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Sample records for high-pressure crystal chemistry

  1. 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.

  2. The high-pressure chemistry of butadiene crystal

    NASA Astrophysics Data System (ADS)

    Citroni, Margherita; Ceppatelli, Matteo; Bini, Roberto; Schettino, Vincenzo

    2003-01-01

    FTIR spectroscopy was applied to the study of the high-pressure reactivity of solid butadiene. The chemical transformation from the ordered phase I was observed to occur only above 270 K. The existence of a threshold temperature for the reaction reveals the central role of the lattice phonons in the activation of the transformation. Below 4.0 GPa only dimerization to 4-vinylcyclohexene occurs, while above this pressure an increasing amount of polymer forms with rising pressure. Room temperature kinetic studies have been performed at different pressures, from 2.1 up to 6.6 GPa, and the sign of the activation volume for the dimerization has been obtained. The dimerization reaction is found to follow a first-order mechanism. A reaction pathway for this process is proposed where the internal rearrangement of a diradical intermediate specie is identified as the rate limiting step. An acceleration of the dimerization process is observed above 4.0 GPa and is ascribed to the simultaneous polymer formation. This effect causes the laser assisted reaction, where a large amount of polymer is produced at any pressure, to be not as selective on polymerization as it is in the liquid phase, since also the dimerization rate is enhanced.

  3. High-pressure crystallography of periodic and aperiodic crystals.

    PubMed

    Hejny, Clivia; Minkov, Vasily S

    2015-03-01

    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

  4. 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

  5. Crystal structure of oligoacenes under high pressure

    SciTech Connect

    Oehzelt, M.; Aichholzer, A.; Resel, R.; Heimel, G.; Venuti, E.; Della Valle, R. G.

    2006-09-01

    We report crystal structures of anthracene, tetracene, and pentacene under pressure. Energy dispersive x-ray diffraction experiments up to 9 GPa were performed. Quasiharmonic lattice dynamics calculations are compared to the experimental results and show excellent agreement. The results are discussed with particular emphasis on the pressure dependence of the unit cell dimensions and the rearrangement of the molecules. The high pressure data also allow an analysis of the equation of state of these substances as a function of molecular length. We report the bulk modulus of tetracene and pentacene (B{sub 0}=9.0 and 9.6 GPa, respectively) and its pressure derivative (B{sub 0}{sup '}=7.9 and 6.4, respectively). We find that the unit-cell volume and bulk modulus at ambient pressure follow a linear relationship with the molecular length.

  6. 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

  7. 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.

  8. High pressure chemistry of red phosphorus by photoactivated simple molecules

    NASA Astrophysics Data System (ADS)

    Ceppatelli, Matteo; Bini, Roberto; Fanetti, Samuele; Caporali, Maria; Peruzzini, Maurizio

    2013-06-01

    High pressure (HP) is very effective in reducing intermolecular distances and inducing unexpected chemical reactions. In particular the photoactivation of the reactants in HP conditions can lead to very efficient and selective processes. The chemistry of phosphorus is currently based on the white molecular form. The red polymeric allotrope, despite more stable and much less toxic, has not attracted much attention so far. However, switching from the white to the red form would benefit any industrial procedure, especially from an environmental point of view. On the other side, water and ethanol are renewable, environmental friendly and largely available molecules, usable as reactants and photoactivators in HP conditions. Here we report a study on the HP photoinduced reactivity of red phosphorus with water and ethanol, showing the possibility of very efficient and selective processes, leading to molecular hydrogen and valuable phosphorus compounds. The reactions have been studied by means of FTIR and Raman spectroscopy and pressure has been generated using DAC and SAC. HP reactivity has been activated by the two-photon absorption of near-UV wavelengths and occured in total absence of solvents, catalysts and radical initiators, at room T and mild pressure conditions (0.2-1.5 GPa).

