technique is shown to be suitable for low-symmetry crystals, and in these cases the transmission of diffracted beams through the cell body results in much higher completeness values than are possible with X-rays. The way is now open for joint X-ray and neutron studies on the same sample under identical conditions.

  13. High pressure phase transformations in yttrium and scandium: Relation to rare earths and actinides crystal structures

    NASA Astrophysics Data System (ADS)

    Grosshans, W. A.; Vohra, Y. K.; Holzapfel, W. B.

    1982-10-01

    The phase transformations in the 4d transition metal yttrium (Y) and the 3d transition metal scandium (Sc) have been studied under pressures up to 45 GPa by energy dispersive X-ray diffraction. The metal Y shows the complete rare earth crystal structure sequence i.e. hcp→Sm-type→dhcp→fcc with increasing pressure. This establishes experimentally the similarity of Y with heavy lanthanides, and that the rare earth crystal structure sequence is driven by s→d transfer without any significant contribution from 4f electrons. The metal Sc does not undergo the rare earth crystal structure sequence with pressure but shows above 20 GPa β-Neptunium (Np) structure (tetragonal, 4 atoms/cell). This structure remains stable up to the highest pressure of 45 GPa. The occurence of the high temperature β-Np structure in trivalent Sc combined with large thermal expansions of Np and plutonium (Pu) suggest that itinerant 5f electrons become localized at high temperature in Np and Pu close to melting. This Mott transition with temperature is similar to the one observed between Pu and americium (Am).

  14. Analysis of CZT crystals and detectors grown in Russia and the Ukraine by high-pressure Bridgman methods

    SciTech Connect

    H. Hermon; M. Schieber; R. B. James; E. Y. Lee; N. Yang; A. J. Antolak; D. H. Morse; C. Hackett; E. Tarver; N. N. P. Kolesnikov; Yu N. Ivanov; V. Komar; M. S. Goorsky; H. Yoon

    2000-01-10

    Sandia National Laboratories (SNL) is leading an effort to evaluate vertical high pressure Bridgman (VHPB) Cd{sub 1-x}Zn{sub x}Te (CZT) crystals grown in the former Soviet Union (FSU) (Ukraine and Russia), in order to study the parameters limiting the crystal quality and the radiation detector performance. The stoichiometry of the CZT crystals, with 0.04 < x < 0.25, has been determined by methods such as proton-induced X-ray emission (PIXE), X-ray diffraction (XRD), microprobe analysis and laser ablation ICP mass spectroscopy (LA-ICP/MS). Other methods such as triaxial double crystal x-ray diffraction (TADXRD), infrared transmission spectroscopy (IR), atomic force microscopy (AFM), thermoelectric emission spectroscopy (TEES) and laser induced transient charge technique (TCT) were also used to evaluate the material properties. The authors have measured the zinc distribution in a CZT ingot along the axial direction and also its homogeneity. The (Cd+Zn)/Te average ratio measured on the Ukraine crystals was 1.2, compared to the ratio of 0.9-1.06 on the Russian ingots. The IR transmission showed highly decorated grain boundaries with precipitates and hollow bubbles. Microprobe elemental analysis and LA-ICP/MS showed carbon precipitates in the CZT bulk and carbon deposits along grain boundaries. The higher concentration of impurities and the imperfect crystallinity lead to shorter electron and hole lifetimes in the range of 0.5--2 {micro}s and 0.1 {micro}s respectively, compared to 3--20 {micro}s and 1--7 {micro}s measured on US spectrometer grade CZT detectors. These results are consistent with the lower resistivity and worse crystalline perfection of these crystals, compared to US grown CZT. However, recently grown CZT from FSU exhibited better detector performance and good response to alpha particles.

  15. Numerical analysis of a side-hole birefringent photonic crystal fiber with high-pressure sensitivity

    NASA Astrophysics Data System (ADS)

    Li, Duanming; Zhang, Wei; Zhou, Guiyao

    2016-09-01

    A birefringent structured side-holes photonic crystal fiber (PCF) with high sensitivity is designed for pressure sensing. Simulation results show that the birefringence and relevant sensitivity are strongly influenced by the air-holes' sizes and the distance between the fiber core and side-hole. The modal birefringence and the polarimetric pressure sensitivity can be up to 3.943×10-3 and -3.67×10-5 MPa-1 at 1.55 μm, respectively. The proposed side-holes PCF possesses promising applications for pressure sensing.

  16. Experiments with phase transitions at very high pressure. [compressed solidifed gases, semiconductors, superconductors, and molecular crystals

    NASA Technical Reports Server (NTRS)

    Spain, I. L.

    1983-01-01

    Diamond cells were constructed for use to 1 Mbar. A refrigerator for cooling diamond cells was adapted for studies between 15 and 300 K. A cryostat for superconductivity studies between 1.5 to 300 K was constructed. Optical equipment was constructed for fluorescence, transmission, and reflectance studies. X-ray equipment was adapted for use with diamond cells. Experimental techniques were developed for X-ray diffraction studies using synchrotron radiation. AC susceptibility techniques were developed for detecting superconducting transitions. The following materials were studied: compressed solidified gases (Xe, Ar), semiconductors (Ge, Si, GaAs), superconductors (Nb3Ge, Nb3Si, Nb3As, CuCl), molecular crystals (I).

  17. The high-pressure phase of lawsonite: A single crystal study of a key mantle hydrous phase

    NASA Astrophysics Data System (ADS)

    O'Bannon, Earl; Beavers, Christine M.; Kunz, Martin; Williams, Quentin

    2017-08-01

    Lawsonite CaAl2Si2O7(OH)2·H2O is an important water carrier in subducting oceanic crusts and the primary hydrous phase in basalt at depths greater than 80 km. We have conducted high-pressure synchrotron single-crystal X-ray diffraction experiments on natural lawsonite at room temperature up to 10.0 GPa to study its high-pressure polymorphism. We find that lawsonite remains orthorhombic with Cmcm symmetry up to 9.3 GPa and shows nearly isotropic compression. Above 9.3 GPa, lawsonite becomes monoclinic with P21/m symmetry. Across the phase transition, the Ca polyhedron becomes markedly distorted, and the average positions of the H2O molecules and hydroxyls change. The changes observed in the H-atom positions under compression are different than the low-temperature changes in this material. We resolve for the first time the H-bonding configuration of the high-pressure monoclinic phase of lawsonite. A bond valence approach is deployed to determine that the phase transition from orthorhombic to monoclinic is primarily driven by the Si2O7 groups, and in particular their bridging oxygen atoms (O1). The changes in the structure strongly indicate that entropy increases across the symmetry-lowering transition and hence that the slope of the phase transition is negative. Monoclinic lawsonite is thus stable under the pressure and temperature conditions that exist in the Earth and is likely to be a major water carrier in colder, deep subducted slabs. Monoclinic lawsonite also likely has enhanced electrical conductivity along its c axis due to its dynamically disordered hydrogen atoms.

  18. Experimental Comparison of Tantalum Material Strength between Single Crystal [100] and [111] Samples at High Pressure and Strain Rates

    NASA Astrophysics Data System (ADS)

    Plechaty, Christopher; Park, Hye-Sook; Cavallo, Rob; Prisbrey, Shon; Rudd, Robert; Wehrenberg, Christopher; Huntington, Channing; Maddox, Brian; May, Mark; Remington, Bruce

    2013-10-01

    Experiments were performed using the OMEGA laser to investigate Ta material strength at high pressure (1 Mbar), and high strain rates (106-108 s-1) . To achieve these pressures and strain rates in experiment without melting the sample, a quasi-isentropic drive was employed to drive the growth of pre-imposed sinusoidal perturbations embedded on the surface of the Ta sample, via the Rayleigh-Taylor (RT) instability. By measuring the ripple amplitude using face-on high energy (~ 22 KeV) radiography, the strength of the Ta sample was inferred from the amount of RT growth observed. Under these experimental conditions, the Ta material strength can be modeled by the Multiscale (MS) model, developed at LLNL. In this study, we performed a side-by-side comparison of the ripple growth on [100] and [111] orientated single-crystal Ta samples for the same shot and drive conditions. The objective was to determine if a difference in the growth predicted by the MS model could be observed at the high pressure and strain rates present in our experiments, and within the error bars of the experimental technique. Prepared by LLNL under Contract DE-AC52-07NA27344.

  19. Single-crystal elasticity of natural Fe-bearing orthoenstatite across a high-pressure phase transition

    NASA Astrophysics Data System (ADS)

    Zhang, Jin S.; Bass, Jay D.

    2016-08-01

    Sound velocities and elastic moduli have been measured on Fe-bearing orthoenstatite (OEN) single crystals up to 12 GPa by Brillouin spectroscopy. The ambient adiabatic bulk modulus (Ks0) and shear modulus (G0) are determined to be 113(1) GPa and 75.9(7) GPa, respectively. A fourth-order finite strain fit to the data yields pressure derivatives of Ks0' = 8.8(1), Ks0″ = -0.68(6), G0' = 2.9(1), and G0″ = -0.40(2). These values are significantly higher than those for other major mantle minerals up to 10.5 GPa but lower than some previous measurements on OEN. A pronounced increase of shear anisotropy was observed at a pressure of 12.06(9) GPa, coinciding with a phase transition from orthoenstatite to a recently discovered high-pressure phase with space group P21/c. A high-pressure phase transition in OEN is unlikely to be the cause of the X discontinuity in the 250-325 km depth range. Rather, a change in seismic anisotropy would be expected to accompany the orthoenstatite-to-P21/c phase transition in the upper mantle at greater depths.

  20. Crystal Structure of Carbon Dioxide at High Pressure: ''Superhard'' Polymeric Carbon Dioxide

    SciTech Connect

    Yoo, C. S.; Cynn, H.; Gygi, F.; Galli, G.; Iota, V.; Nicol, M.; Carlson, S.; Haeusermann, D.; Mailhiot, C.

    1999-12-27

    The crystal structures of two molecular phases (I and III) and a polymeric phase (V) of CO{sub 2} have been investigated to 60 GPa. CO{sub 2}- I (Pa3) transforms to CO{sub 2}- III (Cmca) at 12 GPa with almost no change of density. Although CO{sub 2}- III persists in Cmca to at least 60 GPa at ambient temperature, it transforms when heated to 1800 K above 40 GPa to tridymite (P2{sub 1}2{sub 1}2{sub 1}) CO{sub 2}- V with 15.3% volume change. Each carbon atom of CO{sub 2}- V is tetrahedrally bonded to four oxygen atoms. CO{sub 2}- V is likely superhard with low compressibility B{sub 0}=365 GPa , similar to cubic BN. (c) 1999 The American Physical Society.

  1. High-pressure single-crystal X-ray diffraction study of jadeite and kosmochlor

    NASA Astrophysics Data System (ADS)

    Posner, Esther S.; Dera, Przemyslaw; Downs, Robert T.; Lazarz, John D.; Irmen, Peyton

    2014-10-01

    The crystal structures of natural jadeite, NaAlSi2O6, and synthetic kosmochlor, NaCrSi2O6, were studied at room temperature, under hydrostatic conditions, up to pressures of 30.4 (1) and 40.2 (1) GPa, respectively, using single-crystal synchrotron X-ray diffraction. Pressure-volume data have been fit to a third-order Birch-Murnaghan equation of state yielding V 0 = 402.5 (4) Å3, K 0 = 136 (3) GPa, and K {0/'} = 3.3 (2) for jadeite and V 0 = 420.0 (3) Å3, K 0 = 123 (2) GPa and K {0/'} = 3.61 (9) for kosmochlor. Both phases exhibit anisotropic compression with unit-strain axial ratios of 1.00:1.95:2.09 for jadeite at 30.4 (1) GPa and 1:00:2.15:2.43 for kosmochlor at 40.2 (1) GPa. Analysis of procrystal electron density distribution shows that the coordination of Na changes from 6 to 8 between 9.28 (Origlieri et al. in Am Mineral 88:1025-1032, 2003) and 18.5 (1) GPa in kosmochlor, which is also marked by a decrease in unit-strain anisotropy. Na in jadeite remains six-coordinated at 21.5 (1) GPa. Structure refinements indicate a change in the compression mechanism of kosmochlor at about 31 GPa in both the kinking of SiO4 tetrahedral chains and rate of tetrahedral compression. Below 31 GPa, the O3-O3-O3 chain extension angle and Si tetrahedral volume in kosmochlor decrease linearly with pressure, whereas above 31 GPa the kinking ceases and the rate of Si tetrahedral compression increases by greater than a factor of two. No evidence of phase transitions was observed over the studied pressure ranges.

  2. Effects of FeNi-phosphorus-carbon system on crystal growth of diamond under high pressure and high temperature conditions

    NASA Astrophysics Data System (ADS)

    Hu, Mei-Hua; Bi, Ning; Li, Shang-Sheng; Su, Tai-Chao; Zhou, Ai-Guo; Hu, Qiang; Jia, Xiao-Peng; Ma, Hong-An

    2015-03-01

    This paper reports the crystal growth of diamond from the FeNi-Carbon system with additive phosphorus at high pressures and high temperatures of 5.4-5.8 GPa and 1280-1360 °C. Attributed to the presence of additive phosphorus, the pressure and temperature condition, morphology, and color of diamond crystals change obviously. The pressure and temperature condition of diamond growth increases evidently with the increase of additive phosphorus content and results in the moving up of the V-shape region. The surfaces of the diamonds also become coarse as the additive phosphorus added in the growth system. Raman spectra indicate that diamonds grown from the FeNi-phosphorus-carbon system have more crystal defects and impurities. This work provides a new way to enrich the doping of diamond and improve the experimental exploration for future material applications. Project supported by the Doctoral Fund of Henan Polytechnic University, China (Grant Nos. B2013-013 and B2013-044) and the Research Projects of Science and Technology of the Education Department of Henan Province, China (Grant Nos. 14B430026 and 12A430010).

  3. Solid ammonia at high pressure: A single-crystal x-ray diffraction study to 123GPa

    NASA Astrophysics Data System (ADS)

    Datchi, F.; Ninet, S.; Gauthier, M.; Saitta, A. M.; Canny, B.; Decremps, F.

    2006-05-01

    The high-pressure phases of solid ammonia have been investigated by x-ray diffraction in a diamond anvil cell at room temperature. Despite the first-order solid phase transition at 4GPa , quasi-single crystals of NH3 and ND3 could be obtained and compressed to 123 and 62GPa , respectively. The observed reflections above 4GPa are compatible with the structure determined by neutron diffraction on ND3 . We found strong evidence for an isosymmetric transition at 12GPa in NH3 and 18GPa in ND3 . This transition is more likely due to rearrangements of the hydrogen atoms, whereas the N atoms remain on their quasi-hcp sites. The experimental equation of state (EOS) is compared to the one derived from first-principles calculations. A stiffening of the EOS above 55GPa could indicate the onset of a quantum-disordered regime for some of the H bonds.

  4. High-pressure Raman study of two ferroelectric crystals closely related to PbTiO3

    NASA Astrophysics Data System (ADS)

    Burns, Gerald; Sanjurjo, J. A.; López-Cruz, E.

    1984-12-01

    We report high-pressure Raman measurements of the zone-center phonons in two ferroelectric crystals that closely resemble the ABO3 perovskite crystal PbTiO3. These crystals are (Pb0.22Ba0.78)TiO3, i.e., Ba replacing Pb on the A site, and Pb(Ti0.81Sn0.19)O3, i.e., Sn replacing Ti on the B site. In both cases, at room temperature, we follow the modes and determine Pc, the transition pressure from the ferroelectric tetragonal phase to the cubic phase, to be 4.3 and 9.0 GPa, respectively. By observing the coalescence to the same frequency of the appropriate high-energy A1(TO)+E(TO) pairs of phonons, we determine the second-order character of the phase transitions at Pc. The tendency towards a second-order phase transition seems to be the rule at Pc as long as one makes the measurements at a temperature well below Tc; this is in agreement with theory. Thus, these systems exhibit tricritical points in the (P,T) phase diagram. The soft-E(TO)-phonon frequency (ω0) and damping constant (γ) can be measured to pressures reasonably close to Pc while the mode remains underdamped. These results are discussed in terms of a frequency-independent damping constant for the behavior of ω0 and γ near Pc. In the (Pb,Ba)TiO3 crystal, the hydrostatic pressure increases the intensity of the soft A1(TO) mode making it observable. This seems to happen in general in the perovskites. In the Pb(Ti,Sn)O3 crystal we observe the coupling of the soft E(TO) mode with an extra mode at 59 cm-1; this also has been studied as a function of temperature.

  5. High-pressure Raman study of mono-L-alaninium nitrate crystals

    NASA Astrophysics Data System (ADS)

    Soares, R. A.; Lima, R. J. C.; Façanha Filho, P. F.; Freire, P. T. C.; Lima, J. A.; da Silva Filho, J. G.

    2017-09-01

    Single-crystal samples of mono-L-alaninium nitrate, known for its non-linear optical properties, have been studied by Raman spectroscopy in a diamond-anvil cell up to pressures of 7.4 GPa. The data acquired in this study are consistent with the hypothesis that a phase transition takes place between 3.5 and 4.1 GPa, as suggested by the change of Raman profile in both the low wavenumber and the internal modes spectral regions. A detailed analysis of the vibrational properties in the wavenumber region below 130 cm-1 including the dependence of the wavenumber of the observed modes as a function of pressure as well a comparison with previous papers reporting the Raman spectra of the L-alanine is presented. Correlation between hydrogen bond at room pressure and the occurrence of the phase transition with pressure variation was proposed giving new insights about the problem. Upon decompression to ambient pressure the original spectra were recovered indicating that the phase transition is reversible.

  6. Elasticity of single-crystal superhydrous phase B at simultaneous high pressure-temperature conditions

    NASA Astrophysics Data System (ADS)

    Li, Xinyang; Mao, Zhu; Sun, Ningyu; Liao, Yifan; Zhai, Shuangmeng; Wang, Yi; Ni, Huaiwei; Wang, Jingyun; Tkachev, Sergey N.; Lin, Jung-Fu

    2016-08-01

    We investigated the combined effect of pressure and temperature on the elasticity of single-crystal superhydrous phase B (Shy-B) using Brillouin scattering and X-ray diffraction up to 12 GPa and 700 K. Using the obtained elasticity, we modeled the anisotropy of Shy-B along slab geotherms, showing that Shy-B has a low anisotropy and cannot be the major cause of the observed anisotropy in the region. Modeled velocities of Shy-B show that Shy-B will be shown as positive velocity anomalies at the bottom transition zone. Once Shy-B is transported to the topmost lower mantle, it will exhibit a seismic signature of lower velocities than topmost lower mantle. We speculate that an accumulation of hydrous phases, such as Shy-B, at the topmost lower mantle with a weight percentage of ~17-26% in the peridotite layer as subduction progresses could help explain the observed 2-3% low shear velocity anomalies in the region.

  7. Modeling and design of an advanced high pressure system for III-V compound synthesis and crystal growth

    NASA Astrophysics Data System (ADS)

    Jafri, Ijaz Hussain

    Indium Phosphide (InP) is an important substrate material for opto-electronics and light-wave communications. In many applications InP-based devices are found to be superior in performance than GaAs, Ge or Si based devices. However, its broad use has been limited because of the quality and cost of commercially available substrates. The primary objective of this research is to design and develop an advanced high pressure system to implement the novel technique of "one-step" in-situ synthesis and growth of InP crystals. Detailed numerical modeling and engineering analysis/design is performed to examine the critical issues associated with the growth of large diameter (up to 150 mm) III-V compound crystals. After design and fabrication, experimental work on conducted for InP synthesis. The research indicates that multiple hotzones are needed to reduce the thermal stresses in as-grown crystals. The hotzone insulation package should be strategically designed to allow more heat loss in the axial direction; a water-cooled shaft can help to accomplish this. To reduce gas convection, empty spaces should be minimized. To obtain uniform temperature and dopant distributions, a moderate rotation rate may be appropriate in the proposed configurations; higher rotation rates may cause the flow to become unsteady and turbulent. It may be desirable to use slightly higher rotation rates in the beginning and lower towards the end of growth. The modeling study also supports the use of a magnetic field to suppress flow oscillations and to control interface shape. Several innovations are proposed in the new design. The most significant are the independently-controlled injection system with its unique ball valve and multi-component arrangement that allows flexibility not seen in other high pressure systems, and a multi-span high-resolution weight monitoring system for crucible and crystal/injector. Experiments are conducted to study the effect of pressure, the thermal profiling, and the

  8. Phase diagram and decomposition of 1,1-diamino-2,2-dinitroethene single crystals at high pressures and temperatures

    SciTech Connect

    Dreger, Zbigniew A.; Tao, Yuchuan; Gupta, Yogendra M.

    2016-05-10

    The high pressure-high temperature (HP-HT) phase diagram and decomposition of FOX-7, central to understanding its stability and reactivity, were determined using optical spectroscopy and imaging measurements in hydrostatically compressed and heated single crystals. Boundaries between various FOX-7 phases (α, α’, β, γ, and ε) and melting/decomposition curves were established up to 10 GPa and 750 K. Main findings are: (i) a triple point is observed between α, β, and γ phases ~ 0.6 GPa and ~ 535 K, (ii) previously suggested δ phase is not a new phase but is partly decomposed γ phase, (iii) the α-α’ transition takes place along an isobar, whereas the α’-ε transition pressure decreases with increasing temperature, and (iv) melting/decomposition temperatures increase rapidly with pressure, with an increase in the slope at the onset of the α’-ε transition. Our results differ from the recently reported HP-HT phase diagram for nonhydrostatically compressed polycrystalline FOX-7. In addition, the observed interplay between melting and decomposition suggests the suppression of melting with pressure. Our FTIR measurements at different pressures to 3.5 GPa showed similar decomposition products, suggesting similar decomposition pathways irrespective of the pressure. Lastly, the present results provide new insights into the structural and chemical stability of an important insensitive high explosive (IHE) crystal under well-defined HP-HT conditions.

  9. Phase diagram and decomposition of 1,1-diamino-2,2-dinitroethene single crystals at high pressures and temperatures

    DOE PAGES

    Dreger, Zbigniew A.; Tao, Yuchuan; Gupta, Yogendra M.

    2016-05-10

    The high pressure-high temperature (HP-HT) phase diagram and decomposition of FOX-7, central to understanding its stability and reactivity, were determined using optical spectroscopy and imaging measurements in hydrostatically compressed and heated single crystals. Boundaries between various FOX-7 phases (α, α’, β, γ, and ε) and melting/decomposition curves were established up to 10 GPa and 750 K. Main findings are: (i) a triple point is observed between α, β, and γ phases ~ 0.6 GPa and ~ 535 K, (ii) previously suggested δ phase is not a new phase but is partly decomposed γ phase, (iii) the α-α’ transition takes placemore » along an isobar, whereas the α’-ε transition pressure decreases with increasing temperature, and (iv) melting/decomposition temperatures increase rapidly with pressure, with an increase in the slope at the onset of the α’-ε transition. Our results differ from the recently reported HP-HT phase diagram for nonhydrostatically compressed polycrystalline FOX-7. In addition, the observed interplay between melting and decomposition suggests the suppression of melting with pressure. Our FTIR measurements at different pressures to 3.5 GPa showed similar decomposition products, suggesting similar decomposition pathways irrespective of the pressure. Lastly, the present results provide new insights into the structural and chemical stability of an important insensitive high explosive (IHE) crystal under well-defined HP-HT conditions.« less

  10. Experimental Comparison of Tantalum Material Strength between Single Crystal [100] and [111] Samples at High Pressure and Strain Rates

    NASA Astrophysics Data System (ADS)

    Plechaty, Christopher; Park, Hye-Sook; Cavallo, Rob; Rudd, Robert; Prisbrey, Shon; Maddox, Brian; Wehrenberg, Christopher; May, Mark; Remington, Bruce

    2013-06-01

    Experiments were performed using the OMEGA laser to investigate the strength difference between single crystal [100] and [111] Ta samples at high pressure (1 Mbar), and high strain rates (106- 108 s-1) . To achieve these pressures and strain rates in experiment without melting the sample, a quasi-isentropic drive was employed to drive the growth of pre-imposed sinusoidal perturbations on the surface of the Ta samples, via the Rayleigh-Taylor (RT) instability. By measuring the ripple amplitude using face-on high energy (~22 KeV) radiography, the strength of the Ta sample is inferred from the amount of RT growth observed. Under these experimental conditions, the Ta material strength can be modeled by the Multiscale (MS) model, developed at LLNL. The value of the ``Taylor Factor'' (a MS model parameter), is thought to vary for [100] and [111] crystal orientations. To investigate this difference under these conditions, a comparison of the ripple growth was performed on the two samples for the same shot and drive conditions. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  11. High-pressure synthesis and crystal structure of silicon phosphate hydroxide, SiPO{sub 4}(OH)

    SciTech Connect

    Stearns, Linda A. . E-mail: linda.stearns@asu.edu; Groy, Thomas L.; Leinenweber, Kurt

    2005-09-15

    A new high-pressure phase, silicon phosphate hydroxide, was prepared at 8.3+/-0.5GPa and 1000 deg. C in >98% purity. From X-ray diffraction on a pseudo-merohedrally twinned crystal, it was found that SiPO{sub 4}(OH) crystallizes in a monoclinic cell with space group P2{sub 1}/n (No. 14), a=6.8446(11)A,b=6.8683(13)A,c=6.8446(11)A,{beta}=119.77(1){sup o}, and Z=4. The refinement gave a conventional R{sub obs} of 0.0320 and wR{sub obs} of 0.0864 for the overlapped data from both twin components. In the structure, SiO{sub 6} octahedra form chains along [101], with PO{sub 4} tetrahedra alternating along the chain in the b-direction. The parallel chains link up with tetrahedral corners from other chains to form a 3-dimensional network. SiPO{sub 4}(OH) belongs to a structural family that includes HgSeO{sub 4}.H{sub 2}O. It is also related to the SbOPO{sub 4} structure by a small distortion that lowers the symmetry from C2/c in SbOPO{sub 4} to P2{sub 1}/c(P2{sub 1}/n) in SiPO{sub 4}(OH)

  12. Phase diagram and decomposition of 1,1-diamino-2,2-dinitroethene single crystals at high pressures and temperatures

    SciTech Connect

    Dreger, Zbigniew A.; Tao, Yuchuan; Gupta, Yogendra M.

    2016-05-10

    The high pressure-high temperature (HP-HT) phase diagram and decomposition of FOX-7, central to understanding its stability and reactivity, were determined using optical spectroscopy and imaging measurements in hydrostatically compressed and heated single crystals. Boundaries between various FOX-7 phases (α, α’, β, γ, and ε) and melting/decomposition curves were established up to 10 GPa and 750 K. Main findings are: (i) a triple point is observed between α, β, and γ phases ~ 0.6 GPa and ~ 535 K, (ii) previously suggested δ phase is not a new phase but is partly decomposed γ phase, (iii) the α-α’ transition takes place along an isobar, whereas the α’-ε transition pressure decreases with increasing temperature, and (iv) melting/decomposition temperatures increase rapidly with pressure, with an increase in the slope at the onset of the α’-ε transition. Our results differ from the recently reported HP-HT phase diagram for nonhydrostatically compressed polycrystalline FOX-7. In addition, the observed interplay between melting and decomposition suggests the suppression of melting with pressure. Our FTIR measurements at different pressures to 3.5 GPa showed similar decomposition products, suggesting similar decomposition pathways irrespective of the pressure. Lastly, the present results provide new insights into the structural and chemical stability of an important insensitive high explosive (IHE) crystal under well-defined HP-HT conditions.

  13. Puzzling calcite-III dimorphism: crystallography, high-pressure behavior, and pathway of single-crystal transitions

    NASA Astrophysics Data System (ADS)

    Pippinger, T.; Miletich, R.; Merlini, M.; Lotti, P.; Schouwink, P.; Yagi, T.; Crichton, W. A.; Hanfland, M.

    2015-01-01

    High-pressure phase transformations between the polymorphic forms I, II, III, and IIIb of CaCO3 were investigated by analytical in situ high-pressure high-temperature experiments on oriented single-crystal samples. All experiments at non-ambient conditions were carried out by means of Raman scattering, X-ray, and synchrotron diffraction techniques using diamond-anvil cells in the pressure range up to 6.5 GPa. The composite-gasket resistive heating technique was applied for all high-pressure investigations at temperatures up to 550 K. High-pressure Raman spectra reveal distinguishable characteristic spectral differences located in the wave number range of external modes with the occurrence of band splitting and shoulders due to subtle symmetry changes. Constraints from in situ observations suggest a stability field of CaCO3-IIIb at relatively low temperatures adjacent to the calcite-II field. Isothermal compression of calcite provides the sequence from I to II, IIIb, and finally, III, with all transformations showing volume discontinuities. Re-transformation at decreasing pressure from III oversteps the stability field of IIIb and demonstrates the pathway of pressure changes to determine the transition sequence. Clausius-Clapeyron slopes of the phase boundary lines were determined as: Δ P/Δ T = -2.79 ± 0.28 × 10-3 GPa K-1 (I-II); +1.87 ± 0.31 × 10-3 GPa K-1 (II/III); +4.01 ± 0.5 × 10-3 GPa K-1 (II/IIIb); -33.9 ± 0.4 × 10-3 GPa K-1 (IIIb/III). The triple point between phases II, IIIb, and III was determined by intersection and is located at 2.01(7) GPa/338(5) K. The pathway of transition from I over II to IIIb can be interpreted by displacement with small shear involved (by 2.9° on I/II and by 8.2° on II/IIIb). The former triad of calcite-I corresponds to the [20-1] direction in the P21/ c unit cell of phase II and to [101] in the pseudomonoclinic C setting of phase IIIb. Crystal structure investigations of triclinic CaCO3-III at non-ambient pressure

  14. High-pressure behavior of bromine confined in the one-dimensional channels of zeolite AlPO4-5 single crystals

    NASA Astrophysics Data System (ADS)

    Liu, Zhaodong; Yao, Zhen; Yao, Mingguang; Lv, Jiayin; Chen, Shuanglong; Li, Quanjun; Lv, Hang; Wang, Tianyi; Lu, Shuangchen; Liu, Ran; Liu, Bo; Liu, Jing; Chen, Zhiqiang; Zou, Bo; Cui, Tian; Liu, Bingbing

    2016-09-01

    We present a joint experimental and theoretical study on the high-pressure behavior of bromine confined in the one-dimensional (1D) nanochannels of zeolite AlPO4-5 (AFI) single crystals. Raman scattering experiments indicate that loading bromine into AFI single crystals can lead to the formation of bromine molecular chains inside the nanochannels of the crystals. High-pressure Raman and X-ray diffraction studies demonstrate that high pressure can increase the length of the confined bromine molecular chains and modify the inter- and intramolecular interactions of the molecules. The confined bromine shows a considerably different high-pressure behavior to that of bulk bromine. The pressure-elongated bromine molecular chains can be preserved when the pressure is reduced to ambient pressure. Theoretical simulations explain the experimental results obtained from the Raman spectroscopy and X-ray diffraction studies. Furthermore, we find that the intermolecular distance between confined bromine molecules gradually becomes comparable to the intramolecular bond length in bromine molecules upon compression. This may result in the dissociation of the bromine molecules and the formation of 1D bromine atomic chains at pressures above 24 GPa. Our study suggests that the unique nanoconfinement has a considerable effect on the high-pressure behavior of bromine, and the confined bromine species concomitantly enhance the structural stability of the host AFI single crystals.

  15. High-pressure vibrational and polymorphic response of 1,1-diamino-2,2-dinitroethene single crystals: Raman spectroscopy.

    PubMed

    Dreger, Zbigniew A; Tao, Yuchuan; Gupta, Yogendra M

    2014-07-10

    Raman spectroscopy was used to examine the vibrational and polymorphic behavior of 1,1-diamino-2,2-dinitroethene (FOX-7) to elucidate its structural and chemical stability under high pressure. Measurements were performed on single crystals compressed in a diamond anvil cell, and data were obtained over the entire frequency range of FOX-7 Raman activity. Several new features were observed with increase of pressure: (i) new vibrational peaks and discontinuity in the shifts of the peaks at 2 and 4.5 GPa, (ii) apparent coupling or mixing of several modes, and (iii) changes in the NH2 stretching spectral shape and modes shift. The spectral changes at 2 GPa, in contrast to previous reports, involved only a few peaks and likely resulted from a small molecular transformation. In contrast, changes at 4.5 GPa involved most of the modes, and the pressure for the onset and completion of the changes depended on the pressure medium. A large pressure hysteresis regarding the changes at 4.5 GPa implies a reconstructive transformation. We suggest that this transformation reflects a change in the balance between interlayer (van der Waals) and in-layer (H-bonding) interactions. Despite these transformations, further compression to 40 GPa and subsequent release of pressure did not cause any irreversible changes. This finding implies that FOX-7 has remarkable chemical stability under high pressures. The observed coupling between the various modes with increasing pressure was analyzed within the Fermi resonance model. The potential implication of the coupling of modes for shock insensitivity of FOX-7 is briefly discussed.

  16. High-pressure phases of cordierite from single-crystal X-ray diffraction to 15 GPa

    DOE PAGES

    Finkelstein, Gregory J.; Dera, Przemyslaw K.; Duffy, Thomas S.

    2015-08-14

    High-pressure single-crystal X-ray diffraction experiments were conducted on natural cordierite crystals with composition Mg1.907(18)Fe0.127(6)Al4.01(2)Si4.96(3)Na0.026(3)O18.12(9) using a synchrotron X-ray source. The samples were compressed at 300 K in a diamond anvil cell to a maximum pressure of 15.22(15) GPa with a neon pressure-transmitting medium and a gold pressure calibrant. We observed a recently described orthorhombic to triclinic transition, as well as a further transition to a second triclinic phase. We solved and refined both new triclinic hases in space group P1, and designate them cordierite II and III. The structures of cordierite II and III were refined at 7.52(3) GPa atmore » 15.22(15) GPa, respectively. The lattice parameters at these pressures are a = 15.567(3) Å, b = 9.6235(4) Å, c = 9.0658(6) Å, α = 89.963(5)°, β = 86.252(10)°, and γ = 90.974(8)° for cordierite II, and a = 8.5191(19) Å, b = 8.2448(3) Å, c = 9.1627(4) Å, α = 85.672(4)°, β = 85.986(7)°, and γ = 70.839(10)° for cordierite III. Across the phase transitions there is a significant reduction in the length of the a-axis (~2 Å per phase transition), whereas both the b- and c-axis remain largely unchanged. Cordierite II has four- and five-coordinated Si and Al, while cordierite III has four-, five-, and six-coordinated Si, four- and five-coordinated Al, and five- and six-coordinated Mg. The sequence of high-pressure phases shows increasing polymerization of coordination polyhedra. These results, together with other recent studies, suggest that mixed 4-, 5-, and 6-fold coordination states may occur more commonly in silicate structures compressed at 300 K than previously recognized.« less

  17. High-pressure phases of cordierite from single-crystal X-ray diffraction to 15 GPa

    SciTech Connect

    Finkelstein, Gregory J.; Dera, Przemyslaw K.; Duffy, Thomas S.

    2015-08-14

    High-pressure single-crystal X-ray diffraction experiments were conducted on natural cordierite crystals with composition Mg1.907(18)Fe0.127(6)Al4.01(2)Si4.96(3)Na0.026(3)O18.12(9) using a synchrotron X-ray source. The samples were compressed at 300 K in a diamond anvil cell to a maximum pressure of 15.22(15) GPa with a neon pressure-transmitting medium and a gold pressure calibrant. We observed a recently described orthorhombic to triclinic transition, as well as a further transition to a second triclinic phase. We solved and refined both new triclinic hases in space group P1, and designate them cordierite II and III. The structures of cordierite II and III were refined at 7.52(3) GPa at 15.22(15) GPa, respectively. The lattice parameters at these pressures are a = 15.567(3) Å, b = 9.6235(4) Å, c = 9.0658(6) Å, α = 89.963(5)°, β = 86.252(10)°, and γ = 90.974(8)° for cordierite II, and a = 8.5191(19) Å, b = 8.2448(3) Å, c = 9.1627(4) Å, α = 85.672(4)°, β = 85.986(7)°, and γ = 70.839(10)° for cordierite III. Across the phase transitions there is a significant reduction in the length of the a-axis (~2 Å per phase transition), whereas both the b- and c-axis remain largely unchanged. Cordierite II has four- and five-coordinated Si and Al, while cordierite III has four-, five-, and six-coordinated Si, four- and five-coordinated Al, and five- and six-coordinated Mg. The sequence of high-pressure phases shows increasing polymerization of coordination polyhedra. These results, together with other recent studies, suggest that mixed 4-, 5-, and 6-fold coordination states may occur more commonly in silicate structures compressed at 300 K than previously recognized.

  18. Crystal chemistry of birefringent hydrogrossular

    NASA Astrophysics Data System (ADS)

    Antao, Sytle M.

    2015-06-01

    Crystal structure refinements of two fine-grained, massive, birefringent hydrogarnet samples from South Africa [1. green "jade" and 2. pink "jade"] were carried out with the Rietveld method, cubic space group and monochromatic synchrotron high-resolution powder X-ray diffraction (HRPXRD) data. Electron-microprobe analysis (EMPA) gave bulk compositions as follows: (1) (Ca2.997Mg0.003)Σ3{Al1.794Fe{0.196/3+}Cr{0.004/3+}Mn{0.003/3+}Ti{0.002/4+}}Σ2[(SiO4)2.851(O4H4)0.151]Σ3 and (2) (Ca2.993Mg0.007)Σ3{Al1.977Fe{0.020/3+}Mn{0.003/3+}Cr{0.001/3+}}Σ2[(SiO4)2.272(O4H4)0.730]Σ3. Their crystal structure was modeled well as indicated by the Rietveld refinement statistical indicators where the reduced χ2 and overall R ( F 2) values are 1.133 and 0.0467, respectively, for sample 1 and 1.308 and 0.0342 for sample 2. Two cubic phases are contained in each sample. For phase 1a in sample 1, the weight fraction (%), unit-cell parameter (Å), and O-H bond distance (Å) are as follows: 74.4(1), a = 11.88874(4), and O-H = 0.98(9); the corresponding data for phase 1b are 25.6(1), a = 11.9280(5), and O-H = 0.91(9). For phase 2a in sample 2, the corresponding data are 52.0(1), a = 12.0591(1), and O-H = 0.90(6); the corresponding data for phase 2b are 48.0(1), a = 11.9340(2), and O-H = 0.90(7). The anisotropic displacement ellipsoids for the O atoms show no unusual features and are not elongated along the "Si-O" bond direction, which is written as Z-O, because of the general formula, X3Y2Z3O12, for garnet. Phase 1a is near end-member grossular, ideally Ca3Al2Si3O12. The deficiencies of the site occupancy factors ( sofs) for the Si (=Z) site indicate that there are significant [O4H4]4- replacing [SiO4]4-. The Z-O distance is large in phase 1b, phases 2a, and 2b compared to a typical Z-O distance in anhydrous grossular or phase 1a. The H atoms occur in different environments around the vacant Z site in the two samples, and they may also bond to the O atoms surrounding the X and Y sites

  19. Water-Shale interactions in bench-top and high pressure/high temperature autoclave experiments: Identifying geochemical reaction controlling flow back water chemistry

    NASA Astrophysics Data System (ADS)

    Molnar, I. L.; O'Carroll, D. M.; Willson, C. S.; Gerhard, J.

    2011-12-01

    An important side effect of hydraulic fracturing (HF) in shale gas wells is the production of saline flow-back water. This water often contains total dissolved soil (TDS) concentrations greater than 100,000 ppm which requires expensive treatment and disposal of the produced water. Possible origins of the high TDS content include: 1. Mixing of fresh HF-fluids with highly saline pore fluids in the targeted shale. 2. Migration and mixing of saline brines by newly-formed fractures into the HF-water from neighboring formations. 3. Water rock interactions between the targeted shale and HF-water that include mineral dissolution, pyrite oxidation buffered by carbonate dissolution and cation exchange in newly hydrated clay minerals.. These possibilities are not mutually exclusive and all may be operating to alter flow-back water chemistry. This study will examine geochemical reactions between a productive Gulf Coast shale and manufactured HF-waters using sealed bench top experiments and high temperature/high pressure autoclave experiments. The samples of the shale were collected from core material housed at The Bureau of Economic Geology collected from two wells. The manufactured HF-waters were produced by mixing NaCl, KCl and CaCl2 salts with De-ionized water at approximately 0, 2000 and 20,000 ppm. During experiments, elements that show large increases in aqueous concentrations are Na, Cl, Ca and SO4. Simultaneous increases in Na and Cl, coupled with high Cl/Br ratios, suggest halite dissolution rather than pore space brine is responsible for Na and Cl concentrations. Simultaneous increase in Ca and SO4 suggest anhydrite dissolution. (SEM imaging shows that anhydrite crystals are usually embedded with the framework mineral grains, rather than precipitated in pores during sample drying, which suggests mineral source of Ca and SO4, possibly for Na and Cl as well). Pyrite oxidation and calcium carbonate dissolution were not significant due to no decrease in pH and no

  20. Water-Shale interactions in bench-top and high pressure/high temperature autoclave experiments: Identifying geochemical reaction controlling flow back water chemistry

    NASA Astrophysics Data System (ADS)

    Mickler, P. J.; Lu, J.; Nicot, J.

    2013-12-01

    An important side effect of hydraulic fracturing (HF) in shale gas wells is the production of saline flow-back water. This water often contains total dissolved soil (TDS) concentrations greater than 100,000 ppm which requires expensive treatment and disposal of the produced water. Possible origins of the high TDS content include: 1. Mixing of fresh HF-fluids with highly saline pore fluids in the targeted shale. 2. Migration and mixing of saline brines by newly-formed fractures into the HF-water from neighboring formations. 3. Water rock interactions between the targeted shale and HF-water that include mineral dissolution, pyrite oxidation buffered by carbonate dissolution and cation exchange in newly hydrated clay minerals.. These possibilities are not mutually exclusive and all may be operating to alter flow-back water chemistry. This study will examine geochemical reactions between a productive Gulf Coast shale and manufactured HF-waters using sealed bench top experiments and high temperature/high pressure autoclave experiments. The samples of the shale were collected from core material housed at The Bureau of Economic Geology collected from two wells. The manufactured HF-waters were produced by mixing NaCl, KCl and CaCl2 salts with De-ionized water at approximately 0, 2000 and 20,000 ppm. During experiments, elements that show large increases in aqueous concentrations are Na, Cl, Ca and SO4. Simultaneous increases in Na and Cl, coupled with high Cl/Br ratios, suggest halite dissolution rather than pore space brine is responsible for Na and Cl concentrations. Simultaneous increase in Ca and SO4 suggest anhydrite dissolution. (SEM imaging shows that anhydrite crystals are usually embedded with the framework mineral grains, rather than precipitated in pores during sample drying, which suggests mineral source of Ca and SO4, possibly for Na and Cl as well). Pyrite oxidation and calcium carbonate dissolution were not significant due to no decrease in pH and no

  1. Evolution of nitrogen structure in N-doped diamond crystal after high pressure and high temperature annealing treatment

    NASA Astrophysics Data System (ADS)

    Zheng, You-Jin; Huang, Guo-Feng; Li, Zhan-Chang; Zuo, Gui-Hong

    2014-11-01

    In this paper, we have reported an investigation on the evolution of nitrogen structures in diamond crystals which contain nitrogen donor atoms in the range of 1500 ppm-1600 ppm following an annealing treatment at a high pressure of about 6.5 GPa and high temperatures of 1920 K-2120 K. The annealing treatment was found to completely transform nitrogen atoms originally arranged in a single substitutional form (C-center), into a pair form (A-center), indicated from infrared (IR) spectra. The photoluminescence (PL) spectra revealed that a small fraction of nitrogen atoms remained in C-center form, while some nitrogen atoms in A-center form were further transformed into N3 and H3 center structures. In addition, PL spectra have revealed the existence of two newly observed nitrogen-related structures with zero phonon lines at 611 nm and 711 nm. All these findings above are very helpful in understanding the formation mechanism of natural diamond stones of the Ia-type, which contains nitrogen atoms in an aggregated form.

  2. Crystal structures of (Mg1;#8722;x,Fex)SiO[subscript 3] postperovskite at high pressures

    SciTech Connect

    Yamanaka, Takamitsu; Hirose, Kei; Mao, Wendy L.; Meng, Yue; Ganesh, P.; Shulenburger, Luke; Shen, Guoyin; Hemley, Russell J.

    2012-03-15

    X-ray diffraction experiments on postperovskite (ppv) with compositions (Mg{sub 0.9}Fe{sub 0.1})SiO{sub 3} and (Mg{sub 0.6}Fe{sub 0.4})SiO{sub 3} at Earth core-mantle boundary pressures reveal different crystal structures. The former adopts the CaIrO{sub 3}-type structure with space group Cmcm, whereas the latter crystallizes in a structure with the Pmcm (Pmma) space group. The latter has a significantly higher density ({rho} = 6.119(1) g/cm{sup 3}) than the former ({rho} = 5.694(8) g/cm{sup 3}) due to both the larger amount of iron and the smaller ionic radius of Fe{sup 2+} as a result of an electronic spin transition observed by X-ray emission spectroscopy (XES). The smaller ionic radius for low-spin compared to high-spin Fe{sup 2+} also leads to an ordered cation distribution in the M1 and M2 crystallographic sites of the higher density ppv structure. Rietveld structure refinement indicates that approximately 70% of the total Fe{sup 2+} in that phase occupies the M2 site. XES results indicate a loss of 70% of the unpaired electronic spins consistent with a low spin M2 site and high spin M1 site. First-principles calculations of the magnetic ordering confirm that Pmcm with a two-site model is energetically more favorable at high pressure, and predict that the ordered structure is anisotropic in its electrical and elastic properties. These results suggest that interpretations of seismic structure in the deep mantle need to treat a broader range of mineral structures than previously considered.

  3. High-pressure microfluidics

    NASA Astrophysics Data System (ADS)

    Hjort, K.

    2015-03-01

    When using appropriate materials and microfabrication techniques, with the small dimensions the mechanical stability of microstructured devices allows for processes at high pressures without loss in safety. The largest area of applications has been demonstrated in green chemistry and bioprocesses, where extraction, synthesis and analyses often excel at high densities and high temperatures. This is accessible through high pressures. Capillary chemistry has been used since long but, just like in low-pressure applications, there are several potential advantages in using microfluidic platforms, e.g., planar isothermal set-ups, large local variations in geometries, dense form factors, small dead volumes and precisely positioned microstructures for control of reactions, catalysis, mixing and separation. Other potential applications are in, e.g., microhydraulics, exploration, gas driven vehicles, and high-pressure science. From a review of the state-of-art and frontiers of high pressure microfluidics, the focus will be on different solutions demonstrated for microfluidic handling at high pressures and challenges that remain.

  4. A materials informatics approach for crystal chemistry

    NASA Astrophysics Data System (ADS)

    Kong, Chang Sun

    This thesis addresses one of the fundamental questions in materials crystal chemistry, namely why do atoms arrange themselves in the way they do? The ability to broadly design and predict new phases [i.e. crystal structures] can be partly met using concepts that employ phase homologies. Homologous series of compounds are those that seem chemically diverse but can be expressed in terms of a mathematical formula that is capable of producing each chemical member in that crystal structure. A well-established strategy to help discover new compounds -- or at least to try to develop chemical design strategies for discovery -- is to search, organize and classify homologous compounds from known data. These classification schemes are developed with the hope that they can provide sufficient insight to help us forecast with some certainty, specific new phases or compounds. Yet, while the classification schemes (over a dozen have been reported in the last 50 years) have proved to be instructive, mostly in hindsight, but they have had limited impact, if at all, on the a priori design of materials chemistry. The aim of this research project is to develop a totally new approach to the study of chemical complexity in materials science using the tools of information theory and data science, which link diverse and high dimensional data derived from physical modeling and experiments. A very large scale binary AB2 crystallographic database is used as a data platform to develop a new data mining/informatics protocol based on high dimensional recursive partitioning schemes coupled to information theoretic measures to: (1) Identify which type of structure prototype is preferred over another for a given chemistry of compound; (2) discover new classification schemes of structure/chemistry/property relationships that classical homologies do not detect and finally we; (3) Extract and organize the underlying design rules for the formation of a given structure by quantitatively assessing the

  5. Benzene under high pressure: A story of molecular crystals transforming to saturated networks, with a possible intermediate metallic phase

    SciTech Connect

    Wen, Xiao-Dong; Hoffmann, Roald; Ashcroft, N. W.

    2011-01-01

    In a theoretical study, benzene is compressed up to 300 GPa. The transformations found between molecular phases generally match the experimental findings in the moderate pressure regime (<20 GPa): phase I (Pbca) is found to be stable up to 4 GPa, while phase II (P43212) is preferred in a narrow pressure range of 4–7 GPa. Phase III (P21/c) is at lowest enthalpy at higher pressures. Above 50 GPa, phase V (P21 at 0 GPa; P21/c at high pressure) comes into play, slightly more stable than phase III in the range of 50–80 GP, but unstable to rearrangement to a saturated, four-coordinate (at C), one-dimensional polymer. Actually, throughout the entire pressure range, crystals of graphane possess lower enthalpy than molecular benzene structures; a simple thermochemical argument is given for why this is so. In several of the benzene phases there nevertheless are substantial barriers to rearranging the molecules to a saturated polymer, especially at low temperatures. Even at room temperature these barriers should allow one to study the effect of pressure on the metastable molecular phases. Molecular phase III (P21/c) is one such; it remains metastable to higher pressures up to ~200 GPa, at which point it too rearranges spontaneously to a saturated, tetracoordinate CH polymer. At 300 K the isomerization transition occurs at a lower pressure. Nevertheless, there may be a narrow region of pressure, between P = 180 and 200 GPa, where one could find a metallic, molecular benzene state. We explore several lower dimensional models for such a metallic benzene. We also probe the possible first steps in a localized, nucleated benzene polymerization by studying the dimerization of benzene molecules. Several new (C6H6)2 dimers are predicted.

  6. Chemical doping and high-pressure studies of layered β -PdB i2 single crystals

    NASA Astrophysics Data System (ADS)

    Zhao, Kui; Lv, Bing; Xue, Yu-Yi; Zhu, Xi-Yu; Deng, L. Z.; Wu, Zheng; Chu, C. W.

    2015-11-01

    We have systematically grown large single crystals of the layered compounds β -PdB i2 , and both the hole-doped PdB i2 -xP bx and the electron-doped N axPdB i2 , and studied their magnetic and transport properties. Hall effect measurements on PdB i2 , PdB i1.8P b0.2 , and N a0.057PdB i2 show that the charge transport is dominated by electrons in all of the samples. The electron concentration is substantially reduced upon Pb doping in PdB i2 -xP bx and increased upon Na intercalation in N axPdB i2 , indicating effective hole doping by Pb and electron doping by Na. We observed a monotonic decrease of the superconducting transition temperature (Tc) from 5.4 K in undoped PdB i2 to less than 2 K for x >0.35 in hole-doped PdB i2 -xP bx . Meanwhile, a rapid decrease of Tc with Na intercalation is also observed in the electron-doped N axPdB i2 , which is in disagreement with the theoretical expectation. In addition, both the magnetoresistance and Hall resistance further reveal evidence for a possible spin excitation associated with Fermi surface reconstruction at ˜50 K in the Na-intercalated PdB i2 sample. The complete phase diagram is thus established from hole doping to electron doping. Meanwhile, a high-pressure study of the undoped PdB i2 shows that the Tc is linearly suppressed under pressure with a d Tc/d P coefficient of -0.28 K/GPa.

  7. In situ Raman and synchrotron X-ray diffraction study on crystallization of Choline chloride/Urea deep eutectic solvent under high pressure

    NASA Astrophysics Data System (ADS)

    Yuan, Chaosheng; Chu, Kunkun; Li, Haining; Su, Lei; Yang, Kun; Wang, Yongqiang; Li, Xiaodong

    2016-09-01

    Pressure-induced crystallization of Choline chloride/Urea (ChCl/Urea) deep eutectic solvent (DES) has been investigated by in-situ Raman spectroscopy and synchrotron X-ray diffraction. The results indicated that high pressure crystals appeared at around 2.6 GPa, and the crystalline structure was different from that formed at ambient pressure. Upon increasing the pressure, the Nsbnd H stretching modes of Urea underwent dramatic change after liquid-solid transition. It appears that high pressures may enhance the hydrogen bonds formed between ChCl and Urea. P versus T phase diagram of ChCl/Urea DES was constructed, and the crystallization mechanism of ChCl/Urea DES was discussed in view of hydrogen bonds.