  9. High pressure Raman spectra of monoglycine nitrate single crystal.

    PubMed

    Carvalho, J O; Moura, G M; Dos Santos, A O; Lima, R J C; Freire, P T C; Façanha Filho, P F

    2016-05-15

    Single crystal of monoglycine nitrate has been studied by Raman spectroscopy under high pressures up to 5.5 GPa. The results show changes in lattice modes in the pressure ranges of 1.1-1.6 GPa and 4.0-4.6 GPa. The first change occurs with appearance of bands related to the lattice modes as well as discontinuity in the slope of dΩ/dP of these modes. Moreover, bands associated with the skeleton of glycine suggest that the molecule undergoes conformational modifications. The appearance of a strong band at 55 cm(-1) point to a second phase transition associated with the lattice modes, while the internal modes remain unchanged. These anomalies are probably due to rearrangement of hydrogen bonds. Additionally, decompression to ambient pressure shows that the phase transitions are reversible. Finally, the results show that the nitrate anions play an important role on the stability of the monoglycine nitrate crystal. PMID:26967511

  10. High pressure Raman spectra of monoglycine nitrate single crystal

    NASA Astrophysics Data System (ADS)

    Carvalho, J. O.; Moura, G. M.; Dos Santos, A. O.; Lima, R. J. C.; Freire, P. T. C.; Façanha Filho, P. F.

    2016-05-01

    Single crystal of monoglycine nitrate has been studied by Raman spectroscopy under high pressures up to 5.5 GPa. The results show changes in lattice modes in the pressure ranges of 1.1-1.6 GPa and 4.0-4.6 GPa. The first change occurs with appearance of bands related to the lattice modes as well as discontinuity in the slope of dΩ/dP of these modes. Moreover, bands associated with the skeleton of glycine suggest that the molecule undergoes conformational modifications. The appearance of a strong band at 55 cm- 1 point to a second phase transition associated with the lattice modes, while the internal modes remain unchanged. These anomalies are probably due to rearrangement of hydrogen bonds. Additionally, decompression to ambient pressure shows that the phase transitions are reversible. Finally, the results show that the nitrate anions play an important role on the stability of the monoglycine nitrate crystal.

  11. Observing high-pressure chemistry in graphene bubbles.

    PubMed

    Lim, Candy Haley Yi Xuan; Nesladek, Milos; Loh, Kian Ping

    2014-01-01

    Using IR spectroscopy, high-pressure reactions of molecules were observed in liquids entrapped by graphene nanobubbles formed at the graphene-diamond interface. Nanobubbles formed on graphene as a result of thermally induced bonding of its edges with diamond are highly impermeable, thus providing a good sealing of solvents within. Owing to the optical transparency of graphene and diamond, high-pressure chemical reactions within the bubbles can be probed with vibrational spectroscopy. By monitoring the conformational changes of pressure-sensitive molecules, the pressure within the nanobubble can be calibrated as a function of temperature and it is about 1 GPa at 600 K. The polymerization of buckministerfullerene (C60 ), which is symmetrically forbidden under ambient conditions, is observed to proceed in well-defined stages in the pressurized nanobubbles. PMID:24259233

  12. 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.

  13. Determining complex crystal structures from high pressure single-crystal diffraction data collected on synchrotron sources

    NASA Astrophysics Data System (ADS)

    McMahon, M. I.; Loa, I.; Stinton, G. W.; Lundegaard, L. F.

    2013-08-01

    As part of a Long Term Project, single-crystal diffraction techniques have been developed for use at the high pressure beamlines ID09 and ID27 at the European Synchrotron Radiation Facility, and have been utilised to determine the crystal structures of various high pressure phases, including those with incommensurate structures, at both high and low temperatures. The same techniques have also been used to determine the structures of high pressure phases at the SRS, Diamond and Petra-III synchrotron sources. In this paper, we describe technical details of the methods developed, and describe some of the considerations necessary for planning experiments and collecting and processing the data. We then illustrate the quality of data that can be obtained, and the complexity of the structures that can be refined, using recent results obtained from complex high pressure phases of N2 and Ba.

  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. 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.

  16. 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.

  17. 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.

  18. In situ crystallization of ionic liquid [Emim][PF6] from methanol solution under high pressure.

    PubMed

    Li, Haining; Su, Lei; Zhu, Xiang; Cheng, Xuerui; Yang, Kun; Yang, Guoqiang

    2014-07-24

    The solubility of 1-ethyl-3-methylimidazolium hexafluorophosphate ([Emim][PF6]) in methanol under high pressure is newly measured quantitatively according to the correlation between the ratios of Raman intensity and the concentrations. In situ crystallization and cation conformation of [Emim][PF6] from methanol solution under high pressure have been investigated by using Raman spectroscopy in detail. Remarkably, crystal polymorphism was observed and two crystalline phases (phases I and II) coexisted under high pressure up to ∼ 1.4 GPa. However, only phase II was obtained by recrystallization at ∼ 2 GPa. Our findings may facilitate the development of an effective way for crystallization and purification of ionic liquids under high pressure. PMID:24968114

  19. New synthetic discoveries via high-pressure solid-state chemistry.

    PubMed

    Huppertz, Hubert

    2011-01-01

    Most of the syntheses in solid-state chemistry are performed at constant pressure of ∼1 atm (about 10(5) Pa) by the manipulation of the thermodynamic parameters temperature and composition, leading to a rich variety of compounds. In contrast, the additional variation of pressure has remained virtually unexplored, due to the relatively large costs of maintaining high-pressure conditions and the inevitably tiny sample volumes. In the last two decades, technical advances, developed for studying the properties of minerals, have found access into the preparative solid-state chemistry, opening up tremendously large areas to synthesize new materials. PMID:20859577

  20. Multicomponent A-site ordered perovskite BiMn3(Fe0.25Ti0.75)4O12: High-pressure synthesis, crystal chemistry and magnetic behavior

    NASA Astrophysics Data System (ADS)

    Shimura, Gen; Niwa, Ken; Shirako, Yuichi; Muto, Shunsuke; Kusaba, Keiji; Hasegawa, Masashi

    2016-05-01

    A new multicomponent A-site ordered perovskite-type oxide has been successfully synthesized in the BiFeO3 and MnTiO3 pseudobinary system at high pressure and temperature, 6 GPa and 1300 K. It is found that the oxide is an A-site ordered and B-site disordered perovskite Bi3+Mn2+3(Fe3+0.25Ti4+0.75)4O12 in the space group of the cubic high symmetry Im-3 with a lattice parameter a=7.5937(3) Å. It should be noted that the Mn2+ ions in the A‧-site show a site-splitting, while the Bi3+ ones are in a regular icosahedron position of the A-site. On the other hand, the Fe3+ and Ti4+ ones in the B-site are disordered in this perovskite structure. The temperature dependence of magnetizations and specific heats at low temperatures shows spin-glass-like behaviors below 11 K.

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

    PubMed

    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

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. Single Crystal Growth of Nd-1111 Iron Pnictide Superconductors by High Pressure Synthesis

    NASA Astrophysics Data System (ADS)

    Takemori, Akira; Miyasaka, Shigeki; Tajima, Setsuko; Lee, Sergey; Adachi, Seiji; Chikumoto, Noriko; Tanabe, Keiichi

    To clarify the relationship of the crystal structure, the critical temperature (Tc) and the gap structure in iron pnictide superconductors, the studies on 1111-type iron pnictides with the highest Tc are important. However itis well known that the single crystal growth of 1111-compounds is difficult. In this work, we have established a method for reproducible growth of high quality crystals using high pressure synthesis technique and successfully obtained NdFeAs(O, F) singlecrystals (Tc = 43.5 K) with a typical size of 5002 × 30 µm3.