  8. High pressure Raman and single crystal X-ray diffraction of the alkali/calcium carbonate, shortite

    NASA Astrophysics Data System (ADS)

    Williams, Q. C.; Vennari, C.; O'Bannon, E. F., III

    2015-12-01

    Raman and synchrotron-based single crystal x-ray diffraction data have been collected on shortite (Na2Ca2(CO3)3) up to 10 GPa at 300 K. Shortite is of geological importance due to its presence in the ground-mass of kimberlites, and the alkaline-/carbon-rich character of kimberlitic eruptions. This investigation focuses on shortite's high pressure behavior and is relevant to the behavior of alkali-carbonate systems within Earth's upper mantle. X-ray data demonstrate that shortite's symmetry remains stable at high pressures—retaining orthorhombic C crystal system (Amm2) up to 10 GPa; diffraction data show a 12% volume decrease from room pressure, and a bulk modulus of 71.0(3) GPa. These also demonstrate that the c-axis is twice as compressible as the a- and b-axes. This anisotropic compression is likely due to the orientation of the relatively stiff carbonate groups, a third of which are oriented close to the plane of the a- and b-axes, c axis compression primarily involves the compaction of the 9-fold coordinate sodium and calcium polyhedral. The two distinct carbonate sites within the unit cell give rise to two Raman symmetric stretching modes of the symmetric stretch; the carbonate group stretching vibration which is close to in plane with the a- and b-axes shifts at 3.75 cm-1/GPa as opposed to the carbonate groups which is closer to in plane with the b- and c-axes which shift at 4.25 cm-1/GPa. This furthers evidence for anisotropic compression observed using x-ray diffraction--as the carbonate in plane with the a- and b-axes is compressed, the strength of oxygen bonds along the c-axis with the cations increases, thus decreasing the pressure shift of the mode. The out of plane bending vibration shifts at -0.48 cm-1/GPa, indicating an enhanced interaction of the oxygens with the cations. The multiple in plane bending modes all shift positively, as do at the low frequency lattice modes, indicating that major changes in bonding do not occur up to 10 GPa. The data

  9. In Situ High Temperature High Pressure MAS NMR Study on the Crystallization of AlPO 4 -5

    SciTech Connect

    Zhao, Zhenchao; Xu, Suochang; Hu, Mary Y.; Bao, Xinhe; Hu, Jian Zhi

    2016-01-28

    A damped oscillating crystallization process of AlPO4-5 at the presence of small amount of water is demonstrated by in situ high temperature high pressure multinuclear MAS NMR. Crystalline AlPO4-5 is formed from an intermediate semicrystalline phase via continuous rearrangement of the local structure of amorphous precursor gel. Activated water catalyzes the rearrangement via repeatedly hydrolysis and condensation reaction. Strong interactions between organic template and inorganic species facilitate the ordered rearrangement. During the crystallization process, excess water, phosphate, and aluminums are expelled from the precursor. The oscillating crystallization reflects mass transportation between the solid and liquid phase during the crystallization process. This crystallization process is also applicable to AlPO4-5 crystallized in the presence of a relatively large amount of water.

  10. The crystal structure and crystal chemistry of fernandinite and corvusite

    USGS Publications Warehouse

    Evans, H.T.; Post, J.E.; Ross, D.R.; Nelen, J.A.

    1994-01-01

    Using type material of fernandinite from Minasragra, Peru, and corvusite from the Jack Claim, La Sal Mountains, Utah, the properties and crystal chemistry of these minerals have been determined by Rietveld analysis of the powder X-ray-diffraction patterns. The crystal structure of both species is isotypic with the V2O5 -type layer first found for ??-Ag0.68V2O5; it consists of chains of VO6 octahedra linked by opposite corners (parallel to b) condensed by edge-sharing to form the layer. The vanadium has average valence 4.8, and the resulting layer-charge is balanced by varying amounts of Ca, Na, and K in the interlayer region accompanied by labile water. This study has confirmed the validity of fernandinite as a unique mineral species. It is closely related to corvusite, from which it is distinguished on the basis of the dominant interlayer cation: Ca for fernandinite, Na for curvusite. -Authors

  11. Phonon density of states of single-crystal SrF e2A s2 across the collapsed phase transition at high pressure

    NASA Astrophysics Data System (ADS)

    Wang, Y. Q.; Lu, P. C.; Wu, J. J.; Liu, J.; Wang, X. C.; Zhao, J. Y.; Bi, W.; Alp, E. E.; Park, C. Y.; Popov, D.; Jin, C. Q.; Sun, J.; Lin, J. F.

    2016-07-01

    To help our understanding of the structural and superconducting transitions in ferropnictides, partial phonon density of states (PDOS) of iron in a single-crystal SrF e2A s2 pnictide have been investigated from both out-of-plane and in-plane polarizations with respect to the basal plane of the crystal structure using nuclear resonant inelastic x-ray scattering in a high-pressure diamond anvil cell at ambient temperature. The partial PDOS of iron in the pnictide crystal changes dramatically at approximately 8 GPa, which can be associated with the tetragonal (T) to collapsed tetragonal (CT) isostructural transition as evidenced in high-pressure x-ray diffraction measurements and theoretical calculations. Across the T-CT phase transition, analysis of the PDOS spectra shows a rapid stiffening of the optical phonon modes and a dramatic increase of the Lamb-Mössbauer factor (fLM) and mean force constant which can be associated with the rapid decrease of the c axis and the anomalous expansion of the a axis. Theoretically calculated Fe partial PDOS and lattice parameters of SrF e2A s2 further reveal the strong correlation between the lattice parameters and phonons. Our results show that the T-CT transition can induce significant changes in the vibrational, elastic, and thermodynamic properties of SrF e2A s2 single crystal at high pressure.

  12. Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

    DOE PAGES

    Ok, Salim; Hoyt, David W.; Andersen, Amity; ...

    2017-01-18

    Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nanoporous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, we observed changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed nonporous, 12 nm particle size silica and a mesoporous silica with 200more » nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. There was no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2, 32.6, 56.4, 65.1, 112.7, and 130.3 bar) for pure methane. However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD, and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.« less

  13. Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study.

    PubMed

    Ok, Salim; Hoyt, David W; Andersen, Amity; Sheets, Julie; Welch, Susan A; Cole, David R; Mueller, Karl T; Washton, Nancy M

    2017-02-14

    Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nanoporous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) were observed with (13)C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed nonporous, 12 nm particle size silica and a mesoporous silica with 200 nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. For pure methane, no significant thermal effects were found for the observed (13)C chemical shifts at all pressures studied here (28.2, 32.6, 56.4, 65.1, 112.7, and 130.3 bar). However, the (13)C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of (13)C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD, and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.

  14. Crystal growth and ambient and high pressure study of the re-entrant superconductor Tm(2)Fe(3)Si(5).

    PubMed

    Singh, Yogesh; Ramakrishnan, S

    2008-06-11

    Tm(2)Fe(3)Si(5) is known to undergo a transition to the superconducting state (at ambient or applied pressure depending on the sample) at a temperature T(c1)(∼1.8 K), and at a lower temperature T(N)(≈1 K) it undergoes a transition into a long range antiferromagnetically ordered state. Superconductivity is simultaneously destroyed and the sample re-enters the normal state at T(c2) = T(N). The conditions reported in the literature for the observation of superconductivity in Tm(2)Fe(3)Si(5) are sample dependent, but it is now accepted that stoichiometric Tm(2)Fe(3)Si(5) superconducts only under pressure. Here we report single-crystal growth of stoichiometric Tm(2)Fe(3)Si(5) which does not superconduct at ambient pressure down to 100 mK. Measurements of the anisotropic static magnetic susceptibility χ(T) and isothermal magnetization M(H), ac susceptibility χ(ac)(T), electrical resistivity ρ(T) and heat capacity C(T) at ambient pressure and χ(ac)(T) at high pressure are reported. The magnetic susceptibility along the c axis, χ(c)(T), shows a curvature over the whole temperature range and does not follow the Curie-Weiss behavior, while the magnetic susceptibility along the a axis, χ(a)(T), follows a Curie-Weiss behavior between 130 and 300 K with a Weiss temperature θ and an effective magnetic moment μ(eff) which depend on the temperature range of the fit. The easy axis of magnetization is perpendicular to the c axis and χ(a)/χ(c) = 3.2 at 1.8 K. The ambient pressure χ(ac)(T) and C(T) measurements confirm bulk antiferromagnetic ordering at T(N) = 1.1 K. The sharp drop in χ(ac)(T) below the antiferromagnetic transition is suggestive of the existence of a spin gap. We observe superconductivity only under applied pressures P≥2 kbar. The temperature-pressure phase diagram showing the non-monotonic dependence of the superconducting transition temperature T(c) on pressure P is presented.

  15. Crystal chemistry of the natural vanadium bronzes

    USGS Publications Warehouse

    Evans, H.T.; Hughes, J.M.

    1990-01-01

    The crystal chemistry of the natural vanadium bronze minerals is reviewed on the basis of published information and new studies (mainly by X-ray powder-diffraction methods) using type material wherever possible. The known V bronze minerals are divided into three categories: 1) the hewettite group, 2) the straczekite group, 3) other structure types including navajoite, schubnelite, fervanite, shcherbinaite, bannermanite, and melanovanadite. All known structures associated with the fibrous V bronzes (fiber spacing 3.6 A??) can be considered as various lateral linkages (into sheets or networks) of only two types of polyvanadate chains: 1) a divanadate chain (V2O6)n consisting of alternating square pyramids, and 2) a tetravanadate chain (V4O12)n consisting of four highly condensed single octahedral chains. -from Authors

  16. Extracting Crystal Chemistry from Amorphous Carbon Structures.

    PubMed

    Deringer, Volker L; Csányi, Gábor; Proserpio, Davide M

    2017-03-08

    Carbon allotropes have been explored intensively by ab initio crystal structure prediction, but such methods are limited by the large computational cost of the underlying density functional theory (DFT). Here we show that a novel class of machine-learning-based interatomic potentials can be used for random structure searching and readily predicts several hitherto unknown carbon allotropes. Remarkably, our model draws structural information from liquid and amorphous carbon exclusively, and so does not have any prior knowledge of crystalline phases: it therefore demonstrates true transferability, which is a crucial prerequisite for applications in chemistry. The method is orders of magnitude faster than DFT and can, in principle, be coupled with any algorithm for structure prediction. Machine-learning models therefore seem promising to enable large-scale structure searches in the future.

  17. Structures and Crystal Chemistry of Layered Materials

    NASA Astrophysics Data System (ADS)

    Partin, Daniel Edward

    The crystal chemistry of several layered materials has been explored using a variety of methods, with an emphasis on their structural aspects. In the second part of this work, the structure of several copper oxides that are of significance to the study of superconductors are described. The crystal structures of MgCl_2 and CdCl_2 have been refined using powder X-ray diffraction data. They have the space group Roverline{3}m. For magnesium chloride the unit cell constants are a = 3.6363(1) A, c = 17.6663(5) A. For cadmium chloride they are a = 3.8459(1) A, c = 17.4931(4) A. The structures and their relationship to that of fluorite are discussed within the framework of a Born-Mayer model. The crystal structure of Mg(OD)_2 has been refined from time-of flight (TOF) neutron diffraction data and found to be trigonal, Poverline {3}m1, a = 3.1455(1) A, c = 4.7646(3) A. The data were collected at 305 K. The O-D bond length is 0.937 (1) A (corrected for "riding" motion 0.948 A). An infrared/Raman study of Mg(OH)_2 was conducted in a diamond anvil cell in the pressure range from room pressure up to 7 Gpa. For layered crystals, it was found that as the internally fixed layers are moved apart the Madelung energy of the system becomes constant after a very short distance, although not necessarily that of the given crystal's energy at ambient conditions. The crystal structure of Sr(OD)_2 has been refined from time-of-flight neutron diffraction data and the deuterium positions found. Strontium deuteroxide crystallizes in the space group Pnma, with the unit cell constants of a = 9.8269(5) A, b = 3.9051(2) A, and c = 6.0733(3) A. The crystal structures of SrCuO_2 and Sr_2CuO_3 have been refined by time-of-flight neutron diffraction. For SrCuO_2 the space group is Cmcm, a = 3.57002(2), b = 16.32268(8), c = 3.91100(2); for Sr _2CuO_3 the space group is Immm, a = 3.49900(5), b = 12.7009(2), c = 3.91120(5). In both structures the strontium atoms are coordinated by seven oxygen atoms

  18. High-pressure synthesis and crystal structure of the lithium borate HP-LiB{sub 3}O{sub 5}

    SciTech Connect

    Neumair, Stephanie C.; Vanicek, Stefan; Kaindl, Reinhard; Toebbens, Daniel M.; Wurst, Klaus; Huppertz, Hubert

    2011-09-15

    The new lithium borate HP-LiB{sub 3}O{sub 5} was synthesized under high-pressure/high-temperature conditions of 6 GPa and 1050 deg. C in a multianvil press with a Walker-type module. The compound crystallizes in the space group Pnma (no. 62) with the lattice parameters a=829.7(2), b=759.6(2), and c=1726.8(4) pm (Z=16). The high-pressure compound HP-LiB{sub 3}O{sub 5} is built up from a three-dimensional network of BO{sub 4} tetrahedra and BO{sub 3} groups, which incorporates Li{sup +} ions in channels along the b-axis. Band assignments of measured IR- and Raman spectra were done via quantum-mechanical calculations. Additionally, the thermal behavior of HP-LiB{sub 3}O{sub 5} was investigated. - Graphical abstract: The new high-pressure compound HP-LiB{sub 3}O{sub 5} is built up from a three-dimensional network of BO4 tetrahedra and BO{sub 3} groups, which incorporates Li{sup +} ions in channels along the b-axis. In this paper, the synthesis, the crystal structure, and the properties of HP-LiB{sub 3}O{sub 5} are described. Highlights: > Synthesis of a new lithium borate with the composition HP-LiB{sub 3}O{sub 5} at high pressure. > In contrast to the non-centrosymmetric phase LiB{sub 3}O{sub 5}, this high-pressure phase is centrosymmetric. > First example of ternary alkali borates exhibiting threefold bridging oxygen atoms.

  19. Magnetocaloric effect in a dual-phase coupled LaFe11Si2 crystal prepared by a modified high-pressure zone-melting technique

    NASA Astrophysics Data System (ADS)

    Feng, Shutong; Fang, Yue; Zhai, Qijie; Luo, Zhiping; Zheng, Hongxing

    2016-10-01

    A modified high-pressure optical zone-melting technique was adopted to grow a rare-earth-based LaFe11Si2 crystal in the present work. Dual-phase coupled microstructure was obtained where aligned α(Fe) phase distributed in the La(Fe,Si)13 matrix. Magnetic measurements showed that the produced crystal underwent a second-order magnetic transition in the vicinity of 250 K. Under a magnetic field change of 30 kOe, the refrigeration capacity (RC) of the produced crystal reached up to 162 J/kg. It was confirmed that zone-melting crystal growth technique is an effective approach to strikingly enhance the magnetocaloric effect of La-Fe-Si refrigeration materials.

  20. High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties

    PubMed Central

    2016-01-01

    We report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3+, X = Br– or I–) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites’ precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material’s resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(BrxI1–x)3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors. PMID:27163050

  1. High-pressure single-crystal structures of 3D lead-halide hybrid perovskites and pressure effects on their electronic and optical properties

    DOE PAGES

    Jaffe, Adam; Lin, Yu; Beavers, Christine M.; ...

    2016-04-06

    Here, we report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3+, X = Br– or I–) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites’ precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivitymore » measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material’s resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(BrxI1–x)3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors.« less

  2. High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties.

    PubMed

    Jaffe, Adam; Lin, Yu; Beavers, Christine M; Voss, Johannes; Mao, Wendy L; Karunadasa, Hemamala I

    2016-04-27

    We report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3 (+), X = Br(-) or I(-)) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites' precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material's resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(Br x I1-x )3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors.

  3. Experimental evidence of bulk chemistry constraint on SiO2 solubility in clinopyroxene at high-pressure conditions

    NASA Astrophysics Data System (ADS)

    Kawasaki, Toshisuke; Osanai, Yasuhito

    2015-06-01

    We have experimentally confirmed that the solubility of SiO2 in clinopyroxene at ultrahigh-pressure metamorphic conditions is buffered by coesite and kyanite. The present findings were derived from high-pressure experiments on metapelite glass, powdered andesite and eclogite glass under anhydrous conditions. The metapelite glass and powdered andesite were recrystallised in boron nitride capsules at 8 GPa and 1100-1500 °C. The eclogite glass was heated in an AuPd capsule, both ends of which were welded, at 3 GPa and 1000 °C. Clinopyroxene nucleated from metapelite glass, the bulk composition of which is saturated in both SiO2 and Al2SiO5 components plotting within the Jd (Na,K)(Al,Cr)(Si,Ti)2O6-Qtz (Si,Ti)O2-Grt M3(Al,Cr)2(Si,Ti)3O12-Als (Al,Cr)2(Si,Ti)O5 tetrahedron (M = Fe, Mn, Mg, Ni, Zn, Ca), coexists with garnet, coesite and kyanite. The average excess silica content of the clinopyroxene ranges from 23.4 to 35.4 mol%. In contrast, an andesite experiment saturated in SiO2 but undersaturated in Al2SiO5 within the Jd-Qtz-Aug M(Si,Ti)O3-Grt tetrahedron produced clinopyroxene, garnet and coesite but no kyanite. The average excess silica in the clinopyroxene was 9.7-15.5 mol%, which is comparable to previous experimental data. Experiment on the eclogite glass with similar composition to andesite yielded clinopyroxene, garnet and coesite. An average excess silica content in clinopyroxene counts 6.4 mol%, which is much lower than that obtained from the andesite. The SiO2 content of clinopyroxene coexisting with garnet, coesite and kyanite is much higher than that of clinopyroxene coexisting with garnet and coesite without kyanite. Although the temperature dependence is unclear, the SiO2 solubility increases with pressure and Fe/(Fe+Mg). Clinopyroxene forms the solid solution series Jd-Es □0.5M0.5Al(Si,Ti)2O6 and Aug-Es, rather than Jd-Ts MAl2(Si,Ti)O6 and Es-Ts joins. Our experimental data suggest the probable existence of octahedral Si which may accompany the M2

  4. Co-Determination of Crystal Structures at High Pressure: Combined Application of Theory and Experiment to the AuGa2 Intermetallic analog to High-Pressure SiO2

    NASA Astrophysics Data System (ADS)

    Godwal, B. K.; Stackhouse, S.; Yan, J.; Speziale, S.; Militzer, B.; Jeanloz, R.

    2012-12-01

    The intermetallic compounds AuX2 (X = In, Ga, Al) crystallize in the calcium fluorite (CaF2) structure, making them analogs for SiO2 at TPa pressures. A combination of high-pressure x-ray diffraction experiments and first-principles calculations reveals the sequence of crystal-structural phase transitions in AuGa2 from cubic (Fm3m) to orthorhombic (Pnma) at 10 (± 4) GPa, and then to monoclinic (P21/n) at 33 (± 6) GPa. The post-cotunnite (P1121/a) phase identified as the final step in the phase-transition sequence for other AX2 compounds is found to be unstable. As the structural sequence followed by AuGa2 is similar to that observed in ACl2 (A = Pb, Sn) compounds it implies that AX2 compounds iso-structural to PbCl2 will acquire the monoclinic (P21/n) structure at extreme pressures. Neither theory nor experiment would have been adequate, on their own, in documenting this sequence of phases, but together they confirm a sequence differing from the Fm3m → Pnma → P63/mmc transitions predicted for CaF2, and observed for the intermetallic analog compounds AuIn2 and AuAl2 under pressure. Experimental [and theoretical] values of zero-pressure volume and bulk modulus are 224.5 (± 0.2) [219.5] Å3 and 81 (± 5) [95] GPa; 204.0 (± 1) [204.8] Å3 and 112 (± 12) [96] GPa; and 192 (± 4) [201.1] Å3 and 157 (± 5) [99] GPa for the cubic, orthorhombic and monoclinic phases, respectively.

  5. High-Pressure Freezing and Crystal Structure Studies of TMSCF3: Understanding Nucleophillic-CF3 Transferring Ability (Preprint)

    DTIC Science & Technology

    2008-09-12

    bond polarizability of trimethyl(trifluoromethyl) silane (Preprint) 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Anna Olejniczak...Andrzej Katrusiak (Faculty of Chemistry , Adam Mickiewicz University, 5d. PROJECT NUMBER Poland), Ashwani Vij (AFRL/RZSP) 5e. TASK NUMBER 5f...08440A). 13. SUPPLEMENTARY NOTES For publication in Journal of Fluorine Chemistry , 129 (2008) 1090-1095. 14. ABSTRACT Trimethyl(trifluoromethyl

  6. High-pressure crystal growth and magnetic and electrical properties of the quasi-one dimensional osmium oxide Na{sub 2}OsO{sub 4}

    SciTech Connect

    Shi, Y.G.; Guo, Y.F.; Yu, S.; Arai, M.; Belik, A.A.; Sato, A.; Yamaura, K.; Takayama-Muromachi, E.

    2010-02-15

    Na{sub 2}OsO{sub 4} crystals were grown by a NaCl flux method under high pressure. It crystallizes in the Ca{sub 2}IrO{sub 4}-type structure without having additional elements or metal vacancies, which are usually accommodated. It appears that Na{sub 2}OsO{sub 4} is a metal-stoichiometric Ca{sub 2}IrO{sub 4}-type compound never been synthesized to date. Na{sub 2}OsO{sub 4} has the octahedral environment of Os{sup 6+}O{sub 6} so that the electronic configuration is 5d{sup 2}, suggesting the magnetic S=1 ground state. However, magnetization, electrical resistivity, and specific heat measurements indicated that the non-magnetic S=0 state is much likely for Na{sub 2}OsO{sub 4} than the S=1 state. Band structure calculations and the structure analysis found that the disagreement is probably due to the statically uniaxial compression of the OsO{sub 6} octahedra, resulting in splitting of the t{sub 2{sub g}} band. - Graphical abstract: Na{sub 2}OsO{sub 4} crystals were grown by a NaCl flux method under high pressure. It crystallizes in the Ca{sub 2}IrO{sub 4}-type structure comprising infinite Os{sup 6+}O{sub 6} octahedra (5d{sup 2}) chains. The crystal growth, the crystal structure, and the magnetic and electrical properties are reported.

  7. High-pressure phase diagram and equation of state of solid helium from single-crystal X-ray diffraction to 23.3 GPa

    NASA Technical Reports Server (NTRS)

    Mao, H. K.; Hemley, R. J.; Jephcoat, A. P.; Finger, L. W.; Wu, Y.

    1988-01-01

    Single-crystal X-ray diffraction measurements have been performed on solid He-4 from 15.6 to 23.3 GPa at 300 K with synchrotron radiation. The diffraction patterns demonstrate that the structure of the solid is hexagonal close packed over this pressure-temperature range, contrary to both the interpretation of high-pressure optical studies and to theoretical predictions. The solid is more compressible than is indicated by equations of state calculated with recently determined helium pair potentials. The results suggest that a significant revision of current views of the phase diagram and energetics of dense solid helium is in order.

  8. High-pressure phase diagram and equation of state of solid helium from single-crystal X-ray diffraction to 23.3 GPa

    NASA Technical Reports Server (NTRS)

    Mao, H. K.; Hemley, R. J.; Jephcoat, A. P.; Finger, L. W.; Wu, Y.

    1988-01-01

    Single-crystal X-ray diffraction measurements have been performed on solid He-4 from 15.6 to 23.3 GPa at 300 K with synchrotron radiation. The diffraction patterns demonstrate that the structure of the solid is hexagonal close packed over this pressure-temperature range, contrary to both the interpretation of high-pressure optical studies and to theoretical predictions. The solid is more compressible than is indicated by equations of state calculated with recently determined helium pair potentials. The results suggest that a significant revision of current views of the phase diagram and energetics of dense solid helium is in order.

  9. Sarcosine and betaine crystals upon cooling: structural motifs unstable at high pressure become stable at low temperatures.

    PubMed

    Kapustin, E A; Minkov, V S; Boldyreva, E V

    2015-02-07

    The crystal structures of N-methyl derivatives of the simplest amino acid glycine, namely sarcosine (C3H7NO2) and betaine (C5H11NO2), were studied upon cooling by single-crystal X-ray diffraction and single-crystal polarized Raman spectroscopy. The effects of decreasing temperature and increasing hydrostatic pressure on the crystal structures were compared. In particular, we have studied the behavior upon cooling of those structural motifs in the crystals, which are involved in structural rearrangement during pressure-induced phase transitions. In contrast to their high sensitivity to hydrostatic compression, the crystals of both sarcosine and betaine are stable to cooling down to 5 K. Similarly to most α-amino acids, the crystal structures of the two compounds are most rigid upon cooling in the direction of the main structural motif, namely head-to-tail chains (linked via the strongest N-H···O hydrogen bonds and dipole-dipole interactions in the case of sarcosine, or exclusively by dipole-dipole interactions in the case of betaine). The anisotropy of linear strain in betaine does not differ much upon cooling and on hydrostatic compression, whereas this is not the case for sarcosine. Although the interactions between certain structural motifs in sarcosine and betaine weaken as a result of phase transitions induced by pressure, the same interactions strengthen when volume reduction results from cooling.

  10. High-pressure (up to 10.7 GPa) crystal structure of single-component molecular metal [Au(tmdt)2].

    PubMed

    Okano, Yoshinori; Zhou, Biao; Tanaka, Hishashi; Adachi, Takafumi; Ohishi, Yasuo; Takata, Masaki; Aoyagi, Shinobu; Nishibori, Eiji; Sakata, Makoto; Kobayashi, Akiko; Kobayashi, Hayao

    2009-05-27

    The crystal structure of the single-component molecular metal [Au(tmdt)(2)] was examined at pressures up to 10.7 GPa in order to examine whether the high-pressure structure reflects the crystal's metallic nature. Crystal structure analyses were performed at 0.2, 0.8, 1.3, 3.0, 5.5, and 10.7 GPa on the basis of the powder X-ray diffraction data obtained by using the synchrotron radiation source SPring-8. The unit cell volume at 10.7 GPa was approximately 75% of the initial volume, indicating that [Au(tmdt)(2)] is a 'soft material' like a typical molecular crystal in spite of its metallic nature. The pressure dependences of the bond lengths of the Au(tmdt)(2) molecule were found to be approximately 1 order of magnitude smaller than those of the intermolecular atomic distances. These results seem to justify the commonly accepted conjecture that the molecule usually behaves almost like a rigid body up to a fairly high pressure. It was found that the anisotropy of the lattice compression of the insulating I(2) crystal below 20 GPa can be essentially interpreted on the basis of a very simple 'interatomic repulsion model', which assumes that the molecules in the crystal are packed such that as far as possible, an increase in the interatomic repulsions between neighboring molecules is avoided. However, the maximum decrease in the intermolecular distance in [Au(tmdt)(2)] was observed along the a direction although there were many intermolecular S...S contacts shorter than the van der Waals distance (3.70 A) along this direction. The shortest intermolecular S...S distance was 2.73 A at 10.7 GPa, which is approximately 1 A shorter than the S...S van der Waals distance (3.70 A). The crystal lattice of [Au(tmdt)(2)] is considered to be stabilized by the enhancement of the intermolecular overlapping of the conduction molecular orbitals having large amplitudes on peripheral S atoms. Although the crystal is composed of 'isolated molecules' like a typical insulating molecular

  11. Nanocrystalline diamond micro-anvil grown on single crystal diamond as a generator of ultra-high pressures

    NASA Astrophysics Data System (ADS)

    Samudrala, Gopi K.; Moore, Samuel L.; Velisavljevic, Nenad; Tsoi, Georgiy M.; Baker, Paul A.; Vohra, Yogesh K.

    2016-09-01

    By combining mask-less lithography and chemical vapor deposition (CVD) techniques, a novel two-stage diamond anvil has been fabricated. A nanocrystalline diamond (NCD) micro-anvil 30 μ m in diameter was grown at the center of a [100]-oriented, diamond anvil by utilizing microwave plasma CVD method. The NCD micro-anvil has a diamond grain size of 115 nm and micro-focused Raman and X-ray Photoelectron spectroscopy analysis indicate sp3-bonded diamond content of 72%. These CVD grown NCD micro-anvils were tested in an opposed anvil configuration and the transition metals osmium and tungsten were compressed to high pressures of 264 GPa in a diamond anvil cell.

  12. Experimental verification of the high pressure crystal structures in NH{sub 3}BH{sub 3}

    SciTech Connect

    Huang, Yanping; Huang, Xiaoli; Zhao, Zhonglong; Li, Wenbo; Jiang, Shuqing; Duan, Defang; Bao, Kuo; Zhou, Qiang; Liu, Bingbing; Cui, Tian

    2014-06-28

    A detailed high-pressure study on NH{sub 3}BH{sub 3} has been carried out using in situ synchrotron X-ray diffraction (XRD) and Raman scattering with a diamond anvil cell up to 20 and 33 GPa, respectively. The Rietveld refinement based on the XRD pattern and analysis of Raman data indicate two first-order phase transitions from the ambient pressure I4 mm structure (α-NH{sub 3}BH{sub 3}) to a high pressure Cmc2{sub 1} phase (β-NH{sub 3}BH{sub 3}) at 2.14 GPa, and further into a monoclinic P2{sub 1} (Z = 2) phase (γ-NH{sub 3}BH{sub 3}) at 9.67 GPa. Fitting the measured volumetric compression data to the third order Birch-Murnaghan equation of state reveals a bulk modulus of B{sub 0} = 9.9 ± 0.5 and 17.0 ± 3.0 GPa (with fixed B{sub 0}{sup ′} = 4) for the β-NH{sub 3}BH{sub 3} below and above 5 GPa, respectively. Still, with the splitting of the NBH rock mode in Raman experiment, it is concluded that a second-order isostructural phase transition occurs at 5 GPa. By analyzing the dihydrogen bonding framework, the origin of the isostructural phase transition is attributed to the number of dihydrogen bondings per molecule in the Cmc2{sub 1} phase increasing from 12 to 14 at 5 GPa.

  13. Experimental Verification of the High Pressure Crystal Structures in NH3BH3

    SciTech Connect

    Huang, Yanping; Huang, Xiaoli; Zhao, Zhonglong; Li, Wenbo; Jiang, Shuqing; Duan, Defang; Bao, Kuo; Zhou, Qiang; Liu, Bingbing; Cui, Tian

    2014-06-26

    We performed a detailed study with high-pressure on NH3BH3 and its been carried out using in situ synchrotron X-ray diffraction (XRD) and Raman scattering with a diamond anvil cell up to 20 and 33 GPa, respectively. The Rietveld refinement based on the XRD pattern and analysis of Raman data indicate two first-order phase transitions from the ambient pressure I4 mm structure (α-NH3BH3) to a high pressure Cmc21 phase (β-NH3BH3) at 2.14 GPa, and further into a monoclinic P21 (Z = 2) phase (γ-NH3BH3) at 9.67 GPa. Fitting the measured volumetric compression data to the third order Birch-Murnaghan equation of state reveals a bulk modulus of B 0 = 9.9 ± 0.5 and 17.0 ± 3.0 GPa (with fixed B 0 ' = 4) for the β-NH3BH3 below and above 5 GPa, respectively. Still, with the splitting of the NBH rock mode in Raman experiment, it is concluded that a second-order isostructural phase transition occurs at 5 GPa. Analyzing the dihydrogen bonding framework, the origin of the isostructural phase transition is attributed to the number of dihydrogen bondings per molecule in the Cmc21 phase increasing from 12 to 14 at 5 GPa.

  14. Applications of the Cambridge Structural Database in organic chemistry and crystal chemistry.

    PubMed

    Allen, Frank H; Motherwell, W D Samuel

    2002-06-01

    The Cambridge Structural Database (CSD) and its associated software systems have formed the basis for more than 800 research applications in structural chemistry, crystallography and the life sciences. Relevant references, dating from the mid-1970s, and brief synopses of these papers are collected in a database, DBUse, which is freely available via the CCDC website. This database has been used to review research applications of the CSD in organic chemistry, including supramolecular applications, and in organic crystal chemistry. The review concentrates on applications that have been published since 1990 and covers a wide range of topics, including structure correlation, conformational analysis, hydrogen bonding and other intermolecular interactions, studies of crystal packing, extended structural motifs, crystal engineering and polymorphism, and crystal structure prediction. Applications of CSD information in studies of crystal structure precision, the determination of crystal structures from powder diffraction data, together with applications in chemical informatics, are also discussed.

  15. High pressure effect on the main transition from the ripple gel P'beta phase to the liquid crystal (Lalpha) phase in dipalmitoylphosphatidylcholine. Microcalorimetric study.

    PubMed

    Potekhin, S A; Senin, A A; Abdurakhmanov, N N; Khusainova, R S

    2008-11-01

    Scanning microcalorimetry has been used to study the high pressure effect on the main transition from the ripple gel P'(beta) phase to the liquid crystal (L(alpha)) phase in DPPC (dipalmitoylphosphatidylcholine). It has been demonstrated that an increase of the pressure by 200 MPa shifts the transition to higher temperatures by 36.4 degrees. The pressure increase does not affect the cooperativity of transition but reduces noticeably its enthalpy. The changes of the molar partial volume, isothermal compressibility as well as volume thermal expansibility during transition in DPPC suspension have been estimated. It has been shown that monovalent ions (Na(+), Cl(-)) in solution slightly affect the main thermodynamic parameters of the transition. Calcium ions significantly decrease distinction in compressibility and thermal expansibility between liquid-crystal and ripple gel phases of lipid suspension, which in its turn reflects less difference in their volume fluctuations.

  16. Crystal Chemistry of Ceramic/Metal Systems.

    DTIC Science & Technology

    2007-11-02

    temperature thermal expansion of alkali halides, rare earth oxides, group IV elements, fcc metals, bcc metals, SiC , III-V and II-VI compounds. Analytical...to high pressure thermal expansion of MgO , NaCl, Group IV elements, and W. The bulk modulus and self-diffusion for W and Ta have been predicted to their melting points.

  17. Synthesis, crystal structure, and electronic properties of high-pressure PdF2-type oxides MO2 (M = Ru, Rh, Os, Ir, Pt).

    PubMed

    Shirako, Yuichi; Wang, Xia; Tsujimoto, Yoshihiro; Tanaka, Kie; Guo, Yanfeng; Matsushita, Yoshitaka; Nemoto, Yoshihiro; Katsuya, Yoshio; Shi, Youguo; Mori, Daisuke; Kojitani, Hiroshi; Yamaura, Kazunari; Inaguma, Yoshiyuki; Akaogi, Masaki

    2014-11-03

    The polycrystalline MO2's (HP-PdF2-type MO2, M = Rh, Os, Pt) with high-pressure PdF2 compounds were successfully synthesized under high-pressure conditions for the first time, to the best of our knowledge. The crystal structures and electromagnetic properties were studied. Previously unreported electronic properties of the polycrystalline HP-PdF2-type RuO2 and IrO2 were also studied. The refined structures clearly indicated that all compounds crystallized into the HP-PdF2-type structure, M(4+)O(2-)2, rather than the pyrite-type structure, M(n+)(O2)(n-) (n < 4). The MO2 compounds (M = Ru, Rh, Os, Ir) exhibited metallic conduction, while PtO2 was highly insulating, probably because of the fully occupied t2g band. Neither superconductivity nor a magnetic transition was detected down to a temperature of 2 K, unlike the case of 3d transition metal chalcogenide pyrites.

  18. Structural and elastic anisotropy of crystals at high pressures and temperatures from quantum mechanical methods: The case of Mg{sub 2}SiO{sub 4} forsterite

    SciTech Connect

    Erba, A. Dovesi, R.; Maul, J.; De La Pierre, M.

    2015-05-28

    We report accurate ab initio theoretical predictions of the elastic, seismic, and structural anisotropy of the orthorhombic Mg{sub 2}SiO{sub 4} forsterite crystal at high pressures (up to 20 GPa) and temperatures (up to its melting point, 2163 K), which constitute earth’s upper mantle conditions. Single-crystal elastic stiffness constants are evaluated up to 20 GPa and their first- and second-order pressure derivatives reported. Christoffel’s equation is solved at several pressures: directional seismic wave velocities and related properties (azimuthal and polarization seismic anisotropies) discussed. Thermal structural and average elastic properties, as computed within the quasi-harmonic approximation of the lattice potential, are predicted at high pressures and temperatures: directional thermal expansion coefficients, first- and second-order pressure derivatives of the isothermal bulk modulus, and P-V-T equation-of-state. The effect on computed properties of five different functionals, belonging to three different classes of approximations, of the density functional theory is explicitly investigated.

  19. Crystal structures and compressibility of novel iron borides Fe2B7 and FexB50 synthesized at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Bykova, E.; Gou, H.; Bykov, M.; Hanfland, M.; Dubrovinsky, L.; Dubrovinskaia, N.

    2015-10-01

    We present here a detailed description of the crystal structures of novel iron borides, Fe2B7 and FexB50 with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe2B7 possesses short incompressible B-B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe2B7 (the bulk modulus K0= 259(1.8) GPa, K0‧= 4 (fixed)) is even lower than that of FeB4 and comparable with that of MnB4, known for high bulk moduli among 3d metal borides. FexB50 adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. FexB50 does not show considerable anisotropy in the elastic behavior.

  20. A Physical Chemistry Experiment in Polymer Crystallization Kinetics

    ERIC Educational Resources Information Center

    Singfield, Kathy L.; Chisholm, Roderick A.; King, Thomas L.

    2012-01-01

    A laboratory experiment currently used in an undergraduate physical chemistry lab to investigate the rates of crystallization of a polymer is described. Specifically, the radial growth rates of typical disc-shaped crystals, called spherulites, growing between microscope glass slides are measured and the data are treated according to polymer…

  1. A Physical Chemistry Experiment in Polymer Crystallization Kinetics

    ERIC Educational Resources Information Center

    Singfield, Kathy L.; Chisholm, Roderick A.; King, Thomas L.

    2012-01-01

    A laboratory experiment currently used in an undergraduate physical chemistry lab to investigate the rates of crystallization of a polymer is described. Specifically, the radial growth rates of typical disc-shaped crystals, called spherulites, growing between microscope glass slides are measured and the data are treated according to polymer…

  2. High Pressure Scanning Tunneling Microscopy and High PressureX-ray Photoemission Spectroscopy Studies of Adsorbate Structure,Composition and Mobility during Catalytic Reactions on A Model SingleCrystal

    SciTech Connect

    Montano, Max O.

    2006-01-01

    Our research focuses on taking advantage of the ability of scanning tunneling microscopy (STM) to operate at high-temperatures and high-pressures while still providing real-time atomic resolution images. We also utilize high-pressure x-ray photoelectron spectroscopy (HPXPS) to monitor systems under identical conditions thus giving us chemical information to compare and contrast with the structural and dynamic data provided by STM.

  3. The phase diagram of water at high pressures as obtained by computer simulations of the TIP4P/2005 model: the appearance of a plastic crystal phase.

    PubMed

    Aragones, J L; Conde, M M; Noya, E G; Vega, C

    2009-01-21

    In this work the high pressure region of the phase diagram of water has been studied by computer simulation by using the TIP4P/2005 model of water. Free energy calculations were performed for ices VII and VIII and for the fluid phase to determine the melting curve of these ices. In addition, molecular dynamics simulations were performed at high temperatures (440 K) observing the spontaneous freezing of the liquid into a solid phase at pressures of about 80,000 bar. The analysis of the structure obtained lead to the conclusion that a plastic crystal phase was formed. In the plastic crystal phase the oxygen atoms were arranged forming a body center cubic structure, as in ice VII, but the water molecules were able to rotate almost freely. Free energy calculations were performed for this new phase, and it was found that for TIP4P/2005 this plastic crystal phase is thermodynamically stable with respect to ices VII and VIII for temperatures higher than about 400 K, although the precise value depends on the pressure. By using Gibbs-Duhem simulations, all coexistence lines were determined, and the phase diagram of the TIP4P/2005 model was obtained, including ices VIII and VII and the new plastic crystal phase. The TIP4P/2005 model is able to describe qualitatively the phase diagram of water. It would be of interest to study if such a plastic crystal phase does indeed exist for real water. The nearly spherical shape of water makes possible the formation of a plastic crystal phase at high temperatures. The formation of a plastic crystal phase at high temperatures (with a bcc arrangements of oxygen atoms) is fast from a kinetic point of view occurring in about 2 ns. This is in contrast to the nucleation of ice Ih which requires simulations of the order of hundreds of ns.

  4. SINGLE CRYSTAL DIFFRACTION OF SIDERITE UP TO 54 GPA AND HIGH PRESSURE-HIGH TEMPERATURE PHASES IN THE Fe-C-O SYSTEM (Invited)

    NASA Astrophysics Data System (ADS)

    Lavina, B.; Dera, P. K.; Downs, R. T.

    2009-12-01

    Phases in the Fe-C-O system are of interest for the deep carbon cycle, they might play an important role in buffering the mantle fO2. Carbon is also common in the fluid phases that greatly influence the Earth’s processes. The study of the high pressure behavior of siderite and of the phases synthesized after laser heating offers a good opportunity to illustrate the advantages and importance of single crystal diffraction in the high pressure science. The structure of siderite, FeCO3, has been refined up to 54 GPa across the spin pairing transition. Splitting of the diffraction peaks at the transition pressure provides unequivocal evidence of the sharpness of the spin crossover and of the absence of any intermediate volume and therefore of an intermediate spin state at ambient temperature. Diffraction intensities were collected in about 30 minutes at a bending magnet station (HPCAT, APS) and in about one minute at an insertion device station (GSECARS, APS). The quality of the refinement is unvaried in the investigated range, and the results obtained from the two different radiation and detectors are consistent. The refinements provide an accurate and robust determination of the dependence of bond distances and angles with pressure. Subtle structural rearrangements associated with the collapse of the octahedral cation size will be discussed. In situ laser heating is a very powerful method to study minerals at the actual P-T of the Earth’s deep interior. Overcoming the kinetic barriers required for bond breaking and atom diffusion, high pressure-high temperature phases may be synthesized. The analysis of high-pressure phases is very challenging. Diffraction patterns are usually of moderate quality and resolution, furthermore in addition to the sample, the pattern contains the contribution of other phases such as those used to insulate the anvils, to provide a pressure medium and a pressure marker. In several cases after laser heating, we observed phase transitions

  5. High-pressure structural response of an insensitive energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)

    DOE PAGES

    Dreger, Zbigniew A.; Stash, Adam I.; Yu, Zhi -Gang; ...

    2017-02-28

    The structural response of a novel, insensitive energetic crystal—dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)—was examined under high pressure. Using synchrotron single-crystal X-ray diffraction measurements, details of molecular, intermolecular, and crystal changes were determined to ~10 GPa to understand its structural stability. The experimental results showed that TKX-50 exhibits highly anisotropic compression and significantly lower volume compressibility than currently known energetic crystals. These results are found to be in general agreement with our previous predictions from the DFT calculations. Additionally, the experimental data revealed anomalous compression—an expansion of the unit cell along the a axis (negative linear compressibility, NLC) upon compression to ~3 GPa.more » The structural analyses demonstrated that this unusual effect, the first such observation in an energetic crystal, is a consequence of the highly anisotropic response of 3D motifs, comprised of two parallel anions [(C2N8O2)2–] linked with two cations [(NH3OH)+] through four strong hydrogen bonds. Finally, the present results demonstrate that the structural stability of TKX-50 is controlled by the strong and highly anisotropic intermolecular interactions, and these may contribute to its shock insensitivity.« less

  6. Thermochemical micro imprinting of single-crystal diamond surface using a nickel mold under high-pressure conditions

    NASA Astrophysics Data System (ADS)

    Imoto, Yuji; Yan, Jiwang

    2017-05-01

    Single-crystal diamond is an important material for cutting tools, micro electro mechanical systems, optical devices, and semiconductor substrates. However, the techniques for producing microstructures on diamond surface with high efficiency and accuracy have not been established. This paper proposes a thermochemical imprinting method for transferring microstructures from a nickel (Ni) mold onto single-crystal diamond surface. The Ni mold was micro-structured by a nanoindenter and then pressed against the diamond surface under high temperature and pressure in argon atmosphere. Results show that microstructures on the Ni mold were successfully transferred onto the diamond surface, and their depth increased with both pressure and temperature. Laser micro-Raman spectroscopy, transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses indicate that a graphite layer was formed over the contact area between diamond and Ni during pressing, and after washing by a mixed acid, the graphite layer could be completely removed. This study demonstrated the feasibility of a cost-efficient fabrication method for large-area microstructures on single-crystal diamond.

  7. Crystal chemistry of thorium nitrates and chromates

    SciTech Connect

    Sigmon, Ginger E.; Burns, Peter C.

    2010-07-15

    The structures and infrared spectra of six novel thorium compounds are reported. Th(NO{sub 3}){sub 2}(OH){sub 2}(H{sub 2}O){sub 2} (1) crystallizes in space group C2/c, a=14.050(1), b=8.992(7), c=5.954(5) A, {beta}=101.014(2){sup o}. K{sub 2}Th(NO{sub 3}){sub 6} (2), P-3, a=13.606(1), c=6.641(6) A. (C{sub 12}H{sub 28}N){sub 2}Th(NO{sub 3}){sub 6} (3), P2{sub 1}/c, a=14.643(4), b=15.772(5), c=22.316(5) A, {beta}=131.01(1){sup o}. KTh(NO{sub 3}){sub 5}(H{sub 2}O){sub 2} (4), P2{sub 1}/c, a=10.070(8), b=12.731(9), c=13.231(8) A, {beta}=128.647(4){sup o}. Th(CrO{sub 4}){sub 2}(H{sub 2}O){sub 2} (5), P2{sub 1}/n, a=12.731(1), b=9.469(8), c=12.972(1) A, {beta}=91.793(2){sup o}. K{sub 2}Th{sub 3}(CrO{sub 4}){sub 7}(H{sub 2}O){sub 10} (6), Ama2, a=19.302(8), b=15.580(6), c=11.318(6) A. The coordination polyhedra about Th in these structures are diverse. Th is coordinated by 9 O atoms in 5 and 6, seven of which are from monodentate (CrO{sub 4}) tetrahedra and two are (H{sub 2}O). The Th in compound 1 is coordinated by ten O atoms, four of which are O atoms of two bidentate (NO{sub 3}) triangles and six of which are (OH) and (H{sub 2}O). In compounds 2, 3 and 4 the Th is coordinate by 12 O atoms. In 2 and 3 there are six bidentate (NO{sub 3}) triangles, and in 4 ten of the O atoms are part of five bidentate (NO{sub 3}) triangles and the others are (H{sub 2}O) groups. The structural units of these compounds consist of a chain of thorium and nitrate polyhedra (1), isolated thorium hexanitrate clusters (2, 3), an isolated thorium pentanitrate dihydrate cluster (4), and a sheet (6) and framework (5) of thorium and chromate polyhedra. These structures illustrate the complexity inherent in the crystal chemistry of Th. - Graphical Abstract: The structures and infrared spectra of four new Th nitrates and two Th chromates are reported. The coordination numbers of the Th cations range from nine to 12 in these compounds. Structural units consist of isolated clusters, chains, sheets and

  8. Single-Crystal Equations of State and Hyperfine Fields of Magnesiowüstite at High Pressures

    NASA Astrophysics Data System (ADS)

    Finkelstein, G. J.; Zhang, D.; Jackson, J. M.

    2015-12-01

    In recent years, seismic observations have provided increasing evidence for significant heterogeneity in Earth's lower mantle at both large (i.e. large low shear velocity provinces, or LLSVPs) and comparatively small (ultra-low velocity zones, or ULVZs) scales. One possible source of heterogeneity is variation in the Fe-content of the (Mg,Fe)O component of the lower mantle due to melting events and/or reactions with Earth's outer core. Most previous studies have focused on compositions containing ~10-20 mol% Fe, but small amounts of compositions with an enhanced Fe concentration may strongly impact the elastic properties of the bulk phase assemblage. Here, we present results from two high-precision single-crystal x-ray diffraction studies on (Fe0.78Mg0.22)O magnesiowüstite to pressures of about 55 GPa at 300 K, one using neon and the other using helium as pressure-transmitting media. We observe a noticeably different compression behavior in the two pressure media at pressures greater than about 20 GPa, and compare to previous work on similar compositions. We also conducted a complementary single-crystal time domain synchrotron Mössbauer spectroscopy (SMS) study on the same composition in a helium medium to about 70 GPa to gain insight into the atom-scale properties of the Fe sublattice. We discuss the resulting hyperfine fields as a function of pressure, including the isomer shift, quadrupole splitting, magnetic, and texturing parameters. The advantages of using single crystals for such investigations will also be discussed. Finally, implications for the elastic properties of magnesiowüstite in the deep mantle will be considered.

  9. High-pressure single-crystal X-ray diffraction study on Super Fluorous Phase B up to 7.4 GPa

    NASA Astrophysics Data System (ADS)

    Kuribayashi, T.; Kojitani, H.; Nagase, T.; Akaogi, M.; Mao, H.; Hemley, R.; Kudoh, Y.

    2008-12-01

    Super hydrous phase B (SUP-B), Mg10Si3O14(OH)4, is known as one of dense hydrous magnesium silicate minerals (DHMS). Also, super fluorous phase B (sup-B-F), Mg10Si3O14F4, was firstly synthesized by Hazen et al. (1997). In the crystal structure of SUP-B-F, F replaces OH in sup-B structure. Therefore, differences of behavior between SUP-B-F and SUP-B under high-pressure conditions directory reflect the effect of hydrogen bonding. In this study, to clarify the behavior of SUP-B-F under high-pressure condition, SUP-B-F was synthesized at 21 GPa and 1400°C conditions using the Kawai type multi anvil apparatus installed in Gakushu-in University. Using a synthesized single-crystal (0.04 × 0.04 × 0.03 mm3), high-pressure single-crystal X-ray diffraction measurements were conducted up to 7.4 GPa with synchrotron radiation. Lattice constants were determined at several pressure points up to 7.4 GPa. The isothermal bulk modulus of SUP-B-F, calculated from the Birch-Murnaghan Equation of State, was 154(2) GPa with a pressure derivative K'=4 (assuming). This value is significantly larger than that of super hydrous phase B (142.8(5) GPa with K"f=5.7 by Crichton et al., 1999). The X-ray reflection intensity data set was collected at 5.0 GPa using the four-circle diffractometer installed at the beam line BL-10A in Photon Factory, Japan. 198 reflections were used for structure refinement (the number of measured reflections is 786). After Lorentz- polarization correction and background reduction were applied for all intensity data, the crystallographic equivalent reflections (Orthorhombic, Pnnm) were averaged. Structure refinement results were R=5.0% and wR2=13.1%, respectively.

  10. Constitutive Cyclic Deformation Behavior in Single-crystal and Directionally Solidified SSME High-pressure Fuel Turbopump Airfoil Materials

    NASA Technical Reports Server (NTRS)

    Milligan, W. W.; Huron, E. S.; Antolovich, S. D.

    1985-01-01

    The major goal of the project is to correlate mechanical properties with microstructural deformation behavior and to develop models for constitutive response under a variety of monotonic and cyclic loading cycles, temperatures, strain levels, strain rates, and environments. Two alloys are being studied as candidate SSME turbine blade materials. The first is PWA 1480, which is a single-crystal alloy whose nominal composition is reported. The second alloy being studied is D.S. Mar-M 246 + Hf. This is a directionally solidified material, and its nominal composition is also reported. The major areas of interest for the two materials will be slightly different. The single-crystal alloy lends itself well to fundamental deformation studies, since resolved shear stresses on slip planes are all known and only one grain is present. The D.S. material presents an excellent opportunity to study the effects of slightly misaligned grains on deformation behavior. The two materials will be studied by using approximately the same test matrix, so a good degree of direct comparison will also be possible.

  11. High-pressure optical floating-zone growth of Li(Mn,Fe)PO4 single crystals

    NASA Astrophysics Data System (ADS)

    Neef, Christoph; Wadepohl, Hubert; Meyer, Hans-Peter; Klingeler, Rüdiger

    2017-03-01

    Mm-sized LiMn1-xFexPO4 single crystals with 0 ⩽ x ⩽ 1 were grown by means of the traveling floating-zone technique at elevated Argon pressure of 30 bar. For the various doping levels, the growth process was optimized with respect to the composition-dependant effective light absorption and transparency of the materials. A convex crystal/melt interface, determined by the angle of incident light, was identified to be particularly crucial for a successful growth. The resulting large single crystalline grains are stoichiometric. Structure refinement shows that lattice parameters as well as the atomic positions and bond lengths linearly depend on the Mn:Fe-ratio. Oriented cuboidal samples with several mm3 of volume were used for magnetic studies which imply an antiferromagnetic ground state for all compositions. The Néel-temperature changes from TN = 32.5(5) K in LiMnPO4 to 49.5(5) K in LiFePO4 while the easy magnetic axis in the ordered phase flips from the crystallographic a- to the b-axis upon Fe-doping of x < 0.2 .

  12. Effects of gate insulator using high pressure annealing on the characteristics of solid phase crystallized polycrystalline silicon thin-film transistors

    NASA Astrophysics Data System (ADS)

    Kim, Moojin; Jin, GuangHai

    2009-04-01

    The oxidizing ambient was built using high pressure H2O vapor at 550 °C. For the solid phase crystallization (SPC) polycrystalline silicon (poly-Si) that is annealed for 1 h at 2 MPa, the oxide thickness is about 150 Å. The oxide layer is approximately 90 Å above the original surface of the poly-Si and 60 Å below the original surface. The oxide layer is used as the first gate insulator layer of thin-film transistors (TFTs). The heating at 550 °C with 2 MPa H2O vapor increased the carrier mobility from 17.6 cm2/V s of the conventional SPC process to 30.4 cm2/V s, and it reduced the absolute value of the threshold voltage (Vth) from 4.13 to 3.62 V. The subthreshold swing also decreased from 0.72 to 0.60 V/decade. This improvement is attributed mainly to the reduction in defect density at the oxide/poly-Si interface and in the poly-Si film by the high pressure annealing (HPA) process. Since the realization of excellent performance at the oxide/poly-Si interface and in poly-Si depends on the defect density, the poly-Si having the thermal oxide formed by a combined process of SPC and HPA may be well suited for fabrication of poly-Si TFTs for flat panel displays such as active matrix organic light emitting diodes.