  7. 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)

  8. In situ characterization of formation and growth of high-pressure phases in single-crystal silicon during nanoindentation

    NASA Astrophysics Data System (ADS)

    Huang, Hu; Yan, Jiwang

    2016-04-01

    Pressure-induced intermediate phases of silicon exhibit unique characteristics in mechanics, chemistry, optics, and electrics. Clarifying the formation and growth processes of these new phases is essential for the preparation and application of them. For in situ characterization of the formation and growth of high-pressure phases in single-crystal silicon, a quantitative parameter, namely displacement change of indenter (Δ h) during the unloading holding process in nanoindentation, was proposed. Nanoindentation experiments under various unloading holding loads and loading/unloading rates were performed to investigate their effects on Δ h. Results indicate that Δ h varies significantly before and after the occurrence of pop-out; for the same maximum indentation load, it tends to increase with the decrease in the holding load and to increase with the increase in the loading/unloading rate. Thus, the value of Δ h can be regarded as an indicator that reflects the formation and growth processes of the high-pressure phases. Using Δ h, the initial position for the nucleation of the high-pressure phases, their growth, and their correlation to the loading/unloading rate were predictable.

  9. Synthesis and in situ high pressure Raman spectroscopy study of AlN dendritic crystal

    SciTech Connect

    Li, Xuefei; Kong, Lingnan; Shen, Longhai; Yang, Jinghai; Gao, Ming; Hu, Tingjing; Wu, Xingtong; Li, Ming

    2013-09-01

    Graphical abstract: - Highlights: • The sample is the typical dendritic crystal structure. • The phase transition of AlN dendritic crystal is researched. • The Raman signal of rock salt AlN is observed under high pressure. • Grüneisen parameters and phase transition criterion are discussed. - Abstract: AlN dendritic crystal was synthesized by the direct current arc discharge apparatus. X-ray diffraction (XRD) patterns indicated that the sample is hexagonal AlN and preferentially grown along the a-axis direction. Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) images reveal that the product mainly consists of micron AlN dendritic crystal. In situ high pressure Raman spectra of AlN dendritic crystal has been measured in the pressure ranged from ambient pressure to 32.97 GPa at room temperature by using diamond anvil cell. According to the Raman scattering results, the phase transition from the wurtzite to rock salt was found at about 20.73 GPa by the appearance of a new Raman signal. Above 20.73 GPa, a new Raman signal due to disorder-activated Raman scattering in the rock salt phase was observed. In addition, the pressure coefficients, phase transition criterion, and mode Grüneisen parameters of AlN dendritic crystal, which could be different from that of other AlN, are carefully discussed.

  10. 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.

  11. Development of High Pressure Single Crystal X-Ray Diffraction Study at ESRF ID 30 Beamline

    SciTech Connect

    Dhaussy, A.C.; Mezouar, M.; Mentre, O.

    2004-05-12

    We report about the newly single crystal diffraction set-up development at ID30 beamline at the European Synchrotron Radiation Facility (ESRF). To illustrate the experimental performance of this set-up, we also present X-ray diffraction spectra recorded at high pressure (HP) using dedicated diamond anvil cell (DAC). Using this new setup, high quality synchrotron single crystal X-ray diffraction measurements of Pb2V3O9 have been performed at HP. We evidenced a reordering in the distorted system by resorbing the existing twin. The structure was partially solved by direct methods and refined by the use of the BRUKER suite of programs package.

  12. 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

  13. Facilitating protein crystal cryoprotection in thick-walled plastic capillaries by high-pressure cryocooling

    PubMed Central

    Chen, Yi-Fan; Tate, Mark W.; Gruner, Sol M.