  13. High-temperature treatment of In-doped CZT crystals grown by the high-pressure Bridgman method

    SciTech Connect

    Bolotnikov A.; Fochuk, P.; Nakonechnyi, I.; Kopach, O.; Verzhak, Ye.; Panchuk, O.; Komar, V.; Terzin, I.; Kutnij, V.; Rybka, A.; Nykoniuk, Ye.; Camarda, G.C.; Cui, Y.; Hossain, A.; Kim, K.H.; Yang, G.; James, R.B.

    2012-08-12

    We evaluated the effect of high-temperature treatment of Cd0.9Zn0.1Te:In single crystals using Hall-effect measurements, medium- and high-temperature annealing under various deviations from stoichiometry, and infra-red (IR) transmission microscopy Annealing at ~730 K sharply increased the electrical conductivity (by ~1-2 orders-of-magnitude). Plots of the temperature- and cadmium-pressure dependences of the electrical conductivity, carrier concentration, and mobility were obtained. Treating previously annealed Cd-samples under a Te overpressure at 1070 K allowed us to restore their resistance to its initial high values. The main difference in comparing this material with CdTe was its lowered electron density. We explained our results within the framework of Kröger’s theory of quasi-chemical reactions between point defects in solids.

  14. High-pressure single-crystal elasticity study of CO{sub 2} across phase I-III transition

    SciTech Connect

    Zhang, Jin S. Bass, Jay D.; Shieh, Sean R.; Dera, Przemyslaw; Prakapenka, Vitali

    2014-04-07

    Sound velocities and elastic moduli of solid single-crystal CO{sub 2} were measured at pressures up to 11.7(3) GPa by Brillouin spectroscopy. The aggregate adiabatic bulk modulus (K{sub S}), shear modulus (G), and their pressure derivatives for CO{sub 2} Phase I are K{sub S0} = 3.4(6) GPa, G{sub 0} = 1.8(2) GPa, (dK{sub S}/dP){sub 0} = 7.8(3), (dG/dP){sub 0} = 2.5(1), (d{sup 2}K{sub S}/dP{sup 2}){sub 0} = −0.23(3) GPa{sup −1}, and (d{sup 2}G/dP{sup 2}){sub 0} = −0.10(1) GPa{sup −1}. A small increase of elastic properties was observed between 9.8(1) and 10.5(3) GPa, in agreement with the CO{sub 2} I-III transition pressure determined from previous x-ray diffraction experiments. Above the transition pressure P{sub T}, we observed a mixture dominated by CO{sub 2}-I, with minor CO{sub 2}-III. The CO{sub 2}-I + III mixture shows slightly increased sound velocities compared to pure CO{sub 2}-I. Elastic anisotropy calculated from the single-crystal elasticity tensor exhibits a decrease with pressure beginning at 7.9(1) GPa, which is lower than P{sub T}. Our results coincide with recent X-ray Raman observations, suggesting that a pressure-induced electronic transition is related to local structural and optical changes.

  15. High-Pressure Single-Crystal Neutron Scattering Study of Magnetic and Fe Vacancy Orders in (Tl,Rb)2 Fe4 Se5 Superconductor

    DOE PAGES

    Ye, Feng; Bao, Wei; Chi, Song-Xue; ...

    2014-12-01

    We investigate the magnetic and iron vacancy orders in superconducting (Tl,Rb)2Fe4Se5 single-crystals by using a high-pressure neutron diffraction technique. Similar to the temperature effect, the block antiferromagnetic order gradually decreases upon increasing pressure while the Fe vacancy superstructural order remains intact before its precipitous disappearance at the critical pressure Pc = 8.3 GPa. Combined with previously determined Pc for superconductivity, our phase diagram under pressure reveals the concurrence of the block AFM order, the √5 × √5 iron vacancy order and superconductivity for the 245 superconductor. Lastly, a synthesis of current experimental data in a coherent physical picture is attempted.

  16. High pressure-high temperature phase diagram of an energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)

    DOE PAGES

    Dreger, Z. A.; Breshike, C. J.; Gupta, Y. M.

    2017-05-08

    Raman spectroscopy was used to examine the high pressure-high temperature structural and chemical stability of an insensitive, high-performance energetic crystal – dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50). The phase diagram was determined over 8 GPa and (293-760) K. Under isobaric heating, the melting/decomposition of TKX-50 is preceded by a transformation to two consecutive high-temperature intermediates; a lower-temperature intermediate – diammonium 5,5’-bistetrazole-1,1'-diolate, and a higher-temperature intermediate – dihydroxylammonium 5,5'-bistetrazolate and/or diammonium 5,5'-bistetrazolate. Pressure strongly increases the transition temperatures for these transformations and subsequent decomposition. As a result, significant increase in the chemical stability of TKX-50 and intermediates with pressure was attributed to a suppressionmore » of hydrogen-transfer.« less

  17. Relaxation of the normal electrical resistivity induced by high-pressure in strongly underdoped YBa2Cu3O7-δ single crystals

    NASA Astrophysics Data System (ADS)

    Vovk, R. V.; Khadzhai, G. Ya.; Nazyrov, Z. F.; Goulatis, I. L.; Chroneos, A.

    2012-11-01

    We investigate the relaxation of the normal electrical resistivity, induced by high-pressure in YBa2Cu3O6.45 single crystals. It is determined that the pressure affects to the phase composition of the sample. Under pressure phases with different (but similar) critical temperatures form. It is determined that the application-removal pressure process is completely reversible. Above Tc the temperature dependence of the resistivity in the layers' plane at different hydrostatic pressures can be approximated with high accuracy with the scattering of electrons by phonons model. With increasing pressure, the residual resistance is reduced and the contribution of intraband s-s scattering increases. Additionally, the role of the interband s-d scattering and the Debye temperature is enhanced.

  18. Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5

    PubMed Central

    Ding, Wenjin; Baracchini, Giulia; Klumpp, Michael; Schwieger, Wilhelm; Dittmeyer, Roland

    2016-01-01

    We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example. PMID:27585356

  19. Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5.

    PubMed

    Ding, Wenjin; Baracchini, Giulia; Klumpp, Michael; Schwieger, Wilhelm; Dittmeyer, Roland

    2016-08-25

    We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example.

  20. Concentration-dependent crystal structure, elastic constants and electronic structure of Zr x Ti1- x alloys under high pressure

    NASA Astrophysics Data System (ADS)

    Yuan, Xiao-Li; Xue, Mi-An; Chen, Wen; An, Tian-Qing

    2014-04-01

    The physical properties of Zr x Ti1- x ( x = 0.0, 0.33, 0.5, 0.67, 0.75 and 1.00) alloys were simulated by virtual crystal approximation (VCA) methods which is generally used for disordered solid solutions modeling. The elastic constant, electronic structure and thermal Equation of state (EOS) of disordered Zr x Ti1- x alloys under pressure are investigated by plane-wave pseudo-potential method. Our simulations reveal increasement of variations of the calculated equilibrium volumes and decreasement of Bulk modulus as a function of the alloy compositions. Lattice parameters a and c of alloys with different Zr concentrations decrease linearly with pressure increasing, but the c/avalues are increasing as pressure increases, indicating no phase transitions under pressure from 0 GPa to 100 GPa. The elastic constants and the Bulk modulus to the Shear modulus ratios ( B/G) indicate good ductility of Zr, Zr0.33Ti0.67, Zr0.5Ti0.5, Zr0.75Ti0.25 and Ti, but the Zr0.67Ti0.33 alloy is brittle under 0 K and 0 GPa. The metallic behavior of these alloys was also proved by analyzing partial and total DOS.

  1. Bench-Scale Development of a Hot Carbonate Absorption Process with Crystallization-Enabled High-Pressure Stripping for Post-Combustion CO{sub 2} Capture

    SciTech Connect

    Lu, Yongqi; DeVries, Nicholas; Ruhter, David; Manoranjan, Sahu; Ye, Qing; Ye, Xinhuai; Zhang, Shihan; Chen, Scott; Li, Zhiwei; O'Brien, Kevin

    2014-03-31

    A novel Hot Carbonate Absorption Process with Crystallization-Enabled High-Pressure Stripping (Hot-CAP) has been developed by the University of Illinois at Urbana-Champaign and Carbon Capture Scientific, LLC in this three-year, bench-scale project. The Hot-CAP features a concentrated carbonate solution (e.g., K{sub 2}CO{sub 3}) for CO{sub 2} absorption and a bicarbonate slurry (e.g., KHCO{sub 3}) for high-pressure CO{sub 2} stripping to overcome the energy use and other disadvantages associated with the benchmark monoethanolamine (MEA) process. The project was aimed at performing laboratory- and bench-scale experiments to prove its technical feasibility and generate process engineering and scale-up data, and conducting a techno-economic analysis (TEA) to demonstrate its energy use and cost competitiveness over MEA. To meet project goals and objectives, a combination of experimental, modeling, process simulation, and economic analysis studies were applied. Carefully designed and intensive experiments were conducted to measure thermodynamic and reaction engineering data relevant to four major unit operations in the Hot-CAP (i.e., CO{sub 2} absorption, CO{sub 2} stripping, bicarbonate crystallization, and sulfate reclamation). The rate promoters that could accelerate the CO{sub 2} absorption rate into the potassium carbonate/bicarbonate (PCB) solution to a level greater than that into the 5 M MEA solution were identified, and the superior performance of CO{sub 2} absorption into PCB was demonstrated in a bench-scale packed-bed column. Kinetic data on bicarbonate crystallization were developed and applied for crystallizer design and sizing. Parametric testing of high-pressure CO{sub 2} stripping with concentrated bicarbonate-dominant slurries at high temperatures ({>=}140{degrees}C) in a bench-scale stripping column demonstrated lower heat use than with MEA. The feasibility of a modified process for combining SO{sub 2} removal with CO{sub 2} capture was preliminarily

  2. High-Pressure Vibrational Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Pogson, Mark

    1987-09-01

    Available from UMI in association with The British Library. Requires signed TDF. The study of solids at high pressure and variable temperature enables development of accurate interatomic potential functions over wide ranges of interatomic distances. A review of the main models used in the determination of these potentials is given in Chapter one. A discussion of phonon frequency as a variable physical parameter reflecting the interatomic potential is given. A high pressure Raman study of inorganic salts of the types MSCN, (M = K,Rb,Cs & NH_4^+ ) and MNO_2, (M = K,Na) has been completed. The studies have revealed two new phases in KNO_2 and one new phase in NaNO _2 at high pressure. The accurate phonon shift data have enabled the determination of the pure and biphasic stability regions of the phases of KNO _2. A discussion of the B1, B2 relationship of univalent nitrites is also given. In the series of thiocyanates studied new phases have been found in all four materials. In both the potassium and rubidium salts two new phases have been detected, and in the ceasium salt one new phase has been detected, all at high pressure, from accurate phonon shift data. These transitions are discussed in terms of second-order mechanisms with space groups suggested for all phases, based on Landau's theory of second-order phase transitions. In the ammonium salt one new phase has been detected. This new phase transition has been interpreted as a second-order transition. The series of molecular crystals CH_3 HgX, (X = Cl,Br & I) has been studied at high pressure and at variable temperature. In Chapter five, their phase behaviour at high pressure is detailed along with the pressure dependencies of their phonon frequencies. In the chloride and the bromide two new phases have been detected. In the bromide one has been detected at high temperature and one at high pressure, and latter being interpreted as the stopping of the methyl rotation. In the chloride one phase has been found at

  3. Crystal Chemistry of Th in Fluorapatite

    SciTech Connect

    Y Luo; J Rakovan; Y Tang; M Lupulescu; J Hughes; Y Pan

    2011-12-31

    Through the complementary use of single-crystal X-ray diffraction and X-ray absorption spectroscopy, we present in this paper the first direct results on the site occupancy of thorium in the fluorapatite structure and the structural distortion created by its substitution. Structure refinements based on single-crystal X-ray diffraction data from synthetic Th-doped fluorapatite indicates that Th substitutes almost exclusively in the M2 site. A single-crystal X-ray study of natural fluorapatite from Mineville, New York, also indicated that substituting heavy scatterers (including Th) are concentrated in the apatite M2 site, but definitive site assignments of specific elements were not possible. Extended X-ray absorption fine-structure spectroscopy (EXAFS) was used to probe the local structure of Th in the synthetic fluorapatite (single-crystal form) with a Th concentration of roughly 20000 ppm, as well as Th in the natural Mineville fluorapatite (powder form) with a Th concentration of {approx}2000 ppm. The EXAFS fitting results also indicate that Th partitions into the M2 site and yield a {approx}0.05-0.08 {angstrom} decrease of average M2-O bond distances associated with local structure distortions that are not obtainable from single-crystal X-ray diffraction studies.

  4. High-pressure and high-temperature multianvil synthesis of metastable polymorphs of Bi2O3 : Crystal structure and electronic properties

    NASA Astrophysics Data System (ADS)

    Ghedia, S.; Locherer, T.; Dinnebier, R.; Prasad, D. L. V. K.; Wedig, U.; Jansen, M.; Senyshyn, A.

    2010-07-01

    High-pressure and high-temperature experiments with Bi2O3 using a 6-8 type multianvil device led to the formation of a metastable polymorph (HP-Bi2O3) with noncentrosymmetric trigonal symmetry. This phase relaxes during the course of several months at ambient temperature or more rapidly via annealing, to a second intermediate modification (R-Bi2O3) . Upon further annealing finally the transformation back to the known ambient phase (α-Bi2O3) takes place. Both crystal structures were solved from high-resolution x-ray and neutron powder-diffraction data. The orientation and stereochemical activity of the Bi3+ lone pairs (or inert pairs) is discussed in terms of crystal-chemical considerations and density-functional theory calculations. Whenever suitable, results were verified by experimental determination of the respective properties. The results of the theoretical analyses show that within the structure type of HP-Bi2O3 , bismuth oxide exhibits a pronounced polarization and can be considered as ferroelectric.

  5. On the induction of homogeneous bulk crystallization in Eu-doped calcium aluminosilicate glass by applying simultaneous high pressure and temperature

    SciTech Connect

    Muniz, R. F.; Ligny, D. de; Le Floch, S.; Martinet, C.; Guyot, Y.; Rohling, J. H.; Medina, A. N.; Sandrini, M.; Baesso, M. L.; Andrade, L. H. C.; Lima, S. M.

    2016-06-28

    From initial calcium aluminosilicate glass, transparent glass-ceramics have been successfully synthesized under simultaneous high pressure and temperature (SHPT). Possible homogeneous volumetric crystallization of this glassy system, which was not achieved previously by means of conventional heat treatment, has been put in evidence with a SHPT procedure. Structural, mechanical, and optical properties of glass and glass-ceramic obtained were investigated. Raman spectroscopy and X-ray diffraction allowed to identify two main crystalline phases: merwinite [Ca{sub 3}Mg(SiO{sub 4}){sub 2}] and diopside [CaMgSi{sub 2}O{sub 6}]. A Raman scanning profile showed that the formation of merwinite is quite homogeneous over the bulk sample. However, the sample surface also contains significant diopside crystals. Instrumented Berkovich nanoindentation was applied to determine the effect of SHPT on hardness from glass to glass-ceramic. For Eu-doped samples, the broadband emission due to 4f{sup 6}5d{sup 1} → 4f{sup 7} transition of Eu{sup 2+} was studied in both host systems. Additionally, the {sup 5}D{sub 0} → {sup 7}F{sub J} transition of Eu{sup 3+} was used as an environment probe in the pristine glass and the glass-ceramic.

  6. High-pressure synthesis, crystal structure, and unusual valence state of novel perovskite oxide CaCu3Rh4O12.

    PubMed

    Yamada, Ikuya; Ochi, Mikiko; Mizumaki, Masaichiro; Hariki, Atsushi; Uozumi, Takayuki; Takahashi, Ryoji; Irifune, Tetsuo

    2014-07-21

    A novel perovskite oxide, CaCu3Rh4O12, has been synthesized under high-pressure and high-temperature conditions (15 GPa and 1273 K). Rietveld refinement of synchrotron X-ray powder diffraction data indicates that this compound crystallizes in a cubic AA'3B4O12-type perovskite structure. Synchrotron X-ray absorption and photoemission spectroscopy measurements reveal that the Cu and Rh valences are nearly trivalent. The spectroscopic analysis based on calculations suggests that the appropriate ionic model of this compound is Ca(2+)Cu(∼2.8+)3Rh(∼3.4+)4O12, as opposed to the conventional Ca(2+)Cu(2+)3Rh(4+)4O12. The uncommon valence state of this compound is attributed to the relative energy levels of the Cu 3d and Rh 4d orbitals, in which the large crystal-field splitting energy of the Rh 4d orbitals is substantial.

  7. High-pressure crystal growth and magnetic and electrical properties of the quasi-one dimensional osmium oxide Na{sub 2}OsO{sub 4}.

    SciTech Connect

    Shi, Y. G.; Guo, Y. F.; Yu, S.; Arai, M.; Belik, A. A.; Sato, A.; Yamaura, K.; Takayama-Muromachi, E.; Varga, T.; Mitchell, J. F.; Materials Science Division; National Inst. for Materials Science; JST, Transformative Research Project on Iron Pnictides; Hokkaido Univ.

    2010-02-01

    Na{sub 2}OsO{sub 4} crystals were grown by a NaCl flux method under high pressure. It crystallizes in the Ca{sub 2}IrO{sub 4}-type structure without having additional elements or metal vacancies, which are usually accommodated. It appears that Na{sub 2}OsO{sub 4} is a metal-stoichiometric Ca{sub 2}IrO{sub 4}-type compound never been synthesized to date. Na{sub 2}OsO{sub 4} has the octahedral environment of Os{sup 6+}O{sub 6} so that the electronic configuration is 5d{sup 2}, suggesting the magnetic S=1 ground state. However, magnetization, electrical resistivity, and specific heat measurements indicated that the non-magnetic S=0 state is much likely for Na{sub 2}OsO{sub 4} than the S=1 state. Band structure calculations and the structure analysis found that the disagreement is probably due to the statically uniaxial compression of the OsO{sub 6} octahedra, resulting in splitting of the t{sub 2{sub g}} band.

  8. On the induction of homogeneous bulk crystallization in Eu-doped calcium aluminosilicate glass by applying simultaneous high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Muniz, R. F.; de Ligny, D.; Le Floch, S.; Martinet, C.; Rohling, J. H.; Medina, A. N.; Sandrini, M.; Andrade, L. H. C.; Lima, S. M.; Baesso, M. L.; Guyot, Y.

    2016-06-01

    From initial calcium aluminosilicate glass, transparent glass-ceramics have been successfully synthesized under simultaneous high pressure and temperature (SHPT). Possible homogeneous volumetric crystallization of this glassy system, which was not achieved previously by means of conventional heat treatment, has been put in evidence with a SHPT procedure. Structural, mechanical, and optical properties of glass and glass-ceramic obtained were investigated. Raman spectroscopy and X-ray diffraction allowed to identify two main crystalline phases: merwinite [Ca3Mg(SiO4)2] and diopside [CaMgSi2O6]. A Raman scanning profile showed that the formation of merwinite is quite homogeneous over the bulk sample. However, the sample surface also contains significant diopside crystals. Instrumented Berkovich nanoindentation was applied to determine the effect of SHPT on hardness from glass to glass-ceramic. For Eu-doped samples, the broadband emission due to 4f65d1 → 4f7 transition of Eu2+ was studied in both host systems. Additionally, the 5D0 → 7FJ transition of Eu3+ was used as an environment probe in the pristine glass and the glass-ceramic.

  9. Electron density distribution of FeTiO3 ilmenite under high pressure analyzed by MEM using single crystal diffraction intensities

    NASA Astrophysics Data System (ADS)

    Yamanaka, Takamitsu; Komatsu, Yutaka; Nomori, Hironori

    2007-07-01

    Many of ilmenites ABO3 compounds bearing transition elements have semiconductive, ferroelectric and antiferromagnetic properties. The high-pressure diffraction studies of FeTiO3 have been conducted up to 8.2 GPa using synchrotron radiation in KEK at Tsukuba with diamond anvil cell. The compression mechanism of FeTiO3 ilmenite has been investigated by the structure refinements converged to the reliable factors R = 0.05. The deformations of the FeO6 and TiO6 octahedra were reduced with increasing pressure. In order to elucidate the electric conductivity change with pressure, electron density distribution of ilmenite have been executed by maximum entropy method (MEM) using single-crystal diffraction intensity data. MEM based on F obs( hkl) of FeTiO3 clearly shows electron density in comparison with the difference Fourier synthesis based on F obs( hkl) - F calc( hkl). The radial distribution of the electron density indicates electron localization around the cation positions. The bonding electron density found in bond Fe-O and Ti-O is lowered with pressure. The isotropic temperature factors B iso become smaller with increasing pressure. Nevertheless the thermal vibration is considerably restrained by the compression, the electric conductivity is enhanced with pressure. Neither charge transfer nor electron hopping between Fe and Ti along the c axis in FeTiO3 is plausible under high pressure. But the electric conductivity due to electron super-exchange in Fe-Fe and Ti-Ti has been clarified by the MEM electron density distribution. The anisotropy in the electric conductivity has been clarified.

  10. High-pressure synthesis, crystal structure and magnetic properties of double perovskite oxide Ba{sub 2}CuOsO{sub 6}

    SciTech Connect

    Feng, Hai L.; Arai, Masao; Matsushita, Yoshitaka; Tsujimoto, Yoshihiro; Yuan, Yahua; Sathish, Clastin I.; He, Jianfeng; Tanaka, Masahiko; Yamaura, Kazunari

    2014-09-15

    A new compositional double perovskite oxide Ba{sub 2}CuOsO{sub 6} was synthesized under high-pressure (6 GPa) and high-temperature (1500 °C) conditions. The polycrystalline Ba{sub 2}CuOsO{sub 6} was characterized by synchrotron X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility, isothermal magnetization, and specific heat measurements. The oxide crystallizes in a double-perovskite structure with an I4/m space group, in which Os(VI) and Cu(II) are ordered in the perovskite B-site. Ba{sub 2}CuOsO{sub 6} is electrically insulating with an activation energy of 0.813(2) eV and shows antiferromagnetic-like characteristics at temperatures of ∼55 K and ∼70 K. The results of the first-principle calculation suggested that the spin–orbit interaction of Os(VI) plays a substantial role in the insulating state. The Jahn–Teller distortion of CuO{sub 6} octahedra influences the magnetic characteristics with regard to possible two-dimensional magnetic correlations. - Graphical abstract: A new compositional double perovskite oxide Ba{sub 2}CuOsO{sub 6} synthesized by a high-pressure (6 GPa) and high-temperature (1500 °C) method. - Highlights: • A new compositional double perovskite oxide Ba{sub 2}CuOsO{sub 6} was synthesized. • Ba{sub 2}CuOsO{sub 6} is electrically insulating and antiferromagnetic below ∼70 K. • The Jahn–Teller distortion of CuO{sub 6} has relevance to possible magnetic anisotropy.

  11. First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105).

    PubMed

    Manaa, M Riad; Kuo, I-Feng W; Fried, Laurence E

    2014-08-14

    We report dispersion-corrected density functional theoretical calculations of the unreacted equation of state (EOS) of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105) under hydrostatic compression of up to 45 GPa. Convergence tests for k-points sampling in the Brillouin zone show that a 3 × 1 × 2 mesh is required to reproduce the X-ray crystal structure at ambient conditions, and we confirm our finding with a separate supercell calculation. Our high-pressure EOS yields a bulk modulus of 19.2 GPa, and indicates a tendency towards anisotropic compression along the b lattice vector due to molecular orientations within the lattice. We find that the electronic energy band gap decreases from a semiconductor type of 1.3 eV at 0 GPa to quasi-metallic type of 0.6 eV at 45 GPa. The extensive intermolecular hydrogen bonds involving the oxide (-NO) and dioxide (-NO2) interactions with the amine (-NH2) group showed enhanced interactions with increasing pressure that should be discernible in the mid IR spectral region. We do not find evidence for structural phase transitions or chemically induced transformations within the pressure range of our study. The gas phase heat of formation is calculated at the G4 level of theory to be 22.48 kcal/mol, while we obtain 25.92 kcal/mol using the ccCA-PS3 method. Density functional theory calculations of the crystal and the gas phases provided an estimate for the heat of sublimation of 32.4 kcal/mol. We thus determine the room-temperature solid heat of formation of LLM-105 to be -9.9 or -6.5 kcal/mol based on the G4 or ccCA-PS3 methods, respectively.

  12. First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105)

    SciTech Connect

    Manaa, M. Riad Kuo, I-Feng W.; Fried, Laurence E.

    2014-08-14

    We report dispersion-corrected density functional theoretical calculations of the unreacted equation of state (EOS) of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105) under hydrostatic compression of up to 45 GPa. Convergence tests for k-points sampling in the Brillouin zone show that a 3 × 1 × 2 mesh is required to reproduce the X-ray crystal structure at ambient conditions, and we confirm our finding with a separate supercell calculation. Our high-pressure EOS yields a bulk modulus of 19.2 GPa, and indicates a tendency towards anisotropic compression along the b lattice vector due to molecular orientations within the lattice. We find that the electronic energy band gap decreases from a semiconductor type of 1.3 eV at 0 GPa to quasi-metallic type of 0.6 eV at 45 GPa. The extensive intermolecular hydrogen bonds involving the oxide (–NO) and dioxide (–NO{sub 2}) interactions with the amine (–NH{sub 2}) group showed enhanced interactions with increasing pressure that should be discernible in the mid IR spectral region. We do not find evidence for structural phase transitions or chemically induced transformations within the pressure range of our study. The gas phase heat of formation is calculated at the G4 level of theory to be 22.48 kcal/mol, while we obtain 25.92 kcal/mol using the ccCA-PS3 method. Density functional theory calculations of the crystal and the gas phases provided an estimate for the heat of sublimation of 32.4 kcal/mol. We thus determine the room-temperature solid heat of formation of LLM-105 to be −9.9 or −6.5 kcal/mol based on the G4 or ccCA-PS3 methods, respectively.

  13. The development of cyclophosphate crystal chemistry

    NASA Astrophysics Data System (ADS)

    Durif, André

    2005-06-01

    Among the various condensation schemes occurring in phosphoric anions one of them leads to the formation of cyclic entities. The corresponding salts, for a long time called "metaphosphates" are now denominated cyclophosphates. Built up by a ring of corner-sharing PO 4 tetrahedra, the general formula of their anions is P nO 3 nn- . Today these anions are known for n=3, 4, 5, 6, 8, 9, 10, and 12. The development of the chemistry of cyclophosphates was very slow, spreading along almost two centuries. We report first a short history of the development of each class of cyclophosphates, then we examine their general properties

  14. A density functional study of the high-pressure chemistry of MSiN2(M = Be, Mg, Ca): prediction of high-pressure phases and examination of pressure-induced decomposition

    NASA Astrophysics Data System (ADS)

    Rebecca Römer, S.; Kroll, Peter; Schnick, Wolfgang

    2009-07-01

    Normal pressure modifications and tentative high-pressure phases of the nitridosilicates MSiN2 with M = Be, Mg, or Ca have been thoroughly studied by density functional methods. At ambient pressure, BeSiN2 and MgSiN2 exhibit an ordered wurtzite variant derived from idealized filled β-cristobalite by a C1-type distortion. At ambient pressure, the structure of CaSiN2 can also be derived from idealized filled β-cristobalite by a different type of distortion (D1-type). Energy-volume calculations for all three compounds reveal transition into an NaCl superstructure under pressure, affording sixfold coordination for Si. At 76 GPa BeSiN2 forms an LiFeO2-type structure, corresponding to the stable ambient-pressure modification of LiFeO2, while MgSiN2 and CaSiN2 adopt an LiFeO2-type structure, corresponding to a metastable modification (24 and 60 GPa, respectively). For both BeSiN2 and CaSiN2 intermediate phases appear (for BeSiN2 a chalcopyrite-type structure and for CaSiN2 a CaGeN2-type structure). These two tetragonal intermediate structures are closely related, differing mainly in their c/a ratio. As a consequence, chalcopyrite-type structures exhibit tetrahedral coordination for both cations (M and Si), whereas in CaGeN2-type structures one cation is tetrahedrally (Si) and one bisdisphenoidally (M) coordinated. Both structure types, chalcopyrite and CaGeN2, can also be derived from idealized filled β-cristobalite through a B1-type distortion. The group-subgroup relation of the BeSiN2/MgSiN2, the CaSiN2, the chalcopyrite, the CaGeN2 and the idealized filled β-cristobalite structure is discussed and the displacive phase transformation pathways are illustrated. The zero-pressure bulk moduli were calculated for all phases and have been found to be comparable to compounds such as α- Si3N4, CaIrO3 and Al4C3. Furthermore, the thermodynamic stability of BeSiN2, MgSiN2 and CaSiN2 against phase agglomerates of the binary nitrides M3N2 and Si3N4 under pressure are examined.

  15. Crystal chemistry of the antibiotic doripenem.

    PubMed

    Colombo, Valentina; Masciocchi, Norberto; Palmisano, Giovanni

    2014-11-01

    Doripenem, an ultrabroad spectrum-injectable antibiotic belonging to the wide class of carbapenem beta-lactams, is commonly marketed as powders of a pure monohydrate phase. Here, we have selectively prepared another hydrated phase (a dihydrate) and determined the crystal structure of both forms by state-of-the art powder diffraction methods. Both phases crystallize in the monoclinic P21 space group, and, to some extent, are structurally related. Moreover, by using variable temperature diffractometric analyses, we also discovered a crystalline anhydrous form of doripenem, the structure of which (with two crystallographically independent molecules in the monoclinic P21 space group) remains so far unknown. The thermal interconversion among these phases was further studied by thermogravimetry, differential scanning calorimetry, and thermodiffractometric analyses, and their (metric or stereochemical) mutual relations fully analyzed. The complete structural characterization of the two hydrated phases allows the use of accurate whole pattern profile-fitting procedures for quantitative analyses of these drugs in polycrystalline, or even amorphous, matrices, opening the way to industrial process control and legal protection. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 103:3641-3647, 2014.

  16. Internally Consistent Single-Crystal Elasticity of (Mg0.89Fe0.11)2SiO4 Wadsleyite at High Pressures and High Temperatures

    NASA Astrophysics Data System (ADS)

    Buchen, J.; Marquardt, H.; Kurnosov, A.; Boffa Ballaran, T.; Speziale, S.; Kawazoe, T.

    2016-12-01

    The transition zone in Earth's upper mantle attains a pivotal role in deep Earth dynamics. Various scenarios for the fate of subducted lithospheric slabs have been identified from seismic tomographic images while petrological observations point to potential reservoirs of volatile elements in the transition zone. Among the mineral phases expected to assemble a mantle rock at depths between 410 km and 520 km, wadsleyite stands out with a remarkable hydrogen storage capacity of several weight percent H2O, a volume fraction of about 60 % for a pyrolitic mantle composition, and the potential to cause seismic anisotropy. Interpretations of seismological observations in terms of the thermal and mineralogical state of the upper transition zone rely on the elastic properties of wadsleyite at the prevailing conditions of pressure and temperature including its elastic anisotropy. We have determined internally consistent single-crystal elastic constants for wadsleyite with a relevant composition ((Mg0.89Fe0.11)1.98H0.04SiO4, 0.25(3) wt-% H2O) up to a pressure of 16 GPa at room temperature and conducted first measurements at combined high pressures and high temperatures. Single-crystal segments were cut from oriented thin sections with a focused ion beam and complementary orientations loaded together into the same pressure chamber of resistively heated diamond anvil cells. Using this two-sample approach and a combination of Brillouin spectroscopy and single-crystal X-ray diffraction, all nine independent elastic constants can be obtained under consistent conditions of pressure and temperature. Comparison of our room temperature results with those reported for wadsleyites with different iron contents suggests a very small effect of Fe-Mg substitution on the bulk modulus while the shear modulus decreases with increasing iron content. This differential effect of iron on the elastic moduli bears the potential to be seismically distinguishable from the signatures of temperature or

  17. Thermal conductivity of Glycerol’s liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures

    SciTech Connect

    Andersson, Ove; Johari, G. P.

    2016-02-14

    To investigate the effects of local density fluctuations on phonon propagation in a hydrogen bonded structure, we studied the thermal conductivity κ of the crystal, liquid, and glassy states of pure glycerol as a function of the temperature, T, and the pressure, p. We find that the following: (i) κ{sub crystal} is 3.6-times the κ{sub liquid} value at 140 K at 0.1 MPa and 2.2-times at 290 K, and it varies with T according to 138 × T{sup −0.95}; (ii) the ratio κ{sub liquid} (p)/κ{sub liquid} (0.1 MPa) is 1.45 GPa{sup −1} at 280 K, which, unexpectedly, is about the same as κ{sub crystal} (p)/κ{sub crystal} (0.1 MPa) of 1.42 GPa{sup −1} at 298 K; (iii) κ{sub glass} is relatively insensitive to T but sensitive to the applied p (1.38 GPa{sup −1} at 150 K); (iv) κ{sub glass}-T plots show an enhanced, pressure-dependent peak-like feature, which is due to the glass to liquid transition on heating; (v) continuous heating cold-crystallizes ultraviscous glycerol under pressure, at a higher T when p is high; and (vi) glycerol formed by cooling at a high p and then measured at a low p has a significantly higher κ than the glass formed by cooling at a low p. On heating at a fixed low p, its κ decreases before its glass-liquid transition range at that p is reached. We attribute this effect to thermally assisted loss of the configurational and vibrational instabilities of a glass formed at high p and recovered at low p, which is different from the usual glass-aging effect. While the heat capacity, entropy, and volume of glycerol crystal are less than those for its glass and liquid, κ{sub crystal} of glycerol, like its elastic modulus and refractive index, is higher. We discuss these findings in terms of the role of fluctuations in local density and structure, and the relations between κ and the thermodynamic quantities.

  18. High-pressure optical studies

    SciTech Connect

    Drickamer, H.G.

    1981-01-01

    High pressure experimentation may concern intrinsically high pressure phenomena, or it may be used to gain a better understanding of states or processes at one atmosphere. The latter application is probably more prevelant in condensed matter physics. Under this second rubric one may either use high pressure to perturb various electronic energy levels and from this pressure tuning characterize states or processes, or one can use pressure to change a macroscopic parameter in a controlled way, then measure the effect on some molecular property. In this paper, the pressure tuning aspect is emphasized, with a lesser discussion of macroscopic - molecular relationships. In rare earth chelates the efficiency of 4f-4f emission of the rare earth is controlled by the feeding from the singlet and triplet levels of the organic ligand. These ligand levels can be strongly shifted by pressure. A study of the effect of pressure on the emission efficiency permits one to understand the effect of ligand modification at one atmosphere. Photochromic crystals change color upon irradiation due to occupation of a metastable ground state. In thermochromic crystals, raising the temperature accomplishes the same results. For a group of molecular crystals (anils) at high pressure, the metastable state can be occupied at room temperature. The relative displacement of the energy levels at high pressure also inhibits the optical process. Effects on luminescence intensity are shown to be consistent. In the area of microscopic - molecular relationships, the effect of viscosity and dielectric properties on rates of non-radiative (thermal) and radiative emission, and on peak energy for luminescence is demonstrated. For systems which can emit from either of two excited states depending on the interaction with the environment, the effect of rigidity of the medium on the rate of rearrangement of the excited state is shown.

  19. Crystallization Processes in Mercury's Core Inferred from In-situ High-Pressure Melting Experiments in the Fe-S-Si-C System

    NASA Astrophysics Data System (ADS)

    Martin, A. M.; Van Orman, J. A.; Hauck, S. A., II; Sun, N.; Yu, T.; Wang, Y.

    2014-12-01

    Based upon the high pressure melting temperatures in the Fe-FeS system, an iron "snow" process has been suggested to occur in Mercury's core. However, recent results from the MESSENGER mission indicate very reducing conditions in Mercury, under which a substantial amount of silicon should also dissolve into the core. The presence of Si can significantly modify the chemical and physical properties of Mercury's core (e.g., phase relations, crystallization, density). Moreover, up to 4 wt% C could have been incorporated into the core during the planet formation. In order to test the iron snow hypothesis in a system that is likely to be closer to the actual core composition, we performed in situ high-pressure, high-temperature experiments in the Fe-FeS-Fe2Si-Fe3C system using a multi-anvil press on a synchrotron (Advanced Photon Source, Argonne). To observe low degree eutectic melting, we separated the samples in two parts: (1) an iron rod presaturated with Si and C and (2) a mixture of FeS, Fe2Si and Fe3C. Eutectic melting temperature and phase relations were determined at various pressures between 4.5 and 15.5 GPa using energy dispersive X-ray diffraction and imaging. Temperature was quenched soon after melting in order to preserve the eutectic melt composition. The X-ray images, diffraction spectra and back-scattered electron images of the recovered samples show that eutectic melting occurs in the range of 800 - 900°C in all our experiments. These temperatures are close to the eutectic temperatures in the Fe-FeS-Fe3C system, indicating that Si does not change the eutectic temperatures significantly. Melting therefore occurs at much lower temperature than suggested for the Fe-S-Si system at similar pressures. This difference may be explained by the presence of C and by the higher silicon content in our starting composition. Our experimental setup may also be more suitable for detecting the low degrees of melting in metallic systems. Such low eutectic melting

  20. Some applications of thermodynamics in crystal chemistry

    NASA Astrophysics Data System (ADS)

    Herbstein, Frank H.

    1996-01-01

    The integrated study of polymorphic phase changes in crystals by combining thermodynamic and crystallographic data is illustrated for four one-component systems — tin, carbon, adamantane and fullerene C 60 Ih — of increasing complexity. A brief review of the basic thermodynamics of the solid state (laws of thermodynamics, polymorphism, order of transitions) reminds the reader that enthalpy ( H) and entropy ( S) are experimental quantities derivable from the values of the heat capacity at constant pressure ( CP) measured as a function of temperature ( T). Combination of H and S through the Gibbs function gives the free energy as a function of T ( G = H - TS). For a one-component crystal with two polymorphic forms, the separate roles of the enthalpy and entropy differences between the polymorphs can be distinguished. This is illustrated in quantitative fashion for the two polymorphs of tin at atmospheric pressure, where there is a first-order phase transformation from grey (diamond) to white (metallic) at 286 K. Application of the Clausius-Clapeyron equation ( {dP }/{dT } = {ΔS}/{ΔV}) shows that metallic tin is the stable phase above ≈ 5 kbar at 0 K. This is entirely analogous to the treatment of the pressure dependence of the melting point of ice. In the next stage, pressure is added as a variable in order to treat the graphite-diamond polymorphism of carbon. Adamantane, for which calorimetric, phase-diagram and crystallographic data are available over a considerable range of temperature and pressure, is next reviewed in detail. The polymorphic change from tetragonal (stable below 208.6 K at atmospheric pressure) to cubic is almost, but not quite, first-order in character. A somewhat similar analysis is applied to available calorimetric and crystallographic data for fullerene C60 Ih, where the transition shows appreciable deviations from ideal first-order character. The next stage, not considered here, would be to proceed from the methods of

  1. Nitrous Oxide at High Pressure and Temperature: any Silica-like Polymorphs at High Pressure?

    NASA Astrophysics Data System (ADS)

    Iota, V.; Yoo, C.; Cynn, H.

    2001-12-01

    The crystal structures and phase stabilities of both four and six-fold silicon dioxide (SiO2) polymorphs are fundamental to the Earth's mineral physics and chemistry. The recent discovery of extended-solid phases of carbon dioxide (structurally similar to SiO2 polymorphs), offer a tantalizing new concept of mineral and geo-chemistry, considering the richness of oxygen, carbon, and silicon in the Earth's mantle and crust. In this study, we ask if nitrous oxide (N2O), an isoelectronic molecular analog to CO2, forms similar SiO2-like polymorphs at high pressures and temperatures. Our results based on in-situ and ex-situ Raman and X-ray diffraction measurements indicate that N2O indeed behaves similarly to CO2 at relatively low temperatures below 1000 K at high pressures up to 100 GPa. However, at higher temperatures, we find no transition to a polymeric phase of N2O. Instead, it disproportionates into a novel ionic phase of NO2 dimer (NO+NO3-) and N2. In this paper, we will discuss about the systematic of the phase diagrams of these triatomics, CO2 and N2O, in comparison with the polymorphs of SiO2, the Earth most abundant mineral.

  2. Crystal Chemistry of Th in Apatite: Geochemistry and Environmental Implications

    NASA Astrophysics Data System (ADS)

    Luo, Y.; Rakovan, J.; Elzinga, E.; Pan, Y.; Hughes, J.

    2006-05-01

    Understanding the crystal chemistry of nuclear waste forms is critical to proper evaluation of their potential use and stability. Because of apatite's ability to incorporate rare earth elements and actinides, there is great interest in it as a solid nuclear waste form and an engineered contaminant barrier. However, the crystal chemistry of actinides in the apatite structure is still poorly understood. Through the complementary use of single crystal X-ray diffraction and X-ray absorption spectroscopy, we present here the first direct results on the site occupancy of thorium in apatite structure and the structural distortion created by its substitution. Single crystal X-ray diffraction data were used to refine the structure and site occupancies of a synthetic fluorapatite with approximately 2 wt% Th in the structure. The structure refinements of three separate crystals with R = 0.0167-0.0217 indicate that Th substitutes almost extensively into the Ca2 site. The value of ThCa(2)/ThCa(1), calculated per individual site to account for the different multiplicity of the two Ca sites, is 6.5. X-ray absorption spectroscopy was used to probe the local structure of Th in this synthetic fluorapatite (single crystal form), as well as Th in a natural fluorapatite (powder form) from Mineville, NY with the Th concentration of approximately 2000 ppm. The results from extend X-ray absorption fine structure (EXAFS) also indicate that Th partitions into the Ca2 site and yields Th specific bond distances which are not obtainable from single crystal X-ray diffraction.

  3. The crystal chemistry of four thorium sulfates

    SciTech Connect

    Albrecht, Amanda J.; Sigmon, Ginger E.; Moore-Shay, Laura; Wei, Rebecca; Dawes, Colleen; Szymanowski, Jennifer; Burns, Peter C.

    2011-07-15

    Four thorium sulfate compounds have been synthesized and characterized. [Th(SO{sub 4}){sub 2}(H{sub 2}O){sub 7}].2H{sub 2}O (ThS1) crystallizes in space group P2{sub 1}/m, a=7.2488(4), b=12.1798(7), c=8.0625(5) A, {beta}=98.245(1){sup o}; Na{sub 10}[Th{sub 2}(SO{sub 4}){sub 9}(H{sub 2}O){sub 2}].3H{sub 2}O (ThS2), Pna2{sub 1}, a=17.842(2), b=6.9317(8), c=27.550(3) A; Na{sub 2}[Th{sub 2}(SO{sub 4}){sub 5}(H{sub 2}O){sub 3}].H{sub 2}O (ThS3), C2/c, a=16.639(2), b=9.081(1), c=25.078(3) A, {beta}= 95.322(2){sup o}; [Th{sub 4}(SO{sub 4}){sub 7}(OH){sub 2}(H{sub 2}O){sub 6}].2H{sub 2}O (ThS4), Pnma, a=18.2127(9), b=11.1669(5), c=14.4705(7) A. In all cases the Th cations are coordinated by nine O atoms corresponding to SO{sub 4} tetrahedra, OH groups, and H{sub 2}O groups. The structural unit of ThS1 is an isolated cluster consisting of a single Th polyhedron with two monodentate SO{sub 4} tetrahedra and seven H{sub 2}O groups. A double-wide Th sulfate chain is the basis of ThS2. The structures of ThS3 and ThS4 are frameworks of Th polyhedra and sulfate tetrahedra, and each contains channels that extend through the framework. One of the Th cations in ThS3 is coordinated by a bidentate SO{sub 4} tetrahedron, and ThS4 is unusual in the presence of a pair of Th cations that share a polyhedral face. - Graphical abstract: The structures of four hydrous thorium sulfates are reported that have structural units consisting of finite clusters, chains, and frameworks. Highlights: > Four hydrous thorium sulfates have structural units consisting of finite clusters, chains, and frameworks. > In each the Th cations are coordinated by nine O atoms from SO{sub 4} tetrahedra, OH groups, and H{sub 2}O groups. > The details of the linkages of ThO{sub 9} polyhedra and sulfate tetrahedra vary considerably in these structures.

  4. Bench-Scale Development of a Hot Carbonate Absorption Process with Crystallization-Enabled High Pressure Stripping for Post-Combustion CO{sub 2} Capture

    SciTech Connect

    Lu, Yongqi

    2014-02-01

    This report summarizes the methodology and preliminary results of a techno-economic analysis on a hot carbonate absorption process (Hot-CAP) with crystallization-enabled high pressure stripping for post-combustion CO{sub 2} capture (PCC). This analysis was based on the Hot-CAP that is fully integrated with a sub-critical steam cycle, pulverized coal-fired power plant adopted in Case 10 of the DOE/NETL’s Cost and Performance Baseline for Fossil Energy Plants. The techno-economic analysis addressed several important aspects of the Hot-CAP for PCC application, including process design and simulation, equipment sizing, technical risk and mitigation strategy, performance evaluation, and cost analysis. Results show that the net power produced in the subcritical power plant equipped with Hot-CAP is 611 MWe, greater than that with Econoamine (550 MWe). The total capital cost for the Hot-CAP, including CO{sub 2} compression, is $399 million, less than that for the Econoamine PCC ($493 million). O&M costs for the power plant with Hot-CAP is $175 million annually, less than that with Econoamine ($178 million). The 20-year levelized cost of electricity (LCOE) for the power plant with Hot-CAP, including CO2 transportation and storage, is 119.4 mills/kWh, a 59% increase over that for the plant without CO2 capture. The LCOE increase caused by CO{sub 2} capture for the Hot-CAP is 31% lower than that for its Econoamine counterpart.

  5. Elasticity of single-crystal NAL phase at high pressure: A potential source of the seismic anisotropy in the lower mantle

    NASA Astrophysics Data System (ADS)

    Wu, Ye; Yang, Jing; Wu, Xiang; Song, Maoshuang; Yoshino, Takashi; Zhai, Shuangmeng; Qin, Shan; Huang, Haijun; Lin, Jung-Fu

    2016-08-01

    The new hexagonal aluminous phase, named the NAL phase, is expected to be stable at depths of <1200 km in subducted slabs and believed to constitute 10~30 wt% of subducted mid-ocean ridge basalt together with the CaFe2O4-type aluminous phase. Here elasticity of the single-crystal NAL phase is investigated using Brillouin light scattering coupled with diamond anvil cells up to 20 GPa at room temperature. Analysis of the results shows that the substitution of iron lowers the shear modulus of the NAL phase by ~5% (~6 GPa) but does not significantly affect the adiabatic bulk modulus. The NAL phase exhibits high-velocity anisotropies with AVP = 14.7% and AVS = 15.12% for the Fe-bearing phase at ambient conditions. The high AVS of the NAL phase mainly results from the high anisotropy of the faster VS1 (13.9~15.8%), while the slower VS2 appears almost isotropic (0.1~2.8%) at ambient and high pressures. The AVP and AVS of the NAL phase decrease with increasing pressure but still have large values with AVP = 11.4% and AVS = 14.12% for the Fe-bearing sample at 20.4 GPa. The extrapolated AVP and AVS of the Fe-free and Fe-bearing NAL phases at 40 GPa are larger than those of bridgmanite at the same pressure. Together with its spin transition of iron and structural transition to the CF phase, the presence of the NAL phase with high-velocity anisotropies may contribute to the observed seismic anisotropy around subducted slabs in the uppermost lower mantle.

  6. High-Pressure Synthesis, Crystal Structure, and Magnetic and Transport Properties of a Six-Layered SrRhO3.

    PubMed

    Li, Yan; Cheng, Jinguang; Alonso, José Antonio; Goodenough, John B; Zhou, Jianshi

    2017-07-17

    A SrRhO3 polytype with six-layered (6M) structure was synthesized under high pressure and high temperature. The crystal structure was obtained by refining X-ray powder diffraction with the monoclinic space group C2/c with lattice parameters a = 5.5650(1) Å, b = 9.5967(2) Å, c = 14.0224(4) Å, and β = 92.846(2)°. It is isostructural with SrIrO3 synthesized under ambient pressure and consists of dimers of the face-shared Rh(2)O6 octahedra connected by their vertices to the corner-shared Rh(1)O6 octahedra along the c axis with a stacking of SrO3 layers in the sequence of CCHCCH, where C and H denote cubic and hexagonal closed packing, respectively. With increasing pressure, the 6M SrRhO3 transforms to an orthorhombic perovskite (Pv) phase, having a = 5.5673(1) Å, b = 5.5399(2) Å, c = 7.8550(2) Å in the space group Pbnm. A pressure-temperature phase diagram shows that the 6M-Pv phase boundary moves to lower temperatures with increasing pressure. Both the 6M and the Pv phases of SrRhO3 were characterized by magnetic susceptibility, resistivity, and thermopower; they are all metals with an enhanced and temperature-dependent magnetic susceptibility; no long-range magnetic order has been found. The polytype structures are normally found in ABO3 oxides with the geometric tolerance factor t > 1. SrRhO3 represents another example (in addition to SrIrO3) where the polytype 6M structure can be stabilized with a t < 1.

  7. High-pressure synthesis, crystal structures, and characterization of CdVO{sub 3-{delta}} and solid solutions CdVO{sub 3}-NaVO{sub 3}

    SciTech Connect

    Belik, Alexei A. . E-mail: Alexei.BELIK@nims.go.jp; Takayama-Muromachi, Eiji

    2006-06-15

    CdVO{sub 3-{delta}} and solid solutions of Cd{sub 1-x}Na{sub x}VO{sub 3} with the GdFeO{sub 3}-type perovskite structure were prepared using a high-pressure (6GPa) and high-temperature technique. No significant oxygen and cation deficiency was found in CdVO{sub 3}. Cd{sub 1-x}Na{sub x}VO{sub 3} are formed in the compositional range of 0=Crystal structures of CdVO{sub 3} and Cd{sub 0.8}Na{sub 0.2}VO{sub 3} were refined by X-ray powder diffraction: space group Pnma; Z=4; a=5.33435(7)A, b=7.52320(9)A, and c=5.26394(6)A for CdVO{sub 3} and a=5.32056(9)A, b=7.50289(13)A, and c=5.25902(8)A for Cd{sub 0.8}Na{sub 0.2}VO{sub 3}.

  8. Persistence of the stereochemical activity of the Bi3+ lone electron pair in Bi2Ga4O9 up to 50 GPa and crystal structure of the high-pressure phase.

    PubMed

    Friedrich, Alexandra; Juarez-Arellano, Erick A; Haussühl, Eiken; Boehler, Reinhard; Winkler, Björn; Wiehl, Leonore; Morgenroth, Wolfgang; Burianek, Manfred; Mühlberg, Manfred

    2010-06-01

    The crystal structure of the high-pressure phase of bismuth gallium oxide, Bi(2)Ga(4)O(9), was determined up to 30.5 (5) GPa from in situ single-crystal in-house and synchrotron X-ray diffraction. Structures were refined at ambient conditions and at pressures of 3.3 (2), 6.2 (3), 8.9 (1) and 14.9 (3) GPa for the low-pressure phase, and at 21.4 (5) and 30.5 (5) GPa for the high-pressure phase. The mode-Grüneisen parameters for the Raman modes of the low-pressure structure and the changes of the modes induced by the phase transition were obtained from Raman spectroscopic measurements. Complementary quantum-mechanical calculations based on density-functional theory were performed between 0 and 50 GPa. The phase transition is driven by a large spontaneous displacement of one O atom from a fully constrained position. The density-functional theory (DFT) model confirmed the persistence of the stereochemical activity of the lone electron pair up to at least 50 GPa in accordance with the crystal structure of the high-pressure phase. While the stereochemical activity of the lone electron pair of Bi(3+) is reduced at increasing pressure, a symmetrization of the bismuth coordination was not observed in this pressure range. This shows an unexpected stability of the localization of the lone electron pair and of its stereochemical activity at high pressure.

  9. Elasticity of Single-Crystal Superhydrous Phase B at Simultaneous High Pressure-Temperature Conditions: Implication for the Low-Velocity Layers in the Topmost Lower Mantle

    NASA Astrophysics Data System (ADS)

    Li, X.; Mao, Z.; Sun, N.; Liao, Y.; Zhai, S.; Wang, Y.; Ni, H.; Wang, J.; Tkachev, S. N.; Lin, J. F.

    2016-12-01

    Recent seismic studies have observed low-velocity anomalies in various locations of the Earth's bottom transition zone and the topmost lower mantle which were interpreted as the presence of melting associated with dehydration reactions. Dense hydrous magnesium silicates (DHMS), such as superhydrous phase B (Shy-B, Mg10Si3H4O18) and phase D (Mg1.14Si1.73H2.81O6), are potential carriers to transport water to the Earth's transition zone and lower mantle. Studies on the elasticity of these hydrous phases are thus important to understand the observed low-velocity anomalies and the circulation of water in the region. Although the elasticity of Shy-B has been investigated up to 60 GPa at 300 K, the combined effect of pressure and temperature on the elasticity of Shy-B is unknown. Here, we have studied the elasticity of single-crystal Shy-B (Mg9.38Si2.81H6.01O18) using Brillouin scattering combined with single-crystal X-ray diffraction in an externally-heated diamond anvil cell up to 12 GPa and 700 K at GSECARS of the Advanced Photon Source, Argonne National Laboratory. Using the elasticity obtained at high pressure-temperature conditions, we have modeled the anisotropy and velocities of Shy-B along both hot and cold slab geotherms. Comparing with the major minerals in the bottom transition zone and topmost lower mantle, Shy-B has a low anisotropy and cannot be the major cause for the observed anisotropy in the region. Although the velocity of Shy-B is greater than that of the mantle with a pyrolitic composition at depth of the bottom transition zone, it is much lower at depths of the topmost lower mantle. Considering the low density of Shy-B compared to major lower-mantle minerals, we speculate that an accumulation of 28 wt.% Shy-B in the peridotite layer of the slabs as subduction progresses can produce a 1.7-3.3% low velocity anomalies at depths of the topmost lower mantle and could help explain the observed low-velocity layers in the region.

  10. High pressure ices

    PubMed Central

    Hermann, Andreas; Ashcroft, N. W.; Hoffmann, Roald

    2012-01-01

    H2O will be more resistant to metallization than previously thought. From computational evolutionary structure searches, we find a sequence of new stable and meta-stable structures for the ground state of ice in the 1–5 TPa (10 to 50 Mbar) regime, in the static approximation. The previously proposed Pbcm structure is superseded by a Pmc21 phase at p = 930 GPa, followed by a predicted transition to a P21 crystal structure at p = 1.3 TPa. This phase, featuring higher coordination at O and H, is stable over a wide pressure range, reaching 4.8 TPa. We analyze carefully the geometrical changes in the calculated structures, especially the buckling at the H in O-H-O motifs. All structures are insulating—chemistry burns a deep and (with pressure increase) lasting hole in the density of states near the highest occupied electronic levels of what might be component metallic lattices. Metallization of ice in our calculations occurs only near 4.8 TPa, where the metallic C2/m phase becomes most stable. In this regime, zero-point energies much larger than typical enthalpy differences suggest possible melting of the H sublattice, or even the entire crystal. PMID:22207625

  11. Almandine: Crystal Chemistry, Defects, Inclusions and Physical Properties

    NASA Astrophysics Data System (ADS)

    Geiger, C. A.; Brearley, A. J.; Dachs, E.; Tippelt, G.

    2013-12-01

    Almandine-rich garnet is important in various metamorphic rocks of Earth's crust and garnet in the upper mantle contains a substantial almandine component (Fe3Al2Si3O12). In order to better understand almandine's chemical and physical properties, crystals were synthesized at high pressures and temperatures under different fO2 conditions with different starting materials. The synthetic products were carefully characterized and the role of defects and solid inclusions were given special attention. Almandine in both polycrystalline and in single-crystal form was obtained in the synthesis experiments. Hydrothermal experiments yielded almandine single crystals from roughly 5 microns in size up to approximately one millimeter and show varying physical properties. Fine-grained polycrystalline almandine in the form of compact pellets was obtained from water-free syntheses made in graphite capsules. The crystals were investigated using X-ray powder diffraction, electron microprobe and TEM analysis, and using 57Fe Mössbauer and IR single-crystal spectroscopy. BSE photos on different polycrystalline almandines, synthesized without water, show a variety of fine inclusions and unreacted starting material. TEM results show certain nanosized, 100 nm to less then 10 nm, magnetite inclusions in some synthetic almandines, similar to those observed in natural garnet crystals. A room temperature FTIR single-crystal spectrum of a hydrothermally grown almandine shows two broad OH stretching bands at 3613 cm-1 and approximately 3490 cm-1, both of which split into more bands at 77 K. 57Fe Mössbauer measurements show small but various amounts of Fe3+ in octahedral coordination for many synthetic almandines and whose concentration depends on the synthesis experiment. Various possible local defects in almandine are analyzed using Kröger-Vink notation. The origin of tiny, minor included phases that have been observed in synthetic as well as in natural crystals may be related to defect

  12. Constraining 17O and 27Al NMR spectra of high-pressure crystals and glasses: New data for jadeite, pyrope, grossular, and mullite

    USGS Publications Warehouse

    Kelsey, K.E.; Stebbins, J.F.; Du, L.-S.; Hankins, B.

    2007-01-01

    The 17O NMR spectra of glasses quenched from melts at high pressure are often difficult to interpret due to overlapping peaks and lack of crystalline model compounds. High-pressure aluminosilicate glasses often contain significant amounts of [5]Al and [6]Al, thus these high-pressure glasses must contain oxygen bonded to high-coordinated aluminum. The 17O NMR parameters for the minerals jadeite, pyrope, grossular, and mullite are presented to assist interpretation of glass spectra and to help test quantum chemical calculations. The 17O NMR parameters for jadeite and grossular support previous peak assignments of oxygen bonded to Si and high-coordinated Al in high-pressure glasses as well as quantum chemical calculations. The oxygen tricluster in mullite is very similar to the previously observed tricluster in grossite (CaAl4 O7) and suspected triclusters in glasses. We also present 27Al NMR spectra for pyrope, grossular, and mullite.

  13. The evolution of model catalytic systems; studies of structure, bonding and dynamics from single crystal metal surfaces to nanoparticles, and from low pressure (<10(-3) Torr) to high pressure (>10(-3) Torr) to liquid interfaces.

    PubMed

    Somorjai, Gabor A; York, Roger L; Butcher, Derek; Park, Jeong Y

    2007-07-21

    The material and pressure gap has been a long standing challenge in the field of heterogeneous catalysis and have transformed surface science and biointerfacial research. In heterogeneous catalysis, the material gap refers to the discontinuity between well-characterized model systems and industrially relevant catalysts. Single crystal metal surfaces have been useful model systems to elucidate the role of surface defects and the mobility of reaction intermediates in catalytic reactivity and selectivity. As nanoscience advances, we have developed nanoparticle catalysts with lithographic techniques and colloidal syntheses. Nanoparticle catalysts on oxide supports allow us to investigate several important ingredients of heterogeneous catalysis such as the metal-oxide interface and the influence of noble metal particle size and surface structure on catalytic selectivity. Monodispersed nanoparticle and nanowire arrays were fabricated for use as model catalysts by lithographic techniques. Platinum and rhodium nanoparticles in the 1-10 nm range were synthesized in colloidal solutions in the presence of polymer capping agents. The most catalytically active systems are employed at high pressure or at solid-liquid interfaces. In order to study the high pressure and liquid interfaces on the molecular level, experimental techniques with which we bridged the pressure gap in catalysis have been developed. These techniques include the ultrahigh vacuum system equipped with high pressure reaction cell, high pressure Sum Frequency Generation (SFG) vibration spectroscopy, High Pressure Scanning Tunneling Microscopy (HP-STM), and High Pressure X-ray Photoemission Spectroscopy (HP-XPS), and Quartz Crystal Microbalance (QCM). In this article, we overview the development of experimental techniques and evolution of the model systems for the research of heterogeneous catalysis and biointerfacial studies that can shed light on the long-standing issues of materials and pressure gaps.

  14. Nonicosahedral boron allotrope synthesized at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Chuvashova, Irina; Bykova, Elena; Bykov, Maxim; Prakapenka, Vitali; Glazyrin, Konstantin; Mezouar, Mohamed; Dubrovinsky, Leonid; Dubrovinskaia, Natalia

    2017-05-01

    Theoretical predictions of pressure-induced phase transformations often become long-standing enigmas because of limitations of contemporary available experimental possibilities. Hitherto the existence of a nonicosahedral boron allotrope has been one of them. Here we report on a nonicosahedral boron allotrope, which we denoted as ζ -B, with the orthorhombic α -Ga-type structure (space group Cmce) synthesized in a diamond-anvil cell at extreme high-pressure high-temperature conditions (115 GPa and 2100 K). The structure of ζ -B was solved using single-crystal synchrotron x-ray diffraction and its compressional behavior was studied in the range of very high pressures (115-135 GPa). Experimental validation of theoretical predictions reveals the degree of our up-to-date comprehension of condensed matter and promotes further development of solid-state physics and chemistry.

  15. Crystal structure, equation of state, and elasticity of hydrous aluminosilicate phase, topaz-OH (Al2SiO4(OH)2) at high pressures

    NASA Astrophysics Data System (ADS)

    Mookherjee, Mainak; Tsuchiya, Jun; Hariharan, Anant

    2016-02-01

    We examined the equation of state and high-pressure elasticity of the hydrous aluminosilicate mineral topaz-OH (Al2SiO4(OH)2) using first principles simulation. Topaz-OH is a hydrous phase in the Al2O3-SiO2-H2O (ASH) ternary system, which is relevant for the mineral phase relations in the hydrated sedimentary layer of subducting slabs. Based on recent neutron diffraction experiments, it is known that the protons in the topaz-OH exhibit positional disorder with half occupancy over two distinct crystallographic sites. In order to adequately depict the proton environment in the topaz-OH, we examined five crystal structure models with distinct configuration for the protons in topaz-OH. Upon full geometry optimization we find two distinct space group, an orthorhombic Pbnm and a monoclinic P21/c for topaz-OH. The topaz-OH with the monoclinic P21/c space group has a lower energy compared to the orthorhombic Pbmn space group symmetry. The pressure-volume results for the monoclinic topaz-OH is well represented by a third order Birch-Murnaghan formulation, with V0mon = 348.63 (±0.04) Å3, K0mon = 164.7 (±0.04) GPa, and K0mon = 4.24 (±0.05). The pressure-volume results for the orthorhombic topaz-OH is well represented by a third order Birch-Murnaghan formulation, with V0orth = 352.47 (±0.04) Å3, K0orth = 166.4 (±0.06) GPa, and K0orth = 4.03 (±0.04). While the bulk moduli are very similar for both the monoclinic and orthorhombic topaz-OH, the shear elastic constants and the shear moduli are very sensitive to the position of the proton, orientation of the O-H dipole, and the space group symmetry. The S-wave anisotropy for the orthorhombic and monoclinic topaz-OH are also quite distinct. In the hydrated sedimentary layer of subducting slabs, transformation of a mineral assemblage consisting of coesite (SiO2) and diaspore (AlOOH) to topaz-OH (Al2SiO4(OH)2) is likely to be accompanied by an increase in density, compressional velocity, and shear wave velocity. However

  16. Occurrence and mineral chemistry of high pressure phases, Portrillo basalt, southcentral New Mexico. M.S. Thesis. Final Technical Report, 1 Jun. 1978 - 31 May 1980

    NASA Technical Reports Server (NTRS)

    Hoffer, J. M.; Ortiz, T. S.

    1980-01-01

    Inclusions of clinopyroxenite, kaersutiteclinopyroxenite, kaersutite-rich inclusions, wehrlite and olivine-clinopyroxenite together with megacrysts of feldspar, kaersutite and spinel are found loose on the flanks of cinder cones, as inclusions within lava flows and within the cores of volcanic bombs in the Quaternary alkali-olivine basalt of the West Potrillo Mountains, southcentral New Mexico. Based on petrological and geochemical evidence the megacysts are interpreted to be phenocrysts which formed at great depth rather that xenocrysts of larger crystal aggregates. These large crystals are believed to have formed as stable phases at high temperature and pressure and have partially reacted with the basalt to produce subhedral to anhedral crystal boundaries. It can be demonstrated that the mafic and ultramafic crystal aggregates were derived from an alkali-basalt source rock generated in the mantle. The inclusions are believed to represent a cumulus body or bodies injected within the lower crust or upper mantle.

  17. Electronic phenomena at high pressure

    SciTech Connect

    Drickamer, H.G.

    1981-01-01

    High pressure research is undertaken either to investigate intrinsically high pressure phenomena or in order to get a better understanding of the effect of the chemical environment on properties or processes at one atmosphere. Studies of electronic properties which fall in each area are presented. Many molecules and complexes can assume in the excited state different molecular arrangements and intermolecular forces depending on the medium. Their luminescence emission is then very different in a rigid or a fluid medium. With pressure one can vary the viscosity of the medium by a factor of 10/sup 7/ and thus control the distribution and rate of crossing between the excited state conformations. In rare earth chelates the efficiency of 4f-4f emission of the rare earth is controlled by the feeding from the singlet and triplet levels of the organic ligand. These ligand levels can be strongly shifted by pressure. A study of the effect of pressure on the emission efficiency permits one to understand the effect of ligand chemistry at one atmosphere. At high pressure electronic states can be sufficiently perturbed to provide new ground states. In EDA complexes these new ground states exhibit unusual chemical reactivity and new products.

  18. Single-Crystal X-Ray Diffraction of Orthoenstatite to 48 GPa: New High-Pressure Phases with 4-, 5-, and 6-Coordinated Silicon

    NASA Astrophysics Data System (ADS)

    Finkelstein, G. J.; Dera, P. K.; Duffy, T. S.

    2013-12-01

    Orthopyroxene (opx, (Mg,Fe)SiO3) is one of the major phases in Earth's upper mantle, comprising ~20% of the region by volume. At high pressures and temperatures, this phase undergoes several well-characterized phase transitions. Its behavior at low temperature is less well known, but may be important for cold subducting slabs (1, 2). Previous studies (3, 4) reported that MgSiO3 orthoenstatite persists up to ~12 GPa, and a phase transition above this pressure was recently discovered by Zhang et al. (5). This structure, which we call β-opx (designated HPCEN2 in previous studies), is related to one predicted by theory (6), and has P21/c monoclinic symmetry. It retains an opx topology despite its lower symmetry, distinguishing it from a true clinopyroxene. We conducted single-crystal X-ray diffraction experiments in a diamond anvil cell at GSECARS and HPCAT at the APS. Mg0.91Fe0.09SiO3 orthopyroxene was compressed in a neon pressure medium with a gold pressure standard. In addition to the orthopyroxene to β-opx transition, we observe two further phase changes at ~28 GPa and ~38 GPa. The transitions result in volume reductions of ~2.5% and ~3.9%, respectively. The Si layers in both new structures are intermediate between the opx structure and that of the ilmenite-structured akimotoite polymorph. Akimotoite consists of edge-sharing MgO6 and SiO6 octahedra arranged in alternating honeycomb sheets. A theoretical study suggested clinoenstatite could transform directly to akimotoite at low temperatures through a shear-based mechanism (7). Here, we observe that the path toward akimotoite-like Si layers is stepwise. In the new MgSiO3 structures, the initial chains of SiO4 tetrahedra are partially converted to the characteristic 6-coordinated honeycomb layers. This results in some 5-coordinated Si sites in both structures. Due to the increased coordination number, we are calling the new structures α- and β-post-orthopyroxene (α-popx and β-popx). The Mg layers, however, do

  19. Chromium crystal chemistry mullite-spinel refractory ceramics

    SciTech Connect

    Levy, D.; Gualtieri, A.; Quartieri, S.; Artioli, G.; Valle, M.

    1999-03-15

    A small amount of chromium oxide was added to a mullite-spinel refractory mixture to improve its thermal and mechanical properties. Two different compositions of mullite-spinel refractory were studied to define the crystal structures hosting the chromium cations, and the chromium solubility in spinel (MgAl{sub 2{minus}x}Cr{sub x}O{sub 4}) was determined. Powder X-ray diffraction (XRD), X-ray absorption near edge spectroscopy (XANES), and scanning electron microscopy (SEM) elemental distribution maps were used to determine the chromium crystal chemistry in the system. The observed maximum solubility of chromium in spinel was found at x = 1.2, but the presence of mullite in the mixture caused a strong decrease of this value. The chromium distribution among the crystal phases reflects the different reaction paths of the two samples: a stage involving spinel and melt drives all present chromium in the spinel, while a simultaneous crystallization of spinel-mullite distributes chromium cations between mullite, spinel, and secondary corundum.

  20. High pressure antiferrodistortive phase transition in mixed crystals of EuTiO{sub 3} and SrTiO{sub 3}

    SciTech Connect

    Parisiades, Paraskevas; Saltarelli, Francesco; Liarokapis, Efthymios; Köhler, Jürgen; Bussmann-Holder, Annette

    2016-06-15

    We report a detailed high pressure study on Eu{sub 1−x}Sr{sub x}TiO{sub 3} polycrystalline samples using synchrotron x-ray diffraction. We have observed a second-order antiferrodistortive phase transition for all doping levels which corresponds to the transition that has been previously explored as a function of temperature. The analysis of the compression mechanism by calculating the lattice parameters, spontaneous strains and tilt angles of the TiO{sub 6} octahedra leads to a high pressure phase diagram for Eu{sub 1−x}Sr{sub x}TiO{sub 3}.

  1. Direct arylation of benzene with aryl bromides using high-temperature/high-pressure process windows: expanding the scope of C-H activation chemistry.

    PubMed

    Pieber, Bartholomäus; Cantillo, David; Kappe, C Oliver

    2012-04-16

    A detailed investigation on the direct arylation of benzene with aryl bromides by using first-row transition metals under high-temperature/high-pressure (high-T/p) conditions is described. By employing a parallel reactor platform for rapid reaction screening and discovery at elevated temperatures, various metal/ligand/base combinations were evaluated for their ability to enable biaryl formation through C-H activation. The combination of cobalt(III) acetylacetonate and lithium bis(trimethylsilyl)amide was subjected to further process intensification at 200 °C (15 bar), allowing a significant reduction of the catalyst/base loading and a dramatic increase in catalytic efficiency (turnover frequency) by a factor of 1000 compared to traditional protocols. The high-throughput screening additionally identified novel nickel- and copper-based metal/ligand combinations that favored an amination pathway competing with C-H activation, with the addition of ligands, such as 1,10-phenanthroline, having a profound influence on the selectivity. In addition to metal-based catalysts, high-T/p process windows were also successfully applied to transition-metal-free systems, utilizing 1,10-phenanthroline as organocatalyst.

  2. High Pressure Biomass Gasification

    SciTech Connect

    Agrawal, Pradeep K

    2016-07-29

    According to the Billion Ton Report, the U.S. has a large supply of biomass available that can supplement fossil fuels for producing chemicals and transportation fuels. Agricultural waste, forest residue, and energy crops offer potential benefits: renewable feedstock, zero to low CO2 emissions depending on the specific source, and domestic supply availability. Biomass can be converted into chemicals and fuels using one of several approaches: (i) biological platform converts corn into ethanol by using depolymerization of cellulose to form sugars followed by fermentation, (ii) low-temperature pyrolysis to obtain bio-oils which must be treated to reduce oxygen content via HDO hydrodeoxygenation), and (iii) high temperature pyrolysis to produce syngas (CO + H2). This last approach consists of producing syngas using the thermal platform which can be used to produce a variety of chemicals and fuels. The goal of this project was to develop an improved understanding of the gasification of biomass at high pressure conditions and how various gasification parameters might affect the gasification behavior. Since most downstream applications of synags conversion (e.g., alcohol synthesis, Fischer-Tropsch synthesis etc) involve utilizing high pressure catalytic processes, there is an interest in carrying out the biomass gasification at high pressure which can potentially reduce the gasifier size and subsequent downstream cleaning processes. It is traditionally accepted that high pressure should increase the gasification rates (kinetic effect). There is also precedence from coal gasification literature from the 1970s that high pressure gasification would be a beneficial route to consider. Traditional approach of using thermogravimetric analyzer (TGA) or high-pressure themogravimetric analyzer (PTGA) worked well in understanding the gasification kinetics of coal gasification which was useful in designing high pressure coal gasification processes. However

  3. Phase segregation and the effect of high pressure on the electro-transport in Y0.95Pr0.05Ba2Cu3O7-δ single crystals

    NASA Astrophysics Data System (ADS)

    Vovk, Ruslan V.; Khadzhai, Georgij Ya.; Dobrovolskiy, Oleksandr V.

    2014-06-01

    The effect of high hydrostatic pressures of up to 17 kbar on the basal ab-plane conductivity of lightly praseodymium-doped (x ≈ 0.05) Y1-xPrxBa2Cu3O7-δ single crystals with unidirectional twin boundaries (TBs) is investigated. It is observed that the application of a high pressure leads to a doubling of the pressure derivative value dTc/dP for Pr-doped samples compared to non-doped YBa2Cu3O7-δ samples with optimal oxygen content. Possible mechanisms of the high pressure effect on the critical temperature Tc and the phase segregation in the sample volume are discussed.

  4. High pressure furnace

    DOEpatents

    Morris, Donald E.

    1993-01-01

    A high temperature high pressure furnace has a hybrid partially externally heated construction. A metallic vessel fabricated from an alloy having a composition of at least 45% nickel, 15% chrome, and 10% tungsten is utilized (the preferred alloy including 55% nickel, 22% chrome, 14% tungsten, 2% molybdenum, 3% iron (maximum) and 5% cobalt (maximum). The disclosed alloy is fabricated into 11/4 or 2 inch, 32 mm or 50 mm bar stock and has a length of about 22 inches, 56 cm. This bar stock has an aperture formed therein to define a closed high temperature, high pressure oxygen chamber. The opposite and closed end of the vessel is provided with a small blind aperture into which a thermocouple can be inserted. The closed end of the vessel is inserted into an oven, preferably heated by standard nickel chrome electrical elements and having a heavily insulated exterior.

  5. High pressure oxygen furnace

    DOEpatents

    Morris, Donald E.

    1992-01-01

    A high temperature high pressure oxygen furnace having a hybrid partially externally heated construction is disclosed. A metallic bar fabricated from an alloy having a composition of at least 45% nickel, 15% chrome, and 10% tungsten is utilized (the preferred alloy including 55% nickel, 22% chrome, 14% tungsten, 2% molybdenum, 3% iron (maximum) and 5% cobalt (maximum). The disclosed alloy is fabricated into 11/4 inch bar stock and has a length of about 17 inches. This bar stock is gun drilled for over 16 inches of its length with 0.400 inch aperture to define a closed high temperature, high pressure oxygen chamber. The opposite and closed end of the bar is provided with a small support aperture into which both a support and a thermocouple can be inserted. The closed end of the gun drilled bar is inserted into an oven, preferably heated by standard nickel chrome electrical elements and having a heavily insulated exterior.

  6. High pressure oxygen furnace

    DOEpatents

    Morris, D.E.

    1992-07-14

    A high temperature high pressure oxygen furnace having a hybrid partially externally heated construction is disclosed. A metallic bar fabricated from an alloy having a composition of at least 45% nickel, 15% chrome, and 10% tungsten is utilized, the preferred alloy including 55% nickel, 22% chrome, 14% tungsten, 2% molybdenum, 3% iron (maximum) and 5% cobalt (maximum). The disclosed alloy is fabricated into 11/4 inch bar stock and has a length of about 17 inches. This bar stock is gun drilled for over 16 inches of its length with 0.400 inch aperture to define a closed high temperature, high pressure oxygen chamber. The opposite and closed end of the bar is provided with a small support aperture into which both a support and a thermocouple can be inserted. The closed end of the gun drilled bar is inserted into an oven, preferably heated by standard nickel chrome electrical elements and having a heavily insulated exterior. 5 figs.

  7. High pressure furnace

    DOEpatents

    Morris, D.E.

    1993-09-14

    A high temperature high pressure furnace has a hybrid partially externally heated construction. A metallic vessel fabricated from an alloy having a composition of at least 45% nickel, 15% chrome, and 10% tungsten is utilized (the preferred alloy including 55% nickel, 22% chrome, 14% tungsten, 2% molybdenum, 3% iron (maximum) and 5% cobalt (maximum)). The disclosed alloy is fabricated into 11/4 or 2 inch, 32 mm or 50 mm bar stock and has a length of about 22 inches, 56 cm. This bar stock has an aperture formed therein to define a closed high temperature, high pressure oxygen chamber. The opposite and closed end of the vessel is provided with a small blind aperture into which a thermocouple can be inserted. The closed end of the vessel is inserted into an oven, preferably heated by standard nickel chrome electrical elements and having a heavily insulated exterior. 19 figures.

  8. Secondary metabolites isolation in natural products chemistry: comparison of two semipreparative chromatographic techniques (high pressure liquid chromatography and high performance thin-layer chromatography).

    PubMed

    Do, Thi Kieu Tiên; Hadji-Minaglou, Francis; Antoniotti, Sylvain; Fernandez, Xavier

    2014-01-17

    Chemical investigations on secondary metabolites in natural products chemistry require efficient isolation techniques for characterization purpose as well as for the evaluation of their biological properties. In the case of phytochemical studies, the performance of the techniques is critical (resolution and yield) since the products generally present a narrow range of polarity and physicochemical properties. Several techniques are currently available, but HPLC (preparative and semipreparative) is the most widely used. To compare the performance of semipreparative HPLC and HPTLC for the isolation of secondary metabolites in different types of extracts, we have chosen carvone from spearmint essential oil (Mentha spicata L.), resveratrol from Fallopia multiflora (Thunb.) Haraldson, and rosmarinic acid from rosemary (Rosmarinus officinalis L.) extracts. The comparison was based on the chromatographic separation, the purity and quantity of isolated compounds, the solvent consumption, the duration and the cost of the isolation operations. The results showed that semipreparative HPTLC can in some case offer some advantages over conventional semipreparative HPLC. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Crystal-chemistry and partitioning of REE in whitlockite

    NASA Technical Reports Server (NTRS)

    Colson, R. O.; Jolliff, B. L.

    1993-01-01

    Partitioning of Rare Earth Elements (REE) in whitlockite is complicated by the fact that two or more charge-balancing substitutions are involved and by the fact that concentrations of REE in natural whitlockites are sufficiently high such that simple partition coefficients are not expected to be constant even if mixing in the system is completely ideal. The present study combines preexisting REE partitioning data in whitlockites with new experiments in the same compositional system and at the same temperature (approximately 1030 C) to place additional constraints on the complex variations of REE partition coefficients and to test theoretical models for how REE partitioning should vary with REE concentration and other compositional variables. With this data set, and by combining crystallographic and thermochemical constraints with a SAS simultaneous-equation best-fitting routine, it is possible to infer answers to the following questions: what is the speciation on the individual sites Ca(B), Mg, and Ca(IIA) (where the ideal structural formula is Ca(B)18 Mg2Ca(IIA)2P14O56); how are REE's charge-balanced in the crystal; and is mixing of REE in whitlockite ideal or non-ideal. This understanding is necessary in order to extrapolate derived partition coefficients to other compositional systems and provides a broadened understanding of the crystal chemistry of whitlockite.

  10. Ammothermal Growth of Gan Substrates For Leds: High-Pressure Ammonothermal Process for Bulk Gallium Nitride Crystal Growth for Energy Efficient Commercially Competitive Lighting

    SciTech Connect

    2011-01-01

    Broad Funding Opportunity Announcement Project: The new GaN crystal growth method is adapted from that used to grow quartz crystals, which are very inexpensive and represent the second-largest market for single crystals for electronic applications (after silicon). More extreme conditions are required to grow GaN crystals and therefore a new type of chemical growth chamber was invented that is suitable for large-scale manufacturing. A new process was developed that grows GaN crystals at a rate that is more than double that of current processes. The new technology will enable GaN substrates with best-in-world quality at lowest-in-world prices, which in turn will enable new generations of white LEDs, lasers for full-color displays, and high-performance power electronics.

  11. Achieving unusual oxidation state of matter under high pressure

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoli; Lin, Haiqing; Ma, Yanming; Miao, Maosheng

    2013-03-01

    Pressure has many effects to matter including the reduction of the volume, the increase of the coordination number and the broadening of the band-widths. In the past, most of the high-pressure studies focused on structural and electronic state phase transitions. Using first principles calculations and a bias-free structural search method, we will demonstrate that high pressure can lead to high oxidation state of elements that can never be achieved under ambient condition, making high pressure technique a nice tool to explore many traditional topics in solid state and molecular chemistry. As an example, we will show that Hg can transfer the electrons in its outmost d shell to F atoms and form HgF4 molecular crystals under pressure, thereby acting as a true transition metal. Group IIB elements, including Zn, Cd, and Hg are usually defined as post-transition metals because they are commonly oxidized only to the +2 state. Their d shells are completely filled and do not participate in the formation of chemical bonds. Although the synthesis of HgF4 molecules in gas phase was reported before, the molecules show strong instabilities and dissociate. Therefore, the transition metal propensity of Hg remains an open question.

  12. High pressure effects on U L 3 x-ray absorption in partial fluorescence yield mode and single crystal x-ray diffraction in the heavy fermion compound UCd 11

    DOE PAGES

    Nasreen, Farzana; Antonio, Daniel; VanGennep, Derrick; ...

    2016-02-15

    © 2016 IOP Publishing Ltd. We report a study of high pressure x-ray absorption (XAS) performed in the partial fluorescence yield mode (PFY) at the U L 3 edge (0-28.2 GPa) and single crystal x-ray diffraction (SXD) (0-20 GPa) on the UCd 11 heavy fermion compound at room temperature. Under compression, the PFY-XAS results show that the white line is shifted by +4.1(3) eV at the highest applied pressure of 28.2 GPa indicating delocalization of the 5f electrons. The increase in full width at half maxima and decrease in relative amplitude of the white line with respect to the edgemore » jump point towards 6d band broadening under high pressure. A bulk modulus of K 0 = 62(1) GPa and its pressure derivative, = 4.9(2) was determined from high pressure SXD results. Both the PFY-XAS and diffraction results do not show any sign of a structural phase transition in the applied pressure range.« less

  13. High pressure effects on U L 3 x-ray absorption in partial fluorescence yield mode and single crystal x-ray diffraction in the heavy fermion compound UCd 11

    SciTech Connect

    Nasreen, Farzana; Antonio, Daniel; VanGennep, Derrick; Booth, Corwin H.; Kothapalli, Karunakar; Bauer, Eric D.; Sarrao, John L.; Lavina, Barbara; Iota-Herbei, Valentin; Sinogeikin, Stanislav; Chow, Paul; Xiao, Yuming; Zhao, Yusheng; Cornelius, Andrew L.

    2016-02-15

    © 2016 IOP Publishing Ltd. We report a study of high pressure x-ray absorption (XAS) performed in the partial fluorescence yield mode (PFY) at the U L 3 edge (0-28.2 GPa) and single crystal x-ray diffraction (SXD) (0-20 GPa) on the UCd 11 heavy fermion compound at room temperature. Under compression, the PFY-XAS results show that the white line is shifted by +4.1(3) eV at the highest applied pressure of 28.2 GPa indicating delocalization of the 5f electrons. The increase in full width at half maxima and decrease in relative amplitude of the white line with respect to the edge jump point towards 6d band broadening under high pressure. A bulk modulus of K 0 = 62(1) GPa and its pressure derivative, = 4.9(2) was determined from high pressure SXD results. Both the PFY-XAS and diffraction results do not show any sign of a structural phase transition in the applied pressure range.

  14. High pressure effects on U L3 x-ray absorption in partial fluorescence yield mode and single crystal x-ray diffraction in the heavy fermion compound UCd11

    NASA Astrophysics Data System (ADS)

    Nasreen, Farzana; Antonio, Daniel; VanGennep, Derrick; Booth, Corwin H.; Kothapalli, Karunakar; Bauer, Eric D.; Sarrao, John L.; Lavina, Barbara; Iota-Herbei, Valentin; Sinogeikin, Stanislav; Chow, Paul; Xiao, Yuming; Zhao, Yusheng; Cornelius, Andrew L.

    2016-03-01

    We report a study of high pressure x-ray absorption (XAS) performed in the partial fluorescence yield mode (PFY) at the U L3 edge (0-28.2 GPa) and single crystal x-ray diffraction (SXD) (0-20 GPa) on the UCd11 heavy fermion compound at room temperature. Under compression, the PFY-XAS results show that the white line is shifted by  +4.1(3) eV at the highest applied pressure of 28.2 GPa indicating delocalization of the 5f electrons. The increase in full width at half maxima and decrease in relative amplitude of the white line with respect to the edge jump point towards 6d band broadening under high pressure. A bulk modulus of K 0  =  62(1) GPa and its pressure derivative, K0\\prime   =  4.9(2) was determined from high pressure SXD results. Both the PFY-XAS and diffraction results do not show any sign of a structural phase transition in the applied pressure range.

  15. High pressure effects on U L3 x-ray absorption in partial fluorescence yield mode and single crystal x-ray diffraction in the heavy fermion compound UCd11.

    PubMed

    Nasreen, Farzana; Antonio, Daniel; VanGennep, Derrick; Booth, Corwin H; Kothapalli, Karunakar; Bauer, Eric D; Sarrao, John L; Lavina, Barbara; Iota-Herbei, Valentin; Sinogeikin, Stanislav; Chow, Paul; Xiao, Yuming; Zhao, Yusheng; Cornelius, Andrew L

    2016-03-16

    We report a study of high pressure x-ray absorption (XAS) performed in the partial fluorescence yield mode (PFY) at the U L3 edge (0–28.2 GPa) and single crystal x-ray diffraction (SXD) (0–20 GPa) on the UCd11 heavy fermion compound at room temperature. Under compression, the PFY-XAS results show that the white line is shifted by +4.1(3) eV at the highest applied pressure of 28.2 GPa indicating delocalization of the 5f electrons. The increase in full width at half maxima and decrease in relative amplitude of the white line with respect to the edge jump point towards 6d band broadening under high pressure. A bulk modulus of K0 = 62(1) GPa and its pressure derivative, K0 = 4.9(2) was determined from high pressure SXD results. Both the PFY-XAS and diffraction results do not show any sign of a structural phase transition in the applied pressure range.

  16. HIGH PRESSURE DIES

    DOEpatents

    Wilson, W.B.

    1960-05-31

    A press was invented for subjecting specimens of bismuth, urania, yttria, or thoria to high pressures and temperatures. The press comprises die parts enclosing a space in which is placed an electric heater thermally insulated from the die parts so as not to damage them by heat. The die parts comprise two opposed inner frustoconical parts and an outer part having a double frustoconical recess receiving the inner parts. The die space decreases in size as the inner die parts move toward one another against the outer part and the inner parts, though very hard, do not fracture because of the mode of support provided by the outer part.

  17. Combined single crystal polarized XAFS and XRD at high pressure: probing the interplay between lattice distortions and electronic order at multiple length scales in high T c cuprates

    DOE PAGES

    Fabbris, G.; Hücker, M.; Gu, G. D.; ...

    2016-07-14

    Some of the most exotic material properties derive from electronic states with short correlation length (~10-500 Å), suggesting that the local structural symmetry may play a relevant role in their behavior. In this study, we discuss the combined use of polarized x-ray absorption fine structure and x-ray diffraction at high pressure as a powerful method to tune and probe structural and electronic orders at multiple length scales. Besides addressing some of the technical challenges associated with such experiments, we illustrate this approach with results obtained in the cuprate La1.875Ba0.125CuO4, in which the response of electronic order to pressure can onlymore » be understood by probing the structure at the relevant length scales.« less

  18. Combined single crystal polarized XAFS and XRD at high pressure: probing the interplay between lattice distortions and electronic order at multiple length scales in high Tc cuprates

    NASA Astrophysics Data System (ADS)

    Fabbris, G.; Hücker, M.; Gu, G. D.; Tranquada, J. M.; Haskel, D.

    2016-07-01

    Some of the most exotic material properties derive from electronic states with short correlation length (~10-500 {\\AA}), suggesting that the local structural symmetry may play a relevant role in their behavior. Here we discuss the combined use of polarized x-ray absorption fine structure and x-ray diffraction at high pressure as a powerful method to tune and probe structural and electronic orders at multiple length scales. Besides addressing some of the technical challenges associated with such experiments, we illustrate this approach with results obtained in the cuprate La$_{1.875}$Ba$_{0.125}$CuO$_4$, in which the response of electronic order to pressure can only be understood by probing the structure at the relevant length scales.

  19. Understanding surface structure and chemistry of single crystal lanthanum aluminate.

    PubMed

    Pramana, Stevin S; Cavallaro, Andrea; Qi, Jiahui; Nicklin, Chris L; Ryan, Mary P; Skinner, Stephen J

    2017-03-02

    The surface crystallography and chemistry of a LaAlO3 single crystal, a material mainly used as a substrate to deposit technologically important thin films (e.g. for superconducting and magnetic devices), was analysed using surface X-ray diffraction and low energy ion scattering spectroscopy. The surface was determined to be terminated by Al-O species, and was significantly different from the idealised bulk structure. Termination reversal was not observed at higher temperature (600 °C) and chamber pressure of 10(-10) Torr, but rather an increased Al-O occupancy occurred, which was accompanied by a larger outwards relaxation of Al from the bulk positions. Changing the oxygen pressure to 10(-6) Torr enriched the Al site occupancy fraction at the outermost surface from 0.245(10) to 0.325(9). In contrast the LaO, which is located at the next sub-surface atomic layer, showed no chemical enrichment and the structural relaxation was lower than for the top AlO2 layer. Knowledge of the surface structure will aid the understanding of how and which type of interface will be formed when LaAlO3 is used as a substrate as a function of temperature and pressure, and so lead to improved design of device structures.

  20. Understanding surface structure and chemistry of single crystal lanthanum aluminate

    NASA Astrophysics Data System (ADS)

    Pramana, Stevin S.; Cavallaro, Andrea; Qi, Jiahui; Nicklin, Chris L.; Ryan, Mary P.; Skinner, Stephen J.

    2017-03-01

    The surface crystallography and chemistry of a LaAlO3 single crystal, a material mainly used as a substrate to deposit technologically important thin films (e.g. for superconducting and magnetic devices), was analysed using surface X-ray diffraction and low energy ion scattering spectroscopy. The surface was determined to be terminated by Al-O species, and was significantly different from the idealised bulk structure. Termination reversal was not observed at higher temperature (600 °C) and chamber pressure of 10-10 Torr, but rather an increased Al-O occupancy occurred, which was accompanied by a larger outwards relaxation of Al from the bulk positions. Changing the oxygen pressure to 10-6 Torr enriched the Al site occupancy fraction at the outermost surface from 0.245(10) to 0.325(9). In contrast the LaO, which is located at the next sub-surface atomic layer, showed no chemical enrichment and the structural relaxation was lower than for the top AlO2 layer. Knowledge of the surface structure will aid the understanding of how and which type of interface will be formed when LaAlO3 is used as a substrate as a function of temperature and pressure, and so lead to improved design of device structures.

  1. Understanding surface structure and chemistry of single crystal lanthanum aluminate

    PubMed Central

    Pramana, Stevin S.; Cavallaro, Andrea; Qi, Jiahui; Nicklin, Chris L.; Ryan, Mary P.; Skinner, Stephen J.

    2017-01-01

    The surface crystallography and chemistry of a LaAlO3 single crystal, a material mainly used as a substrate to deposit technologically important thin films (e.g. for superconducting and magnetic devices), was analysed using surface X-ray diffraction and low energy ion scattering spectroscopy. The surface was determined to be terminated by Al-O species, and was significantly different from the idealised bulk structure. Termination reversal was not observed at higher temperature (600 °C) and chamber pressure of 10−10 Torr, but rather an increased Al-O occupancy occurred, which was accompanied by a larger outwards relaxation of Al from the bulk positions. Changing the oxygen pressure to 10−6 Torr enriched the Al site occupancy fraction at the outermost surface from 0.245(10) to 0.325(9). In contrast the LaO, which is located at the next sub-surface atomic layer, showed no chemical enrichment and the structural relaxation was lower than for the top AlO2 layer. Knowledge of the surface structure will aid the understanding of how and which type of interface will be formed when LaAlO3 is used as a substrate as a function of temperature and pressure, and so lead to improved design of device structures. PMID:28252044

  2. HIGH PRESSURE GAS REGULATOR

    DOEpatents

    Ramage, R.W.

    1962-05-01

    A gas regulator operating on the piston and feedback principle is described. The device is particularly suitable for the delicate regulation of high pressure, i.e., 10,000 psi and above, gas sources, as well as being perfectly adaptable for use on gas supplies as low as 50 psi. The piston is adjustably connected to a needle valve and the movement of the piston regulates the flow of gas from the needle valve. The gas output is obtained from the needle valve. Output pressure is sampled by a piston feedback means which, in turn, regulates the movement of the main piston. When the output is other than the desired value, the feedback system initiates movement of the main piston to allow the output pressure to be corrected or to remain constant. (AEC)

  3. High pressure mechanical seal

    NASA Technical Reports Server (NTRS)

    Babel, Henry W. (Inventor); Anderson, Raymond H. (Inventor)

    1996-01-01

    A relatively impervious mechanical seal is formed between the outer surface of a tube and the inside surface of a mechanical fitting of a high pressure fluid or hydraulic system by applying a very thin soft metal layer onto the outer surface of the hard metal tube and/or inner surface of the hard metal fitting. The thickness of such thin metal layer is independent of the size of the tube and/or fittings. Many metals and alloys of those metals exhibit the requisite softness, including silver, gold, tin, platinum, indium, rhodium and cadmium. Suitably, the coating is about 0.0025 millimeters (0.10 mils) in thickness. After compression, the tube and fitting combination exhibits very low leak rates on the order or 10.sup.-8 cubic centimeters per second or less as measured using the Helium leak test.

  4. High pressure mechanical seal

    NASA Technical Reports Server (NTRS)

    Babel, Henry W. (Inventor); Fuson, Phillip L. (Inventor); Chickles, Colin D. (Inventor); Jones, Cherie A. (Inventor); Anderson, Raymond H. (Inventor)

    1995-01-01

    A relatively impervious mechanical seal is formed between the outer surface of a tube and the inside surface of a mechanical fitting of a high pressure fluid or hydraulic system by applying a very thin soft metal layer onto the outer surface of the hard metal tube and/or inner surface of the hard metal fitting, prior to swaging the fitting onto the tube. The thickness of such thin metal layer is independent of the size of the tube and/or fittings. Many metals and alloys of those metals exhibit the requisite softness, including silver, gold, nickel, tin, platinum, indium, rhodium and cadmium. Suitably, the coating is about 0.0025 millimeters (0.10 mils) in thickness. After swaging, the tube and fitting combination exhibits very low leak rates on the order or 10.sup.-8 cubic centimeters per second or less as meaured using the Helium leak test.

  5. Chromium at High Pressure

    NASA Astrophysics Data System (ADS)

    Jaramillo, Rafael

    2012-02-01

    Chromium has long served as the archetype of spin density wave magnetism. Recently, Jaramillo and collaborators have shown that Cr also serves as an archetype of magnetic quantum criticality. Using a combination of x-ray diffraction and electrical transport measurements at high pressures and cryogenic temperatures in a diamond anvil cell, they have demonstrated that the N'eel transition (TN) can be continuously suppressed to zero, with no sign of a concurrent structural transition. The order parameter undergoes a broad regime of exponential suppression, consistent with the weak coupling paradigm, before deviating from a BCS-like ground state within a narrow but accessible quantum critical regime. The quantum criticality is characterized by mean field scaling of TN and non mean field scaling of the transport coefficients, which points to a fluctuation-induced reconstruction of the critical Fermi surface. A comparison between pressure and chemical doping as means to suppress TN sheds light on different routes to the quantum critical point and the relevance of Fermi surface nesting and disorder at this quantum phase transition. The work by Jaramillo et al. is broadly relevant to the study of magnetic quantum criticality in a physically pure and theoretically tractable system that balances elements of weak and strong coupling. [4pt] [1] R. Jaramillo, Y. Feng, J. Wang & T. F. Rosenbaum. Signatures of quantum criticality in pure Cr at high pressure. Proc. Natl. Acad. Sci. USA 107, 13631 (2010). [0pt] [2] R. Jaramillo, Y. Feng, J. C. Lang, Z. Islam, G. Srajer, P. B. Littlewood, D. B. McWhan & T. F. Rosenbaum. Breakdown of the Bardeen-Cooper-Schrieffer ground state at a quantum phase transition. Nature 459, 405 (2009).

  6. High-pressure minerals in shocked meteorites

    NASA Astrophysics Data System (ADS)

    Tomioka, Naotaka; Miyahara, Masaaki

    2017-09-01

    Heavily shocked meteorites contain various types of high-pressure polymorphs of major minerals (olivine, pyroxene, feldspar, and quartz) and accessory minerals (chromite and Ca phosphate). These high-pressure minerals are micron to submicron sized and occur within and in the vicinity of shock-induced melt veins and melt pockets in chondrites and lunar, howardite-eucrite-diogenite (HED), and Martian meteorites. Their occurrence suggests two types of formation mechanisms (1) solid-state high-pressure transformation of the host-rock minerals into monomineralic polycrystalline aggregates, and (2) crystallization of chondritic or monomineralic melts under high pressure. Based on experimentally determined phase relations, their formation pressures are limited to the pressure range up to 25 GPa. Textural, crystallographic, and chemical characteristics of high-pressure minerals provide clues about the impact events of meteorite parent bodies, including their size and mutual collision velocities and about the mineralogy of deep planetary interiors. The aim of this article is to review and summarize the findings on natural high-pressure minerals in shocked meteorites that have been reported over the past 50 years.

  7. Large single crystal diamond grown in FeNiMnCo-S-C system under high pressure and high temperature conditions

    NASA Astrophysics Data System (ADS)

    Zhang, He; Li, Shangsheng; Su, Taichao; Hu, Meihua; Li, Guanghui; Ma, Hongan; Jia, Xiaopeng

    2016-11-01

    Large diamonds have successfully been synthesized from FeNiMnCo-S-C system at temperatures of 1255-1393 °C and pressures of 5.3-5.5 GPa. Because of the presence of sulfur additive, the morphology and color of the large diamond crystals change obviously. The content and shape of inclusions change with increasing sulfur additive. It is found that the pressure and temperature conditions required for the synthesis decrease to some extent with the increase of S additive, which results in left down of the V-shape region. The Raman spectra show that the introduction of additive sulfur reduces the quality of the large diamond crystals. The x-ray photoelectron spectroscopy (XPS) spectra show the presence of S in the diamonds. Furthermore, the electrical properties of the large diamond crystals are tested by a four-point probe and the Hall effect method. When sulfur in the cell of diamond is up to 4.0 wt.%, the resistance of the diamond is 9.628×105 Ω·cm. It is shown that the large single crystal samples are n type semiconductors. This work is helpful for the further research and application of sulfur-doped semiconductor large diamond. Project supported by the National Natural Science Foundation of China (Grant No. 51172089), the Education Department of Henan Province, China (Grant No. 12A430010), and the Fundamental Research Funds for the Universities of Henan Province, China (Grant No. NSFRF140110).

  8. Phase Transition Mechanisms in the Mineral Titanite CaTiOSiO4 Under High Pressure - a X-ray Single Crystal Study Between 7 GPa and 10 GPa

    NASA Astrophysics Data System (ADS)

    Rath, S.; Kunz, M.; Miletich, R.

    2001-12-01

    The monoclinic mineral titanite is a common accessory in many acid and intermediate igneous rock, gneises, mica shists and amphiboles. The structure of titanite is characterized by corner-linked chains of TiO6 -octahedra parallel to [100] connected via isolated SiO4 -tetrahedra. CaO7 polyhedra build chains along [101]. The octahedral Ti atoms show typical out-of-center distortions. Its behavior under high pressure can give information about the driving forces of the phase transition in ABOCO4 silicates. The behavior of titanite under high pressure has been studied up to 7 GPa and 850oK with powder diffraction, respectively [1], [2], [3] and several phase transitions were found. The structure remains monoclinic but changes from P21/a to A2/a at 3.6 GPa. Here we present evidence for a new A2/a P-1 phase transition at 10.5 GPa. At this pressure the cell metric decreased to the following values: a= 6.829(4) Å , b= 8.594(2) Å , c= 6.352(1) Å, α = 90.18(2)° , β = 112.78(2)° , γ = 89.70(2)° and V= 343.7(2) Å3. Structure refinement results of high-pressure X-ray single crystal studies at pressures from 7 to 10 GPa will be presented. In addition, we compare the titanite results to the phase transition in the topological identical malayaite CaSnSiO_4 at 5 GPa, where a similar phase transition has previously been observed [4]. [1] Angel, R.J.; Kunz, M.; Miletich, R.; Woodland, A.B.; Koch, M. and Xirouchakis, D. (1999); High-pressure phase transition in CaTiOSiO_4 titanite; Phase Transitions, 68, 533 - 543 [2] Bismayer, U.; Zhang, M.; Groat, L.A.; Salje, E.K.H and Meyer, H.-W. (1999); The \\beta - \\gamma Phase Transition in Titanite and the Isosymmetric Analogue in Malayaite; Phase Transitions, 68, 545 - 556 [3] Kunz, M., Arlt, T. and Stolz, J. (2000): In situ powder diffraction of titanite (CaTiSiO_4) at high pressure and high temperature, American Mineralogist, 85, 1465 - 1473 [4] Rath, St, Kunz, M. and Miletich, R. (2001) Pressure induced phase transition in

  9. High-pressure synthesis, long-term stability of single crystals of diboron trioxide, B2O3, and an empirical electronic polarizability of [3]B3+

    NASA Astrophysics Data System (ADS)

    Burianek, Manfred; Birkenstock, Johannes; Mair, Philipp; Kahlenberg, Volker; Medenbach, Olaf; Shannon, Robert D.; Fischer, Reinhard X.

    2016-07-01

    Single crystals of B2O3 are needed for the precise determination of the refractive indices used to calculate the electronic polarizability α of 3-coordinated boron. The α(B) values in turn are used to predict mean refractive indices of borate minerals. Since the contribution of boron to the total polarizability of a mineral is very low, the synthetic compound B2O3 represents an ideal model system because of its high molar content of boron. Millimeter-sized crystals were synthesized at 1 GPa in a piston-cylinder apparatus. The samples were heated above the liquidus (800 °C), subsequently cooled at 15 °C/h to 500 °C and finally quenched. The refractive indices were determined by the immersion method using a microrefractometer spindle stage. The refractive indices n o = 1.653 (3) and n e = 1.632 (3) correspond to a total polarizability for B2O3 of α = 4.877 Å3. These values were used to determine the electronic polarizability of boron of α(B) = 0.16 Å3. Although the surface of the B2O3 crystals was coated with a hydrous film immediately after being exposed to air, its bulk crystallinity is retained for a period of at least 2 months.

  10. High-pressure single crystal X-ray diffraction study of the linear metal chain compound Co3(dpa)4Br2·CH2Cl2.

    PubMed

    Madsen, S R; Overgaard, J; Stalke, D; Iversen, B B

    2015-05-21

    The crystal structure of the linear metal chain compound Co3(dpa)4Br2·CH2Cl2 (1) has been investigated up to a pressure of 13.6(2) GPa in a diamond anvil cell (DAC) using single crystal X-ray diffraction. The structure remains orthorhombic as the unit cell volume is reduced by 30% at 12.8 GPa. At 13.6(2) GPa the diffraction pattern is of very poor quality and not even reliable unit cell parameters can be determined. Peak broadening resulting from non-hydrostatic conditions was avoided by annealing the loaded DAC prior to data collection, allowing reliable structural models to be refined up to a pressure of 11.8(2) GPa. On increasing pressure, the disordered CH2Cl2 crystal solvent molecule gradually becomes redistributed from one site to another. Hirshfeld surface analysis suggests that the redistribution is a result of repulsive HH interactions. Pressure also affects the molecular geometry, in particular the Co-Co and Co-Br bond lengths which decrease by 4% and 12%, respectively, at 11.8(2) GPa.

  11. [High Pressure Gas Tanks

    NASA Technical Reports Server (NTRS)

    Quintana, Rolando

    2002-01-01

    Four high-pressure gas tanks, the basis of this study, were especially made by a private contractor and tested before being delivered to NASA Kennedy Space Center. In order to insure 100% reliability of each individual tank the staff at KSC decided to again submit the four tanks under more rigorous tests. These tests were conducted during a period from April 10 through May 8 at KSC. This application further validates the predictive safety model for accident prevention and system failure in the testing of four high-pressure gas tanks at Kennedy Space Center, called Continuous Hazard Tracking and Failure Prediction Methodology (CHTFPM). It is apparent from the variety of barriers available for a hazard control that some barriers will be more successful than others in providing protection. In order to complete the Barrier Analysis of the system, a Task Analysis and a Biomechanical Study were performed to establish the relationship between the degree of biomechanical non-conformities and the anomalies found within the system on particular joints of the body. This relationship was possible to obtain by conducting a Regression Analysis to the previously generated data. From the information derived the body segment with the lowest percentage of non-conformities was the neck flexion with 46.7%. Intense analysis of the system was conducted including Preliminary Hazard Analysis (PHA), Failure Mode and Effect Analysis (FMEA), and Barrier Analysis. These analyses resulted in the identification of occurrences of conditions, which may be becoming hazardous in the given system. These conditions, known as dendritics, may become hazards and could result in an accident, system malfunction, or unacceptable risk conditions. A total of 56 possible dendritics were identified. Work sampling was performed to observe the occurrence each dendritic. The out of control points generated from a Weighted c control chart along with a Pareto analysis indicate that the dendritics "Personnel not

  12. High pressure capillary connector

    DOEpatents

    Renzi, Ronald F.

    2005-08-09

    A high pressure connector capable of operating at pressures of 40,000 psi or higher is provided. This connector can be employed to position a first fluid-bearing conduit that has a proximal end and a distal end to a second fluid-bearing conduit thereby providing fluid communication between the first and second fluid-bearing conduits. The connector includes (a) an internal fitting assembly having a body cavity with (i) a lower segment that defines a lower segment aperture and (ii) an interiorly threaded upper segment, (b) a first member having a first member aperture that traverses its length wherein the first member aperture is configured to accommodate the first fluid-bearing conduit and wherein the first member is positioned in the lower segment of the internal fitting assembly, and (c) a second member having a second member aperture that traverses its length wherein the second member is positioned in the upper segment of the fitting assembly and wherein a lower surface of the second member is in contact with an upper surface of the first member to assert a compressive force onto the first member and wherein the first member aperture and the second member aperture are coaxial.

  13. Crystallization of an amorphous B-C-N precursor with a Li-B-N catalyst at high pressures and temperatures

    SciTech Connect

    Li Dongxu; Yu Dongli; Wang Peng; Li Yingmei; He Julong; Xu Bo; Liu Zhongyuan; Tian Yongjun

    2009-11-15

    An orthorhombic B-C-N compound was synthesized using an amorphous B-C-N precursor and a Li-B-N catalyst at 6 GPa and 1773 K. The results of energy dispersive spectrometry and electronic energy loss spectrometry suggest a stoichiometry of B:C:N = 1:3.3:1. In addition, the Li-B-N catalyst improves the crystallizations of the B-C-N compound, graphite and BN and therefore might be a profitable catalyst in ultrahigh pressure experiments.