    2009-01-01

    Many steps in the X-ray crystallographic solution of protein structures have been automated. However, the harvesting and cryocooling of crystals still rely primarily on manual handling, frequently with consequent mechanical damage. An attractive alternative is to grow crystals directly inside robust plastic capillaries that may be cryocooled and mounted on the beamline goniometer. In this case, it is still desirable to devise a way to cryoprotect the crystals, which is difficult owing to the poor thermal conductivity of thick plastic capillary walls and the large thermal mass of the capillary and internal mother liquor. A method is described to circumvent these difficulties. It is shown that high-pressure cryocooling substantially reduced the minimal concentrations of cryoprotectants required to cryocool water inside capillaries without formation of ice crystals. The minimal concentrations of PEG 200, PEG 400 and glycerol necessary for complete vitrification under pressure cryocooling were determined. PMID:19529790

  14. 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.

  15. 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

  16. Luminescence of LiNbO3:MgO,Cr crystals under high pressure

    NASA Astrophysics Data System (ADS)

    Kamińska, A.; Dmochowski, J. E.; Suchocki, A.; Garcia-Sole, J.; Jaque, F.; Arizmendi, L.

    1999-09-01

    The results of high-pressure studies of LiNbO3:Cr(0.2%), Mg crystals doped with two concentrations of magnesium (2% and 5.5%) are reported. The results reveal information about the electronic structure of different Cr3+ centers in lithium niobate crystals. There are three major Cr3+ centers (denoted by α, β, and γ) in the crystal with 2% of magnesium. These centers correspond to Cr3+ ions in Li+ sites with different crystal field. At ambient pressure the α center experiences strong crystal field and the β and γ centers are the intermediate crystal-field centers. The energy differences between the 4T2 and 2E levels are positive and negative for the β and the γ centers, respectively. Additional broadband luminescence observed in the sample with 5.5% of magnesium even at pressure of almost 100 kbar testifies that another very weak crystal-field center exists in this crystal. This center (denoted by δ) correponds to Cr3+ ions located in Nb5+ sites. The R lines of the Cr3+ centers exhibit very large redshift with pressure of about 3 cm-1/kbar.

  17. 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.

  18. 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. PMID:26732344

  19. 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.

  20. High pressure chemistry of red phosphorus by photo-activated simple molecules

    NASA Astrophysics Data System (ADS)

    Ceppatelli, M.; Fanetti, S.; Bini, R.; Caporali, M.; Peruzzini, M.

    2014-05-01

    High pressure (HP) is very effective in reducing intermolecular distances and inducing unexpected chemical reactions. In addition the photo-activation of the reactants in HP conditions can lead to very efficient and selective processes. The chemistry of phosphorus is currently based on the white molecular form. The red polymeric allotrope, despite more stable and much less toxic, has not attracted much attention so far. However, switching from the white to the red form would benefit any industrial procedure, especially from an environmental point of view. On the other side, water and ethanol are renewable, environmental friendly and largely available molecules, usable as reactants and photo-activators in HP conditions. Here we report a study on the HP photo-induced reactivity of red phosphorus with water and ethanol, showing the possibility of very efficient and selective processes, leading to molecular hydrogen and valuable phosphorus compounds. The reactions have been studied by means of FTIR and Raman spectroscopy and pressure has been generated using membrane Diamond (DAC) and Sapphire (SAC) anvil cells. HP reactivity has been activated by the two-photon absorption of near-UV wavelengths and occurred in total absence of solvents, catalysts and radical initiators, at room T and mild pressure conditions (0.2-1.5 GPa).

  1. Coupled convection, segregation, and thermal stress modeling of low and high pressure Czochralski crystal growth

    NASA Astrophysics Data System (ADS)