  14. Crystal and magnetic structures and physical properties of a new pyroxene NaMnGe2O6 synthesized under high pressure

    SciTech Connect

    Yan, Jiaqiang; Tian, Wei; May, Andrew F; Cheng, J G; Zhou, J.-S.; Garlea, Vasile O; Neuefeind, Joerg C; Steinfink, Hugo; Lynch, V

    2013-01-01

    A new pyroxene NaMnGe2O6 has been synthesized at 3 GPa and 800 C, and fully characterized by x-ray single-crystal diffraction and neutron powder diffraction, measurements of magnetization and specific heat. Like other majority sodium pyroxenes, NaMnGe2O6 crystallizes into a monoclinic C2/c structure with unit-cell parameters a = 9.859(2) , b = 8.7507(18) , c = 5.5724(11) , and =105.64(3) at room temperature. The crystal structure is featured by quasi-one-dimensional chains of skew edge-sharing MnO6 octahedra running along the crystallographic c axis; these chains are connected by non-magnetic GeO4 tetrahedra, so as to lead to a low-dimensional magnetism. The highly distorted MnO6 octahedron consisting of three Mn-O bond lengths, i.e. 1.918 , 1.991 , and 2.198 , is consistent with the Jahn-Teller effect at Mn3+ in a cubic crystal field. A long-range cooperative Jahn-Teller distortion is formed by ordering longest Mn-O bonds between two neighboring octahedra along the chain direction. No orbital order-disorder transition has been found up to 750 K as checked by magnetic susceptibility. Like other alkali-metal pyroxenes with S > , NaMnGe2O6 (S = 2) was found to undergo a long-range antiferromagnetic ordering at TN = 7 K at low magnetic field due to the exchange interactions along and between chains. Due to the peculiar structural features and the corresponding magnetic coupling, the weak AF spin ordering gives way to a ferromagnetic-like state at a sufficiently high magnetic field. Specific-heat measurements demonstrated that a large portion of the magnetic entropy, i.e. > 60 %, has been removed above TN as a result of strong spin correlations within the quasi-one-dimensional Mn3+-spin chains. Neutron powder diffraction study suggests a commensurate magnetic structure defined by k = [0 0 0.5] with Mn moments aligned along the c axis. The present study on NaMnGe2O6 completed the evolution of magnetic properties as a function of the d-orbital occupancy from d1 to d5 in

  15. Specific features of insulator-metal transitions under high pressure in crystals with spin crossovers of 3 d ions in tetrahedral environment

    NASA Astrophysics Data System (ADS)

    Lobach, K. A.; Ovchinnikov, S. G.; Ovchinnikova, T. M.

    2015-01-01

    For Mott insulators with tetrahedral environment, the effective Hubbard parameter U eff is obtained as a function of pressure. This function is not universal. For crystals with d 5 configuration, the spin crossover suppresses electron correlations, while for d 4 configurations, the parameter U eff increases after a spin crossover. For d 2 and d 7 configurations, U eff increases with pressure in the high-spin (HS) state and is saturated after the spin crossover. Characteristic features of the insulator-metal transition are considered as pressure increases; it is shown that there may exist cascades of several transitions for various configurations.

  16. Laser techniques in high-pressure geophysics

    NASA Technical Reports Server (NTRS)

    Hemley, R. J.; Bell, P. M.; Mao, H. K.

    1987-01-01

    Laser techniques in conjunction with the diamond-anvil cell can be used to study high-pressure properties of materials important to a wide range of problems in earth and planetary science. Spontaneous Raman scattering of crystalline and amorphous solids at high pressure demonstrates that dramatic changes in structure and bonding occur on compression. High-pressure Brillouin scattering is sensitive to the pressure variations of single-crystal elastic moduli and acoustic velocities. Laser heating techniques with the diamond-anvil cell can be used to study phase transitions, including melting, under deep-earth conditions. Finally, laser-induced ruby fluorescence has been essential for the development of techniques for generating the maximum pressures now possible with the diamond-anvil cell, and currently provides a calibrated in situ measure of pressure well above 100 gigapascals.

  17. Laser techniques in high-pressure geophysics

    NASA Technical Reports Server (NTRS)

    Hemley, R. J.; Bell, P. M.; Mao, H. K.

    1987-01-01

    Laser techniques in conjunction with the diamond-anvil cell can be used to study high-pressure properties of materials important to a wide range of problems in earth and planetary science. Spontaneous Raman scattering of crystalline and amorphous solids at high pressure demonstrates that dramatic changes in structure and bonding occur on compression. High-pressure Brillouin scattering is sensitive to the pressure variations of single-crystal elastic moduli and acoustic velocities. Laser heating techniques with the diamond-anvil cell can be used to study phase transitions, including melting, under deep-earth conditions. Finally, laser-induced ruby fluorescence has been essential for the development of techniques for generating the maximum pressures now possible with the diamond-anvil cell, and currently provides a calibrated in situ measure of pressure well above 100 gigapascals.

  18. Specific features of insulator-metal transitions under high pressure in crystals with spin crossovers of 3d ions in tetrahedral environment

    SciTech Connect

    Lobach, K. A. Ovchinnikov, S. G.; Ovchinnikova, T. M.

    2015-01-15

    For Mott insulators with tetrahedral environment, the effective Hubbard parameter U{sub eff} is obtained as a function of pressure. This function is not universal. For crystals with d{sup 5} configuration, the spin crossover suppresses electron correlations, while for d{sup 4} configurations, the parameter U{sub eff} increases after a spin crossover. For d{sup 2} and d{sup 7} configurations, U{sub eff} increases with pressure in the high-spin (HS) state and is saturated after the spin crossover. Characteristic features of the insulator-metal transition are considered as pressure increases; it is shown that there may exist cascades of several transitions for various configurations.

  19. Crystal and magnetic structures and physical properties of a new pyroxene NaMnGe2O6 synthesized under high pressure.

    PubMed

    Cheng, Jinguang; Tian, Wei; Zhou, Jianshi; Lynch, Vincent M; Steinfink, Hugo; Manthiram, Arumugam; May, Andrew F; Garlea, Vasile O; Neuefeind, Joerg C; Yan, Jiaqiang

    2013-02-20

    A new pyroxene compound, NaMnGe(2)O(6), has been synthesized at 3 GPa and 800 °C and fully characterized by X-ray single-crystal diffraction, neutron powder diffraction, and measurements of magnetization and specific heat. NaMnGe(2)O(6) crystallizes into a monoclinic C2/c structure with unit-cell parameters a = 9.859(2) Å, b = 8.7507(18) Å, c = 5.5724(11) Å, and β = 105.64(3)° at 153 K. A cooperative Jahn-Teller distortion is formed by an ordering of the longest Mn-O bonds between two neighboring octahedra along the chain direction. This feature distinguishes NaMnGe(2)O(6) from other pyroxene compounds without Jahn-Teller active cations and suggests that the Jahn-Teller distortion competes with the intrinsic local distortion in the pyroxene structure. No orbital order-disorder transition has been found up to 750 K. Like other alkali-metal pyroxenes with S > (1)/(2), NaMnGe(2)O(6) (S = 2) was found to undergo a long-range antiferromagnetic (AF) ordering at T(N) = 7 K due to intrachain and interchain exchange interactions. Due to the peculiar structural features and the corresponding magnetic coupling, the weak AF spin ordering gives way to a ferromagnetic-like state at a sufficiently high magnetic field. Specific-heat measurements demonstrated that a large portion of the magnetic entropy, >60%, has been removed above T(N) as a result of strong spin correlations within the quasi-one-dimensional Mn(3+)-spin chains. The Reitveld refinement of neutron powder diffraction data gives a commensurate magnetic structure defined by k = [0 0 0.5] with Mn moments aligned mainly along the c-axis with a small component along both a- and b-axes.

  20. High-Pressure Single-Crystal Neutron Scattering Study of Magnetic and Fe Vacancy Orders in (Tl,Rb)2 Fe4 Se5 Superconductor

    SciTech Connect

    Ye, Feng; Bao, Wei; Chi, Song-Xue; Santos, Antonio M. dos; Molaison, Jamie J.; Fang, Ming-Hu; Wang, Hang-Dong; Mao, Qian-Hui; Wang, Jin-Chen; Liu, Juan-Juan; Sheng, Jie-Ming

    2014-12-01

    We investigate the magnetic and iron vacancy orders in superconducting (Tl,Rb)2Fe4Se5 single-crystals by using a high-pressure neutron diffraction technique. Similar to the temperature effect, the block antiferromagnetic order gradually decreases upon increasing pressure while the Fe vacancy superstructural order remains intact before its precipitous disappearance at the critical pressure Pc = 8.3 GPa. Combined with previously determined Pc for superconductivity, our phase diagram under pressure reveals the concurrence of the block AFM order, the √5 × √5 iron vacancy order and superconductivity for the 245 superconductor. Lastly, a synthesis of current experimental data in a coherent physical picture is attempted.

  1. Information-theoretic approach for the discovery of design rules for crystal chemistry.

    PubMed

    Kong, Chang Sun; Luo, Wei; Arapan, Sergiu; Villars, Pierre; Iwata, Shuichi; Ahuja, Rajeev; Rajan, Krishna

    2012-07-23

    In this work, it is shown that for the first time that, using information-entropy-based methods, one can quantitatively explore the relative impact of a wide multidimensional array of electronic and chemical bonding parameters on the structural stability of intermetallic compounds. Using an inorganic AB2 compound database as a template data platform, the evolution of design rules for crystal chemistry based on an information-theoretic partitioning classifier for a high-dimensional manifold of crystal chemistry descriptors is monitored. An application of this data-mining approach to establish chemical and structural design rules for crystal chemistry is demonstrated by showing that, when coupled with first-principles calculations, statistical inference methods can serve as a tool for significantly accelerating the prediction of unknown crystal structures.

  2. Effect of high pressure on the electrical resistivity of optimally doped YBa2Cu3O7-δ single crystals with unidirectional planar defects

    NASA Astrophysics Data System (ADS)

    Vovk, R. V.; Vovk, N. R.; Khadzhai, G. Ya.; Goulatis, I. L.; Chroneos, A.

    2013-08-01

    In the present work the effect of hydrostatic pressure up to 10 kbar on in-plane electrical resistivity of well-structured YBa2Cu3O7-δ (δ<0.15, Тс≈91 K, ΔТс≈0.3 K) single crystals was investigated. The influence of the twin boundaries on the electrical resistivity was minimized. The resistivities temperature dependences in the interval Тс up to 300 K can be approximated by taking into account the linear term at high temperatures and the fluctuation conductivity (Maki-Thompson model) near Тс. The parameters of the linear dependence of R(T) are decreasing as the pressure is increasing. Тс increases linearly when the pressure increases with the derivative dTc/dP≈0.080 K/kbar. Among the Maki-Thompson model parameters the inter-layer distance, d, can be considered to be independent from pressure, the transverse coherence length, ξc(0)∼0.1d.

  3. Lattice dynamics of wurtzite and rocksalt AlN under high pressure: Effect of compression on the crystal anisotropy of wurtzite-type semiconductors

    NASA Astrophysics Data System (ADS)

    Manjón, Francisco Javier; Errandonea, Daniel; Romero, Aldo Humberto; Garro, Núria; Serrano, Jorge; Kuball, Martin

    2008-05-01

    Raman spectra of aluminum nitride (AlN) under pressure have been measured up to 25GPa , i.e., beyond the onset of the wurtzite-to-rocksalt phase transition around 20GPa . The experimental pressure coefficients for all the Raman-active modes of the wurtzite phase are reported and compared to those obtained from ab initio lattice dynamical calculations, as well as to previous experimental and theoretical results. The pressure coefficients of all the Raman-active modes in wurtzite-type semiconductors (AlN, GaN, InN, ZnO, and BeO), as well as the relatively low bulk modulus and phase transition pressure in wurtzite AlN, are discussed in the light of the pressure dependence of the structural crystal anisotropy in wurtzite semiconductors. On pressure release, AlN partially returns to the wurtzite phase below 1.3GPa but the presence of a rocksalt phase in AlN was observed at pressures as low as 1.3GPa , as evidenced by comparing the experimental Raman spectra to calculated one- and two-phonon densities of states of the rocksalt phase.

  4. Metallicity of boron carbides at high pressure

    NASA Astrophysics Data System (ADS)

    Dekura, Haruhiko; Shirai, Koun; Yanase, Akira

    2010-03-01

    Electronic structure of semiconducting boron carbide at high pressure has been theoretically investigated, because of interests in the positive pressure dependence of resistivity, in the gap closure, and in the phase transition. The most simplest form B12(CCC) is assumed. Under assumptions of hydrostatic pressure and neglecting finite-temperature effects, boron carbide is quite stable at high pressure. The crystal of boron carbide is stable at least until a pressure higher than previous experiments showed. The gap closure occurs only after p=600 GPa on the assumption of the original crystal symmetry. In the low pressure regime, the pressure dependence of the energy gap almost diminishes, which is an exceptional case for semiconductors, which could be one of reasons for the positive pressure dependence of resistivity. A monotonous increase in the apex angle of rhombohedron suggests that the covalent bond continues to increase. The C chain inserted in the main diagonal of rhombohedral structure is the chief reason of this stability.

  5. High-pressure neutron diffraction

    SciTech Connect

    Xu, Hongwu

    2011-01-10

    This lecture will cover progress and prospect of applications of high-pressure neutron diffraction techniques to Earth and materials sciences. I will first introduce general high-pressure research topics and available in-situ high-pressure techniques. Then I'll talk about high-pressure neutron diffraction techniques using two types of pressure cells: fluid-driven and anvil-type cells. Lastly, I will give several case studies using these techniques, particularly, those on hydrogen-bearing materials and magnetic transitions.

  6. Minor element partitioning between fcc Fe metal and Fe-S liquid at high pressure: The role of crystal lattice strain

    NASA Astrophysics Data System (ADS)

    Stewart, Andrew J.; van Westrenen, Wim; Schmidt, Max W.; Günther, D.

    2009-07-01

    We present a new approach to model element distribution between solid and liquid metal phases, based on experimentally determined data for the partitioning of P, S, selected transition metals, and chalcophile elements between face-centred cubic (fcc) Fe and Fe-S liquid at pressures of 9, 15 and 23 GPa and temperatures between 1523 and 1773 K. Solid/liquid partition coefficients ( D) for the transition metals V, Cr, Mn, Fe, Co, and Ni range from a minimum D of 0.16-0.64 for V to a maximum D of 1.1-1.2 for Co, indicating modest but significant fractionation. D for the chalcophile elements Cu, Zn, Ga, Sn, and Pb varies from 0.029-0.051 for DPb up to 1.6-2.4 for DGa and for non-metals from 0.02-0.04 for S to 0.23-0.66 for P. A modified lattice strain model (as in common use for silicate mineral-melt partitioning) describes the variations in D values for the first row transition metals through the deviance in metal radius from the ideal site radius of Fe in solid metal, indicating that these metals all substitute into the iron site of the solid phase. Variations in D values for the chalcophile elements can also be rationalized using a lattice strain model, but chalcophiles occupy a different site in the solid metal, probably related to the presence of sulphur defects. We show that the lattice strain model can be applied to previously published low pressure experimental data, as well as to third-row transition metals as to first-row transition metals and chalcophiles. The fact that solid-liquid metal D values are amenable to interpretation using lattice strain models paves the way for the development of a new class of element partitioning models applicable to metallic core crystallization processes.

  7. High-pressure ultrasonic study of the commensurate-incommensurate spin-density-wave transition in an antiferromagnetic Cr-0.3 at. % Ru alloy single crystal

    NASA Astrophysics Data System (ADS)

    Cankurtaran, M.; Saunders, G. A.; Wang, Q.; Ford, P. J.; Alberts, H. L.

    1992-12-01

    A comprehensive experimental study has been made of the elastic and nonlinear acoustic behavior of a dilute Cr alloy as it undergoes a commensurate (C)-incommensurate (I) spin-density-wave transition. Simultaneous measurements of the temperature dependence of ultrasonic wave velocity and attenuation of longitudinal and shear 10-MHz ultrasonic waves propagated along both the [100] and the [110] direction of Cr-0.3 at. % Ru alloy single crystal have been made in the temperature range 200-300 K. The temperature dependence of ultrasonic attenuation for each mode is characterized by a spikelike peak centered at TCI (=238.6 K) (on cooling) and at TIC (=255.6 K) (on warming). The velocities of both longitudinal and shear ultrasonic waves exhibit a large and steep increase at TCI on cooling and a similar drop at TIC on warming with a pronounced hysteresis between TIC and TCI. These observations show that the transition between the commensurate and incommensurate phases is first order. Measurements of the effects of hydrostatic pressure (up to 0.15 GPa) on the velocities of ultrasonic waves, which were made at several fixed temperatures between 248 and 297 K, show similar features: a steep increase at PCI (increasing pressure) and a similar drop at PIC (decreasing pressure) with a well-defined hysteresis. Both TCI and TIC increase strongly and approximately linearly with pressure, the mean values of dTCI/dP and dTIC/dP being (333+/-3) K/GPa and (277+/-5) K/GPa, respectively. The pressure and temperature dependencies of the anomalies in the ultrasonic wave velocity have been used to locate both the C-I and I-C boundaries on the magnetic P-T phase diagram. There is a triple point (at about 315 K and 0.22 GPa) where the paramagnetic, commensurate, and incommensurate spin-density-wave phases coexist. Results for the complete sets of the elastic stiffness tensor components and their hydrostatic pressure derivatives have been used to evaluate the acoustic-mode Gr

  8. Crystal structures and compressibility of novel iron borides Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} synthesized at high pressure and high temperature

    SciTech Connect

    Bykova, E.; Gou, H.; Bykov, M.; Hanfland, M.; Dubrovinsky, L.; Dubrovinskaia, N.

    2015-10-15

    We present here a detailed description of the crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe{sub 2}B{sub 7} (the bulk modulus K{sub 0}= 259(1.8) GPa, K{sub 0}′= 4 (fixed)) is even lower than that of FeB{sub 4} and comparable with that of MnB{sub 4}, known for high bulk moduli among 3d metal borides. Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. Fe{sub x}B{sub 50} does not show considerable anisotropy in the elastic behavior. - Graphical abstract: Crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} (x=1.01(1), 1.04(1), 1.32(1)). - Highlights: • Novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50}, were synthesized under HPHT conditions. • Fe{sub 2}B{sub 7} has a unique orthorhombic structure (space group Pbam). • Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds that results in high bulk modulus. • Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B composed of B{sub 12} icosahedra. • In Fe{sub x}B{sub 50} intraicosahedral bonds are stiffer than intericosahedral ones.

  9. Crystal structure of the high-pressure phase of the oxonitridosilicate chloride Ce4[Si4O(3 + x)N(7 - x)]Cl(1 - x)O(x), x approximately = 0.2.

    PubMed

    Friedrich, Alexandra; Haussühl, Eiken; Morgenroth, Wolfgang; Lieb, Alexandra; Winkler, Björn; Knorr, Karsten; Schnick, Wolfgang

    2006-04-01

    The structural compression mechanism of Ce4[Si4O(3 + x)N(7 - x)]Cl(1 - x)O(x), x approximately = 0.2, was investigated by in situ single-crystal synchrotron X-ray diffraction at pressures of 3.0, 8.5 and 8.6 GPa using the diamond-anvil cell technique. On increasing pressure the low-pressure cubic structure first undergoes only minor structural changes. Between 8.5 and 8.6 GPa a first-order phase transition occurs, accompanied by a change of the single-crystal colour from light orange to dark red. The main structural mechanisms, leading to a volume reduction of about 5% at the phase transition, are an increase in and a rearrangement of the Ce coordination, the loss of the Ce2, Ce3 split position, and a bending of some of the inter-polyhedral Si-N-Si angles in the arrangement of the corner-sharing Si tetrahedra. The latter is responsible for the short c axis of the orthorhombic high-pressure structure compared with the cell parameter of the cubic low-pressure structure.

  10. High-pressure synthesis and crystal structures of the strontium oxogallates Sr{sub 2}Ga{sub 2}O{sub 5} and Sr{sub 5}Ga{sub 6}O{sub 14}

    SciTech Connect

    Kahlenberg, Volker; Goettgens, Valerie; Mair, Philipp; Schmidmair, Daniela

    2015-08-15

    High-pressure synthesis experiments in a piston–cylinder apparatus at 1.5 GPa/3.0 GPa and 1000 °C resulted in the formation of single-crystals of Sr{sub 2}Ga{sub 2}O{sub 5} and Sr{sub 5}Ga{sub 6}O{sub 14}, respectively. The structures of both compounds have been solved from single-crystal diffraction data sets using direct methods. The first compound is orthorhombic with space group type Pbca (a=10.0021(4) Å, b=9.601(4) Å, c=10.6700(4) Å, V=1024.6(4) Å{sup 3}, M{sub r}=394.68 u, Z=8, D{sub x}=5.12 g/cm{sup 3}) and belongs to the group of single layer gallates. Individual sheets are parallel to (0 0 1) and can be built from the condensation of unbranched vierer single chains running along [0 1 0]. The layers are characterized by the presence of four- and strongly elliptical eight-membered rings of corner connected tetrahedra in UUDD and UUUUDDDD conformation. Strontium atoms are sandwiched between the tetrahedral layers for charge compensation and are coordinated by six and seven oxygen ligands, respectively. Sr{sub 2}Ga{sub 2}O{sub 5} is isotypic with several other double sulfides and selenides. To the best of our knowledge, it is the first example of an oxide with this structure type. From a structural point of view, Sr{sub 5}Ga{sub 6}O{sub 14} is a phyllogallate as well. The crystal structure adopts the monoclinic space group P2{sub 1}/c (a=8.1426(3) Å, b=8.1803(3) Å, c=10.8755(4) Å, β=91.970(4)° V=723.98(5) Å{sup 3}, M{sub r}=1080.42 u, Z=2, D{sub x}=4.96 g/cm{sup 3}). Individual sheets extend along (0 0 1). Basic building units are unbranched dreier single chains parallel to [1 0 0]. The layers contain tertiary (Q{sup 3}) und quaternary (Q{sup 4}) connected [GaO{sub 4}]-tetrahedra in the ratio 2:1 resulting in a Ga:O ratio of 3:7 and the formation of exclusively five-membered rings. Linkage between adjacent tetrahedral sheets is provided by three symmetrically independent strontium ions which are surrounded by six to eight oxygen atoms. The layers

  11. Electrokinetically pumped high pressure sprays

    DOEpatents

    Schoeniger, Joseph S.; Paul, Phillip H.; Schoeniger, Luke

    2002-01-01

    An electrokinetic pump capable of producing high pressure is combined with a nozzle having a submicron orifice to provide a high pressure spray device. Because of its small size, the device can be contained within medical devices such as an endoscope for delivering biological materials such as DNA, chemo therapeutic agents, or vaccines to tissues and cells.

  12. Electrokinetically pumped high pressure sprays

    DOEpatents

    Schoeniger, Joseph S.; Paul, Phillip H.; Schoeniger, Luke

    2005-11-01

    An electrokinetic pump capable of producing high pressure is combined with a nozzle having a submicron orifice to provide a high pressure spray device. Because of its small size, the device can be contained within medical devices such as an endoscope for delivering biological materials such as DNA, chemo therapeutic agents, or vaccines to tissues and cells.

  13. Silicon clathrates and carbon analogs: high pressure synthesis, structure, and superconductivity.

    PubMed

    Yamanaka, Shoji

    2010-02-28

    Compounds with cage-like structures of elemental silicon and carbon are comparatively reviewed. Barium containing silicon clathrate compounds isomorphous with type I gas hydrates were prepared using high pressure and high temperature (HPHT) conditions, and found to become superconductors. The application of HPHT conditions to Zintl binary silicides have produced a number of silicon-rich cage-like structures including new clathrate structures; most of them are superconductors. Carbon analogs of silicon clathrates can be prepared by 3D polymerization of C(60) under HPHT conditions, which are new allotropes of carbon with expanded framework structures. The crystal chemistry and characteristic properties of some related compounds are also reviewed.

  14. The crystal chemistry of inorganic metal borohydrides and their relation to metal oxides.

    PubMed

    Černý, Radovan; Schouwink, Pascal

    2015-12-01

    The crystal structures of inorganic homoleptic metal borohydrides are analysed with respect to their structural prototypes found amongst metal oxides in the inorganic databases such as Pearson's Crystal Data [Villars & Cenzual (2015). Pearson's Crystal Data. Crystal Structure Database for Inorganic Compounds, Release 2014/2015, ASM International, Materials Park, Ohio, USA]. The coordination polyhedra around the cations and the borohydride anion are determined, and constitute the basis of the structural systematics underlying metal borohydride chemistry in various frameworks and variants of ionic packing, including complex anions and the packing of neutral molecules in the crystal. Underlying nets are determined by topology analysis using the program TOPOS [Blatov (2006). IUCr CompComm. Newsl. 7, 4-38]. It is found that the Pauling rules for ionic crystals apply to all non-molecular borohydride crystal structures, and that the latter can often be derived by simple deformation of the close-packed anionic lattices c.c.p. and h.c.p., by partially removing anions and filling tetrahedral or octahedral sites. The deviation from an ideal close packing is facilitated in metal borohydrides with respect to the oxide due to geometrical and electronic considerations of the BH4(-) anion (tetrahedral shape, polarizability). This review on crystal chemistry of borohydrides and their similarity to oxides is a contribution which should serve materials engineers as a roadmap to design new materials, synthetic chemists in their search for promising compounds to be prepared, and materials scientists in understanding the properties of novel materials.

  15. High pressure synthesis gas fermentation

    SciTech Connect

    Not Available

    1992-01-01

    The construction of the high pressure gas phase fermentation system has been completed. Photographs of the various components of the system are presented, along with an operating procedure for the equipment.

  16. High Pressure Industrial Water Facility

    NASA Technical Reports Server (NTRS)

    1992-01-01

    In conjunction with Space Shuttle Main Engine testing at Stennis, the Nordberg Water Pumps at the High Pressure Industrial Water Facility provide water for cooling the flame deflectors at the test stands during test firings.

  17. Prediction of crystal structures from crystal chemistry rules by simulated annealing

    NASA Astrophysics Data System (ADS)

    Pannetier, J.; Bassas-Alsina, J.; Rodriguez-Carvajal, J.; Caignaert, V.

    1990-07-01

    THE prediction of the structure of inorganic crystalline solids from the knowledge of their chemical composition is still a largely unresolved problem1-3. The usual approach to this problem is to minimize, for a selection of candidate models, the potential energy of the system with respect to the structural parameters of these models: the solution is the arrangement that comes out lowest in energy. Methods using this procedure may differ in the origin (ab initio or empirical) of the interatomic potentials used, but they usually restrict themselves to optimizing a structural arrangement within the constraints of given symmetry and bond topology. As a result, they do not truly address the problem of predicting the unknown structure of a real compound. The method we describe here is an attempt at solving the following problem: given the chemical composition of a crystalline compound and the values of its unit-cell parameters, find its structure (topology and bond distances) by optimizing the arrangement of ions, atoms or molecules in accordance with a set of prescribed rules. The procedure uses simple, empirical crystal chemistry arguments (Pauling's principles for ionic compounds4) and a powerful stochastic search procedure, known as simulated annealing5 to identify the best atomic model or models. We discuss the potential of the method for structure determination and refinement, using results obtained for several known inorganic structures, and by the determination of a previously unknown structure. Although the approach is limited to the case of inorganic compounds, it is nevertheless very general, and would apply to any crystalline structure provided that the principles governing the architecture of the solid can be properly described.

  18. High pressure studies of potassium perchlorate

    DOE PAGES

    Pravica, Michael; Wang, Yonggang; Sneed, Daniel; ...

    2016-07-29

    Two experiments are reported on KClO4 at extreme conditions. A static high pressure Raman study was first conducted to 18.9 GPa. Evidence for at least two new phases was observed: one between 2.4 and 7.7 GPa (possibly sluggish), and the second near 11.7 GPa. Then, the X-ray induced decomposition rate of potassium perchlorate (KClO4 hv→ KCl + 2O2) was studied up to 15.2 GPa. The time-dependent growth of KCl and O2 was monitored. The decomposition rate slowed at higher pressures. As a result, we present the first direct evidence for O2 crystallization at higher pressures, demonstrating that O2 molecules aggregatemore » at high pressure.« less

  19. High pressure studies of potassium perchlorate

    SciTech Connect

    Pravica, Michael; Wang, Yonggang; Sneed, Daniel; Reiser, Sharissa; White, Melanie

    2016-07-29

    Two experiments are reported on KClO4 at extreme conditions. A static high pressure Raman study was first conducted to 18.9 GPa. Evidence for at least two new phases was observed: one between 2.4 and 7.7 GPa (possibly sluggish), and the second near 11.7 GPa. Then, the X-ray induced decomposition rate of potassium perchlorate (KClO4 hv→ KCl + 2O2) was studied up to 15.2 GPa. The time-dependent growth of KCl and O2 was monitored. The decomposition rate slowed at higher pressures. As a result, we present the first direct evidence for O2 crystallization at higher pressures, demonstrating that O2 molecules aggregate at high pressure.

  20. Crystal chemistry and structure refinement of five hydrated calcium borates

    USGS Publications Warehouse

    Clark, J.R.; Appleman, D.E.; Christ, C.L.

    1964-01-01

    The crystal structures of the five known members of the series Ca2B6O11??xH2O (x = 1, 5, 5, 7, 9, and 13) have been refined by full-matrix least-squares techniques, yielding bond distances and angles with standard errors of less than 0??01 A?? and 0??5??, respectively. The results illustrate the crystal chemical principles that govern the structures of hydrated borate compounds. The importance of hydrogen bonding in the ferroelectric transition of colemanite is confirmed by more accurate proton assignments. ?? 1964.

  1. High-pressure synthesis, crystal structure, and magnetic properties of KSbO3-type 5d oxides K0.84OsO3 and Bi2.93Os3O11

    PubMed Central

    Yuan, Yahua; Feng, Hai L; Shi, Youguo; Tsujimoto, Yoshihiro; Belik, Alexei A; Matsushita, Yoshitaka; Arai, Masao; He, Jianfeng; Tanaka, Masahiko; Yamaura, Kazunari

    2014-01-01

    5d Solid-state oxides K0.84OsO3 (Os5.16+; 5d 2.84) and Bi2.93Os3O11 (Os4.40+; 5d 3.60) were synthesized under high-pressure and high-temperature conditions (6 GPa and 1500–1700 °C). Their crystal structures were determined by synchrotron x-ray diffraction and their 5d electronic properties and tunnel-like structure motifs were investigated. A KSbO3-type structure with a space group of Im-3 and Pn-3 was determined for K0.84OsO3 and Bi2.93Os3O11, respectively. The magnetic and electronic transport properties of the polycrystalline compounds were compared with those obtained theoretically. It was revealed that the 5d tunnel-like structures are paramagnetic with metallic charge conduction at temperatures above 2 K. This was similar to what was observed for structurally relevant 5d oxides, including Bi3Re3O11 (Re4.33+; 5d 2.66) and Ba2Ir3O9 (Ir4.66+; 5d 4.33). The absence of long-range magnetic order seems to be common among 5d KSbO3-like oxides, regardless of the number of 5d electrons (between 2.6 and 4.3 per 5d atom). PMID:27877729

  2. Impact of crystal chemistry upon the physics of strongly correlated electrons in oxides.

    PubMed

    Raveau, Bernard

    2013-01-02

    Transition-metal oxides have been widely studied for understanding the physics of strongly electron-correlated systems. The crucial role of crystal chemistry for the discovery of three families: the high T(c) superconducting cuprates, the colossal magnetoresistance manganates, the thermoelectric, and multiferroic cobaltates, is explored. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Visualizing Molecular Chirality in the Organic Chemistry Laboratory Using Cholesteric Liquid Crystals

    ERIC Educational Resources Information Center

    Popova, Maia; Bretz, Stacey Lowery; Hartley, C. Scott

    2016-01-01

    Although stereochemistry is an important topic in second-year undergraduate organic chemistry, there are limited options for laboratory activities that allow direct visualization of macroscopic chiral phenomena. A novel, guided-inquiry experiment was developed that allows students to explore chirality in the context of cholesteric liquid crystals.…

  4. Visualizing Molecular Chirality in the Organic Chemistry Laboratory Using Cholesteric Liquid Crystals

    ERIC Educational Resources Information Center

    Popova, Maia; Bretz, Stacey Lowery; Hartley, C. Scott

    2016-01-01

    Although stereochemistry is an important topic in second-year undergraduate organic chemistry, there are limited options for laboratory activities that allow direct visualization of macroscopic chiral phenomena. A novel, guided-inquiry experiment was developed that allows students to explore chirality in the context of cholesteric liquid crystals.…

  5. Crystal chemistry of hydrothermally grown ternary alkali rare earth fluorides.

    PubMed

    McMillen, Colin D; Comer, Sara; Fulle, Kyle; Sanjeewa, Liurukara D; Kolis, Joseph W

    2015-12-01

    The structural variations of several alkali metal rare earth fluoride single crystals are summarized. Two different stoichiometric formulations are considered, namely those of ARE2F7 and ARE3F10 (A = K, Rb, Cs; RE = Y, La-Lu), over a wide range of ionic radii of both the alkali and rare earth (RE) ions. Previously reported and several new single-crystal structures are considered. The new single crystals are grown using hydrothermal methods and the structures are compared with literature reports of structures grown from both melts and hydrothermal fluids. The data reported here are combined with the literature data to gain a greater understanding of structural subtleties surrounding these systems. The work underscores the importance of the size of the cations to the observed structure type and also introduces synthetic technique as a contributor to the same. New insights based on single-crystal structure analysis in the work introduce a new disordered structure type in the case of ARE2F7, and examine the trends and boundaries of the ARE3F10 stoichiometry. Such fundamental structural information is useful in understanding the potential applications of these compounds as optical materials.

  6. Crystal Model Kits for Use in the General Chemistry Laboratory.

    ERIC Educational Resources Information Center

    Kildahl, Nicholas J.; And Others

    1986-01-01

    Dynamic crystal model kits are described. Laboratory experiments in which students use these kits to build models have been extremely successful in providing them with an understanding of the three-dimensional structures of the common cubic unit cells as well as hexagonal and cubic closest-packing of spheres. (JN)

  7. High pressure synthesis gas conversion. Task 3: High pressure profiles

    SciTech Connect

    Not Available

    1993-05-01

    The purpose of this research project was to build and test a high pressure fermentation system for the production of ethanol from synthesis gas. The fermenters, pumps, controls, and analytical system were procured or fabricated and assembled in our laboratory. This system was then used to determine the effects of high pressure on growth and ethanol production by C. 1jungdahlii. The limits of cell concentration and mass transport relationships were found in CSTR and immobilized cell reactors (ICR). The minimum retention times and reactor volumes were found for ethanol production in these reactors.

  8. High pressure synthesis and crystal structure of a ternary superconductor Ca{sub 2}Al{sub 3}Si{sub 4} containing layer structured calcium sub-network isomorphous with black phosphorus

    SciTech Connect

    Tanaka, Masashi; Zhang, Shuai; Tanaka, Yuki; Inumaru, Kei; Yamanaka, Shoji

    2013-02-15

    The Zintl compound CaAl{sub 2}Si{sub 2} is peritectically decomposed to a mixture of Ca{sub 2}Al{sub 3}Si{sub 4} and aluminum metal at temperatures above 600 Degree-Sign C under a pressure of 5 GPa. The new ternary compound Ca{sub 2}Al{sub 3}Sl{sub 4} crystalizes with the space group Cmc2{sub 1} and the lattice parameters a=5.8846(8), b=14.973(1), and c=7.7966(5) A. The structure is composed of aluminum silicide framework [Al{sub 3}Si{sub 4}] and layer structured [Ca{sub 2}] network interpenetrating with each other. The electron probe microanalysis (EPMA) shows the formation of solid solutions Ca{sub 2}Al{sub 3-x}Si{sub 4+x} (x<0.6). The layer structured [Ca{sub 2}] sub-network is isomorphous with black phosphorus. The new ternary compound shows superconductivity with a transition temperature (T{sub c}) of 6.4 K. The band structure calculation suggests that the superconductivity should occur through the conduction bands mainly composed of 3p orbitals of the aluminum silicide framework. - Graphical abstract: A new ternary superconductor Ca{sub 2}Al{sub 3}Si{sub 4} has been prepared under high pressure and high temperature conditions, which includes layer structured calcium sub-network isomorphous with black phosphorus. Highlights: Black-Right-Pointing-Pointer A typical Zintl compound CaAl{sub 2}Si{sub 2} melts congruently at ambient pressure. Black-Right-Pointing-Pointer Under high pressure CaAl{sub 2}Si{sub 2} decomposes to Ca{sub 2}Al{sub 3}Si{sub 4} and Al at {approx}600 Degree-Sign C. Black-Right-Pointing-Pointer Ca{sub 2}Al{sub 3}Si{sub 4} contains Ca sub-network isomorphous with black phosphorus. Black-Right-Pointing-Pointer Ca{sub 2}Al{sub 3}Si{sub 4} shows superconductivity with a transition temperature of 6.4 K.

  9. Crystal chemistry of ordered rocksalt-type Ca2NF

    NASA Astrophysics Data System (ADS)

    Al-Azzawi, Mohanad; Zeller, Matthias; Li, Dingqiang; Wagner, Timothy R.

    2017-10-01

    Ordered rocksalt-type Ca2NF has a cubic unit cell that is doubled along [100] relative to the rocksalt-type polymorph due to N/F ordering. Crystals for the present study were prepared from a pure, dry KCuF3 precursor by reaction with Ca metal under nitrogen, and analyzed via high resolution single crystal X-ray diffraction. From this analysis, as well as qualitative compositional analysis using energy dispersive spectroscopy, it was determined that interstitial fluoride ions previously interpreted as Frenkel defects are actually due to a non-stoichiometric defect. The refined composition is Ca2N0.925F1.23, and the ordered cubic phase has space group Fd 3 bar m (No. 227) with a = 10.0301(5) Å and Z = 16.

  10. GPCR crystal structures: Medicinal chemistry in the pocket.

    PubMed

    Shonberg, Jeremy; Kling, Ralf C; Gmeiner, Peter; Löber, Stefan

    2015-07-15

    Recent breakthroughs in GPCR structural biology have significantly increased our understanding of drug action at these therapeutically relevant receptors, and this will undoubtedly lead to the design of better therapeutics. In recent years, crystal structures of GPCRs from classes A, B, C and F have been solved, unveiling a precise snapshot of ligand-receptor interactions. Furthermore, some receptors have been crystallized in different functional states in complex with antagonists, partial agonists, full agonists, biased agonists and allosteric modulators, providing further insight into the mechanisms of ligand-induced GPCR activation. It is now obvious that there is enormous diversity in the size, shape and position of the ligand binding pockets in GPCRs. In this review, we summarise the current state of solved GPCR structures, with a particular focus on ligand-receptor interactions in the binding pocket, and how this can contribute to the design of GPCR ligands with better affinity, subtype selectivity or efficacy.

  11. Chemistry at high pressures and temperatures: in-situ synthesis and characterization of {beta}-Si{sub 3}N{sub 4} by DAC X-ray/laser-heating studies

    SciTech Connect

    Yoo, C.-S.; Akella, J.; Nicol, M.

    1996-01-01

    We have developed in-situ XRD technique at high pressures and temperatures by integrating the angle-resolved synchrotron XRD method, laser-heating system, and diamond anvil cell together. Using this technique, we have studied the direct elementary reactions of nitrogen with Si, yielding technologically important {beta}-Si{sub 3}N{sub 4}. These reactions do not occur at ambient temperatures at high pressures up to 50 GPa, but proceed exothermically at high temperatures at moderate pressures. It implies that the reaction is kinetically limited by a large activation barrier.

  12. Evolution of Effluent Chemistry at Crystal Geyser, Green River, Utah

    NASA Astrophysics Data System (ADS)

    Han, W. S.; Park, E.; Choung, S.; Kim, C. Y.; Piao, J.; Han, G.

    2016-12-01

    Several cold-water geysers and springs are located adjacent to the Green River in Utah where two major east-west faults, the Little Grand Wash and the Salt Wash Graben faults, trend roughly parallel to each other. Among these springs and geysers is Crystal Geyser, located immediately north of the Little Grand Wash fault and approximately 6 km south of the town of Green River. In this study, the fluid mechanics of the regularly erupting Crystal Geyser was investigated by instrumenting its conduit with pressure, temperature, pH, EC, and dissolved oxygen sensors, measuring every 1 minute during and between eruptions. The single eruption cycle at Crystal geyser lasted over four days and was composed of four parts: Minor Eruption (mEP), Major Eruption (MEP), Aftershock Eruption (Ae) and Recharge (R). Current eruption patterns exhibit a bimodal distribution although previous measurements and anecdotal evidence suggests that this pattern was different prior to recent seismic activity. Based on chemical characteristics, the primary sourcing aquifers characterized to be both Entrada and Navajo Sandstones with minor contribution from Paradox Formation brine. Contemporaneously, dissolved ionic species vary 0-44% while transition from mEP, MEP and R even if the degree of changes was different from individual ion. Generally, Na+, K+, Cl- and SO42- regularly decrease at the onset and throughout the MEP. These species then increase in concentration during the mEP. Conversely, Ca2+, Mg2+, Fe2+ and Sr2+ decrease and increase in concentration during the MEP and mEP, respectively. Inverse geochemical modeling was conducted to characterize the contribution of Crystal geyser effluents from endmembers of Entrada Sandstone, Navajo Sandstone and Paradox Formations. Results of inverse modeling show that, during the mEP, the Navajo, Entrada and brine supply 62-65%, 33-36% and 1%, respectively. During the MEP, the contribution shifts to 53-56%, 42-45% and 1% for the Navajo, Entrada and Brine

  13. Deformation Twinning of a Silver Nanocrystal under High Pressure

    SciTech Connect

    Huang, Xiaojing; Yang, Wenge; Harder, Ross; Sun, Yugang; Liu, Ming; Chu, Yong S.; Robinson, Ian K.; Mao, Ho-kwang

    2015-11-01

    Within a high-pressure environment, crystal deformation is controlled by complex processes such as dislocation motion, twinning, and phase transitions, which change materials' microscopic morphology and alter their properties. Understanding a crystal's response to external stress provides a unique opportunity for rational tailoring of its functionalities. It is very challenging to track the strain evolution and physical deformation from a single nanoscale crystal under high-pressure stress. Here, we report an in situ three-dimensional mapping of morphology and strain evolutions in a single-crystal silver nanocube within a high-pressure environment using the Bragg Coherent Diffractive Imaging (CDI) method. We observed a continuous lattice distortion, followed by a deformation twining process at a constant pressure. The ability to visualize stress-introduced deformation of nanocrystals with high spatial resolution and prominent strain sensitivity provides an important route for interpreting and engineering novel properties of nanomaterials.

  14. The High Pressure Nervous Syndrome and Other High Pressure Effects.

    DTIC Science & Technology

    Many of the problems of exposing man to a high pressure environment depend overtly on the properties of gases in the gaseous phase--such as the...or to changes in pressure. These are the subject of this chapter. The distinction is an arbitrary one, since both hyperbaric arthralgia and the high

  15. High pressure liquid level monitor

    DOEpatents

    Bean, Vern E.; Long, Frederick G.

    1984-01-01

    A liquid level monitor for tracking the level of a coal slurry in a high-pressure vessel including a toroidal-shaped float with magnetically permeable bands thereon disposed within the vessel, two pairs of magnetic field generators and detectors disposed outside the vessel adjacent the top and bottom thereof and magnetically coupled to the magnetically permeable bands on the float, and signal processing circuitry for combining signals from the top and bottom detectors for generating a monotonically increasing analog control signal which is a function of liquid level. The control signal may be utilized to operate high-pressure control valves associated with processes in which the high-pressure vessel is used.

  16. Electrokinetic high pressure hydraulic system

    DOEpatents

    Paul, Phillip H.; Rakestraw, David J.; Arnold, Don W.; Hencken, Kenneth R.; Schoeniger, Joseph S.; Neyer, David W.

    2003-06-03

    An electrokinetic high pressure hydraulic pump for manipulating fluids in capillary-based system. The pump uses electro-osmotic flow to provide a high pressure hydraulic system, having no moving mechanical parts, for pumping and/or compressing fluids, for providing valve means and means for opening and closing valves, for controlling fluid flow rate, and manipulating fluid flow generally and in capillary-based systems (microsystems), in particular. The compact nature of the inventive high pressure hydraulic pump provides the ability to construct a micro-scale or capillary-based HPLC system that fulfills the desire for small sample quantity, low solvent consumption, improved efficiency, the ability to run samples in parallel, and field portability. Control of pressure and solvent flow rate is achieved by controlling the voltage applied to an electrokinetic pump.

  17. Electrokinetic high pressure hydraulic system

    DOEpatents

    Paul, Phillip H.; Rakestraw, David J.; Arnold, Don W.; Hencken, Kenneth R.; Schoeniger, Joseph S.; Neyer, David W.

    2001-01-01

    An electrokinetic high pressure hydraulic pump for manipulating fluids in capillary-based systems. The pump uses electro-osmotic flow to provide a high pressure hydraulic system, having no moving mechanical parts, for pumping and/or compressing fluids, for providing valve means and means for opening and closing valves, for controlling fluid flow rate, and manipulating fluid flow generally and in capillary-based systems (Microsystems), in particular. The compact nature of the inventive high pressure hydraulic pump provides the ability to construct a micro-scale or capillary-based HPLC system that fulfills the desire for small sample quantity, low solvent consumption, improved efficiency, the ability to run samples in parallel, and field portability. Control of pressure and solvent flow rate is achieved by controlling the voltage applied to an electrokinetic pump.

  18. Exotic stable cesium polynitrides at high pressure

    PubMed Central

    Peng, Feng; Han, Yunxia; Liu, Hanyu; Yao, Yansun

    2015-01-01

    New polynitrides containing metastable forms of nitrogen are actively investigated as potential high-energy-density materials. Using a structure search method based on the CALYPSO methodology, we investigated the stable stoichiometries and structures of cesium polynitrides at high pressures. Along with the CsN3, we identified five new stoichiometric compounds (Cs3N, Cs2N, CsN, CsN2, and CsN5) with interesting structures that may be experimentally synthesizable at modest pressures (i.e., less than 50 GPa). Nitrogen species in the predicted structures have various structural forms ranging from single atom (N) to highly endothermic molecules (N2, N3, N4, N5, N6) and chains (N∞). Polymeric chains of nitrogen were found in the high-pressure C2/c phase of CsN2. This structure contains a substantially high content of single N-N bonds that exceeds the previously known nitrogen chains in pure forms, and also exhibit metastability at ambient conditions. We also identified a very interesting CsN crystal that contains novel N44− anion. To our best knowledge, this is the first time a charged N4 species being reported. Results of the present study suggest that it is possible to obtain energetic polynitrogens in main-group nitrides under high pressure. PMID:26581175

  19. Exotic stable cesium polynitrides at high pressure

    DOE PAGES

    Peng, Feng; Han, Yunxia; Liu, Hanyu; ...

    2015-11-19

    New polynitrides containing metastable forms of nitrogen are actively investigated as potential high energy-density materials. Using a structure search method based on the CALYPSO methodology, we investigated the stable stoichiometries and structures of cesium polynitrides at high pressures. Along with the CsN3, we identified five new stoichiometric compounds (Cs3N, Cs2N, CsN, CsN2, and CsN5) with interesting structures that may be experimentally synthesizable at modest pressures (i.e., less than 50 GPa). Nitrogen species in the predicted structures have various structural forms ranging from single atom (N) to highly endothermic molecules (N2, N3 , N4, N5, N6) and chains (N∞). Polymeric chainsmore » of nitrogen were found in the high-pressure C2/c phase of CsN2. This structure contains a substantially high content of single N-N bonds that exceeds the previously known nitrogen chains in pure forms, and also exhibit metastability at ambient conditions. We also identified a very interesting CsN crystal that contains novel N44- anion. In conclusion, to our best knowledge, this is the first time a charged N4 species being reported. Results of the present study suggest that it is possible to obtain energetic polynitrogens in main-group nitrides under high pressure.« less

  20. Crystallographic Structure, Intermolecular Packing Energetics, Crystal Morphology and Surface Chemistry of Salmeterol Xinafoate (Form I).

    PubMed

    Moldovan, Alexandru A; Rosbottom, Ian; Ramachandran, Vasuki; Pask, Christopher M; Olomukhoro, Oboroghene; Roberts, Kevin J

    2017-03-01

    Single crystals of salmeterol xinafoate (form I), prepared from slow cooled supersaturated propan-2-ol solutions, crystallize in a triclinic P1¯ symmetry with 2 closely related independent salt pairs within the asymmetric unit, with an approximately double-unit cell volume compared with the previously published crystal structure. Synthonic analysis of the bulk intermolecular packing confirms the similarity in packing energetics between the 2 salt pairs. The strongest synthons, as expected, are dominated by coulombic interactions. Morphologic prediction reveals a plate-like morphology, dominated by the {001}, {010}, and {100} surfaces, consistent with experimentally grown crystals. Although surface chemistry of the slow-growing {001} face comprises large sterically hindering phenyl groups, although weaker coulombic interactions still prevail from the alcohol group present on the phenyl and hydroxymethyl groups. The surface chemistry of the faster growing {010} and {100} faces are dominated by the significantly stronger cation/anion interactions occurring between the carboxylate and protonated secondary ammonium ion groups. The importance of understanding the cohesive and adhesive nature of the crystal surfaces of an active pharmaceutical ingredient, with respect to their interaction with other active pharmaceutical ingredient crystals and how that may affect formulation design, is highlighted.

  1. High pressure synthesis gas fermentation

    SciTech Connect

    Not Available

    1991-01-01

    Construction of the high pressure gas phase fermentation system is nearing completion. All non-explosion proof components will be housed separately in a gas-monitored plexiglas cabinet. A gas-monitoring system has been designed to ensure the safety of the operations in case of small or large accidental gas releases. Preliminary experiments investigating the effects of high pressure on Clostridium 1jungdahlii have shown that growth and CO uptake are not negatively affected and CO uptake by an increased total pressure of 100 psig at a syngas partial pressure of 10 psig.

  2. Nanomaterials under high-pressure.

    PubMed

    San-Miguel, Alfonso

    2006-10-01

    The use of high-pressure for the study and elaboration of homogeneous nanostructures is critically reviewed. Size effects, the interaction between nanostructures and guest species or the interaction of the nanosystem with the pressure transmitting medium are emphasized. Phase diagrams and the possibilities opened by the combination of pressure and temperature for the elaboration of new nanomaterials is underlined through the examination of three different systems: nanocrystals, nano-cage materials which include fullerites and group-14 clathrates, and single wall nanotubes. This tutorial review is addressed to scientist seeking an introduction or a panoramic view of the study of nanomaterials under high-pressure.

  3. Electrokinetic high pressure hydraulic system

    DOEpatents

    Paul, Phillip H.; Rakestraw, David J.

    2000-01-01

    A compact high pressure hydraulic pump having no moving mechanical parts for converting electric potential to hydraulic force. The electrokinetic pump, which can generate hydraulic pressures greater than 2500 psi, can be employed to compress a fluid, either liquid or gas, and manipulate fluid flow. The pump is particularly useful for capillary-base systems. By combining the electrokinetic pump with a housing having chambers separated by a flexible member, fluid flow, including high pressure fluids, is controlled by the application of an electric potential, that can vary with time.

  4. Water solubility in pyrope at high pressures

    NASA Astrophysics Data System (ADS)

    Mookherjee, M.; Karato, S.-

    2006-12-01

    To address how much water is stored within the Earth's mantle, we need to understand the water solubility in the nominally anhydrous minerals. Much is known about olivine and pyroxene. Garnet is another important component, approaching 40% by volume in the transition zone. Only two studies on water solubility in pyrope at high-pressures exist which contradict each other. Lu and Keppler (1997) observed increase in water solubility in a natural pyrope up to 200 ppm wt of water, till 10 GPa. They concluded that the proton is located in the interstitial site. Withers et al. (1998) on the contrary, observed increasing water content in Mg-rich pyrope till 6 GPa, then sudden decrease of water, beyond detection, at 7 GPa. Based on infrared spectra, Withers et al. (1998), concluded hydrogarnet (Si^{4+} replaced by 4H+ to form O4H4) substitution in synthetic magnesium rich pyrope. They argued that at high pressure owing to larger volume, hydrogarnet substitution is unstable and water is expelled out of garnet. In transition zone conditions, however, majorite garnet seems to contain around 600-700 ppm wt of water (Bolfan-Casanova et al. 2000; Katayama et al. 2003). The cause for such discrepancy is not clear and whether garnet could store a significant amount of water at mantle condition is unconstrained. In order to understand the solubility mechanism of water in pyrope at high-pressure, we have conducted high- pressure experiments on naturally occurring single crystals of pyrope garnet (from Arizona, Aines and Rossman, 1984). To ascertain water-saturated conditions, we use olivine single-crystal as an internal standard. Preliminary results indicate that natural pyrope is capable of dissolving water at high-pressures, however, water preferentially enters olivine than in pyrope. We are undertaking systematic study to estimate the solubility of water in pyrope as a function of pressure. This will enable us to develop solubility models to understand the defect mechanisms

  5. Crystal Chemistry, Synthesis, and Characterization of Infrared Optical Materials

    DTIC Science & Technology

    1988-01-01

    elemental analysis . FfIR. ano thermogravimemc analysis . I.N-FRODUCTON Compounds that are candidates for use as long-waveleng-th (8-12 in) infrared...structure. It is likely. t±.erefore. that this report of Caln-S4 is erroneous. ana that the reported diffracuon data correspond to in2S3 . A compound ,. .n...Accurate elemental compositions of crystals thought to be new compounds were determined by ICP emission analysis dCAP/OES. Perkin Elmer 6500). Oxidative

  6. High-pressure water facility

    NASA Technical Reports Server (NTRS)

    2006-01-01

    NASA Test Operations Group employees, from left, Todd Pearson, Tim Delcuze and Rodney Wilkinson maintain a water pump in Stennis Space Center's high-pressure water facility. The three were part of a group of employees who rode out Hurricane Katrina at the facility and helped protect NASA's rocket engine test complex.

  7. High-pressure water facility

    NASA Image and Video Library

    2006-02-15

    NASA Test Operations Group employees, from left, Todd Pearson, Tim Delcuze and Rodney Wilkinson maintain a water pump in Stennis Space Center's high-pressure water facility. The three were part of a group of employees who rode out Hurricane Katrina at the facility and helped protect NASA's rocket engine test complex.

  8. High pressure neon arc lamp

    DOEpatents

    Sze, Robert C.; Bigio, Irving J.

    2003-07-15

    A high pressure neon arc lamp and method of using the same for photodynamic therapies is provided. The high pressure neon arc lamp includes a housing that encloses a quantity of neon gas pressurized to about 500 Torr to about 22,000 Torr. At each end of the housing the lamp is connected by electrodes and wires to a pulse generator. The pulse generator generates an initial pulse voltage to breakdown the impedance of the neon gas. Then the pulse generator delivers a current through the neon gas to create an electrical arc that emits light having wavelengths from about 620 nanometers to about 645 nanometers. A method for activating a photosensitizer is provided. Initially, a photosensitizer is administered to a patient and allowed time to be absorbed into target cells. Then the high pressure neon arc lamp is used to illuminate the target cells with red light having wavelengths from about 620 nanometers to about 645 nanometers. The red light activates the photosensitizers to start a chain reaction that may involve oxygen free radicals to destroy the target cells. In this manner, a high pressure neon arc lamp that is inexpensive and efficiently generates red light useful in photodynamic therapy is provided.

  9. High-pressure water facility

    NASA Technical Reports Server (NTRS)

    2006-01-01

    NASA Test Operations Group employees, from left, Todd Pearson, Tim Delcuze and Rodney Wilkinson maintain a water pump in Stennis Space Center's high-pressure water facility. The three were part of a group of employees who rode out Hurricane Katrina at the facility and helped protect NASA's rocket engine test complex.

  10. High pressure paint gun injuries.

    PubMed

    Booth, C M

    1977-11-19

    Despite their use for the past 20 years the dangers of injuries from high pressure paint guns are not widely known. Two cases treated incorrectly through ignorance in our casualty department resulted in amputation of digits. Paint solvents are far moe damaging than paint of grease injection. All cases should be treated urgently by an experienced surgeon as fairly extensive surgery may be needed.

  11. High-pressure synthesis, crystal structures, and magnetic properties of 5d double-perovskite oxides Ca2MgOsO6 and Sr2MgOsO6.

    PubMed

    Yuan, Yahua; Feng, Hai L; Ghimire, Madhav Prasad; Matsushita, Yoshitaka; Tsujimoto, Yoshihiro; He, Jianfeng; Tanaka, Masahiko; Katsuya, Yoshio; Yamaura, Kazunari

    2015-04-06

    Double-perovskite oxides Ca2MgOsO6 and Sr2MgOsO6 have been synthesized under high-pressure and high-temperature conditions (6 GPa and 1500 °C). Their crystal structures and magnetic properties were studied by a synchrotron X-ray diffraction experiment and by magnetic susceptibility, specific heat, isothermal magnetization, and electrical resistivity measurements. Ca2MgOsO6 and Sr2MgOsO6 crystallized in monoclinic (P21/n) and tetragonal (I4/m) double-perovskite structures, respectively; the degree of order of the Os and Mg arrangement was 96% or higher. Although Ca2MgOsO6 and Sr2MgOsO6 are isoelectric, a magnetic-glass transition was observed for Ca2MgOsO6 at 19 K, while Sr2MgOsO6 showed an antiferromagnetic transition at 110 K. The antiferromagnetic-transition temperature is the highest in the family. A first-principles density functional approach revealed that Ca2MgOsO6 and Sr2MgOsO6 are likely to be antiferromagnetic Mott insulators in which the band gaps open, with Coulomb correlations of ∼1.8-3.0 eV. These compounds offer a better opportunity for the clarification of the basis of 5d magnetic sublattices, with regard to the possible use of perovskite-related oxides in multifunctional devices. The double-perovskite oxides Ca2MgOsO6 and Sr2MgOsO6 are likely to be Mott insulators with a magnetic-glass (MG) transition at ∼19 K and an antiferromagnetic (AFM) transition at ∼110 K, respectively. This AFM transition temperature is the highest among double-perovskite oxides containing single magnetic sublattices. Thus, these compounds offer valuable opportunities for studying the magnetic nature of 5d perovskite-related oxides, with regard to their possible use in multifunctional devices.

  12. Cold chemistry with electronically excited Ca{sup +} Coulomb crystals

    SciTech Connect

    Gingell, Alexander D.; Bell, Martin T.; Oldham, James M.; Softley, Timothy P.; Harvey, Jeremy N.

    2010-11-21

    Rate constants for chemical reactions of laser-cooled Ca{sup +} ions and neutral polar molecules (CH{sub 3}F, CH{sub 2}F{sub 2}, or CH{sub 3}Cl) have been measured at low collision energies (/k{sub B}=5-243 K). Low kinetic energy ensembles of {sup 40}Ca{sup +} ions are prepared through Doppler laser cooling to form ''Coulomb crystals'' in which the ions form a latticelike arrangement in the trapping potential. The trapped ions react with translationally cold beams of polar molecules produced by a quadrupole guide velocity selector or with room-temperature gas admitted into the vacuum chamber. Imaging of the Ca{sup +} ion fluorescence allows the progress of the reaction to be monitored. Product ions are sympathetically cooled into the crystal structure and are unambiguously identified through resonance-excitation mass spectrometry using just two trapped ions. Variations of the laser-cooling parameters are shown to result in different steady-state populations of the electronic states of {sup 40}Ca{sup +} involved in the laser-cooling cycle, and these are modeled by solving the optical Bloch equations for the eight-level system. Systematic variation of the steady-state populations over a series of reaction experiments allows the extraction of bimolecular rate constants for reactions of the ground state ({sup 2}S{sub 1/2}) and the combined excited states ({sup 2}D{sub 3/2} and {sup 2}P{sub 1/2}) of {sup 40}Ca{sup +}. These results are analyzed in the context of capture theories and ab initio electronic structure calculations of the reaction profiles. In each case, suppression of the ground state rate constant is explained by the presence of a submerged or real barrier on the ground state potential surface. Rate constants for the excited states are generally found to be in line with capture theories.

  13. Mineral chemistry of the Tissint meteorite: Indications of two-stage crystallization in a closed system

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Baziotis, Ioannis P.; Asimow, Paul D.; Bodnar, Robert J.; Taylor, Lawrence A.

    2016-12-01

    The Tissint meteorite is a geochemically depleted, olivine-phyric shergottite. Olivine megacrysts contain 300-600 μm cores with uniform Mg# ( 80 ± 1) followed by concentric zones of Fe-enrichment toward the rims. We applied a number of tests to distinguish the relationship of these megacrysts to the host rock. Major and trace element compositions of the Mg-rich core in olivine are in equilibrium with the bulk rock, within uncertainty, and rare earth element abundances of melt inclusions in Mg-rich olivines reported in the literature are similar to those of the bulk rock. Moreover, the P Kα intensity maps of two large olivine grains show no resorption between the uniform core and the rim. Taken together, these lines of evidence suggest the olivine megacrysts are phenocrysts. Among depleted olivine-phyric shergottites, Tissint is the first one that acts mostly as a closed system with olivine megacrysts being the phenocrysts. The texture and mineral chemistry of Tissint indicate a crystallization sequence of: olivine (Mg# 80 ± 1) → olivine (Mg# 76) + chromite → olivine (Mg# 74) + Ti-chromite → olivine (Mg# 74-63) + pyroxene (Mg# 76-65) + Cr-ulvöspinel → olivine (Mg# 63-35) + pyroxene (Mg# 65-60) + plagioclase, followed by late-stage ilmenite and phosphate. The crystallization of the Tissint meteorite likely occurred in two stages: uniform olivine cores likely crystallized under equilibrium conditions; and a fractional crystallization sequence that formed the rest of the rock. The two-stage crystallization without crystal settling is simulated using MELTS and the Tissint bulk composition, and can broadly reproduce the crystallization sequence and mineral chemistry measured in the Tissint samples. The transition between equilibrium and fractional crystallization is associated with a dramatic increase in cooling rate and might have been driven by an acceleration in the ascent rate or by encounter with a steep thermal gradient in the Martian crust.

  14. Deformation Twinning of a Silver Nanocrystal under High Pressure

    SciTech Connect

    Huang, Xiaojing; Yang, Wenge; Harder, Ross; Sun, Yugang; Lu, Ming; Chu, Yong S.; Robinson, Ian K.; Mao, Ho-kwang

    2015-10-20

    Within a high-pressure environment, crystal deformation is controlled by complex processes such as dislocation motion, twinning, and phase transitions, which change materials’ microscopic morphology and alter their properties. Understanding a crystal’s response to external stress provides a unique opportunity for rational tailoring of its functionalities. It is very challenging to track the strain evolution and physical deformation from a single nanoscale crystal under high-pressure stress. Here, we report an in situ three-dimensional mapping of morphology and strain evolutions in a single-crystal silver nanocube within a high-pressure environment using the Bragg Coherent Diffractive Imaging (CDI) method. We observed a continuous lattice distortion, followed by a deformation twining process at a constant pressure. The ability to visualize stress-introduced deformation of nanocrystals with high spatial resolution and prominent strain sensitivity provides an important route for interpreting and engineering novel properties of nanomaterials.

  15. Development of high pressure gas cells at ISIS

    NASA Astrophysics Data System (ADS)

    Kirichek, O.; Done, R.; Goodway, C. M.; Kibble, M. G.; Evans, B.; Bowden, Z. A.

    2012-02-01

    High-pressure research is one of the fastest-growing areas of natural science, and one that attracts as diverse communities as those of physics, bio-physics, chemistry, materials science and earth science. In condensed matter physics there are a number of highly topical areas, such as quantum criticality, pressure-induced superconductivity or non-Fermi liquid behaviour, where pressure is a fundamental parameter. Reliable, safe and user-friendly high pressure gas handling systems with gas pressures up to 1GPa should make a significant impact on the range of science possible. The ISIS facility is participating in the NMI3 FP7 sample environment project supported by the European Commission which includes high pressure gas cell development. In this paper the progress in designing, manufacturing and testing a new generation of high pressure gas cells for neutron scattering experiments is discussed.

  16. [Study on crystal chemistry and spectra of feldspar from Zhoukoudian granodiorite].

    PubMed

    Zhang, Yong-wang; Zeng, Jian-hui; Liu, Yan; Guo, Jian-yu

    2009-09-01

    The chemical composition and spectra characteristic of feldspar from Zhoukoudian granodiorite were systematically analyzed. Based on the field work, some feldspar samples were selected for crystal chemistry and structure analysis through EMPA, IR, LRM and XRD. The compositions of the feldspar range between Ab (85.21) Or (0.18) An (9.11) and Ab (90.06) Or (3.00) An (13.27) by electronic microscope probe analysis. According to the XRD peak and its diffraction intensity, the mineral species was found the unit cell parameters were calculated. The absorption bands and peaks of infrared and Raman spectra were also assigned and the results show that the characteristics of its infrared and Raman spectra are in accordance with the ideal atlas of albite. The infrared spectra show that all the analyzed feldspar grains contain structural hydrogen, which occur as OH-. On the basis of the above analyses, the crystal chemistry and structure characteristics of feldspar were summarized.

  17. Measurement of the Order Parameter in a Room Temperature Liquid Crystal: An Experiment for the Physical Chemistry Laboratory.

    ERIC Educational Resources Information Center

    DuPre, Donald B.; Chapoy, L. Lawrence

    1979-01-01

    Presented here is a laboratory experiment for a course in physical chemistry. Students are requested to directly measure the degree of orientational order in a liquid crystal at room temperature. A minimum amount of equipment is necessary. (Author/SA)

  18. High-temperature vesuvianite: crystal chemistry and surface considerations

    NASA Astrophysics Data System (ADS)

    Elmi, Chiara; Brigatti, Maria Franca; Pasquali, Luca; Montecchi, Monica; Laurora, Angela; Malferrari, Daniele; Nannarone, Stefano

    2011-06-01

    A multi-methodical approach has been applied for characterizing the bulk and surface crystal chemical features of a high-temperature vesuvianite crystal from skarns of Mount Somma-Vesuvius Volcano (Naples, Italy). Vesuvianite belongs to the space group P4/ nnc with unit cell parameters a = 15.633(1) Å, c = 11.834(1) Å and chemical formula (Ca18.858 Na0.028 Ba0.004 K0.006 Sr0.005 □0.098)19.000 (Al8.813 Ti0.037 Mg2.954 Mn0.008 Fe{0.114/2+} Fe{1.375/3+} Cr0.008 B0.202)13.511 Si18.000(O0.261 F0.940 OH7.799)9.000. Structure refinement, which converges at R = 0.0328, demonstrates a strong positional disorder down the fourfold axes, indicating that the Y1 site is split into two positions (Y1A and Y1B) alternatively occupied. However, because of X4 proximity to Y1B and Y1A, X4 cannot be occupied if Y1B or Y1A are. Overall Y1 occupancy (Y1A + Y1B) reaches approximately 0.5, as common in vesuvianite and occupancy of Y1B site is extremely limited. Moreover, T1 position, limitedly occupied, accommodates the excess of cations generally related to Y position. A small quantity (0.202 apfu) of boron is sited at the T2 site that, like T1, is poorly occupied. The determination of the amount of each element on the (100) vesuvianite surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si2p, Al2p, Mg1s, and Ca2p core levels, evidences that a greater amount of aluminum and a smaller amount of calcium characterize the surface with respect to the bulk. Although both of these features require further investigation, we may consider the Al increase can be related to preferential orientation of Al-rich sites on the (100) plane. Furthermore, the surface structure of vesuvianite suggests that Al, Ca, and Mg cations maintain coordination features at the surface similar to the bulk. Silica, however, while presenting fourfold coordination, shows also a [1]-fold small coordinated component at binding energy 99.85 eV, due to broken Si-O bonds at

  19. High-pressure injection injuries.

    PubMed

    Neal, N C; Burke, F D

    1991-11-01

    A retrospective review of the 11 patients attending the Hand Unit at the Derbyshire Royal Infirmary over the last 5 years with high-pressure injection injuries is presented. The machines and materials that cause these injuries are outlined and the methods of treatment and rehabilitation are described in detail. The study demonstrates the morbidity of high-pressure injection injuries, particularly those inflicted by paint spray guns, and highlights a frequent delay between injury and decompression of the injured part. We wish to emphasize the importance of early diagnosis, referral, exploration and rehabilitation to ensure an optimal outcome, and to point out that failure to refer early is becoming an increasing focus of negligence claims.

  20. High-pressure creep tests

    NASA Technical Reports Server (NTRS)

    Bhattacharyya, S.; Lamoureux, J.; Hales, C.

    1986-01-01

    The automotive Stirling engine, presently being developed by the U.S. Department of Energy and NASA, uses high-pressure hydrogen as a working fluid; its long-term effects on the properties of alloys are relatively unknown. Hence, creep-rupture testing of wrought and cast high-temperature alloys in high-pressure hydrogen is an essential part of the research supporting the development of the Stirling cycle engine. Attention is given to the design, development, and operation of a 20 MPa hydrogen high-temperature multispecimen creep-rupture possessing high sensitivity. This pressure vessel allows for the simultaneous yet independent testing of six specimens. The results from one alloy, XF-818, are presented to illustrate how reported results are derived from the raw test data.

  1. Cryogenic High Pressure Sensor Module

    NASA Technical Reports Server (NTRS)

    Chapman, John J. (Inventor); Shams, Qamar A. (Inventor); Powers, William T. (Inventor)

    1999-01-01

    A pressure sensor is provided for cryogenic, high pressure applications. A highly doped silicon piezoresistive pressure sensor is bonded to a silicon substrate in an absolute pressure sensing configuration. The absolute pressure sensor is bonded to an aluminum nitride substrate. Aluminum nitride has appropriate coefficient of thermal expansion for use with highly doped silicon at cryogenic temperatures. A group of sensors, either two sensors on two substrates or four sensors on a single substrate are packaged in a pressure vessel.

  2. Cryogenic, Absolute, High Pressure Sensor

    NASA Technical Reports Server (NTRS)

    Chapman, John J. (Inventor); Shams. Qamar A. (Inventor); Powers, William T. (Inventor)

    2001-01-01

    A pressure sensor is provided for cryogenic, high pressure applications. A highly doped silicon piezoresistive pressure sensor is bonded to a silicon substrate in an absolute pressure sensing configuration. The absolute pressure sensor is bonded to an aluminum nitride substrate. Aluminum nitride has appropriate coefficient of thermal expansion for use with highly doped silicon at cryogenic temperatures. A group of sensors, either two sensors on two substrates or four sensors on a single substrate are packaged in a pressure vessel.

  3. High pressure rinsing system comparison

    SciTech Connect

    D. Sertore; M. Fusetti; P. Michelato; Carlo Pagani; Toshiyasu Higo; Jin-Seok Hong; K. Saito; G. Ciovati; T. Rothgeb

    2007-06-01

    High pressure rinsing (HPR) is a key process for the surface preparation of high field superconducting cavities. A portable apparatus for the water jet characterization, based on the transferred momentum between the water jet and a load cell, has been used in different laboratories. This apparatus allows to collected quantitative parameters that characterize the HPR water jet. In this paper, we present a quantitative comparison of the different water jet produced by various nozzles routinely used in different laboratories for the HPR process

  4. High pressure paint gun injuries.

    PubMed Central

    Booth, C M

    1977-01-01

    Despite their use for the past 20 years the dangers of injuries from high pressure paint guns are not widely known. Two cases treated incorrectly through ignorance in our casualty department resulted in amputation of digits. Paint solvents are far moe damaging than paint of grease injection. All cases should be treated urgently by an experienced surgeon as fairly extensive surgery may be needed. Images FIG 1 FIG 2 FIG 3 FIG 4 PMID:589172

  5. The facile and low temperature synthesis of nanophase hydroxyapatite crystals using wet chemistry.

    PubMed

    Dhand, Vivek; Rhee, K Y; Park, Soo-Jin

    2014-03-01

    A simple and facile wet chemistry route was used to synthesize nanophase hydroxyapatite (HaP) crystals at low temperature. The synthesis was carried out at a pH of 11.0 and at a temperature of 37°C. The resulting samples were washed several times and subjected to further analysis. XRD studies revealed that the HaP crystals were polycrystalline in nature with a crystallite size of ~15-60 ± 5 nm. SEM-EDXA images confirmed the presence of calcium (Ca), phosphorous (P), and oxygen (O) peaks. Likewise, FTIR confirmed the presence of characteristic phosphate and hydroxyl peaks in samples. Lastly, HRTEM images clearly showed distinctive lattice fringes positioned in the 100 and 002 planes. TGA analysis shows that HaP crystals can withstand higher calcination temperatures and are thermally stable.

  6. Synchrotron radiation and high pressure: new light on materials under extreme conditions.

    PubMed

    Hemley, Russell J; Mao, Ho-kwang; Struzhkin, Viktor V

    2005-03-01

    With the steady development of static high-pressure techniques in recent years, it is now possible to probe in increasing detail the novel behavior of materials subjected to extreme conditions of multimegabar pressures (>300 GPa) and temperatures from cryogenic states to thousands of degrees. By and large, the growth in this area has been made possible by accelerating developments in diamond-anvil cell methods coupled with new synchrotron radiation techniques. Significant advances have occurred in high-pressure powder and single-crystal diffraction, spectroscopy, inelastic scattering, radiography, and infrared spectroscopy. A brief overview of selected highlights in each of these classes of experiments is presented that illustrate both the state-of-the-art as well as current technical and scientific challenges. The experiments have been made possible by the development of a spectrum of new techniques at both third- and second-generation high-energy sources together with key advances in high-pressure technology. The results have implications for a variety of problems in physics, chemistry, materials science, geoscience, planetary science, and biology.

  7. Exotic stable cesium polynitrides at high pressure

    SciTech Connect

    Peng, Feng; Han, Yunxia; Liu, Hanyu; Yao, Yansun

    2015-11-19

    New polynitrides containing metastable forms of nitrogen are actively investigated as potential high energy-density materials. Using a structure search method based on the CALYPSO methodology, we investigated the stable stoichiometries and structures of cesium polynitrides at high pressures. Along with the CsN3, we identified five new stoichiometric compounds (Cs3N, Cs2N, CsN, CsN2, and CsN5) with interesting structures that may be experimentally synthesizable at modest pressures (i.e., less than 50 GPa). Nitrogen species in the predicted structures have various structural forms ranging from single atom (N) to highly endothermic molecules (N2, N3 , N4, N5, N6) and chains (N). Polymeric chains of nitrogen were found in the high-pressure C2/c phase of CsN2. This structure contains a substantially high content of single N-N bonds that exceeds the previously known nitrogen chains in pure forms, and also exhibit metastability at ambient conditions. We also identified a very interesting CsN crystal that contains novel N44- anion. In conclusion, to our best knowledge, this is the first time a charged N4 species being reported. Results of the present study suggest that it is possible to obtain energetic polynitrogens in main-group nitrides under high pressure.

  8. New trends in chemistry and materials science in extremely tight space

    SciTech Connect

    Song, Yang; Manaa, M. Riad

    2012-01-26

    Pressure plays a critical role in regulating the structures and properties of materials. Since Percy Bridgeman was recognized by the 1946 Nobel Prize in Physics for his contribution in high-pressure physics, high-pressure research has remained an interdisciplinary scientific frontier with many extraordinary breakthroughs. Over the past decade or so, in particular, high-pressure chemistry and materials research has undergone major advances with the discovery of numerous exotic structures and properties. Furthermore, brand new classes of inorganic materials of unusual stoichiometries and crystal structures, which have a wide range of optical, mechanical, electronic and magnetic properties, have been produced at high pressures.

  9. New trends in chemistry and materials science in extremely tight space

    DOE PAGES

    Song, Yang; Manaa, M. Riad

    2012-01-26

    Pressure plays a critical role in regulating the structures and properties of materials. Since Percy Bridgeman was recognized by the 1946 Nobel Prize in Physics for his contribution in high-pressure physics, high-pressure research has remained an interdisciplinary scientific frontier with many extraordinary breakthroughs. Over the past decade or so, in particular, high-pressure chemistry and materials research has undergone major advances with the discovery of numerous exotic structures and properties. Furthermore, brand new classes of inorganic materials of unusual stoichiometries and crystal structures, which have a wide range of optical, mechanical, electronic and magnetic properties, have been produced at high pressures.

  10. Stable Lithium Argon compounds under high pressure

    PubMed Central

    Li, Xiaofeng; Hermann, Andreas; Peng, Feng; Lv, Jian; Wang, Yanchao; Wang, Hui; Ma, Yanming

    2015-01-01

    High pressure can fundamentally alter the bonding patterns of chemical elements. Its effects include stimulating elements thought to be “inactive” to form unexpectedly stable compounds with unusual chemical and physical properties. Here, using an unbiased structure search method based on CALYPSO methodology and density functional total energy calculations, the phase stabilities and crystal structures of Li−Ar compounds are systematically investigated at high pressure up to 300 GPa. Two unexpected LimArn compounds (LiAr and Li3Ar) are predicted to be stable above 112 GPa and 119 GPa, respectively. A detailed analysis of the electronic structure of LiAr and Li3Ar shows that Ar in these compounds attracts electrons and thus behaves as an oxidizing agent. This is markedly different from the hitherto established chemical reactivity of Ar. Moreover, we predict that the P4/mmm phase of Li3Ar has a superconducting transition temperature of 17.6 K at 120 GPa. PMID:26582083

  11. Electrochemical studies at high pressure

    SciTech Connect

    Cruanes, M.T.

    1993-01-01

    This research has dealt with the development and application of a methodology that permits electrochemical measurements at high pressure. The initial efforts focused on the design and construction of an electrochemical cell functional at hydrostatic pressures as high as 10 kbar. This cell was equipped with an Ag/AgCl/KCl (0.1M) reference electrode which provides reliable control of the potential at all pressures. The potential of this reference electrode can be considered to be constant with pressure. Measurements of formal potentials (E[degrees][prime]) of several transition-metal complexes vs the Ag/AgCl electrode rendered volumes of reactions whose magnitudes support the prediction of the negligible pressure dependence of the reference electrode. The main systems that have been investigated at high pressure are surface-modified electrodes. The author studied the effect of compression on the dynamics of charge transport in quaternized poly(4-vinylpyridine) (QPVP) films placed on gold electrodes, loaded with potassium ferricyanide, and equilibrated in potassium nitrate. Pressure accomplished the continuous change in the structure of the polymer network. This change causes a pronounced restriction in the propagation of charge and in the motion of mass. This high-pressure methodology has also allowed the spatial characterization of electron transfer events taking place between a gold electrode and ferrocene molecules covalently attached to the end of 1-undodecanethiol chains self-assembled on the electrode surface. The volumes of reaction and activation for the oxidation process are both positive, indicating that a volume expansion is associated with the formation of ferricinium. A model is proposed in which the creation of a vacancy in the self-assembled monolayer, for the accommodation of the ferricinium ion or a charge-compensating anion, is coupled with the electron transfer step.

  12. Crystal structure of coesite, a high-pressure form of SiO/sub 2/, at 15 and 298 K from single-crystal neutron and x-ray diffraction data: test of bonding models

    SciTech Connect

    Smyth, J.R.; Smith, J.V.; Artioli, G.; Kvick, A.

    1987-02-12

    The crystal structure of a natural coesite from an eclogite rock fragment in the Roberts Victor kimberlite, South Africa, was determined at 15 K by neutron diffraction (a = 7.1357 (13) A, b = 12.3835 (26) A, c = 7.1859 (11) A, ..beta.. = 120.375 (16)/sup 0/, C2/c), and at approx.298 K by X-ray diffraction. Cell dimensions measured by neutron diffraction at 292 K (7.1464 (9), 12.3796 (19), and 7.1829 (8) A, 120.283 (9)/sup 0/) differed from those determined by X-ray diffraction, probably because of a systematic absorption error for the latter. The strongly anisotropic nature of the thermal expansion is explained qualitatively by the relatively large changes (approx.1%) in the distances between the nonbonded oxygen neighbors and the relatively small changes of Si-O-Si and O-Si-O angles in the compact three-dimensional framework. There is a good, but not perfect, negative correlation between the eight independent Si-O distances and the five independent values for sec theta(Si-O-Si) at 15 K. It is weaker than that for 298 K, and the scatter from a straight-line prediction from molecular-orbital models for small clusters (e.g., H/sub 6/Si/sub 2/O/sub 7/) implies that it is desirably to consider additional forces, including repulsive forces between nonbonded oxygen neighbors. The combined at a for Si-O and Si-O-Si in coesite, quartz, and cristobalite at 10-15 K show less scatter than those for approx.298 K, in accordance with the greater thermal response of framework geometry in the more open structures.

  13. Improved high pressure turbine shroud

    NASA Technical Reports Server (NTRS)

    Bessen, I. I.; Rigney, D. V.; Schwab, R. C.

    1977-01-01

    A new high pressure turbine shroud material has been developed from the consolidation of prealloyed powders of Ni, Cr, Al and Y. The new material, a filler for cast turbine shroud body segments, is called Genaseal. The development followed the identification of oxidation resistance as the primary cause of prior shroud deterioration, since conversion to oxides reduces erosion resistance and increases spalling under thermal cycled engine conditions. The NICrAlY composition was selected in preference to NIAL and FeCRALY alloys, and was formulated to a prescribed density range that offers suitable erosion resistance, thermal conductivity and elastic modulus for improved behavior as a shroud.

  14. Electokinetic high pressure hydraulic system

    DOEpatents

    Paul, Phillip H.; Rakestraw, David J.

    2000-01-01

    A compact high pressure hydraulic system having no moving parts for converting electric potential to hydraulic force and for manipulating fluids. Electro-osmotic flow is used to provide a valve and means to compress a fluid or gas in a capillary-based system. By electro-osmotically moving an electrolyte between a first position opening communication between a fluid inlet and outlet and a second position closing communication between the fluid inlet and outlet the system can be configured as a valve. The system can also be used to generate forces as large as 2500 psi that can be used to compress a fluid, either a liquid or a gas.

  15. High pressure gas metering project

    SciTech Connect

    Tripp, L.R.

    1980-07-07

    The initial research and development of a system that uses high pressure helium gas to pressurize vessels over a wide range of pressurization rates, vessel volumes, and maximum test pressures are described. A method of controlling the mass flow rate in a test vessel was developed by using the pressure difference across a capillary tube. The mass flow rate is related to the pressurization rate through a real gas equation of state. The resulting mass flow equation is then used in a control algorithm. Plots of two typical pressurization tests run on a manually operated system are included.

  16. Nano Materials Under High Pressures

    SciTech Connect

    Karmakar, S.; Garg, Nandini; Sharma, Surinder M.

    2010-12-01

    Materials comprising of units or particles of the size of a few nano-meters have significantly different high pressure behavior than their bulk counterparts. This is abundantly elucidated in our studies on transition metals encapsulated in carbon nanotubes. Carbon nanotubes filled with Argon also show that it affects the behavior of tubes as well as argon. Studies on nano-crystalline Si displays an interesting crystalline-amorphous reversible transition, unique of its kind in elemental solids. We also demonstrate that in some cases of nanocrystalline samples, a phase perceived to be an intermediate-transient may be actually realized.

  17. Structure and stability of hydrous minerals at high pressure

    NASA Technical Reports Server (NTRS)

    Duffy, T. S.; Fei, Y.; Meade, C.; Hemley, R. J.; Mao, H. K.

    1994-01-01

    The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

  18. Structure and stability of hydrous minerals at high pressure

    NASA Technical Reports Server (NTRS)

    Duffy, T. S.; Fei, Y.; Meade, C.; Hemley, R. J.; Mao, H. K.

    1994-01-01

    The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

  19. Structure and stability of hydrous minerals at high pressure

    NASA Astrophysics Data System (ADS)

    Duffy, T. S.; Fei, Y.; Meade, C.; Hemley, R. J.; Mao, H. K.

    The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

  20. High-pressure structures of yttrium hydrides

    DOE PAGES

    Liu, Lu -Lu; Sun, Hui -Juan; Wang, C. Z.; ...

    2017-07-14

    In this study, the crystal structures of YH3 and YH4 at high pressure (100–250 GPa) have been explored using a genetic algorithm combined with first-principles calculations. New structures of YH3 with space group symmetries of P21/m and I4/mmm were predicted. The electronic structures and the phonon dispersion properties of various YH3 and YH4 structures at different temperatures and pressures were investigated. Among YH3 phases, the P21/m structure of YH3 was found to have a relatively high superconducting transformation temperature T c of 19 K at 120 GPa, which is reduced to 9 K at 200 GPa. Other YH3 structures havemore » much lower T cs. Compared with YH3, the T c of the YH4 compound is much higher, i.e. 94 K at 120 GPa and 55 K at 200 GPa.« less

  1. High pressure xenon ionization detector

    DOEpatents

    Markey, J.K.

    1989-11-14

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0 to 30 C. 2 figs.

  2. High pressure xenon ionization detector

    DOEpatents

    Markey, John K.

    1989-01-01

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0.degree. to 30.degree. C.

  3. Crystal chemistry of layered structures formed by linear rigid silyl-capped molecules.

    PubMed

    Lumpi, Daniel; Kautny, Paul; Stöger, Berthold; Fröhlich, Johannes

    2015-09-01

    The crystallization behavior of methylthio- or methylsulfonyl-containing spacer extended Z,Z-bis-ene-yne molecules capped with trimethylsilyl groups obtained by (tandem) thiophene ring fragmentation and of two non-spacer extended analogs were investigated. The rigid and linear molecules generally crystallized in layers whereby the flexibility of the layer interfaces formed by the silyl groups leads to a remarkably rich crystal chemistry. The molecules with benzene and thiophene spacers both crystallized with C2/c symmetry and can be considered as merotypes. Increasing the steric bulk of the core by introduction of ethylenedioxythiophene (EDOT) gave a structure incommensurately modulated in the [010] direction. Further increase of steric demand in the case of a dimethoxythiophene restored periodicity along [010] but resulted in a doubling of the c vector. Two different polytypes were observed, which feature geometrically different layer interfaces (non-OD, order-disorder, polytypes), one with a high stacking fault probability. Oxidation of the methylthio groups of the benzene-based molecule to methylsulfonyl groups led to three polymorphs (two temperature-dependent), which were analyzed by Hirshfeld surface d e/d i fingerprint plots. The analogously oxidized EDOT-based molecule crystallized as systematic twins owing to its OD polytypism. Shortening of the backbone by removal of the aryl core resulted in an enantiomorphic structure and a further shortening by removal of a methylthio-ene fragment again in a systematically twinned OD polytype.

  4. Crystal chemistry of natural and synthetic trioctahedral micas: Exploring the limits of geometric crystal chemical models

    NASA Astrophysics Data System (ADS)

    Mercier, Patrick H. J.

    Seventy-five synthetic powder trioctahedral mica samples (between Mg, Co, Ni, and Fe end members, with different degrees of oxidation, vacancy and Al/Si contents, and including an OH/F substitution series) were studied by room-temperature powder X-ray diffraction. The iron-bearing samples were studied by 57Fe Mossbauer spectroscopy. Subsets of the samples were also characterized by scanning electron microscopy combined with energy dispersive spectroscopy, optical microscopy, X-ray fluorescence spectroscopy, and gas chromatography. Lattice parameters (refined under the 1M stacking polytype, space group C2/m) were determined for all powder samples and iron site populations ([4]Fe 3+, [6]Fe2+, and [6]Fe 2+) were obtained from Mossbauer spectroscopy. The relation (c/a)cosbeta* = 113 was found to hold exactly (within experimental error) for all synthetic powders whereas it does not hold in general for synthetic and natural 1M single-crystals. The above relation is predicted to hold for geometric home-octahedral sheets (having equal M1 and M2 site bond lengths) and not to hold for geometric meso-octahedral sheets (having unequal M1 and M2 site bond lengths). The counter-rotation of the M2 site of 1M single-crystals exactly (within experimental error) follows the geometric meso-octahedral sheet model, which, assuming a uniform octahedral sheet height and site-specific M1 and M2 bond lengths, predicts site-specific flattening angles and a counter-rotation angle for the M2 site which is uniquely determined by the bond length difference between the M1 and M2 sites. A geometric meso-octahedral 2:1 layer silicate was shown to require corrugated tetrahedral sheets composed of bond-distorted tetrahedra. Key geometric meso-octahedral distortions in 1M single-crystals were identified and elucidated: (i) intra-layer top-bottom displacements within a TOT layer; and (ii) a tetrahedral bending angle between the apical bond and the pyramidal base formed by the three basal bonds. Plots

  5. Effects of Mg on diamond growth and properties in Fe-C system under high pressure and high temperature condition

    NASA Astrophysics Data System (ADS)

    Huang, Guo-Feng; Zheng, You-Jin; Li, Zhan-Chang; Gao, Qiang; Ma, Zhuo; Shi, Si-Ming; Jiang, Bao-Gang; Zhao, He

    2016-08-01

    Diamond crystal crystallized in Fe-Mg-C system with Archimedes buoyancy as a driving force is established under high pressure and high temperature conditions. The experimental results indicate that the addition of the Mg element results in the nitrogen concentration increasing from 87 ppm to 271 ppm in the diamond structure. The occurrence of the {100} plane reveals that the surface character is remarkably changed due to the addition of Mg. Micro-Raman spectra indicate that the half width of full maximum is in a range of 3.01 cm-1-3.26 cm-1, implying an extremely good quality of diamond specimens in crystallization. Project supported by the Natural Science Foundation of Inner Mongolia Autonomous Region, China (Grant No. 2013MS0809) and the Open Project of Key Laboratory of Functional Materials Physics and Chemistry (Jilin Normal University) of the Ministry of Education of China (Grant No. 201608).

  6. Crystal chemistry on a lattice: The case of BZN and BZN-related pyrochlores

    SciTech Connect

    Liu Yun; Withers, Ray L. . E-mail: withers@rsc.anu.edu.au; Welberry, T.R.; Wang Hong; Du Huiling

    2006-07-15

    This paper uses a diagnostic, highly structured diffuse intensity distribution to investigate the local crystal chemistry of (Bi{sub 1.5}Zn{sub 0.5-} {sub {delta}} )(Zn{sub 0.5}Nb{sub 1.5})O{sub 7-} {sub {delta}} (BZN) as well as Sn{sup 4+} and Ti{sup 4+}, B site substituted, BZN-related pyrochlore phases. The structured diffuse distribution of the B site substituted material is found to be remarkably similar to that observed for BZN itself. In the special case of (Bi{sub 1.5}Zn{sub 0.5})(Ti{sub 1.5}Nb{sub 0.5})O{sub 7} (BZNT), the continuous G{+-}<10l>* type diffuse streaking characteristic of BZN-related pyrochlores has virtually condensed out to give just G{+-}<001>* 'satellite reflections' and a P-centred, close to a superstructure phase of average pyrochlore unit cell dimensions. Bond valence sum considerations are used to investigate the local crystal chemistry of this BZNT phase and to derive a plausible model for this superstructure phase. Monte Carlo modelling is used to confirm the plausibility of the model proposed. The underlying crystal chemistry of BZN and BZN-related pyrochlores is shown to result from strong local Bi/Zn ordering rules and associated large amplitude structural relaxation. - Graphical abstract: A typical <00l> zone axis EDP of of (Bi{sub 1.5}Zn{sub 0.5})(Ti{sub 1.5}Nb{sub 0.5})O{sub 7} (BZNT)

  7. High pressure synthesis gas fermentation

    SciTech Connect

    Not Available

    1991-01-01

    The purpose of this research project is to build and test a pressure fermentation system for the production of ethanol from synthesis gas. The fermenters, pumps, controls, and analytical system will be procured or fabricated and assembled in our laboratory. This system will then be used to determine the effects of high pressure on growth and ethanol production by clostridium ljungdahlii. The limits of cell concentration and mass transport relationships will be found in continuous stirred tank reactor and immobilized cell reactors. The minimum retention times and reactor volumes will be found for ethanol production in these reactors. Retention times of a few seconds are expected to result from these experiments. 2 figs., 2 tabs.

  8. Steam Oxidation at High Pressure

    SciTech Connect

    Holcomb, Gordon R.; Carney, Casey

    2013-07-19

    A first high pressure test was completed: 293 hr at 267 bar and 670{degrees}C; A parallel 1 bar test was done for comparison; Mass gains were higher for all alloys at 267 bar than at 1 bar; Longer term exposures, over a range of temperatures and pressures, are planned to provide information as to the commercial implications of pressure effects; The planned tests are at a higher combination of temperatures and pressures than in the existing literature. A comparison was made with longer-term literature data: The short term exposures are largely consistent with the longer-term corrosion literature; Ferritic steels--no consistent pressure effect; Austenitic steels--fine grain alloys less able to maintain protective chromia scale as pressure increases; Ni-base alloys--more mass gains above 105 bar than below. Not based on many data points.

  9. Computational Chemistry Approach to Interpret the Crystal Violet Adsorption on Golbasi Lignite Activated Carbon

    NASA Astrophysics Data System (ADS)

    Depci, Tolga; Sarikaya, Musa; Prisbrey, Keith A.; Yucel, Aysegul

    2016-10-01

    In this paper, adsorption mechanism of Crystal Violet (CV) dye from the aqueous solution on the activated carbon prepared from Golbasi lignite was explained and interpreted by a computational chemistry approach and experimental studies. Molecular dynamic simulations and Ab initio frontier orbital analysis indicated relatively high energy and electron transfer processes during adsorption, and molecular dynamics simulations showed CV dye molecules moving around on the activated carbon surface after adsorption, facilitating penetration into cracks and pores. The experimental results supported to molecular dynamic simulation and showed that the monolayer coverage occurred on the activated carbon surface and each CV dye ion had equal sorption activation energy.

  10. Crystal chemistry of hydroxyl and water in silicate minerals. Final technical report

    SciTech Connect

    Smyth, J.R.

    1998-06-01

    This was a project to investigate the crystal chemistry of OH and H{sub 2}O substitution in silicate minerals by use of X-ray and neutron diffraction methods combined with IR spectroscopy and to interpret and generalize the results using an electrostatic model for these mineral structures. Using these data together with published H position data electrostatic parameters for H sites were calculated from a simple electrostatic model. The data were then used to refine the model for incorporation of H into the wadsleyite structure. This has led to recent work on the synthesis and characterization of hydrous wadsleyites.

  11. Phase equilibria and crystal chemistry of rubidium niobates and rubidium tantalates

    NASA Technical Reports Server (NTRS)

    Minor, D. B.; Roth, R. S.; Parker, H. S.; Brower, W. S.

    1977-01-01

    The phase equilibria relations and crystal chemistry of portions of the Rb2O-Nb2O5 and Rb2O-Ta2O5 systems were investigated for structures potentially useful as ionic conductors. A hexagonal tungsten bronze-type (HTB) structure was found in both systems as well as three hexagonal phases with mixed HTB-pyrochlore type structures. Ion exchange experiments between various alkali ions are described for several phases. Unit cell dimensions and X-ray diffraction powder patterns are reported.

  12. Phase equilibria and crystal chemistry of rubidium niobates and rubidium tantalates

    NASA Technical Reports Server (NTRS)

    Minor, D. B.; Roth, R. S.; Parker, H. S.; Brower, W. S.

    1977-01-01

    The phase equilibria relations and crystal chemistry of portions of the Rb2O-Nb2O5 and Rb2O-Ta2O5 systems were investigated for structures potentially useful as ionic conductors. A hexagonal tungsten bronze-type (HTB) structure was found in both systems as well as three hexagonal phases with mixed HTB-pyrochlore type structures. Ion exchange experiments between various alkali ions are described for several phases. Unit cell dimensions and X-ray diffraction powder patterns are reported.

  13. High-pressure oxidation of ethane

    DOE PAGES

    Hashemi, Hamid; Jacobsen, Jon G.; Rasmussen, Christian T.; ...

    2017-05-02

    Here, ethane oxidation at intermediate temperatures and high pressures has been investigated in both a laminar flow reactor and a rapid compression machine (RCM). The flow-reactor measurements at 600–900 K and 20–100 bar showed an onset temperature for oxidation of ethane between 700 and 825 K, depending on pressure, stoichiometry, and residence time. Measured ignition delay times in the RCM at pressures of 10–80 bar and temperatures of 900–1025 K decreased with increasing pressure and/or temperature. A detailed chemical kinetic model was developed with particular attention to the peroxide chemistry. Rate constants for reactions on the C2H5O2 potential energy surfacemore » were adopted from the recent theoretical work of Klippenstein. In the present work, the internal H-abstraction in CH3CH2OO to form CH2CH2OOH was treated in detail. Modeling predictions were in good agreement with data from the present work as well as results at elevated pressure from literature. The experimental results and the modeling predictions do not support occurrence of NTC behavior in ethane oxidation. Even at the high-pressure conditions of the present work where the C2H5 + O2 reaction yields ethylperoxyl rather than C2H4 + HO2, the chain branching sequence CH3CH2OO → CH2CH2OOH → +O2 OOCH2CH2OOH → branching is not competitive, because the internal H-atom transfer in CH3CH2OO to CH2CH2OOH is too slow compared to thermal dissociation to C2H4 and HO2.« less

  14. Transition Metals in the Transition Zone: Crystal Chemistry of Minor Element Substitution in Wadsleyite

    NASA Astrophysics Data System (ADS)

    Zhang, L.

    2015-12-01

    As the most abundant solid phase at depths of 410 to 525 km, wadsleyite constitutes a large geochemical reservoir in the Earth. In order to better understand minor element substitution and cation ordering in wadsleyite, we have synthesized wadsleyite coexisting with pyroxene with 2 to 3 weight percent each of TiO2, Cr2O3, V2O3, CoO, NiO, and ZnO under hydrous conditions in separate experiments at 1300ºC and 15GPa. We have refined the crystal structures of these wadsleyites, analyzed the compositions by electron microprobe, and estimated M3 vacancy contents from b/a cell-parameter ratios. Trivalent cations, Fe, Cr and V, show a strong preference for M3 over M1 and M2 and significant substitution up to 2.8% at the tetrahedral site. Divalent Ni, Co, and Zn show site preferences similar to those of Fe2+ with M1≈ M3 > M2 > T. This site preference appears to be due crystal field stabilization energies rather than cation radius effects. Trivalent Cr, and V have much greater solubilities in wadsleyite than in olivine and so may be enriched in a melt or an accessory phase if hydrous melting occurs on upward convection across the wadsleyite-olivine boundary and may be useful as indicators of high pressure origin.

  15. High-Pressure Design of Advanced BN-Based Materials.

    PubMed

    Kurakevych, Oleksandr O; Solozhenko, Vladimir L

    2016-10-20

    The aim of the present review is to highlight the state of the art in high-pressure design of new advanced materials based on boron nitride. Recent experimental achievements on the governing phase transformation, nanostructuring and chemical synthesis in the systems containing boron nitride at high pressures and high temperatures are presented. All these developments allowed discovering new materials, e.g., ultrahard nanocrystalline cubic boron nitride (nano-cBN) with hardness comparable to diamond, and superhard boron subnitride B13N₂. Thermodynamic and kinetic aspects of high-pressure synthesis are described based on the data obtained by in situ and ex situ methods. Mechanical and thermal properties (hardness, thermoelastic equations of state, etc.) are discussed. New synthetic perspectives, combining both soft chemistry and extreme pressure-temperature conditions are considered.

  16. Hibonite: Crystal Chemistry and Origin of Blue Coloration in Meteoritic Assemblages

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Burns, V. M.

    1985-01-01

    The blue color and optical spectra of hibonite, a common constituent of refractory inclusions in carbonaceous chondrites, are discussed. Because they may be manifestations of exotic cation species stabilized in unusual coordination sites in the hibonite crystalstructure. Hibonite, ideally CaAl12O19, is conducive to atomic substitution of host Ca2+ and Al3+ ions by a variety of lanthanide and first series transition elements. The latter cations are responsible for the colors of many rock-forming minerals as a result of intraelectronic or intervalence transitions. The visible-region spectra of most oxide and silicate minerals are generally well understood. Assignments of absorption bands in meteoritic hibonite optical spectra due to uncertainties of cation valencies and complexities in the crystal structure are examined. The crystal chemistry of hibonite is reviewed, Mossbauer spectral measurements of iron-bearing hibonite and electronic transitions that may be responsible for the blue coloration of meteoritic hibonites are discussed.

  17. Crystal structure and crystal chemistry of melanovanadite, a natural vanadium bronze.

    USGS Publications Warehouse

    Konnert, J.A.; Evans, H.T.

    1987-01-01

    The crystal structure of melanovanadite from Minas Ragra, Peru, has been determined in space group P1. The triclinic unit cell (non-standard) has a 6.360(2), b 18.090(9), c 6.276(2) A, alpha 110.18(4)o, beta 101.62(3)o, gamma 82.86(4)o. A subcell with b' = b/2 was found by crystal-structure analysis to contain CaV4O10.5H2O. The subcell has a layer structure in which the vanadate sheet consists of corner-shared tetrahedral VO4 and double square-pyramidal V2O8 groups, similar to that previously found in synthetic CsV2O5. Refinement of the full structure (R = 0.056) showed that the Ca atom, which half-occupies a general position in the subcell, is 90% ordered at one of these sites in the whole unit cell. Bond length-bond strength estimates indicate that the tetrahedra contain V5+, and the square pyramids, V4+.-J.A.Z.

  18. Dissociation of methane under high pressure.

    PubMed

    Gao, Guoying; Oganov, Artem R; Ma, Yanming; Wang, Hui; Li, Peifang; Li, Yinwei; Iitaka, Toshiaki; Zou, Guangtian

    2010-10-14

    Methane is an extremely important energy source with a great abundance in nature and plays a significant role in planetary physics, being one of the major constituents of giant planets Uranus and Neptune. The stable crystal forms of methane under extreme conditions are of great fundamental interest. Using the ab initio evolutionary algorithm for crystal structure prediction, we found three novel insulating molecular structures with P2(1)2(1)2(1), Pnma, and Cmcm space groups. Remarkably, under high pressure, methane becomes unstable and dissociates into ethane (C(2)H(6)) at 95 GPa, butane (C(4)H(10)) at 158 GPa, and further, carbon (diamond) and hydrogen above 287 GPa at zero temperature. We have computed the pressure-temperature phase diagram, which sheds light into the seemingly conflicting observations of the unusually low formation pressure of diamond at high temperature and the failure of experimental observation of dissociation at room temperature. Our results support the idea of diamond formation in the interiors of giant planets such as Neptune.

  19. Electrical Transport Experiments at High Pressure

    SciTech Connect

    Weir, S

    2009-02-11

    High-pressure electrical measurements have a long history of use in the study of materials under ultra-high pressures. In recent years, electrical transport experiments have played a key role in the study of many interesting high pressure phenomena including pressure-induced superconductivity, insulator-to-metal transitions, and quantum critical behavior. High-pressure electrical transport experiments also play an important function in geophysics and the study of the Earth's interior. Besides electrical conductivity measurements, electrical transport experiments also encompass techniques for the study of the optoelectronic and thermoelectric properties of materials under high pressures. In addition, electrical transport techniques, i.e., the ability to extend electrically conductive wires from outside instrumentation into the high pressure sample chamber have been utilized to perform other types of experiments as well, such as high-pressure magnetic susceptibility and de Haas-van Alphen Fermi surface experiments. Finally, electrical transport techniques have also been utilized for delivering significant amounts of electrical power to high pressure samples, for the purpose of performing high-pressure and -temperature experiments. Thus, not only do high-pressure electrical transport experiments provide much interesting and valuable data on the physical properties of materials extreme compression, but the underlying high-pressure electrical transport techniques can be used in a number of ways to develop additional diagnostic techniques and to advance high pressure capabilities.

  20. Carbon Nanotubes as High-Pressure Cylinders and Nanoextruders

    NASA Astrophysics Data System (ADS)

    Sun, L.; Banhart, F.; Krasheninnikov, A. V.; Rodríguez-Manzo, J. A.; Terrones, M.; Ajayan, P. M.

    2006-05-01

    Closed-shell carbon nanostructures, such as carbon onions, have been shown to act as self-contracting high-pressure cells under electron irradiation. We report that controlled irradiation of multiwalled carbon nanotubes can cause large pressure buildup within the nanotube cores that can plastically deform, extrude, and break solid materials that are encapsulated inside the core. We further showed by atomistic simulations that the internal pressure inside nanotubes can reach values higher than 40 gigapascals. Nanotubes can thus be used as robust nanoscale jigs for extruding and deforming hard nanomaterials and for modifying their properties, as well as templates for the study of individual nanometer-sized crystals under high pressure.

  1. Crystal Chemistry of MgAl2O4 Spinel Solid Solution

    NASA Astrophysics Data System (ADS)

    Yoshiasa, Akira; Maekawa, Hidemi; Sugiyama, Kazumasa

    Considerable efforts have been devoted to the structural studies of spinel group minerals or type compounds because of their importance as constituents of the Earth’s crust and mantle. Despite their simple structures, many spinel type compounds exhibit complex disordering phenomena involving the mixing of cation on two sites, which have important consequences for both thermodynamic and physical properties. The cation distributions and the structural variation in MgAl2-xGaxO4 solid-solution have been clarified using 27Al MAS NMR measurements and single crystal X-ray diffraction. The determined local distance in the solid solution corresponds with the bond distance expected from the effective ionic radii except Al-O distance in the tetrahedral site. We have revealed that the Al-O distance in the tetrahedral site in spinel solid solution is about 0.15 Å longer than the expected value. Boron is the same group element as Al and Ga and its ionic radius is considerably small. Single crystals of MgAl2-xBxO4 spinel were synthesized under high pressure and high temperature. The maximum content of boron was about x = 0.13 at 1273 K and 11 GPa. The smallest B ion occupies the octahedral site in top priority in the spinel solid solution of the Mg-Al-B systems. The B3+ ions can replace considerably bigger Al3+ ion under pressure. These spinel solid-solutions are largely disordered crystals. Only the positional shifts of oxygen ion have been relaxing the disorder in the solid solution.

  2. Topaz and Kyanite Luminescence Under High Pressure

    NASA Astrophysics Data System (ADS)

    O'Bannon, E. F., III; Williams, Q. C.