    Zou, Yunfeng

    Czochralski (Cz) method is a dominant single crystal growth technology for microelectronics applications. The demand for large diameter, low defect density, and uniform single crystals has motivated extensive research on Cz Si growth as well as high pressure liquid-encapsulated Czochralski (HPLEC) growth of III-V compound crystals, e.g., GaAs and InP. The transport phenomena of Cz growth is quite complex, particularly under the industrial growth conditions. The relationship between the process parameters and material properties is further complicated by convective flows of the gas if a high pressure condition is to be maintained for the growth. Two important factors that greatly influence the quality of the crystals, are: (a) impurity and dopant distributions and (b) thermal stresses in the crystal. A comprehensive model which incorporates all of the major physical mechanisms of HPLEC growth, has been developed. For numerical simulation, a novel scheme of combined finite volume (FVM) and finite element (FEM) methods has been devised for thermal-mechanical calculations, that uses multizone adaptive grid generation (MAGG) technique for both FVM and FEM modules. By combining the FVM for thermal transport modeling and FEM for solid stress calculations, valuable experiences in both fields have been employed, and a reliable and robust predictive tool for a large class of problems has been developed. This requires minimum effort and cost in both software development and computing environment and shows a great promise. It makes the investigation of coupled thermal convection and stress phenomena much easier to perform. A two time-scale, mass conserving scheme has also been developed to perform macro-segregation calculations. Both Cz and HPLEC (high pressure liquid-encapsulant Czochralski) processes have been investigated. It is found that both melt and gas convective flows have significant influence on stress distribution in the crystal. It is shown that pure conduction

  2. 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. PMID:27128858

  3. High-pressure catalytic reactions over single-crystal metal surfaces

    NASA Astrophysics Data System (ADS)

    Rodriguez, JoséA.; Wayne Goodman, D.

    1991-11-01

    Studies dealing with high-pressure catalytic reactions over single-crystal surfaces are reviewed. The coupling of an apparatus for the measurement of reaction kinetics at elevated pressures with an ultrahigh vacuum system for surface analysis allows detailed study of structure sensitivity, the effects of promoters and inhibitors on catalytic activity, and, in certain cases, identification of reaction intermediates by post-reaction surface analysis. Examples are provided which demonstrate the relevance of single-crystal studies for modeling the behaviour of high-surface-area supported catalysts. Studies of CO methanation and CO oxidation over single-crystal surfaces provide convincing evidence that these reactions are structure insensitive. For structure-sensitive reactions (ammonia synthesis, alkane hydrogenolysis, alkane isomerization, water-gas shift reaction, etc.) model single-crystal studies allow correlations to be established between surface structure and catalytic activity. The effects of both electronegative (S and P) and electropositive (alkali metals) impurities upon the catalytic activity of metal single crystals for ammonia synthesis, CO methanation, alkane hydrogenolysis, ethylene epoxidation and water-gas shift are discussed. The roles of "ensemble" and "ligand" effects in bimetallic catalysts are examined in light of data obtained using surfaces prepared by vapor-depositing one metal onto a crystal face of a dissimilar metal.

  4. 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

    2014-01-01

    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. PMID:24879582

  5. High pressure nano-crystalline microstructure of shock compressed single crystal iron

    SciTech Connect

    Hawreliak, J; Kalantar, D; Stolken, J; Remington, B; Lorenzana, H; Wark, J

    2007-12-11

    We discuss the first grain size measurements made during shock compression using in situ x-ray diffraction. Our experiments have shown unambiguously that single crystal iron shock loaded above 13 GPa along the [100] direction will transform from the ambient {alpha}-phase (BCC) to a highly ordered polycrystalline {epsilon}-phase (HCP). Here, we present a detailed shape analysis of the diffraction peaks using a modified Warren-Averbach method to quantify the microstructure of shock compressed high pressure iron. The {epsilon}-phase was determined through this method to have grain sizes between of 2 and 15 nm, in reasonable agreement with results from large scale MD simulations. We conclude that single crystal iron becomes nano-crystalline in shock transforming from the {alpha} to {epsilon} phase.

  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. Diffusion of oxygen in bulk GaN crystals at high temperature and at high pressure

    NASA Astrophysics Data System (ADS)

    Sadovyi, B.; Nikolenko, A.; Weyher, J. L.; Grzegory, I.; Dziecielewski, I.; Sarzynski, M.; Strelchuk, V.; Tsykaniuk, B.; Belyaev, O.; Petrusha, I.; Turkevich, V.; Kapustianyk, V.; Albrecht, M.; Porowski, S.