    2014-12-01

    The luminescence spectra of Cr3+ in heat-treated topaz Al2SiO4(OH,F)2 and natural kyanite Al2SiO5 were measured from 650 - 800 nm in a hydrostatic environment up to pressures of 15 GPa. The R1 and R2 peaks of topaz shift at average rates of 0.30 nm/GPa and 0.22 nm/GPa, respectively, implying that the deformation of the Cr3+ octahedra increases with pressure. Three peaks are fit under each R line of topaz at both room and high pressure, and these peaks are associated with different Al sites into which the Cr substitutes. The shift of the R lines in topaz under pressure is remarkably linear, which appears to be a general feature of many Cr3+-bearing oxides: the underlying cause of this linearity may lie in anharmonic coupling with lattice vibrations. In this context, we also characterize the frequency shifts of two vibronic peaks within topaz. The R1 and R2 peaks of kyanite shift at 0.37 nm/GPa and 0.88 nm/GPa respectively. Two peaks are fit under R1 and three peaks are fit under R2 of kyanite at both room and high pressure; this result is also consistent with three different Cr3+ sites in this material. The R lines in kyanite are notably optically anisotropic, depending strongly on crystallographic orientation: this is most strongly manifested in the R2 peak. The Cr3+ luminescence in these materials provides a sensitive probe of pressure-dependent shifts in the local geometry of the Al-sites in these materials, which are analyzed in the context of previous single-crystal x-ray diffraction measurements.

  3. Trace Element Partitioning Between Metal and Melt at High Pressure

    NASA Astrophysics Data System (ADS)

    Campbell, A. J.; Moses, M.; Fei, Y.

    2004-12-01

    Fractionations between siderophile trace elements are produced during crystallization of solid metal from a molten planetary core. It has been proposed (e.g., Brandon et al., 2003) that fractionations of Re/Os and Pt/Os produced during crystallization of Earth's inner core are recorded in rocks whose source regions lie at the core-mantle boundary. However, the possible effects of pressure, temperature, composition, and metal crystal structure on metal-melt partitioning have not been fully evaluated experimentally. Accordingly, we have begun to measure the partitioning of major and trace siderophile elements between Fe-rich metal and metal-sulfide melt at high pressures and temperatures using laser ablation ICP-MS of multi-anvil press samples. The starting materials included iron meteorite powder (having natural abundances of PGEs at the /sim10 ppm level) and troilite. In some cases Ru powder was also added to the starting material to promote transformation of the Fe-rich metal to the hcp structure, as described by Campbell et al. (2003). The powders were loaded into an MgO or BN sample capsule in a 10/5 multi-anvil press assembly, and pressurized to 14.5 GPa. The sample chamber thickness was held to <0.4 mm to minimize the temperature gradient experienced by the samples. Melting was achieved at temperatures of 975 C or above, and run durations were 6 to 24 hours. The recovered run products were polished and examined by SEM or electron microprobe before LA-ICP-MS analysis. Laser ablation spot sizes ranged from 15 to 50 microns, depending on the available grain size. Partition coefficients (D) were determined for Co, Ni, Ru, Re, Os, Ir, and Pt. Errors on the D values were based on the reproduceability of at least 3 measurements in each phase, and were <10% for major elements and <25% for trace elements. The effects of temperature and composition were evaluated and implications on the chemistry of the core will be discussed. Brandon A. D. et al. (2003) EPSL 206

  4. Single crystal structures of thallium (I) thorium fluorides and crystal chemistry of monovalent tetravalent cation pentafluorides

    NASA Astrophysics Data System (ADS)

    Oudahmane, Abdelghani; El-Ghozzi, Malika; Jouffret, Laurent; Avignant, Daniel

    2015-12-01

    Two thallium (I) thorium (IV) fluorides, TlTh3F13 and TlThF5 were obtained by solid state synthesis and their crystal structures determined from single crystal X-ray diffraction data recorded at room temperature with an APEX-II CCD diffractometer. TlTh3F13 is orthorhombic, space group Pmc21, with a=8.1801(2) Å, b=7.4479(2) Å, c=8.6375(2) Å, V=526.24(2) Å3, Z=2 and TlThF5 is monoclinic, space group P21/n, with a=8.1128(5) Å, b=7.2250(4) Å, c=8.8493(6) Å, β=116.683(3)°, V=463.46(5) Å3, Z=4. The structure of TlTh3F13 comprises layers of corner and edge-sharing ThF9 polyhedra further linked by chains of trans connected tricapped trigonal prisms ThF9 through corners and edges. The three dimensional thorium frameworks delimits channels parallel to [0 0 1] where the 11-coordinated Tl+ ions are arranged into double columns located in mirror planes of the structure. TlTh3F13 is isotypic with RbTh3F13, RbU3F13 and with one of the two polymorphs of CsTh3F13. The structure of TlThF5 may be regarded as a layer structure built up from the regular succession of 2∞[ M ‧F5 ] - corrugated layers further held by the Tl+ ions along the [1 0 1 ̅] direction. The layers are built up from edge and corner-sharing thorium polyhedra where each (ThF9)5- monocapped square antiprism is connected to five others by sharing three edges and two corners. TlThF5 is isostructural with β-NH4UF5 and with one of the polymorphs of CsThF5. A comparison of the different structural types of MM‧F5 pentafluorides is presented and a diagram of repartition of their structures is given. From the comparison of the Tl structures with their Rb or Cs homologs, where very similar monovalent cation environments are observed it should be concluded to a stereochemically inactivity of the 6s2 lone pair of Tl(I) in both TlTh3F13 and TlThF5, contrary to what is observed in richer Tl(I) content Tl3ThF7 fluorothorate.

  5. High Pressure Electrolyzer System Evaluation

    NASA Technical Reports Server (NTRS)

    Prokopius, Kevin; Coloza, Anthony

    2010-01-01

    This report documents the continuing efforts to evaluate the operational state of a high pressure PEM based electrolyzer located at the NASA Glenn Research Center. This electrolyzer is a prototype system built by General Electric and refurbished by Hamilton Standard (now named Hamilton Sunstrand). It is capable of producing hydrogen and oxygen at an output pressure of 3000 psi. The electrolyzer has been in storage for a number of years. Evaluation and testing was performed to determine the state of the electrolyzer and provide an estimate of the cost for refurbishment. Pressure testing was performed using nitrogen gas through the oxygen ports to ascertain the status of the internal membranes and seals. It was determined that the integrity of the electrolyzer stack was good as there were no appreciable leaks in the membranes or seals within the stack. In addition to the integrity testing, an itemized list and part cost estimate was produced for the components of the electrolyzer system. An evaluation of the system s present state and an estimate of the cost to bring it back to operational status was also produced.

  6. Silicon nanowires under high pressure

    NASA Astrophysics Data System (ADS)

    Wang, Yuejian

    2009-03-01

    Silicon nanowires (Si NWs), one-dimensional single crystalline, have recently drawn extensive attention, thanks to their robust applications in electrical and optical devices as well as in the strengthening of diamond/SiC superhard composites. Here, we conducted high-pressure synchrotron diffraction experiments in a diamond anvil cell to study phase transitions and compressibility of Si NWs. Our results revealed that the onset pressure for the Si I-II transformation in Si NWs is approximately 2.0 GPa lower than previously determined values for bulk Si, a trend that is consistent with the analysis of misfit in strain energy. The bulk modulus of Si-I NWs derived from the pressure-volume measurements is 123 GPa, which is comparable to that of Si-V NWs but 25% larger than the reported values for bulk silicon. The reduced compressibility in Si NWs indicates that the unique wire-like structure in nanoscale plays vital roles in the elastic behavior of condensed matter..

  7. Crystal-plane-controlled surface chemistry and catalytic performance of surfactant-free Cu2 O nanocrystals.

    PubMed

    Hua, Qing; Cao, Tian; Bao, Huizhi; Jiang, Zhiquan; Huang, Weixin

    2013-10-01

    Surfactant-free Cu2 O nanocrystals, including cubes exposing {100} crystal planes, octahedra exposing {111} crystal planes, and rhombic dodecahedra exposing {110} crystal planes, were used as model catalysts to study the effect of the crystal plane on the surface chemistry and catalytic performance for CO oxidation of Cu2 O nanocrystals. The catalytic performance follows the order of octahedra rhombic dodecahedra>cubes; this suggests that Cu2 O(111) is most active in catalyzing CO oxidation among Cu2 O (111), (110), and (100) surfaces. CO temperature-programmed reduction results demonstrate that Cu2 O octahedra are the most easily reduced of the Cu2 O cubes, octahedra, and rhombic dodecahedra. Diffuse reflectance FTIR spectra show that CO chemisorption on Cu2 O nanocrystals depends on their shape and the chemisorption temperature. CO chemisorption is strongest on rhombic dodecahedra at 30°C, but at 150°C on octahedra. Both the reducibility and chemisorption ability of various Cu2 O nanocrystals toward CO are consistent with their catalytic performance in CO oxidation. The observed surface chemistry and catalytic performance in CO oxidation of various Cu2 O nanocrystals can be well correlated with their exposed crystal plane and surface composition/structure. Cu2 O octahedra expose the {111} crystal plane with coordinated, unsaturated Cu(I) sites, and thus, are most active in chemisorbing CO and catalyzing CO oxidation. These results nicely demonstrate the crystal-plane-controlled surface chemistry and catalytic performance of oxide catalysts.

  8. Elasticity of Mantle Minerals and their High-Pressure Polymorphs at High Pressures and Temperatures

    NASA Astrophysics Data System (ADS)

    Liebermann, R. C.; Li, B.; Kung, J.; Weidner, D. J.

    2002-12-01

    In his 1952 paper, Francis Birch concluded "New phases are required to account for the high elasticity of the deeper part of the mantle (below 900 km), and it is suggested that, beginning at about 200 to 300 km, there is a gradual shift toward high-pressure modifications of the ferro-magnesian silicates, probably close-packed oxides, with the transition complete at about 800 to 900 km." In the subsequent quarter century, experimental evidence for such transitions to high-pressure polymorphs emerged in laboratories around the world, most notably in those of Akimoto in Japan and Ringwood in Australia; these studies confirmed the existence of stable silicate phases with the wadsleyite, ringwoodite, majorite, ilmenite [now akimotoite], and perovskite structures. In the 1970s and 1980s, single crystal and polycrystalline specimens of these high-pressure phases were synthesized, thereby enabling studies of their elastic properties in the laboratory at ambient conditions [see Brillouin studies of the Weidner and Basssett laboratories, and ultrasonic studies by Mizutani and Fujisawa in Japan and Liebermann and colleagues in Australia]. This work often started with experiments on crystal chemical analogues of mantle silicates, following the original suggestions of Goldschmidt and Bernal in the 1930s (repeated by Birch in 1952), and then moved on to the real mantle compositions. Prior to 1988, most of these acoustic experiments were conducted versus presssure at room temperature or versus temperature at room presssure; these conditions fell far short of those achieved in the Earth's mantle. Substantial progress has been made in the past decade, making it feasible to perform acoustic experiments at conditions approaching those for the transition zone (at depths greater than 400 km); this progress has been achieved in many laboratories, including those at the University of Washington, Geophysical Laboratory, Bayreuth Geoinstitut, Nagoya University, Australian National

  9. Crystal chemistry and self-lubricating properties of monochalcogenides gallium selenide and tin selenide

    SciTech Connect

    Erdemir, A.

    1993-02-01

    This paper describes the fundamentals of the crystal chemistry and self-lubricating mechanisms of two monochalcogenides; tin selenide and gallium selenide. Specifically, it enumerates their inter-atomic array and bond structure in crystalline states, and correlates this fundamental knowledge with their self-lubricating capacity. Friction tests assessing the self-lubricating performance of gallium and tin selenides were carried out on a pin-on-disk machine. Specifically, large crystalline pieces of gallium selenide and tin selenide were cut and cleaved into flat squares and subsequently rubbed against the sapphire balls. In another case, the fine powders (particle size {approx} 50--100 {mu}m) of gallium selenide and tin selenide were manually fed into the sliding interfaces of 440C pins and 440C disks. For the specific test conditions explored, it was found that the friction coefficients of the sapphire/gallium selenide and sapphire/tin selenide pairs were {approx} 0.23 and {approx} 0.35, respectively. The friction coefficients of 440C pin/440C disk test pairs with gallium selenide and tin selenide powders were on the orders of {approx} 0.22 and {approx} 0.38, respectively. For comparison, a number of parallel friction tests were performed with MoS{sub 2} powders and compacts and the results of these tests were also reported. The friction data together with the crystal-chemical knowledge and the electron microscopic evidence supported the conclusion that the lubricity and self-lubricating mechanisms of these solids are closely related to their crystal chemistry and the nature of interlayer bonding.

  10. Crystal structure and chemistry of lithium-bearing trioctahedral micas-3T

    USGS Publications Warehouse

    Brigatti, M.F.; Kile, D.E.; Poppi, L.

    2003-01-01

    Chemical analyses and crystal structure refinements were performed on lithian siderophyllite-3T crystals from granitic pegmatites of the anorogenic Pikes Peak batholith (Colorado) to characterize the crystal chemistry and relations with trioctahedral lithium-bearing micas showing different stacking sequences. Chemical data show that the studied samples fall on the siderophyllite-polylithionite join, closer to the siderophyllite end-member. Single-crystal X-ray refinements were carried out on three samples (two of which were taken from core and rim of the same crystal) in space-group P31 12 (the agreement factor, Robs, varies between 0.034 and 0.036). Mean bond distances and mean electron counts of M1, M2 and M3 octahedral sites indicate an ordered cation distribution with M1 and M3 positions substantially larger than M2. In the sample with the largest iron content, the M2 mean electron count increases as well as the mean distance, whereas remains smaller than or . The tetrahedral cation-oxygen atom mean distances range from 1.614 to 1.638 A and from 1.663 to 1.678 A for T1 and T2 sites, respectively, being consistent with Al3+ enrichment in the T2 sites. The tetrahedral rotation angle, α, is generally small (3.1 ≤ α ≤ 4.6) and decreases with siderophyllite content. As Fe increases, the T1 tetrahedron becomes flatter (112.4 ≤ t1 ≤ 110.5??), whereas T2 tetrahedron distortion appears unchanged (110.7 ≤ T2 ≤ 110.9).

  11. Volume and pressure dependences of the electronic, vibrational, and crystal structures of C s2CoC l4 : Identification of a pressure-induced piezochromic phase at high pressure

    NASA Astrophysics Data System (ADS)

    Nataf, L.; Aguado, F.; Hernández, I.; Valiente, R.; González, J.; Sanz-Ortiz, M. N.; Wilhelm, H.; Jephcoat, A. P.; Baudelet, F.; Rodríguez, F.

    2017-01-01

    This work investigates the high-pressure structure of C s2CoC l4 and how it affects the electronic and vibrational properties using optical absorption, Raman spectroscopy, x-ray diffraction, and x-ray absorption in the 0-15 GPa range. In particular, we focus on the electronic and local structures of C o2 + , since compression of C s2CoC l4 yields structural transformations associated with change of coordination around C o2 + , which are eventually responsible for the intense piezochromism at 7 GPa. This study provides a complete characterization of the electronic and vibrational structures of C s2CoC l4 in the Pnma phase as a function of the cell volume and the local CoC l4 bond length, RCo-Cl, as well as its corresponding equation of state. In addition, our interest is to elucidate whether the phase transition undergone by C s2CoC l4 at 7 GPa leads to a perovskite-layer-type structure where C o2 + is sixfold coordinated, decomposes into CsCl +CsCoC l3 , or it involves an unknown phase with different coordination sites for C o2 + . We show that C o2 + is sixfold coordinated in the high-pressure phase. The analysis of optical spectra and x-ray diffraction data suggests the formation of an interconnected structure of exchange-coupled C o2 + through edge-sharing octahedra at high pressure.

  12. Surface design for controlled crystallization: the role of surface chemistry and nanoscale pores in heterogeneous nucleation.

    PubMed

    Diao, Ying; Myerson, Allan S; Hatton, T Alan; Trout, Bernhardt L

    2011-05-03

    Current industrial practice for control of primary nucleation (nucleation from a system without pre-existing crystalline matter) during crystallization from solution involves control of supersaturation generation, impurity levels, and solvent composition. Nucleation behavior remains largely unpredictable, however, due to the presence of container surfaces, dust, dirt, and other impurities that can provide heterogeneous nucleation sites, thus making the control and scale-up of processes that depend on primary nucleation difficult. To develop a basis for the rational design of surfaces to control nucleation during crystallization from solution, we studied the role of surface chemistry and morphology of various polymeric substrates on heterogeneous nucleation using aspirin as a model compound. Nucleation induction time statistics were utilized to investigate and quantify systematically the effectiveness of polymer substrates in inducing nucleation. The nucleation induction time study revealed that poly(4-acryloylmorpholine) and poly(2-carboxyethyl acrylate), each cross-linked by divinylbenzene, significantly lowered the nucleation induction time of aspirin while the other polymers were essentially inactive. In addition, we found the presence of nanoscopic pores on certain polymer surfaces led to order-of-magnitude faster aspirin nucleation rates when compared with surfaces without pores. We studied the preferred orientation of aspirin crystals on polymer films and found the nucleation-active polymer surfaces preferentially nucleated the polar facets of aspirin, guided by hydrogen bonds. A model based on interfacial free energies was also developed which predicted the same trend of polymer surface nucleation activities as indicated by the nucleation induction times.

  13. Transition metals in the transition zone: Crystal chemistry of minor element substitution in wadsleyite

    SciTech Connect

    Zhang, Li; Smyth, Joseph R.; Allaz, Julien; Kawazoe, Takaaki; Jacobsen, Steven D.; Jin, Zhenmin

    2016-10-01

    the wadsleyite-olivine boundary and may be useful as indicators of high pressure origin.

  14. Transition metals in the transition zone: Crystal chemistry of minor element substitution in wadsleyite

    DOE PAGES

    Zhang, Li; Smyth, Joseph R.; Allaz, Julien; ...

    2016-10-01

    As the most abundant solid phase at depths of 410 to 525 km, wadsleyite constitutes a large geochemical reservoir in the Earth. In order to better understand the implications of minor element substitution and cation ordering in wadsleyite, we have synthesized wadsleyites coexisting with pyroxenes with about 3 wt% of either TiO2, Cr2O3, V2O3, CoO, NiO, or ZnO under hydrous conditions in separate experiments at 1300 °C and 15 GPa. We have refined the crystal structures of these wadsleyites by single-crystal X-ray diffraction, analyzed the compositions by electron microprobe, and estimated M3 vacancy concentration from b/a cell-parameter ratios. According tomore » the crystal structure refinements, trivalent cations Fe3+, Cr3+ and V3+, show a strong preference for M3 over M1 and M2 and significant substitution up to 2.7 % (atomic percent) at the tetrahedral site (T site). Divalent cations, Ni2+, Co2+, and Zn2+ show site preferences similar to those of Fe2+ with M1≈ M3 > M2 > T. Transition metal site preferences appear to correlate with crystal field stabilization energies (CFSE) and are inconsistent with cation radius effects. The avoidance of Ni2+, Co2+ and Fe2+ for the M2 site in both wadsleyite and olivine can be influenced by CFSE, which has a positive correlation with site preferences at octahedral sites, indicating that avoidance of the lower-symmetry M2 site is stronger for cations having lower (greater absolute value) CFSE. Ti4+ substitutes primarily into the M3 octahedron, rather than M1, M2, or T sites. Electron microprobe analysis reveals that Ti4+, Cr3+, and V3+ have greater solubility in wadsleyite than in olivine. Furthermore these transition metal cations may be enriched in a melt or an accessory phase if hydrous melting occurs on upward convection across the wadsleyite-olivine boundary and may be useful as indicators of high pressure origin.« less

  15. High Pressure Materials Research: Novel Extended Phases of Molecular Triatomics

    SciTech Connect

    Yoo, Choong-Shik

    2006-01-27

    Application of high pressure significantly alters the interatomic distance and thus the nature of intermolecular interaction, chemical bonding, molecular configuration, crystal structure, and stability of solid. With modern advances in high-pressure technologies, it is feasible to achieve a large (often up to a several-fold) compression of lattice, at which condition material can be easily forced into a new physical and chemical configuration. The high-pressure thus offers enhanced opportunities to discover new phases, both stable and metastable ones, and to tune exotic properties in a wide-range of atomistic length scale, substantially greater than (often being several orders of) those achieved by other thermal (varing temperatures) and chemical (varying composition or making alloys) means. Simple molecular solids like H{sub 2}, C, CO{sub 2}, N{sub 2}, O{sub 2}, H{sub 2}O, CO, NH{sub 3}, and CH{sub 4} are bounded by strong covalent intramolecular bonds, yet relatively weak intermolecular bonds of van der Waals and/or hydrogen bonds. The weak intermolecular bonds make these solids highly compressible (i.e., low bulk moduli typically less than 10 GPa), while the strong covalent bonds make them chemically inert at least initially at low pressures. Carboncarbon single bonds, carbon-oxygen double bonds and nitrogen-nitrogen triple bonds, for example, are among the strongest. These molecular forms are, thus, often considered to remain stable in an extended region of high pressures and high temperatures. High stabilities of these covalent molecules are also the basis of which their mixtures are often presumed to be the major detonation products of energetic materials as well as the major constituents of giant planets. However, their physical/chemical stabilities are not truly understood at those extreme pressure-temperature conditions. In fact, an increasing amount of experimental evidences contradict the assumed stability of these materials at high pressures and

  16. Periodic changes in effluent chemistry at cold-water geyser: Crystal geyser in Utah

    DOE PAGES

    Han, Weon Shik; Watson, Z. T.; Kampman, Niko; ...

    2017-04-20

    Crystal geyser is a CO2-driven cold-water geyser which was originally drilled in the late 1930’s in Green River, Utah. By utilizing a suite of temporal groundwater sample datasets, in situ monitoring of temperature, pressure, pH and electrical conductivity from multiple field trips to Crystal geyser from 2007 to 2014, periodic trends in groundwater chemistry from the geyser effluent were identified. Based on chemical characteristics, the primary sourcing aquifers are characterized to be both the Entrada and Navajo Sandstones with a minor contribution from Paradox Formation brine. The single eruption cycle at Crystal geyser lasted over four days and was composedmore » of four parts: Minor Eruption (mEP), Major Eruption (MEP), Aftershock Eruption (Ae) and Recharge (R). During the single eruption cycle, dissolved ionic species vary 0–44% even though the degree of changes for individual ions are different. Generally, Na+, K+, Cl-and SO42- regularly decrease at the onset and throughout the MEP. These species then increase in concentration during the mEP. In contrast, Ca2+, Mg2+, Fe2+ and Sr2+ increase and decrease in concentration during the MEP and mEP, respectively. The geochemical inverse modeling with PHREEQC was conducted to characterize the contribution from three end-members (Entrada Sandstone, Navajo Sandstone and Paradox Formation brine) to the resulting Crystal geyser effluent. Results of the inverse modeling showed that, during the mEP, the Navajo, Entrada and brine supplied 62–65%, 36–33% and 1–2%, respectively. During the MEP, the contribution shifted to 53–56%, 45–42% and 1–2% for the Navajo, Entrada and Paradox Formation brine, respectively. Finally, these changes in effluent characteristics further support the hypothesis by Watson et al. (2014) that the mEP and MEP are driven by different sources and mechanisms.« less

  17. Periodic changes in effluent chemistry at cold-water geyser: Crystal geyser in Utah

    NASA Astrophysics Data System (ADS)

    Han, Weon Shik; Watson, Z. T.; Kampman, Niko; Grundl, Tim; Graham, Jack P.; Keating, Elizabeth H.

    2017-07-01

    Crystal geyser is a CO2-driven cold-water geyser which was originally drilled in the late 1930's in Green River, Utah. Utilizing a suite of temporal groundwater sample datasets, in situ monitoring of temperature, pressure, pH and electrical conductivity from multiple field trips to Crystal geyser from 2007 to 2014, periodic trends in groundwater chemistry from the geyser effluent were identified. Based on chemical characteristics, the primary sourcing aquifers are characterized to be both the Entrada and Navajo Sandstones with a minor contribution from Paradox Formation brine. The single eruption cycle at Crystal geyser lasted over four days and was composed of four parts: Minor Eruption (mEP), Major Eruption (MEP), Aftershock Eruption (Ae) and Recharge (R). During the single eruption cycle, dissolved ionic species vary 0-44% even though the degree of changes for individual ions are different. Generally, Na+, K+, Cl- and SO42- regularly decrease at the onset and throughout the MEP. These species then increase in concentration during the mEP. Conversely, Ca2+, Mg2+, Fe2+ and Sr2+ increase and decrease in concentration during the MEP and mEP, respectively. The geochemical inverse modeling with PHREEQC was conducted to characterize the contribution from three end-members (Entrada Sandstone, Navajo Sandstone and Paradox Formation brine) to the resulting Crystal geyser effluent. Results of the inverse modeling showed that, during the mEP, the Navajo, Entrada and brine supplied 62-65%, 36-33% and 1-2%, respectively. During the MEP, the contribution shifted to 53-56%, 45-42% and 1-2% for the Navajo, Entrada and Paradox Formation brine, respectively. The changes in effluent characteristics further support the hypothesis by Watson et al. (2014) that the mEP and MEP are driven by different sources and mechanisms.

  18. Zeeman Effect in Ruby at High Pressures

    NASA Astrophysics Data System (ADS)

    Dan, Ioana

    2012-02-01

    We have developed a versatile fiber-coupled system for magneto-optical spectroscopy measurements at high pressure. The system is based on a miniature Cu-alloy Diamond Anvil Cell (from D'Anvils, Ltd) fitted with a custom-designed He gas-actuated membrane for in-situ pressure control, and coupled with a He transfer cryostat incorporating a superconducting magnet (from Quantum Designs). This system allows optical measurements (Raman, photoluminescence, reflectivity) within wide ranges of pressures (up to 100GPa), temperatures (4.2-300K) and magnetic fields (0-9T). We employ this system to examine the effect of pressure and non-hydrostatic stress on the Zeeman split d-d transitions of Cr^3+ in ruby (Al2O3: Cr^3+). We determine the effect of pressure and non-hydrostaticity on the trigonal crystal field in this material, and discuss the use of the Zeman-split ruby fluorescence as a possible probe for deviatoric stresses in diamond anvil cell experiments.

  19. High-pressure structures of yttrium hydrides

    NASA Astrophysics Data System (ADS)

    Liu, Lu-Lu; Sun, Hui-Juan; Wang, C. Z.; Lu, Wen-Cai

    2017-08-01

    In this work, the crystal structures of YH3 and YH4 at high pressure (100-250 GPa) have been explored using a genetic algorithm combined with first-principles calculations. New structures of YH3 with space group symmetries of P21/m and I4/mmm were predicted. The electronic structures and the phonon dispersion properties of various YH3 and YH4 structures at different temperatures and pressures were investigated. Among YH3 phases, the P21/m structure of YH3 was found to have a relatively high superconducting transformation temperature T c of 19 K at 120 GPa, which is reduced to 9 K at 200 GPa. Other YH3 structures have much lower T cs. Compared with YH3, the T c of the YH4 compound is much higher, i.e. 94 K at 120 GPa and 55 K at 200 GPa.

  20. Computational chemistry modeling and design of photoswitchable alignment materials for optically addressable liquid crystal devices

    NASA Astrophysics Data System (ADS)

    Marshall, K. L.; Sekera, E. R.; Xiao, K.

    2015-09-01

    Photoalignment technology based on optically switchable "command surfaces" has been receiving increasing interest for liquid crystal optics and photonics device applications. Azobenzene compounds in the form of low-molar-mass, watersoluble salts deposited either directly on the substrate surface or after dispersion in a polymer binder have been almost exclusively employed for these applications, and ongoing research in the area follows a largely empirical materials design and development approach. Recent computational chemistry advances now afford unprecedented opportunities to develop predictive capabilities that will lead to new photoswitchable alignment layer materials with low switching energies, enhanced bistability, write/erase fatigue resistance, and high laser-damage thresholds. In the work described here, computational methods based on the density functional theory and time-dependent density functional theory were employed to study the impact of molecular structure on optical switching properties in photoswitchable methacrylate and acrylamide polymers functionalized with azobenzene and spiropyran pendants.

  1. Examining metal nanoparticle surface chemistry using hollow-core, photonic-crystal, fiber-assisted SERS.

    PubMed

    Eftekhari, Fatemeh; Lee, Anna; Kumacheva, Eugenia; Helmy, Amr S

    2012-02-15

    In this Letter, we demonstrate the efficacy of hollow core photonic crystal fibers (HCPCFs) as a surface-enhanced Raman spectroscopy (SERS) platform for investigating the ligand exchange process on the surface of gold nanoparticles. Raman measurements carried out using this platform show the capability to monitor minute amounts of surface ligands on gold nanoparticles used as an SERS substrate. The SERS signal from an HCPCF exhibits a tenfold enhancement compared to that in a direct sampling scheme using a cuvette. Using exchange of cytotoxic cetyltrimethylammonium bromide with α-methoxy-ω-mercaptopoly(ethylene glycol) on the surface of gold nanorods as an exemplary system, we show the feasibility of using HCPCF SERS to monitor the change in surface chemistry of nanoparticles.

  2. High-Pressure Lightweight Thrusters

    NASA Technical Reports Server (NTRS)

    Holmes, Richard; McKechnie, Timothy; Shchetkovskiy, Anatoliy; Smirnov, Alexander

    2013-01-01

    Returning samples of Martian soil and rock to Earth is of great interest to scientists. There were numerous studies to evaluate Mars Sample Return (MSR) mission architectures, technology needs, development plans, and requirements. The largest propulsion risk element of the MSR mission is the Mars Ascent Vehicle (MAV). Along with the baseline solid-propellant vehicle, liquid propellants have been considered. Similar requirements apply to other lander ascent engines and reaction control systems. The performance of current state-ofthe- art liquid propellant engines can be significantly improved by increasing both combustion temperature and pressure. Pump-fed propulsion is suggested for a single-stage bipropellant MAV. Achieving a 90-percent stage propellant fraction is thought to be possible on a 100-kg scale, including sufficient thrust for lifting off Mars. To increase the performance of storable bipropellant rocket engines, a high-pressure, lightweight combustion chamber was designed. Iridium liner electrodeposition was investigated on complex-shaped thrust chamber mandrels. Dense, uniform iridium liners were produced on chamber and cylindrical mandrels. Carbon/carbon composite (C/C) structures were braided over iridium-lined mandrels and densified by chemical vapor infiltration. Niobium deposition was evaluated for forming a metallic attachment flange on the carbon/ carbon structure. The new thrust chamber was designed to exceed state-of-the-art performance, and was manufactured with an 83-percent weight savings. High-performance C/Cs possess a unique set of properties that make them desirable materials for high-temperature structures used in rocket propulsion components, hypersonic vehicles, and aircraft brakes. In particular, more attention is focused on 3D braided C/Cs due to their mesh-work structure. Research on the properties of C/Cs has shown that the strength of composites is strongly affected by the fiber-matrix interfacial bonding, and that weakening

  3. Survey of High-Pressure Effects in Solids.

    DTIC Science & Technology

    1979-11-01

    nitride; and sintering those crystals. In this study we consider what, if any, research on theo- retical high-pressure physics would be likely to...72 Flash X-Ray Diffraction .......................... 73 References ......................................... 73 IV. NOTE ON FACTORS...V) Relation for Solid Xenon at 850K ... 3 3.1. Wigner-Seitz Electron Energy Levels for Iodine, Xenon, and Cesium, Showing Also Lanthanum and Barium

  4. High-pressure phase transition in {gamma}-hexanitrohexaazaisowurtzitane

    SciTech Connect

    Russell, T.P.; Miller, P.J.; Piermarini, G.J.; Block, S.

    1992-06-25

    FTIR, EDXD, and PLM; data for a new high-pressure polymorph, {zeta}-HNIW, which is formed from {gamma}-HNIW at 0.7 +/- 0.05 GPa and room temperature. The {gamma}-{zeta} transformation is rapid and reversible in single crystals in a hydrostatic pressure transmitting medium, but the {zeta} form could not be retrieved to ambient conditions. 12 refs., 6 figs., 2 tabs.

  5. Combined single crystal polarized XAFS and XRD at high pressure: probing the interplay between lattice distortions and electronic order at multiple length scales in high T c cuprates

    SciTech Connect

    Fabbris, G.; Hücker, M.; Gu, G. D.; Tranquada, J. M.; Haskel, D.

    2016-07-14

    Some of the most exotic material properties derive from electronic states with short correlation length (~10-500 Å), suggesting that the local structural symmetry may play a relevant role in their behavior. In this study, we discuss the combined use of polarized x-ray absorption fine structure and x-ray diffraction at high pressure as a powerful method to tune and probe structural and electronic orders at multiple length scales. Besides addressing some of the technical challenges associated with such experiments, we illustrate this approach with results obtained in the cuprate La1.875Ba0.125CuO4, in which the response of electronic order to pressure can only be understood by probing the structure at the relevant length scales.

  6. Combined single crystal polarized XAFS and XRD at high pressure: probing the interplay between lattice distortions and electronic order at multiple length scales in high T c cuprates

    SciTech Connect

    Fabbris, G.; Hücker, M.; Gu, G. D.; Tranquada, J. M.; Haskel, D.

    2016-07-14

    Some of the most exotic material properties derive from electronic states with short correlation length (~10-500 Å), suggesting that the local structural symmetry may play a relevant role in their behavior. In this study, we discuss the combined use of polarized x-ray absorption fine structure and x-ray diffraction at high pressure as a powerful method to tune and probe structural and electronic orders at multiple length scales. Besides addressing some of the technical challenges associated with such experiments, we illustrate this approach with results obtained in the cuprate La1.875Ba0.125CuO4, in which the response of electronic order to pressure can only be understood by probing the structure at the relevant length scales.

  7. Phase Transitions of Triflate-Based Ionic Liquids under High Pressure.

    PubMed

    Faria, Luiz F O; Ribeiro, Mauro C C

    2015-11-05

    Raman spectroscopy has been used to study phase transitions of ionic liquids based on the triflate anion, [TfO](-), as a function of pressure or temperature. Raman spectra of ionic liquids containing the cations 1-butyl-3-methylimidazolium, [C4C1Im](+), 1-octyl-3-methylimidazolium, [C8C1Im](+), 1-butyl-2,3-dimethylimidazolium, [C4C1C1Im](+), and 1-butyl-1-methylpyrrolidinium, [C4C1Pyr](+), were compared. Vibrational frequencies and binding energy of ionic pairs were calculated by quantum chemistry methods. The ionic liquids [C4C1Im][TfO] and [C4C1Pyr][TfO] crystallize at 1.0 GPa when the pressure is increased in steps of ∼ 0.2 GPa from the atmospheric pressure, whereas [C8C1Im][TfO] and [C4C1C1Im][TfO] do not crystallize up to 2.3 GPa of applied pressure. The low-frequency range of the Raman spectrum of [C4C1Im][TfO] indicates that the system undergoes glass transition, rather than crystallization, when the pressure applied on the liquid has been increased above 2.0 GPa in a single step. Strong hysteresis of spectral features (frequency shift and bandwidth) of the high-pressure crystalline phase when the pressure was released stepwise back to the atmospheric pressure has been found .

  8. High pressure Raman spectroscopy of H2O-CH3OH mixtures.

    PubMed

    Hsieh, Wen-Pin; Chien, Yu-Hsiang

    2015-02-23

    Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

  9. High-pressure behavior of hydrous phases

    NASA Astrophysics Data System (ADS)

    Mookherjee, M.; Tsuchiya, J.; Hermann, A.; Speziale, S.

    2016-12-01

    One of the most distinguishing features of the Earth is its surface water, which is a crucial component in making it a habitable planet. How this water is partitioned among the various reservoirs within the Earth's interior is of considerable interest to the Solid Earth Sciences community. In convergent plate margins such as subduction zone, the hydrous phases in the subducting slabs deliver water into the Earth's interior. Upon reaching greater depths, depending on the limits of their thermodynamic stability, the hydrous phases dehydrate, releasing water. A fraction of water is released back into the hydrosphere through arc volcanism. Recent estimates show that the worldwide flux of water from subducting slabs amounts to about one ocean mass over the age of the Earth. The water in the Earth's interior is stored in several distinct forms: as aqueous fluids; hydrous silicate melts; nominally anhydrous phases; grain boundaries, and various hydrous phases. Among these multiple hosts, hydrous phases are particularly important because they influence solid earth processes in the crust and mantle. The thermodynamic stability of hydrous phases dictates how efficiently they transport and store water in the Earth's interior. Their presence severely affects the onset of melting. Hydrous phases that are likely to be stable at higher pressures are often not recorded in natural samples. It is possible that these hydrous phases are not sampled by melts that arise from depths that are shallower than where high-pressure hydrous phases may occur. It is also possible that these hydrous phases do not survive exhumation. In addition, many hydrous phases might have limited thermal stability. High-pressure experiments and first-principles simulations based on density functional theory (DFT) have been crucial in enhancing our understanding of hydrous phases that are likely to be present in the Earth's mantle and subduction zones. In this study, we present DFT results and compare them with

  10. Pargasite at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Comboni, Davide; Lotti, Paolo; Gatta, G. Diego; Merlini, Marco; Liermann, Hanns-Peter; Frost, Daniel J.

    2017-08-01

    The P-T phase stability field, the thermoelastic behavior and the P-induced deformation mechanisms at the atomic scale of pargasite crystals, from the "phlogopite peridotite unit" of the Finero mafic-ultramafic complex (Ivrea-Verbano Formation, Italy), have been investigated by a series of in situ experiments: (a) at high pressure (up to 20.1 GPa), by single-crystal synchrotron X-ray diffraction with a diamond anvil cell, (b) at high temperature (up to 823 K), by powder synchrotron X-ray diffraction using a hot air blower device, and (c) at simultaneous HP-HT conditions, by single-crystal synchrotron X-ray diffraction with a resistive-heated diamond anvil cell (P max = 16.5 GPa, T max = 1200 K). No phase transition has been observed within the P-T range investigated. At ambient T, the refined compressional parameters, calculated by fitting a second-order Birch-Murnaghan Equation of State (BM-EoS), are: V 0 = 915.2(8) Å3 and K P0,T0 = 95(2) GPa (β P0,T0 = 0.0121(2) GPa-1) for the unit-cell volume; a 0 = 9.909(4) Å and K(a) P0,T0 = 76(2) GPa for the a-axis; b 0 = 18.066(7) Å and K(b) P0,T0 = 111(2) GPa for the b-axis; c 0 = 5.299(5) Å and K(c) P0,T0 = 122(12) GPa for the c-axis [K(c) P0,T0 K(b) P0,T0 > K(a) P0,T0]. The high-pressure structure refinements (at ambient T) show a moderate contraction of the TO4 double chain and a decrease of its bending in response to the hydrostatic compression, along with a pronounced compressibility of the A- and M(4)-polyhedra [K P0, T0(A) = 38(2) GPa, K P0, T0(M4) = 79(5) GPa] if compared to the M(1)-, M(2)-, M(3)-octahedra [K P0, T0(M1,2,3) ≤ 120 GPa] and to the rigid tetrahedra [K P0, T0(T1,T2) 300 GPa]. The thermal behavior, at ambient pressure up to 823 K, was modelled with Berman's formalism, which gives: V 0 = 909.1(2) Å3, α0 = 2.7(2)·10-5 K-1 and α1 = 1.4(6)·10-9 K-2 [with α0(a) = 0.47(6)·10-5 K-1, α0(b) = 1.07(4)·10-5 K-1, and α0(c) = 0.97(7)·10-5 K-1]. The petrological implications for the experimental

  11. Properties Data for Adhesion and Surface Chemistry of Aluminum: Sapphire-Aluminum, Single-Crystal Couple

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa; Pohlchuck, Bobby; Whitle, Neville C.; Hector, Louis G., Jr.; Adams, Jim

    1998-01-01

    An investigation was conducted to examine the adhesion and surface chemistry of single-crystal aluminum in contact with single-crystal sapphire (alumina). Pull-off force (adhesion) measurements were conducted under loads of 0. I to I mN in a vacuum of 10(exp -1) to 10(exp -9) Pa (approx. 10(exp -10) to 10(exp -11) torr) at room temperature. An Auger electron spectroscopy analyzer incorporated directly into an adhesion-measuring vacuum system was primarily used to define the chemical nature of the surfaces before and after adhesion measurements. The surfaces were cleaned by argon ion sputtering. With a clean aluminum-clean -sapphire couple the mean value and standard deviation of pull-off forces required to separate the surfaces were 3015 and 298 micro-N, respectively. With a contaminated aluminum-clean sapphire couple these values were 231 and 241 micro-N. The presence of a contaminant film on the aluminum surface reduced adhesion by a factor of 13. Therefore, surfaces cleanliness, particularly aluminum cleanliness, played an important role in the adhesion of the aluminum-sapphire couples. Pressures on the order of 10(exp -8) to 10(exp -9) Pa (approx. 10(exp -10) to 10(exp -11) torr) maintained a clean aluminum surface for only a short time (less then 1 hr) but maintained a clean sapphire surface, once it was achieved, for a much longer time.

  12. Crystal chemistry and solid lubricating properties of the monochalcogenides gallium selenide and tin selenide

    NASA Astrophysics Data System (ADS)

    Erdemir, Ali

    1994-07-01

    The interatomic array and bond structure in crystalline states of the monochalcogenides tin selenide and gallium selenide are described and correlated with their solid lubricating capacity. Friction tests assessing their solid lubricating performance were carried out on pin-on-disk machine. Specifically, large crystalline pieces of each inorganic solid were cut and cleaved into flat squares and subsequently rubbed against sapphire balls. In another case, fine powders of gallium selenide and tin selenide and tin selenide were manually fed into the sliding interfaces of 440C pins and 440C disks. For the specific test conditions explored, friction coefficients of the sapphirel gallium selenide and sapphire/tin selenide pairs were approximately 0.23 and approximately 0.35, respectively. The friction coefficients of 440C pin/440C disk test pairs with gallium selenide and tin selenide powders were approximately 0.22 and approximately 0.38, respectively. For comparison, a number of parallel friction tests were also performed with MoS2 powders and compacts, and the results of these tests are reported. The friction data, together with the crystal-chemical knowledge and electron microscopy evidence, supported the conclusion that the solid lubricating capabilities and lubrication mechanisms of these solids are closely related to their crystal chemistry and the nature of their interlayer bonding.

  13. Amorphization of Serpentine at High Pressure and High Temperature

    PubMed

    Irifune; Kuroda; Funamori; Uchida; Yagi; Inoue; Miyajima

    1996-06-07

    Pressure-induced amorphization of serpentine was observed at temperatures of 200° to 300°C and pressures of 14 to 27 gigapascals with a combination of a multianvil apparatus and synchrotron radiation. High-pressure phases then crystallized rapidly when the temperature was increased to 400°C. These results suggest that amorphization of serpentine is an unlikely mechanism for generating deep-focus earthquakes, as the temperatures of subducting slabs are significantly higher than those of the rapid crystallization regime.

  14. Nanoscale coherent intergrowthlike defects in a crystal of La1.9Ca1.1Cu2O6 +δ made superconducting by high-pressure oxygen annealing

    NASA Astrophysics Data System (ADS)

    Hu, Hefei; Zhu, Yimei; Shi, Xiaoya; Li, Qiang; Zhong, Ruidan; Schneeloch, John A.; Gu, Genda; Tranquada, John M.; Billinge, Simon J. L.

    2014-10-01

    Superconductivity with Tc=53.5 K has been induced in a large La1.9Ca1.1Cu2O6 (La-2126) single crystal by annealing in a high partial pressure of oxygen at 1200 °C. Using transmission electron microscopy techniques, we show that a secondary Ca-doped La2CuO4 (La-214) phase, not present in the as-grown crystal, appears as a coherent intergrowthlike defect as a consequence of the annealing. A corresponding secondary superconducting transition near 13 K is evident in the magnetization measurement. Electron energy-loss spectroscopy reveals a pre-edge peak at the O-K edge in the superconducting La-2126 phase, which is absent in the as-grown crystal, confirming the hole doping by interstitial oxygen.

  15. Nanoscale coherent intergrowthlike defects in a crystal of La1.9Ca1.1Cu2O6+δ made superconducting by high-pressure oxygen annealing

    DOE PAGES

    Hu, Hefei; Zhu, Yimei; Shi, Xiaoya; ...

    2014-10-28

    Superconductivity with Tc = 53.5 K has been induced in a large La₁.₉Ca₁.₁Cu₂O₆ (La-2126) single crystal by annealing in a high partial-pressure of oxygen at 1200°C. Using transmission electron microscopy (TEM) techniques, we show that a secondary Ca-doped La₂CuO₄ (La-214) phase, not present in the as-grown crystal, appears as a coherent “intergrowth” as a consequence of the annealing. A corresponding secondary superconducting transition near 13 K is evident in the magnetization measurement. In this study, electron energy loss spectroscopy (EELS) reveals a pre-edge peak at the O K edge in the superconducting La-2126 phase, which is absent in the as-grownmore » crystal, confirming the hole-doping by interstitial oxygen.« less

  16. Comment on ``Trace-element crystal chemistry of mantle eclogites'' by F.A. Caporuscio and J.R. Smyth

    NASA Astrophysics Data System (ADS)

    Taylor, Lawrence A.; Neal, Clive R.

    1993-02-01

    Caporuscio and Smyth have presented crystal chemical study on eleven mantle-derived eclogites from the Bellsbank (8) and Roberts Victor (3) kimberlites, South Africa. They combine these results with experimental partition coefficients and geochemical modelling to argue for a high pressure igneous cumulate origin from a MORB-like melt for these eclogites. In particular, they highlight the kyanite-bearing eclogites (grospydites), especially the presence of a “middle rare-earth-element (MREE) enrichment”, which may also be considered in terms of LREE and HREE depletions. Caporuscio and Smyth, as well as Smyth et al., cite this phenomenon as evidence for an origin by igneous accumulation of hyperaluminous clinopyroxene at high pressure. However, this type of REE pattern has also been interpreted as depicting a positive Eu anomaly inherited from a subducted, plagioclase-rich oceanic crustal protolith (Shervais et al., Taylor and Neal, Neal et al.). This manuscript presents an alternative interpretation of the data presented by Caporuscio and Smyth. The results presented here demonstrate that high-pressure igneous accumulation of hyperaluminous pyroxene from a MORB-like liquid, followed by exsolution of major amounts of garnet and kyanite, is unlikely to account for all chemical signatures exhibited by grospydites. Our approach is to undertake quantitative geochemical modelling of these processes using the actual samples and literature values quoted by Caporuscio and Smyth.

  17. NETL- High-Pressure Combustion Research Facility

    SciTech Connect

    2013-07-08

    NETL's High-Pressure Combustion Facility is a unique resource within the National Laboratories system. It provides the test capabilities needed to evaluate new combustion concepts for high-pressure, high-temperature hydrogen and natural gas turbines. These concepts will be critical for the next generation of ultra clean, ultra efficient power systems.

  18. High pressure apparatus for magnetization measurements

    SciTech Connect

    Uwatoko, Y.; Hotta, T.; Mori, H.

    1997-10-01

    A hydrostatic high pressure micro cell for studying heavy-fermion materials in a commercial magnetometer is developed. Experiments of pressures up to 10 kbar and temperature range 2 K {le} T {le} 300 K have been carried out. The sensitivity of measurement of under high pressure is as same as ambient pressure one within experimental error.

  19. NETL- High-Pressure Combustion Research Facility

    ScienceCinema

    None

    2016-07-12

    NETL's High-Pressure Combustion Facility is a unique resource within the National Laboratories system. It provides the test capabilities needed to evaluate new combustion concepts for high-pressure, high-temperature hydrogen and natural gas turbines. These concepts will be critical for the next generation of ultra clean, ultra efficient power systems.

  20. Elastomers Compatible With High-Pressure Oxygen

    NASA Technical Reports Server (NTRS)

    Martin, Jon W.

    1987-01-01

    Compatibility increased by fluorination. Report describes experiments aimed at improving compatibility of some fluorinated elastomers with high-pressure oxygen. Such elastomers needed for seals, gaskets, and positive-expulsion devices used with high-pressure oxygen. Oxygen - compatibility tests carried out on five elastomers chosen on the basis of literature survey.

  1. Ultra high pressure liquid chromatography for crude plant extract profiling.

    PubMed

    Eugster, Philippe J; Guillarme, Davy; Rudaz, Serge; Veuthey, Jean-Luc; Carrupt, Pierre-Alain; Wolfender, Jean-Luc

    2011-01-01

    Ultra high pressure liquid chromatography (UHPLC) systems operating at very high pressures and using sub-2 microm packing columns have allowed a remarkable decrease in analysis time and increase in peak capacity, sensitivity, and reproducibility compared to conventional HPLC. This technology has rapidly been widely accepted by the analytical community and is being gradually applied to various fields of plant analysis such as QC, profiling and fingerprinting, dereplication, and metabolomics. For many applications, an important improvement of the overall performances has been reported. In this review, the basic principles of UHPLC are summarized, and practical information on the type of columns used and phase chemistry available is provided. An overview of the latest applications to natural product analysis in complex mixtures is given, and the potential and limitations as well as some new trends in the development of UHPLC are discussed.

  2. High-pressure synthesis, crystal structure, and electromagnetic properties of CdRh2O4: an analogous oxide of the postspinel mineral MgAl2O4.

    PubMed

    Wang, Xia; Guo, Yanfeng; Shi, Youguo; Belik, Alexei A; Tsujimoto, Yoshihiro; Yi, Wei; Sun, Ying; Shirako, Yuichi; Arai, Masao; Akaogi, Masaki; Matsushita, Yoshitaka; Yamaura, Kazunari

    2012-06-18

    The postspinel mineral MgAl(2)O(4) exists only under the severe pressure conditions in the subducted oceanic lithosphere in the Earth's deep interior. Here we report that its analogous oxide CdRh(2)O(4) exhibits a structural transition to a quenchable postspinel phase under a high pressure of 6 GPa at 1400 °C, which is within the general pressure range of a conventional single-stage multianvil system. In addition, the complex magnetic contributions to the lattice and metal nonstoichiometry that often complicate investigations of other analogues of MgAl(2)O(4) are absent in CdRh(2)O(4). X-ray crystallography revealed that this postspinel phase has an orthorhombic CaFe(2)O(4) structure, thus making it a practical analogue for investigations into the geophysical role of postspinel MgAl(2)O(4). Replacement of Mg(2+) with Cd(2+) appears to be effective in lowering the pressure required for transition, as was suggested for CdGeO(3). In addition, Rh(3+) could also contribute to this reduction, as many analogous Rh oxides of aluminous and silicic minerals have been quenched from lower-pressure conditions.

  3. Collision condition indicted by High Pressure Phases in a Chondrite

    NASA Astrophysics Data System (ADS)

    Kato, Y.; Sekine, T.; Kayama, M.; Miyahara, M.; Yamaguchi, A.

    2012-12-01

    It has been generally recognized that there were many collisions during planetary accretion. Chondrites include the materials at the time of formation of the solar system. It is essential to unravel the shock history in meteorites and the parent planet in order to understand such collisional processes. In this study, we investigate a thin section of ordinary chondrite Y-790729 classified as L6 in which high-pressure minerals are found in the about 620-μm-wide shock vein. The mineralogical and chemical features give us detailed information to constrain the shock conditions. We have tried to constrain the P-T condition from the viewpoints of the mineral assemblage and cathodoluminescense (CL) spectroscopy. Y-790729 consists mostly of olivine and pyroxene and has shock veins. To identify high pressure phases, we used an optical microscope, a scanning electron microscope (SEM), micro Raman spectroscopy, and electron probe micro analyzer (EPMA). In addition, scanning electron microscopy-cathodoluminescence (SEM-CL) analysis, detectable shock-induced defect centers, was used to characterize the shock metamorphism in feldspar minerals. The presence of shock vein, maskelynite, and high pressure phases confirms shock record. 7 high pressure phases of ringwoodite, high-pressure clinoenstatite (HPC), majorite, merrillite, lingunite, high-pressure chromite and akimotoite were found in this section. All of them exist only in a shock vein, but maskelynite occurs everywhere in the section. From these observations, it is obvious that the shock vein experienced the high pressure and high temperature generated by shock wave. If some of the high pressure minerals are equilibrated, the P-T condition can be estimated. Based on the equilibrium phase diagram of MgSiO3 polymorphs (Presnall. 1995), the P-T conditions for crystallization of majorite, HPC and akimotoite is about 17 GPa and 1600 oC, because the compositions of the three phases are close to MgSiO3. It is consistent with the

  4. Crystallization of pegmatites: Insights from chemistry of garnet, Jacumba pegmatites, San Diego County, California

    NASA Astrophysics Data System (ADS)

    Thompson, M.; Sirbescu, M. C.