    2016-09-01

    Experimental studies of diffusion of oxygen in bulk wurtzite-type GaN crystals grown by Halide Vapor Phase Epitaxy (HVPE) are reported. Oxygen concentration profiles were studied in as-grown GaN crystals and also after annealing of crystals at temperatures up to 3400 K and pressures up to 9 GPa. Investigated crystals contained large conical defects i.e. pinholes of significantly higher oxygen concentration (NO=(2-4)×1019 cm-3) than that in the bulk matrix (NO<1×1017 cm-3). The pinholes were revealed by a photo-etching method in as-grown and annealed GaN samples. Confocal micro-Raman spectroscopy was applied to measure the profiles of free electron concentration, which directly corresponds to the concentration of oxygen impurity. Lateral scanning across the interfaces between pinholes and matrix in the as-grown HVPE GaN crystals showed sharp step-like carrier concentration profiles. Annealing at high temperature and high pressure resulted in the diffusion blurring of the profiles. Analysis of obtained data allowed for the first time for estimation of oxygen diffusion coefficients DO(T, P). The obtained values of DO(T, P) are anomalously small similarly to the values obtained by Harafuji et al. by molecular dynamic calculations for self-diffusion of nitrogen. Whereas oxygen and nitrogen are on the same sublattice it could explain the similarity of their diffusion coefficients.

  8. Removing Impurity of cBN Crystal Prepared at High Pressure and High Temperature

    NASA Astrophysics Data System (ADS)

    Ji, Xiao-Rui; Yang, Xiao-Hong

    2012-03-01

    The black cubic boron nitride (cBN) single crystal is synthesized by using hBN-LiH and hBN-Li3N-B as the raw materials at high temperature and high pressure (HTHP). The colors of the cBN crystal synthesized in an hBN-Li3N-B system vary from transparent yellow, half-transparent and then opaque black with the increasing B content in the raw materials. It is worth noting that a trigonal shadow is presented at the center of the cBN crystal synthesized in the hBN-Li3N-B system but can not be found in the hBN-LiH system. Analyzing the Raman spectrum, we find that the darkening and the trigonal shadow in the cBN crystal may be due to the presence of excess B atoms. The above-mentioned phenomenon can be determined by removing impurity capacity and growth environment of the cBN crystal.

  9. 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.

  10. High-pressure Brillouin study on plastic crystals of neopentane and adamantane

    NASA Astrophysics Data System (ADS)

    Sasaki, Shigeo; Horibe, Yasuhiro; Kume, Tetsuji

    2013-06-01

    Spherical top molecules neopentane and adamantane with Td symmetry crystallize face centered cubic (fcc) plastic crystals in which molecules are rather freely rotating at fcc lattice points. In the case of fcc plastic crystalline methane, the value of elastic anisotropy A is above 5 which is large than A ~ 2.5 of rare gas solids without molecular rotation, and shows strong pressure dependence because of the enhancement of the molecular rotation-translation (R-T) coupling by compression. Therefore, the purpose of the present study is to carry out the high-pressure Brillouin measurements for the fcc plastic crystals of neopentane and adamantane up to 0.75 and 0.5 GPa, respectively, and to clarify the dependence of the R-T coupling on pressure and molecular weight. The obtained value of A of fcc neopentane is 6.1 at 0.18 GPa and steeply increase up to 12.8 at 0.72 GPa. This remarkably large A values and its strong pressure dependence indicate that the R-T coupling effect in the plastic phase of neopentane is obviously large in comparison with methane. On the other hand, the plastic crystal of adamantane shows almost constant (A = 2.5) which is nearly the same as the rare gas solids, suggesting no R-T coupling effect.

  11. 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.

  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. 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).