    2013-12-01

    Systematic mineral and textural variations from the border zone to the core of a zoned pegmatite sheet may reflect the kinetic or equilibrium fractionation processes that occurred during sequential crystallization of the pegmatite magma. Rhythmic layering, also named 'line rock', is a salient textural feature of world famous San Diego Co. pegmatites, that consists of alternating garnet × tourmaline layers and albite - quartz layers, mm's to cm's thick. Slowly diffusing, incompatible elements in the felsic magma including B, Fe, and Mn may become enriched in boundary layers formed ahead of rapidly crystallized quartzo-felspathic assemblages. This study explores whether the chemistry of garnet concentrated in the border and foot-wall zones and dispersed in the graphic feldspar, core, and pocket zones of Garnet Ledge pegmatite, Jacumba district, might fingerprint the diffusion-controlled oscillatory boundary layers. The lithium-cesium-tantalum (LCT) Jacumba pegmatite district, late product of the Eastern Peninsular Ranges Batholith, consists of numerous subparallel dikes, 3 to 7 m thick, intruding pre-batholitic metasedimentary rocks. The composite aplite-pegmatite dikes are texturally diverse. Comb-textured tourmaline, other unidirectional textures, garnet × tourmaline 'line rock', and coarse graphic K-feldspar crystals occur in the outer zones, followed by massive feldspar-quartz cores, vuggy cleavlandite- euhedral garnet, and miarolitic cavities. The Jacumba pegmatites have produced gem spodumene, beryl, and garnet from several open cuts such as the Beebe Hole and Pack Rat - Garnet Ledge workings. Systematic mineralogical and textural variations, and SEM-EDS garnet compositions were recorded from border to core at Garnet Ledge outcrop and thin section scale, focusing on continuous traverses across the line rock. Garnet from Garnet Ledge belongs to the spessartine-almandine series (Sp42 to Sp65) with minor contents of Mg, Ca, and Ti, consistent with garnet

  5. Crystal chemistry of volcanic allanites indicative of naturally induced oxidation-dehydrogenation

    NASA Astrophysics Data System (ADS)

    Hoshino, Mihoko; Kimata, Mitsuyoshi; Chesner, Craig A.; Nishida, Norimasa; Shimizu, Masahiro; Akasaka, Takeshi

    2010-05-01

    The crystal chemistry of volcanic allanites from both the Youngest Toba Tuff (YTT), Sumatra, Indonesia and SK100 volcanic ash beds (SK100-VAB), Niigata, Japan has been examined by electron microprobe analysis (EMPA), Fourier-transform infrared spectroscopic analysis (FTIR), and single-crystal structure analysis. In the FTIR study, based on the Diamond ATR accessory, YTT and SK100- VAB allanites were observed to have different OH contents, respectively: the former has 0.64 wt% H2O (OH: 0.40 apfu.), while the latter has 1.65 wt% H2O (OH: 1.00 apfu.). The crystal structures of these two allanites have been refined to individual R indices (3.64 and 4.25) based on 1350 observed reflections (|Fo| > 4sig|Fo|) measured using a single-crystal diffractometer with MoKα X-radiation. The OH-poor YTT allanite has a shorter b axis, a longer c axis, and larger β value than the relatively OH-rich SK100-VAB one. The bond valence sums of O4 (accepter oxygen for H atom) and O10 (donor oxygen for H atom) are 1.962 and 1.709 v.u. for YTT allanite (valence sum: 3.671 v.u.) and 1.754 and 1.271 v.u. for SK100-VAB one (valence sum: 3.025 v.u.). The difference from the ideal total bond valence value (4.00 v.u.) of O4 and O10 in YTT allanite (0.33 v.u.) is smaller than that in SK100-VAB (0.98 v.u.). These difference values are also broadly consistent with the corresponding differences in OH content between the YTT (OH: 0.40 apfu.) and SK100-VAB allanites (OH: 1.00 apfu.) determined by FTIR- ATR. Chemical analyses, FTIR-ATR and crystal structure refinement of YTT and SK100-VAB allanites yielded the following crystal chemical formula: YTT: (Ca0.83Mn2+ 0.06Fe2+ 0.11)(La0.24Ce0.32Pr0.04Nd0.11Sm0.02Th0.04Ca0.21)(Al0.73Fe3+ 0.19Ti0.08)(Al0.89Fe3+ 0.11)(Fe2+ 0.22Fe3+ 0.62Mg0.16)(SiO4)Si2O7O1.6(OH)0.4, SK100-VAB: (Ca0.81Fe2+ 0.13Mn2+ 0.06)(La0.22Ce0.34Pr0.05Nd0.13Sm0.02Th0.02Ca0.22)(Al0.76Fe3+ 0.19Ti0.05)Al1.00(Fe2+ 0.73Fe3+ 0.17Mg0.10)(Si0.96Al0.04O4)Si2O7O(OH). Therefore, it is concluded that

  6. Method of producing a high pressure gas

    DOEpatents

    Bingham, Dennis N.; Klingler, Kerry M.; Zollinger, William T.

    2006-07-18

    A method of producing a high pressure gas is disclosed and which includes providing a container; supplying the container with a liquid such as water; increasing the pressure of the liquid within the container; supplying a reactant composition such as a chemical hydride to the liquid under pressure in the container and which chemically reacts with the liquid to produce a resulting high pressure gas such as hydrogen at a pressure of greater than about 100 pounds per square inch of pressure; and drawing the resulting high pressure gas from the container.

  7. Design of high pressure waterjet nozzles

    NASA Technical Reports Server (NTRS)

    Mazzoleni, Andre P.

    1994-01-01

    The Hydroblast Research Cell at Marshall Space Flight Center is used to investigate the use of high pressure waterjets to strip paint, grease, adhesive and thermal spray coatings from various substrates. Current methods of cleaning often use ozone depleting chemicals (ODC) such as chlorinated solvents. High pressure waterjet cleaning has proven to be a viable alternative to the use of solvents. A popular method of waterjet cleaning involves the use of a rotating, multijet, high pressure water nozzle which is robotically controlled. This method enables rapid cleaning of a large area, but problems such as incomplete coverage and damage to the substrate from the waterjet have been observed. This report summarizes research consisting of identifying and investigating the basic properties of rotating, multijet, high pressure water nozzles, and how particular designs and modes of operation affect such things as stripping rate, standoff distance and completeness of coverage. The study involved computer simulations, an extensive literature review, and experimental studies of different nozzle designs.

  8. High pressure elasticity and thermal properties of depleted uranium

    DOE PAGES

    Jacobsen, M. K.; Velisavljevic, N.

    2016-04-28

    Studies of the phase diagram of uranium have revealed a wealth of high pressure and temperature phases. Under ambient conditions the crystal structure is well defined up to 100 gigapascals (GPa), but very little information on thermal conduction or elasticity is available over this same range. This work has applied ultrasonic interferometry to determine the elasticity, mechanical, and thermal properties of depleted uranium to 4.5 GPa. Results show general strengthening with applied load, including an overall increase in acoustic thermal conductivity. Further implications are discussed within. Lastly, this work presents the first high pressure studies of the elasticity and thermalmore » properties of depleted uranium metal and the first real-world application of a previously developed containment system for making such measurements.« less

  9. High pressure elasticity and thermal properties of depleted uranium

    SciTech Connect

    Jacobsen, M. K. Velisavljevic, N.

    2016-04-28

    Studies of the phase diagram of uranium have revealed a wealth of high pressure and temperature phases. Under ambient conditions the crystal structure is well defined up to 100 gigapascals (GPa), but very little information on thermal conduction or elasticity is available over this same range. This work has applied ultrasonic interferometry to determine the elasticity, mechanical, and thermal properties of depleted uranium to 4.5 GPa. Results show general strengthening with applied load, including an overall increase in acoustic thermal conductivity. Further implications are discussed within. This work presents the first high pressure studies of the elasticity and thermal properties of depleted uranium metal and the first real-world application of a previously developed containment system for making such measurements.

  10. High-pressure polymorphism of acetylsalicylic acid (aspirin): Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Crowell, Ethan L.; Dreger, Zbigniew A.; Gupta, Yogendra M.

    2015-02-01

    Micro-Raman spectroscopy was used to elucidate the high-pressure polymorphic behavior of acetylsalicylic acid (ASA), an important pharmaceutical compound known as aspirin. Using a diamond anvil cell (DAC), single crystals of the two polymorphic phases of aspirin existing at ambient conditions (ASA-I and ASA-II) were compressed to 10 GPa. We found that ASA-I does not transform to ASA-II, but instead transforms to a new phase (ASA-III) above ∼2 GPa. It is demonstrated that this transformation primarily introduces structural changes in the bonding and arrangement of the acetyl groups and is reversible upon the release of pressure. In contrast, a less dense ASA-II shows no transition in the pressure range studied, though it appears to exhibit a disordered structure above 7 GPa. Our results suggest that ASA-III is the most stable polymorph of aspirin at high pressures.

  11. High pressure elasticity and thermal properties of depleted uranium

    NASA Astrophysics Data System (ADS)

    Jacobsen, M. K.; Velisavljevic, N.

    2016-04-01

    Studies of the phase diagram of uranium have revealed a wealth of high pressure and temperature phases. Under ambient conditions the crystal structure is well defined up to 100 gigapascals (GPa), but very little information on thermal conduction or elasticity is available over this same range. This work has applied ultrasonic interferometry to determine the elasticity, mechanical, and thermal properties of depleted uranium to 4.5 GPa. Results show general strengthening with applied load, including an overall increase in acoustic thermal conductivity. Further implications are discussed within. This work presents the first high pressure studies of the elasticity and thermal properties of depleted uranium metal and the first real-world application of a previously developed containment system for making such measurements.

  12. The high-pressure compressibility of B12P2

    NASA Astrophysics Data System (ADS)

    Gao, Yang; Zhou, Mi; Wang, Haiyan; Ji, Cheng; Whiteley, C. E.; Edgar, J. H.; Liu, Haozhe; Ma, Yanzhang

    2017-03-01

    In situ high pressure synchrotron X-ray diffraction measurements were performed on icosahedral boron phosphide (B12P2) to 43.2 GPa. No structural phase transition occurs over this pressure range. The bulk modulus of B12P2 is KOT = 207 ± 7 GPa with pressure derivative of K'OT = 6.6 ± 0.8 . The structure is most compressible along the chain formed by phosphorus and boron atoms in the crystal structure. It is believed that the compressibility of boron-rich compounds at close to ambient pressure is determined by the boron icosahedral structure, while the inclusive atoms (both boron and non-boron) between the icosahedra determine the high-pressure compressibility and structure stability.

  13. An Inexpensive Sampleable Reactor for High-Pressure Chemistry.

    ERIC Educational Resources Information Center

    Shumate, R. E.; Riley, D. P.

    1984-01-01

    Describes how to modify the commercially available and inexpensive Griffin-Worden (Kontes) glass pressure reactors to permit sampling of homogeneous reactions, without changing the relative concentration of species present. All required parts necessary for the modification are commercially available. (JN)

  14. Multicomponent fuel vaporization at high pressures.

    SciTech Connect

    Torres, D. J.; O'Rourke, P. J.

    2002-01-01

    We extend our multicomponent fuel model to high pressures using a Peng-Robinson equation of state, and implement the model into KIVA-3V. Phase equilibrium is achieved by equating liquid and vapor fugacities. The latent heat of vaporization and fuel enthalpies are also corrected for at high pressures. Numerical simulations of multicomponent evaporation are performed for single droplets for a diesel fuel surrogate at different pressures.

  15. Manufacturing Diamond Under Very High Pressure

    NASA Technical Reports Server (NTRS)

    Voronov, Oleg

    2007-01-01

    A process for manufacturing bulk diamond has been made practical by the invention of the High Pressure and Temperature Apparatus capable of applying the combination of very high temperature and high pressure needed to melt carbon in a sufficiently large volume. The apparatus includes a reaction cell wherein a controlled static pressure as high as 20 GPa and a controlled temperature as high as 5,000 C can be maintained.

  16. High Pressure Waterjet Cutting Industrial Needs Survey

    DTIC Science & Technology

    1989-08-25

    Report No. LO High Pressure Waterjet Cutting Industrial Needs Survey N Contract Number N00140-88-C-RC21 I John Klavuhn and Bruce Baker Metalworking...NO. NO ACCESSION NO. Washington, DC 20360-5100 1I TITLE (Include Security Classification) High Pressure Waterjet Cutting Industrial Needs Survey 12...block number) FIELD GROUP SUB-GROUP FIELD__ GROUP____UB-GROUP Waterjet cutting , abrasive waterjet cutting ’. ABSTRACT (Continue on reverse if

  17. Ultra High Pressure (UHP) Technology (BRIEFING SLIDES)

    DTIC Science & Technology

    2008-08-25

    AFRL-RX-TY-TP-2008-4600 POSTPRINT ULTRA HIGH PRESSURE ( UHP ) TECHNOLOGY (BRIEFING SLIDES) Patrick D. Sullivan Air Force Research...Since the discovery of the unprecedented effectiveness of 1500 psi Ultra High Pressure ( UHP ) technology in September of 2002 , AFRL scientists and... engineers have sought to increase Aircraft Rescue Fire Fighting (ARFF) performance by moving to higher flow rates to obtain greater throw distance and

  18. High Pressure Materials Research: Novel Extended Phases of Molecular Triatomics

    SciTech Connect

    Yoo, C

    2004-05-26

    Application of high pressure significantly alters the interatomic distance and thus the nature of intermolecular interaction, chemical bonding, molecular configuration, crystal structure, and stability of solid [1]. With modern advances in high-pressure technologies [2], it is feasible to achieve a large (often up to a several-fold) compression of lattice, at which condition material can be easily forced into a new physical and chemical configuration [3]. The high-pressure thus offers enhanced opportunities to discover new phases, both stable and metastable ones, and to tune exotic properties in a wide-range of atomistic length scale, substantially greater than (often being several orders of) those achieved by other thermal (varying temperatures) and chemical (varying composition or making alloys) means. Simple molecular solids like H{sub 2}, C, CO{sub 2}, N{sub 2}, O{sub 2}, H{sub 2}O, CO, NH{sub 3}, and CH{sub 4} are bounded by strong covalent intramolecular bonds, yet relatively weak intermolecular bonds of van der Waals and/or hydrogen bonds. The weak intermolecular bonds make these solids highly compressible (i.e., low bulk moduli typically less than 10 GPa), while the strong covalent bonds make them chemically inert at least initially at low pressures. Carbon-carbon single bonds, carbon-oxygen double bonds and nitrogen-nitrogen triple bonds, for example, are among the strongest. These molecular forms are, thus, often considered to remain stable in an extended region of high pressures and high temperatures. High stabilities of these covalent molecules are also the basis of which their mixtures are often presumed to be the major detonation products of energetic materials as well as the major constituents of giant planets. However, their physical/chemical stabilities are not truly understood at those extreme pressure-temperature conditions. In fact, an increasing amount of experimental evidences contradict the assumed stability of these materials at high

  19. Crystal Chemistry and Ceramic Processing of Rare Earth Chalcogenide Optical and Electronic Materials

    NASA Astrophysics Data System (ADS)

    Vaughan, Cheryl Marie

    1990-01-01

    The thesis is concerned with the development of new IR transmitting materials for the 8-14 micrometer atomspheric window. The strategy was to investigate, in detail, the synthesis, crystal chemistry, processing, optical, and electronic properties of the rare earth sulfide as candidate materials. The rare earths crystallize in five known structures. Study of their temperature stabilities during long reaction times showed that alpha (orthorhombic, Pnma) exists as the low temperature form, and gamma (cubic, I| 43d) exists as the high temperature form in the large rare earths. Delta (monoclinic, P2/m) exists in the smaller rare earths from Ho through Tm over all temperature ranges, and episilon (trigonal, R| 3c) forms from Yb and Lu. Beta (tetragonal, I4/acd), which is reported in literature as a mid temperature range, oxygen stabilized rare earth sulfide, appears to be an oxysulfide and is an intermediate step between the oxide and sulfide from La through Nd. Extremely fine-grained precursor oxides were synthesized by evaporative decomposition of solution. An ultrasonic dispersion of aqueous nitrate salts is misted into a hot walled furnace. The 2-5 micrometer resulting oxides were predominantly well-crystallized spherical particles. The sesquisulfides could be readily synthesized by direct reaction of the oxides with flowing H_2S in the presence of graphite. These reactive, fine-grained, EDS-derived sulfides could be sintered into ceramic compacts that achieved 92 -98 percent of theoretical density. Sintering temperatures from 1200^circ-1400 ^circC and time of 80-120 minutes in flowing H_2S produced the best ceramics. This method of preparation is superior to the method using stock 25-35 micrometer starting materials which only received 70-78 percent of theoretical density. The measurement of the electronic absorption edge yielded band gaps of 1.6-2.6 eV. The first-order transverse and longitudinal phonon frequencies obtained by specular reflectance FTIR spectroscopy

  20. Advanced Synchrotron Techniques at High Pressure Collaborative Access Team (HPCAT)

    NASA Astrophysics Data System (ADS)

    Shen, G.; Sinogeikin, S. V.; Chow, P.; Kono, Y.; Meng, Y.; Park, C.; Popov, D.; Rod, E.; Smith, J.; Xiao, Y.; Mao, H.

    2012-12-01

    High Pressure Collaborative Access Team (HPCAT) is dedicated to advancing cutting-edge, multidisciplinary, high-pressure science and technology using synchrotron radiation at Sector 16 of the Advanced Photon Source (APS) of Argonne National Laboratory. At HPCAT an array of novel x-ray diffraction and spectroscopic techniques has been integrated with high pressure and extreme temperature instrumentation for studies of structure and materials properties at extreme conditions.. HPCAT consists of four active independent beamlines performing a large range of various experiments at extreme conditions. 16BM-B beamline is dedicated to energy dispersive and white Laue X-ray diffraction. The majority of experiments are performed with a Paris-Edinburgh large volume press (to 7GPa and 2500K) and include amorphous and liquid structure measurement, white beam radiography, elastic sound wave velocity measurement of amorphous solid materials, with viscosity and density measurement of liquid being under development. 16BM-D is a monochromatic diffraction beamline for powder and single crystal diffraction at high pressure and high (resistive heating) / low (cryostats) temperature. The additional capabilities include high-resolution powder diffraction and x-ray absorption near edge structure (XANES) spectroscopy. The insertion device beamline of HPCAT has two undulators in canted mode (operating independently) and LN cooled Si monochromators capable of providing a large range of energies. 16IDB is a microdiffraction beamline mainly focusing on high-pressure powder and single crystal diffraction in DAC at high temperatures (double-sided laser heating and resistive heating) and low temperature (various cryostats). The modern instrumentation allows high-quality diffraction at megabar pressures from light element, fast experiments with pulsed laser heating, fast dynamic experiments with Pilatus detector, and so on. 16ID-D beamline is dedicated to x-ray scattering and spectroscopy research

  1. Hexacoordinated nitrogen(V) stabilized by high pressure

    NASA Astrophysics Data System (ADS)

    Kurzydłowski, Dominik; Zaleski-Ejgierd, Patryk

    2016-11-01

    In all of its known connections nitrogen retains a valence shell electron count of eight therefore satisfying the golden rule of chemistry - the octet rule. Despite the diversity of nitrogen chemistry (with oxidation states ranging from + 5 to -3), and despite numerous efforts, compounds containing nitrogen with a higher electron count (hypervalent nitrogen) remain elusive and are yet to be synthesized. One possible route leading to nitrogen’s hypervalency is the formation of a chemical moiety containing pentavalent nitrogen atoms coordinated by more than four substituents. Here, we present theoretical evidence that a salt containing hexacoordinated nitrogen(V), in the form of an NF6- anion, could be synthesized at a modest pressure of 40 GPa (=400 kbar) via spontaneous oxidation of NF3 by F2. Our results indicate that the synthesis of a new class of compounds containing hypervalent nitrogen is within reach of current high-pressure experimental techniques.

  2. The Effects of Chemistry and Crystal Structure on the Lubrication Properties of Sputtered MoS2 Films

    DTIC Science & Technology

    1988-05-25

    view rejection, applied laser spectroscopy, laser chemistry, laser optoelectronics, solar cell physics, battery electrochemistry, space vacuum and...The f~oAs of~ Cem stry and Crystal Structure on the Lubrication Properties of Sputtered MoS2 Films PAUL D. FLEISCHAUER and R. BAUER Chemisty and...ABSTRACT (Continue on reverse if necessary and identify by block number) Lubricating films of MoS2 have been prepared by sputter deposition onto steel

  3. High-temperature, high-pressure hydrothermal synthesis, crystal structure, and solid-state NMR spectroscopy of Cs2(UO2)(Si2O6) and variable-temperature powder X-ray diffraction study of the hydrate phase Cs2(UO2)(Si2O6) x 0.5H2O.

    PubMed

    Chen, Chih-Shan; Chiang, Ray-Kuang; Kao, Hsien-Ming; Lii, Kwang-Hwa

    2005-05-30

    A new uranium(VI) silicate, Cs2(UO2)(Si2O6), has been synthesized by a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction and solid-state NMR spectroscopy. It crystallizes in the orthorhombic space group Ibca (No. 73) with a = 15.137(1) A, b = 15.295(1) A, c = 16.401(1) A, and Z = 16. Its structure consists of corrugated achter single chains of silicate tetrahedra extending along the c axis linked together via corner-sharing by UO6 tetragonal bipyramids to form a 3-D framework which delimits 8- and 6-ring channels. The Cs+ cations are located in the channels or at sites between channels. The 29Si and 133Cs MAS NMR spectra are consistent with the crystal structure as determined from X-ray diffraction, and the resonances in the spectra are assigned. Variable-temperature in situ powder X-ray diffraction study of the hydrate Cs2(UO2)(Si2O6) x 0.5H2O indicates that the framework structure is stable up to 800 degrees C and transforms to the structure of the title compound at 900 degrees C. A comparison of related uranyl silicate structures is made.

  4. Theoretical Thermodynamics of Mixtures at High Pressures

    NASA Technical Reports Server (NTRS)

    Hubbard, W. B.

    1985-01-01

    The development of an understanding of the chemistry of mixtures of metallic hydrogen and abundant, higher-z material such as oxygen, carbon, etc., is important for understanding of fundamental processes of energy release, differentiation, and development of atmospheric abundances in the Jovian planets. It provides a significant theoretical base for the interpretation of atmospheric elemental abundances to be provided by atmospheric entry probes in coming years. Significant differences are found when non-perturbative approaches such as Thomas-Fermi-Dirac (TFD) theory are used. Mapping of the phase diagrams of such binary mixtures in the pressure range from approx. 10 Mbar to approx. 1000 Mbar, using results from three-dimensional TFD calculations is undertaken. Derivation of a general and flexible thermodynamic model for such binary mixtures in the relevant pressure range was facilitated by the following breakthrough: there exists an accurate nd fairly simple thermodynamic representation of a liquid two-component plasma (TCP) in which the Helmholtz free energy is represented as a suitable linear combination of terms dependent only on density and terms which depend only on the ion coupling parameter. It is found that the crystal energies of mixtures of H-He, H-C, and H-O can be satisfactorily reproduced by the same type of model, except that an effective, density-dependent ionic charge must be used in place of the actual total ionic charge.

  5. Novel Stable Compounds in the C-H-O Ternary System at High Pressure

    PubMed Central

    Saleh, Gabriele; Oganov, Artem R.

    2016-01-01

    The chemistry of the elements is heavily altered by high pressure, with stabilization of many new and often unexpected compounds, the emergence of which can profoundly change models of planetary interiors, where high pressure reigns. The C-H-O system is one of the most important planet-forming systems, but its high-pressure chemistry is not well known. Here, using state-of-the-art variable-composition evolutionary searches combined with quantum-mechanical calculations, we explore the C-H-O system at pressures up to 400 GPa. Besides uncovering new stable polymorphs of high-pressure elements and known molecules, we predicted the formation of new compounds. A 2CH4:3H2 inclusion compound forms at low pressure and remains stable up to 215 GPa. Carbonic acid (H2CO3), highly unstable at ambient conditions, was predicted to form exothermically at mild pressure (about 1 GPa). As pressure rises, it polymerizes and, above 314 GPa, reacts with water to form orthocarbonic acid (H4CO4). This unexpected high-pressure chemistry is rationalized by analyzing charge density and electron localization function distributions, and implications for general chemistry and planetary science are also discussed. PMID:27580525

  6. Novel Stable Compounds in the C-H-O Ternary System at High Pressure

    NASA Astrophysics Data System (ADS)

    Saleh, Gabriele; Oganov, Artem R.

    2016-09-01

    The chemistry of the elements is heavily altered by high pressure, with stabilization of many new and often unexpected compounds, the emergence of which can profoundly change models of planetary interiors, where high pressure reigns. The C-H-O system is one of the most important planet-forming systems, but its high-pressure chemistry is not well known. Here, using state-of-the-art variable-composition evolutionary searches combined with quantum-mechanical calculations, we explore the C-H-O system at pressures up to 400 GPa. Besides uncovering new stable polymorphs of high-pressure elements and known molecules, we predicted the formation of new compounds. A 2CH4:3H2 inclusion compound forms at low pressure and remains stable up to 215 GPa. Carbonic acid (H2CO3), highly unstable at ambient conditions, was predicted to form exothermically at mild pressure (about 1 GPa). As pressure rises, it polymerizes and, above 314 GPa, reacts with water to form orthocarbonic acid (H4CO4). This unexpected high-pressure chemistry is rationalized by analyzing charge density and electron localization function distributions, and implications for general chemistry and planetary science are also discussed.

  7. Metastable high-pressure transformations of orthoferrosilite Fs82

    NASA Astrophysics Data System (ADS)

    Dera, Przemyslaw; Finkelstein, Gregory J.; Duffy, Thomas S.; Downs, Robert T.; Meng, Yue; Prakapenka, Vitali; Tkachev, Sergey

    2013-08-01

    High-pressure single-crystal X-ray diffraction experiments with natural ferrosilite Fs82 (Fe2+0.82Mg0.16Al0.01Ca0.01)(Si0.99Al0.01)O3 orthopyroxene (opx) reveal that at ambient temperature the sample does not transform to the clinopyroxene (cpx) structure, as reported earlier for a synthetic Fs100 end-member (Hugh-Jones et al., 1996), but instead undergoes a series of two polymorphic transitions, first above 10.1(1) GPa, to the monoclinic P21/c phase β-opx (distinctly different from both P21/c and C2/c cpx), also observed in natural enstatite (Zhang et al., 2012), and then, above 12.3(1) GPa to a high-pressure orthorhombic Pbca phase γ-opx, predicted for MgSiO3 by atomistic simulations (Jahn, 2008). The structures of phases α, β and γ have been determined from the single-crystal data at pressures of 2.3(1), 11.1(1), and 14.6(1) GPa, respectively. The two new high-pressure transitions, very similar in their character to the P21/c-C2/c transformation of cpx, make opx approximately as dense as cpx above 12.3(1) GPa and significantly change the elastic anisotropy of the crystal, with the [1 0 0] direction becoming almost twice as stiff as in the ambient α-opx phase. Both transformations involve mainly tetrahedral rotation, are reversible and are not expected to leave microstructural evidence that could be used as a geobarometric proxy. The high Fe2+ content in Fs82 shifts the α-β transition to slightly lower pressure, compared to MgSiO3, and has a very dramatic effect on reducing the (meta) stability range of the β-phase.

  8. Fuel droplet burning rates at high pressures.

    NASA Technical Reports Server (NTRS)

    Canada, G. S.; Faeth, G. M.

    1973-01-01

    Combustion of methanol, ethanol, propanol-1, n-pentane, n-heptane, and n-decane was observed in air under natural convection conditions, at pressures up to 100 atm. The droplets were simulated by porous spheres, with diameters in the range from 0.63 to 1.90 cm. The pressure levels of the tests were high enough so that near-critical combustion was observed for methanol and ethanol. Due to the high pressures, the phase-equilibrium models of the analysis included both the conventional low-pressure approach as well as high-pressure versions, allowing for real gas effects and the solubility of combustion-product gases in the liquid phase. The burning-rate predictions of the various theories were similar, and in fair agreement with the data. The high-pressure theory gave the best prediction for the liquid-surface temperatures of ethanol and propanol-1 at high pressure. The experiments indicated the approach of critical burning conditions for methanol and ethanol at pressures on the order of 80 to 100 atm, which was in good agreement with the predictions of both the low- and high-pressure analysis.

  9. Piston cylinder cell for high pressure ultrasonic pulse echo measurements

    SciTech Connect

    Kepa, M. W. Huxley, A. D.; Ridley, C. J.; Kamenev, K. V.

    2016-08-15

    Ultrasonic techniques such as pulse echo, vibrating reed, or resonant ultrasound spectroscopy are powerful probes not only for studying elasticity but also for investigating electronic and magnetic properties. Here, we report on the design of a high pressure ultrasonic pulse echo apparatus, based on a piston cylinder cell, with a simplified electronic setup that operates with a single coaxial cable and requires sample lengths of mm only. The design allows simultaneous measurements of ultrasonic velocities and attenuation coefficients up to a pressure of 1.5 GPa. We illustrate the performance of the cell by probing the phase diagram of a single crystal of the ferromagnetic superconductor UGe{sub 2}.

  10. Energy efficient engine high-pressure turbine detailed design report

    NASA Technical Reports Server (NTRS)

    Thulin, R. D.; Howe, D. C.; Singer, I. D.

    1982-01-01

    The energy efficient engine high-pressure turbine is a single stage system based on technology advancements in the areas of aerodynamics, structures and materials to achieve high performance, low operating economics and durability commensurate with commercial service requirements. Low loss performance features combined with a low through-flow velocity approach results in a predicted efficiency of 88.8 for a flight propulsion system. Turbine airfoil durability goals are achieved through the use of advanced high-strength and high-temperature capability single crystal materials and effective cooling management. Overall, this design reflects a considerable extension in turbine technology that is applicable to future, energy efficient gas-turbine engines.

  11. Piston cylinder cell for high pressure ultrasonic pulse echo measurements.

    PubMed

    Kepa, M W; Ridley, C J; Kamenev, K V; Huxley, A D

    2016-08-01

    Ultrasonic techniques such as pulse echo, vibrating reed, or resonant ultrasound spectroscopy are powerful probes not only for studying elasticity but also for investigating electronic and magnetic properties. Here, we report on the design of a high pressure ultrasonic pulse echo apparatus, based on a piston cylinder cell, with a simplified electronic setup that operates with a single coaxial cable and requires sample lengths of mm only. The design allows simultaneous measurements of ultrasonic velocities and attenuation coefficients up to a pressure of 1.5 GPa. We illustrate the performance of the cell by probing the phase diagram of a single crystal of the ferromagnetic superconductor UGe2.

  12. Piston cylinder cell for high pressure ultrasonic pulse echo measurements

    NASA Astrophysics Data System (ADS)

    Kepa, M. W.; Ridley, C. J.; Kamenev, K. V.; Huxley, A. D.

    2016-08-01

    Ultrasonic techniques such as pulse echo, vibrating reed, or resonant ultrasound spectroscopy are powerful probes not only for studying elasticity but also for investigating electronic and magnetic properties. Here, we report on the design of a high pressure ultrasonic pulse echo apparatus, based on a piston cylinder cell, with a simplified electronic setup that operates with a single coaxial cable and requires sample lengths of mm only. The design allows simultaneous measurements of ultrasonic velocities and attenuation coefficients up to a pressure of 1.5 GPa. We illustrate the performance of the cell by probing the phase diagram of a single crystal of the ferromagnetic superconductor UGe2.

  13. High pressure studies on nanometer sized clusters: Structural, optical, and cooperative properties

    SciTech Connect

    Tolbert, Sarah Helen

    1995-05-01

    High-pressure Se EXAFS is used to study pressure-induced structural transformations in CdSe nanocrystals. The transformation is wurtzite to rock salt, at a pressure much higher than in bulk. High-pressure XRD is used to confirm the EXAFS results. Diffraction peak widths indicate that nanocrystals do not fragment upon transformation. Optical absorption correlates with structural transformations and is used to measure transition pressures; transformation pressure increases smoothly as nanocrystal size decreases. Thermodynamics of transformation is modeled using an elevated surface energy in the high-pressure phase. High-pressure study of Si nanocrystals show large increases in transformation pressure in crystallites to 500{angstrom} diameter, and an overall change in crystallite shape upon transformation is seen from XRD line widths. C{sub 60} single crystals were studied using Raman scattering; results provide information about the clusters` rotational state. Optical properties of high-pressure phase CdSe clusters were studied.

  14. Curved and conformal high-pressure vessel

    SciTech Connect

    Croteau, Paul F.; Kuczek, Andrzej E.; Zhao, Wenping

    2016-10-25

    A high-pressure vessel is provided. The high-pressure vessel may comprise a first chamber defined at least partially by a first wall, and a second chamber defined at least partially by the first wall. The first chamber and the second chamber may form a curved contour of the high-pressure vessel. A modular tank assembly is also provided, and may comprise a first mid tube having a convex geometry. The first mid tube may be defined by a first inner wall, a curved wall extending from the first inner wall, and a second inner wall extending from the curved wall. The first inner wall may be disposed at an angle relative to the second inner wall. The first mid tube may further be defined by a short curved wall opposite the curved wall and extending from the second inner wall to the first inner wall.

  15. Thermal Transport at Static High-Pressures

    NASA Astrophysics Data System (ADS)

    Pangilinan, G. I.; Ladouceur, H. D.; Russell, T. P.

    2000-03-01

    Static properties and dynamic processes at high pressures and high temperatures are critically dependent on thermal properties of materials. Measurements of thermal properties at high pressures have only slowly developed through the years. Here we present a novel method, utilizing gem anvil cells, to measure specific heat, thermal conductivity and thermal diffusivity. The method involves launching a thermal wave in a sample. Subsequently, a localized sensor measures the temporal behavior of the temperature at a fixed point downstream in the material. A pulsed laser is used to deliver the heating pulse, while time-resolved fluorescence from a ruby sphere is used to measure the temperature. The thermal properties are inferred from the temporal behavior of the temperature and the heat conduction equations with appropriate boundary conditions. The thermal properties of table salt (NaCl) are obtained using this method. Impact to current and future high-pressure research, including materials science and geophysics will be addressed.

  16. Carbon in iron phases under high pressure

    NASA Astrophysics Data System (ADS)

    Huang, L.; Skorodumova, N. V.; Belonoshko, A. B.; Johansson, B.; Ahuja, R.

    2005-11-01

    The influence of carbon impurities on the properties of iron phases (bcc, hcp, dhcp, fcc) has been studied using the first-principles projector augmented-wave (PAW) method for a wide pressure range. It is shown that the presence of ~6 at. % of interstitial carbon has a little effect on the calculated structural sequence of the iron phases under high pressure. The bcc -> hcp transition both for pure iron and iron containing carbon takes place around 9 GPa. According to the enthalpies comparison, the solubility of carbon into the iron solid is decreased by high pressure. The coexistence of iron carbide (Fe3C) + pure hcp Fe is most stable phase at high pressure compared with other phases. Based on the analysis of the pressure-density dependences for Fe3C and hcp Fe, we suggest that there might be some fraction of iron carbide present in the core.

  17. High pressure electrical insulated feed thru connector

    DOEpatents

    Oeschger, Joseph E.; Berkeland, James E.

    1979-11-13

    A feed-thru type hermetic electrical connector including at least one connector pin feeding through an insulator block within the metallic body of the connector shell. A compression stop arrangement coaxially disposed about the insulator body is brazed to the shell, and the shoulder on the insulator block bears against this top in a compression mode, the high pressure or internal connector being at the opposite end of the shell. Seals between the pin and an internal bore at the high pressure end of the insulator block and between the insulator block and the metallic shell at the high pressure end are hermetically brazed in place, the first of these also functioning to transfer the axial compressive load without permitting appreciable shear action between the pin and insulator block.

  18. Elasticity of methane hydrate phases at high pressure.

    PubMed

    Beam, Jennifer; Yang, Jing; Liu, Jin; Liu, Chujie; Lin, Jung-Fu

    2016-04-21

    Determination of the full elastic constants (cij) of methane hydrates (MHs) at extreme pressure-temperature environments is essential to our understanding of the elastic, thermodynamic, and mechanical properties of methane in MH reservoirs on Earth and icy satellites in the solar system. Here, we have investigated the elastic properties of singe-crystal cubic MH-sI, hexagonal MH-II, and orthorhombic MH-III phases at high pressures in a diamond anvil cell. Brillouin light scattering measurements, together with complimentary equation of state (pressure-density) results from X-ray diffraction and methane site occupancies in MH from Raman spectroscopy, were used to derive elastic constants of MH-sI, MH-II, and MH-III phases at high pressures. Analysis of the elastic constants for MH-sI and MH-II showed intriguing similarities and differences between the phases' compressional wave velocity anisotropy and shear wave velocity anisotropy. Our results show that these high-pressure MH phases can exhibit distinct elastic, thermodynamic, and mechanical properties at relevant environments of their respective natural reservoirs. These results provide new insight into the determination of how much methane exists in MH reservoirs on Earth and on icy satellites elsewhere in the solar system and put constraints on the pressure and temperature conditions of their environment.

  19. Elasticity of methane hydrate phases at high pressure

    NASA Astrophysics Data System (ADS)

    Beam, Jennifer; Yang, Jing; Liu, Jin; Liu, Chujie; Lin, Jung-Fu

    2016-04-01

    Determination of the full elastic constants (cij) of methane hydrates (MHs) at extreme pressure-temperature environments is essential to our understanding of the elastic, thermodynamic, and mechanical properties of methane in MH reservoirs on Earth and icy satellites in the solar system. Here, we have investigated the elastic properties of singe-crystal cubic MH-sI, hexagonal MH-II, and orthorhombic MH-III phases at high pressures in a diamond anvil cell. Brillouin light scattering measurements, together with complimentary equation of state (pressure-density) results from X-ray diffraction and methane site occupancies in MH from Raman spectroscopy, were used to derive elastic constants of MH-sI, MH-II, and MH-III phases at high pressures. Analysis of the elastic constants for MH-sI and MH-II showed intriguing similarities and differences between the phases' compressional wave velocity anisotropy and shear wave velocity anisotropy. Our results show that these high-pressure MH phases can exhibit distinct elastic, thermodynamic, and mechanical properties at relevant environments of their respective natural reservoirs. These results provide new insight into the determination of how much methane exists in MH reservoirs on Earth and on icy satellites elsewhere in the solar system and put constraints on the pressure and temperature conditions of their environment.

  20. Theoretical Predictions of Phase Transitions at Ultra-high Pressures

    NASA Astrophysics Data System (ADS)

    Boates, Brian

    2013-06-01

    We present ab initio calculations of the high-pressure phase diagrams of important planetary materials such as CO2, MgSiO3, and MgO. For CO2, we predict a series of distinct liquid phases over a wide pressure (P) and temperature (T) range, including a first-order transition to a dense polymer liquid. We have computed finite-temperature free energies of liquid and solid CO2 phases to determine the melting curve beyond existing measurements and investigate possible phase separation transitions. The interaction of these phase boundaries with the mantle geotherm will also be discussed. Furthermore, we find evidence for a vast pressure-temperature regime where molten MgSiO3 decomposes into liquid SiO2 and solid MgO, with a volume change of approximately 1.2 percent. The demixing transition is driven by the crystallization of MgO ? the reaction only occurs below the high-pressure MgO melting curve. The predicted transition pressure at 10,000 K is in close proximity to an anomaly reported in recent laser-driven shock experiments of MgSiO3. We also present new results for the high-pressure melting curve of MgO and its B1-B2 solid phase transition, with a triple point near 364 GPa and 12,000 K.

  1. Ionic High-Pressure Form of Elemental Boron

    SciTech Connect

    Oganov, A.; Chen, J; Gatti, C; Ma, Y; Ma, Y; Glass, C; Liu, Z; Yu, T; Kurakevych, O; et. al.

    2009-01-01

    This Letter presents the results of high-pressure experiments and ab initio evolutionary crystal structure predictions, and found a new boron phase that we named gamma-B28. This phase is comprised of icosahedral B12 clusters and B2 pairs in a NaCl-type arrangement, stable between 19 and 89 GPa, and exhibits evidence for charge transfer (for which our best estimate is delta approximately 0.48) between the constituent clusters to give (B2)delta+(B12)delta-. We have recently found that the same high-pressure boron phase may have given rise to the Bragg reflections reported by Wentorf in 1965 (ref. 1), although the chemical composition was not analysed and the data (subsequently deleted from the Powder Diffraction File database) seems to not have been used to propose a structure model. We also note that although we used the terms 'partially ionic' and 'ionic' to emphasize the polar nature of the high-pressure boron phase and the influence this polarity has on several physical properties of the elemental phase, the chemical bonding in gamma-B28 is predominantly covalent.

  2. Hydrogen at high pressure and temperatures

    SciTech Connect

    Nellis, W J

    1999-09-30

    Hydrogen at high pressures and temperatures is challenging scientifically and has many real and potential applications. Minimum metallic conductivity of fluid hydrogen is observed at 140 GPa and 2600 K, based on electrical conductivity measurements to 180 GPa (1.8 Mbar), tenfold compression, and 3000 K obtained dynamically with a two-stage light-gas gun. Conditions up to 300 GPa, sixfold compression, and 30,000 K have been achieved in laser-driven Hugoniot experiments. Implications of these results for the interior of Jupiter, inertial confinement fusion, and possible uses of metastable solid hydrogen, if the metallic fluid could be quenched from high pressure, are discussed.

  3. High pressure freon decontamination of remote equipment

    SciTech Connect

    Wilson, C.E.

    1987-01-01

    A series of decontamination tests using high pressure FREON 113 was conducted in the 200 Area of the Hanford site. The intent of these tests was to evaluate the effectiveness of FREON 113 in decontamination of manipulator components, tools, and equipment items contaminated with mixed fission products. The test results indicated that high pressure FREON 113 is very effective in removing fissile material from a variety of objects and can reduce both the quantity and the volume of the radioactive waste material presently being buried.

  4. Superelastic carbon spheres under high pressure

    NASA Astrophysics Data System (ADS)

    Li, Meifen; Guo, Junjie; Xu, Bingshe

    2013-03-01

    We report a superelastic deformation behavior of carbon spheres by the in situ Raman spectroscopy in a high-pressure diamond anvil cell. The carbon spheres produced by arc discharging in toluene have a mean diameter of 200 nm and an onion-like multilayer graphitic structure. We find that the elastic coefficients, during both the compression and decompression processes, remain a constant up to 10 GPa, indicating a superior high-pressure structural stability. Such superelastic behavior is related to the isotropic and concentric configuration of carbon spheres and provides additional insight into improving the microscopic mechanical properties of small-scale particles.

  5. High pressure water jet cutting and stripping

    NASA Technical Reports Server (NTRS)

    Hoppe, David T.; Babai, Majid K.

    1991-01-01

    High pressure water cutting techniques have a wide range of applications to the American space effort. Hydroblasting techniques are commonly used during the refurbishment of the reusable solid rocket motors. The process can be controlled to strip a thermal protective ablator without incurring any damage to the painted surface underneath by using a variation of possible parameters. Hydroblasting is a technique which is easily automated. Automation removes personnel from the hostile environment of the high pressure water. Computer controlled robots can perform the same task in a fraction of the time that would be required by manual operation.

  6. High pressure water jet mining machine

    DOEpatents

    Barker, Clark R.

    1981-05-05

    A high pressure water jet mining machine for the longwall mining of coal is described. The machine is generally in the shape of a plowshare and is advanced in the direction in which the coal is cut. The machine has mounted thereon a plurality of nozzle modules each containing a high pressure water jet nozzle disposed to oscillate in a particular plane. The nozzle modules are oriented to cut in vertical and horizontal planes on the leading edge of the machine and the coal so cut is cleaved off by the wedge-shaped body.

  7. X-ray Crystallography at High Pressure to Probe Conformational Fluctuations in Biological Macromolecules

    SciTech Connect

    Girard, Eric; Fourme, Roger; Kahn, Richard; Dhaussy, Anne-Claire; Ascone, Isabella; Mezouar, Mohamed

    2007-01-19

    Macromolecular crystals can be compressed hydrostatically at room temperature in a diamond anvil cell. The quality of diffraction data recorded on the ESRF ID30/ID27 beamlines using a parallel X-ray beam of ultra-short wavelength can meet usual standards. The 3D structures of proteins (monomeric, dimeric and tetrameric) and of a virus have been refined both at atmospheric and at high pressure. High pressure is a way to explore the high energy landscape of macromolecular systems, from the fully folded state to the unfolded state. High energy conformers of biological significance can be selected and trapped under high pressure.

  8. High pressure transport and structural studies on Nb3Ga superconductor

    DOE PAGES

    Mkrtcheyan, Vahe; Kumar, Ravhi; Baker, Jason; ...

    2014-11-24

    We investigated the crystal structure of A-15 superconductor Nb3Ga with a critical temperature Tc = 16.5 K by high pressure x-ray diffraction (HPXRD) using synchrotron x-rays and a diamond anvil cell under Ne pressure medium. Furthermore, the high pressure structural results indicate that Nb3Ga is stable up to 41 GPa. The P-V plot shows an anomaly around 15 GPa even though there are no pressure induced structural transitions are observed. High pressure resistance measurements were performed up to 0.5 GPa to understand the variation of Tc under pressure. Finally, our results show a positive pressure effect on Tc.

  9. High Pressure Solution Kinetics of Metal Complexes.

    ERIC Educational Resources Information Center

    Suvachittanont, Surapong

    1983-01-01

    Describes use of activation volumes derived from the effect of pressure reaction rates in aiding the understanding of reaction mechanism. Topics discussed include determination and interpretation of activation volumes, high pressure equipment/techniques, and application of activation volumes in mechanistic elucidation of several inorganic…

  10. High Pressure Solution Kinetics of Metal Complexes.

    ERIC Educational Resources Information Center

    Suvachittanont, Surapong

    1983-01-01

    Describes use of activation volumes derived from the effect of pressure reaction rates in aiding the understanding of reaction mechanism. Topics discussed include determination and interpretation of activation volumes, high pressure equipment/techniques, and application of activation volumes in mechanistic elucidation of several inorganic…

  11. Feedthrough Seal For High-Pressure Vessel

    NASA Technical Reports Server (NTRS)

    Williams, R.; Mullins, O.; Smith, D.; Teasley, G.

    1984-01-01

    Combination of ceramic and plastic withstands many depressurizations. Stack of washers surrounds leadthrough electrode. Under pressure washers expand to fill leadthrough hole in high-pressure vessel. Seal thus formed withstands 20 or more pressurization/depressurization cycles. Seal composed of neoprene, polytetrafluoroethylene, nylon and high-purity, high-density commercial alumina ceramic.

  12. High pressure studies of planetary matter

    SciTech Connect

    Ross, M.

    1989-06-01

    Those materials which are of greatest interest to the physics of the deep planetary interiors are Fe, H/sub 2/, He and the Ices. These are sufficiently diverse and intensively studied to offer an overview of present day high pressure research. 13 refs., 1 fig.

  13. Hurricane risk mitigation - High Pressure Gas Facility

    NASA Technical Reports Server (NTRS)

    2008-01-01

    A worker pours concrete as part of a nitrogen risk mitigation project at the High Pressure Gas Facility at Stennis Space Center. The concrete slab will provide the foundation needed to place new pumps at the site and is part of ongoing hurricane-related mitigation work at Stennis.

  14. High Pressure Inactivation of HAV within Mussels

    USDA-ARS?s Scientific Manuscript database

    The potential of hepatitis A virus (HAV) to be inactivated within Mediterranean mussels (Mytilus galloprovincialis) and blue mussels (Mytilus edulis) by high pressure processing was evaluated. HAV was bioaccumulated within mussels to approximately 6-log10 PFU by exposure of mussels to HAV-contamina...

  15. High-field/high-pressure ESR

    NASA Astrophysics Data System (ADS)

    Sakurai, T.; Okubo, S.; Ohta, H.

    2017-07-01

    We present a historical review of high-pressure ESR systems with emphasis on our recent development of a high-pressure, high-field, multi-frequency ESR system. Until 2000, the X-band system was almost established using a resonator filled with dielectric materials or a combination of the anvil cell and dielectric resonators. Recent developments have shifted from that in the low-frequency region, such as X-band, to that in multi-frequency region. High-pressure, high-field, multi-frequency ESR systems are classified into two types. First are the systems that use a vector network analyzer or a quasi-optical bridge, which have high sensitivity but a limited frequency region; the second are like our system, which has a very broad frequency region covering the THz region, but lower sensitivity. We will demonstrate the usefulness of our high-pressure ESR system, in addition to its experimental limitations. We also discuss the recent progress of our system and future plans.

  16. Small, high-pressure liquid hydrogen turbopump

    NASA Technical Reports Server (NTRS)

    Csomor, A.; Sutton, R.

    1977-01-01

    A high pressure, liquid hydrogen turbopump was designed, fabricated, and tested to a maximum speed of 9739 rad/s and a maximum pump discharge pressure of 2861 N/sq. cm. The approaches used in the analysis and design of the turbopump are described, and fabrication methods are discussed. Data obtained from gas generator tests, turbine performance calibration, and turbopump testing are presented.

  17. Hurricane risk mitigation - High Pressure Gas Facility

    NASA Image and Video Library

    2008-07-29

    A worker pours concrete as part of a nitrogen risk mitigation project at the High Pressure Gas Facility at Stennis Space Center. The concrete slab will provide the foundation needed to place new pumps at the site and is part of ongoing hurricane-related mitigation work at Stennis.

  18. High-Pressure Raman Spectroscopy of Natural Nyerereite

    NASA Astrophysics Data System (ADS)

    Vennari, C.; Williams, Q. C.

    2016-12-01

    Raman spectroscopy has been collected on a natural sample of nyerereite (ideally: NaCa2(CO3)2) in situ at high pressures at 300 K. Nyerereite is of geological importance because it has been observed as inclusions in diamonds and olivine and in the ground mass of the natrocarbonatite magma in the Oldoinyo Lengai Volcano, Tanzania. As such, the high pressure behavior of nyerereite is relevant to the formation and stability of alkali carbonate-rich regions at depth, and hence the source materials for carbonatite magmas. Nyerereite crystallizes in the orthorhombic crystal system Cmc21 within which there are two distinct carbonate sites. Although the ideal chemical formula is NaCa2(CO3)2, there is partial defect substitution of sulfate groups (SO42-) for the carbonate groups in natural samples. At room pressure, the low frequency (lattice modes) peaks and carbonate ion symmetric stretching (v1) and in-plane bending (v4) vibrations are indistinguishable from those of endmember nyerereite; additionally, the symmetric stretch of the, and the sulfate tetrahedron (v1) is clearly resolvable. The in-plane bends of the carbonate group are consistent with a phase transition occurring at around 5 GPa, as one peak disappears below 5 GPa and the highest frequency component of this vibration splits above 5 GPa. The symmetric stretching vibrations of the carbonate and the sulfate ion shift monotonically through this transition at rates of 2.79 and 3.09 cm-1/GPa, and the sulfate vibration increases with pressure at a rate of 4.39 cm-1/GPa. Thus, the spectral signature of this possible transition is consistent with a subtle distortion of one of the carbonate ion sites in this material near 5 GPa. Thus, at the high pressure and temperature conditions associated with its encapsulation within xenoliths, nyerereite may undergo complex local bonding changes relative to its ambient pressure/temperature structure.

  19. Elasticity of orthoenstatite at high-pressure

    NASA Astrophysics Data System (ADS)

    Zhang, D.; Jackson, J. M.; Chen, B.; Zhao, J.; Yan, J.

    2011-12-01

    Orthoenstatite is an abundant yet complex mineral in Earth's upper mantle. Despite its abundance, the properties of orthopyroxene at high pressure remain ambiguous (e.g., Zhang et al. 2011; Jahn 2008; Kung et al. 2004). We explored select properties of a synthetic powdered orthoenstatite (Mg0.8757Fe0.13)2Si2O6 sample by X-ray diffraction (XRD) and nuclear resonance inelastic X-ray scattering (NRIXS) as a function of pressure in a neon pressure medium at 300 K. The XRD measurements were carried out at beamline 12.2.2 of the Advanced Light Source (Berkeley, CA), and the sample was studied up to 34 GPa. NRIXS measurements were carried out at sector 3ID-B of the Advanced Photon Source (Chicago, IL) in the pressure range of 3 to 17 GPa. From the raw NRIXS data, the partial phonon density of states (DOS) was derived (e.g., Sturhahn 2004). The volume (or pressure) dependence of several properties, such as the Lamb-Mössbauer factor, mean force constant, specific heat, vibrational entropy, and vibrational kinetic energy were determined from the DOS. We will discuss our results from these combined studies and the implications for Earth's upper mantle. References Zhang, D., J.M. Jackson, W. Sturhahn, and Y. Xiao (2011): Local structure variations observed in orthoenstatite at high-pressures. American Mineralogist, in press. Jahn, S. (2008) High-pressure phase transitions in MgSiO3 orthoenstatite studied by atomistic computer simulation. American Mineralogist, 93(4), 528-532. Kung, J., Li, B., Uchida, T., Wang, Y., Neuville, D., and Liebermann, R. (2004) In situ measurements of sound velocities and densities across the orthopyroxene high-pressure clinopyroxene transition in MgSiO3 at high pressure. Physics of the Earth and Planetary Interiors, 147(1), 27-44. Sturhahn, W. (2004): Nuclear Resonant Spectroscopy. J. Phys. Condens. Matter, 16, S497-S530.

  20. Advanced Diagnostics for High Pressure Spray Combustion.

    SciTech Connect

    Skeen, Scott A.; Manin, Julien Luc; Pickett, Lyle M.

    2014-06-01

    The development of accurate predictive engine simulations requires experimental data to both inform and validate the models, but very limited information is presently available about the chemical structure of high pressure spray flames under engine- relevant conditions. Probing such flames for chemical information using non- intrusive optical methods or intrusive sampling techniques, however, is challenging because of the physical and optical harshness of the environment. This work details two new diagnostics that have been developed and deployed to obtain quantitative species concentrations and soot volume fractions from a high-pressure combusting spray. A high-speed, high-pressure sampling system was developed to extract gaseous species (including soot precursor species) from within the flame for offline analysis by time-of-flight mass spectrometry. A high-speed multi-wavelength optical extinction diagnostic was also developed to quantify transient and quasi-steady soot processes. High-pressure sampling and offline characterization of gas-phase species formed following the pre-burn event was accomplished as well as characterization of gas-phase species present in the lift-off region of a high-pressure n-dodecane spray flame. For the initial samples discussed in this work several species were identified, including polycyclic aromatic hydrocarbons (PAH); however, quantitative mole fractions were not determined. Nevertheless, the diagnostic developed here does have this capability. Quantitative, time-resolved measurements of soot extinction were also accomplished and the novel use of multiple incident wavelengths proved valuable toward characterizing changes in soot optical properties within different regions of the spray flame.