  14. Thermal Diffused Scattering (TDS) - a new tool for determining single crystal elasticity at high-pressure condition

    NASA Astrophysics Data System (ADS)

    Zhang, J.

    2015-12-01

    X-ray thermal diffuse scattering (TDS) has been used to determine phonon dispersion relation of solids since 1940s (Wehinger et al. 2013; Ding et al. 2006; Xu and Chiang 2005). However, its application in high-pressure mineral physics has not been widely recognized. Sound velocities of Earth materials at relevant high pressure (P) and temperature (T) conditions are essential for interpreting seismic data, which provides by now the most accurate image of the Earth interior. Comparing with other commonly used techniques for measuring sound velocities in the high-pressure mineral physics community, it has significant advantages and disadvantages. Firstly, it could be used for measuring any single crystals at extreme P-T conditions using diamond anvil cell (DAC), not limited to transparent samples or nuclear resonant isotopes; Secondly, single-crystal elastic constants could be obtained through TDS, and hence directional dependences of sound velocities are available; Finally, experimental setup for TDS measurement is very easy, essentially identical to what is used for routine high-pressure single-crystal X-ray diffraction experiments. However, TDS is much less straightforward in data interpretation, which usually involves micro force constant modeling between the nearest neighbor atoms. We developed dependable data collection procedures for TDS measurement under high-pressure conditions. Measurements with single-crystal Si and foresterite under ambient and high-pressure conditions are successful. Using the python code package we developed for analyzing TDS data, we successfully reproduced the previously determined single-crystal elastic moduli of Si and foresterite using Brillouin spectroscopy and ultrasonics. The experimental uncertainty of the single crystal elastic moduli determined from TDS approach is within 4% or better.

  15. Stability of amino acids and their oligomerization under high-pressure conditions: implications for prebiotic chemistry.

    PubMed

    Otake, Tsubasa; Taniguchi, Takashi; Furukawa, Yoshihiro; Kawamura, Fumio; Nakazawa, Hiromoto; Kakegawa, Takeshi

    2011-10-01

    The polymerization of amino acids leading to the formation of peptides and proteins is a significant problem for the origin of life. This problem stems from the instability of amino acids and the difficulty of their oligomerization in aqueous environments, such as seafloor hydrothermal systems. We investigated the stability of amino acids and their oligomerization reactions under high-temperature (180-400°C) and high-pressure (1.0-5.5 GPa) conditions, based on the hypothesis that the polymerization of amino acids occurred in marine sediments during diagenesis and metamorphism, at convergent margins on early Earth. Our results show that the amino acids glycine and alanine are stabilized by high pressure. Oligomers up to pentamers were formed, which has never been reported for alanine in the absence of a catalyst. The yields of peptides at a given temperature and reaction time were higher under higher-pressure conditions. Elemental, infrared, and isotopic analyses of the reaction products indicated that deamination is a key degradation process for amino acids and peptides under high-pressure conditions. A possible NH(3)-rich environment in marine sediments on early Earth may have further stabilized amino acids and peptides by inhibiting their deamination. PMID:21961531

  16. 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

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

    PubMed

    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, sp(2) and sp(3) 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 sp(2) C-C hybridization are metals, while the δ- phase characterized by a sp(3)C-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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  19. Piezochromism in nickel salicylaldoximato complexes: tuning crystal-field splitting with high pressure.

    PubMed

    Byrne, Peter J; Richardson, Patricia J; Chang, John; Kusmartseva, Anna F; Allan, David R; Jones, Anita C; Kamenev, Konstantin V; Tasker, Peter A; Parsons, Simon

    2012-06-18

    The crystal structures of bis(3-fluoro-salicylaldoximato)nickel(II) and bis(3-methoxy-salicylaldoximato)nickel(II) have been determined at room temperature between ambient pressure and approximately 6 GPa. The principal effect of pressure is to reduce intermolecular contact distances. In the fluoro system molecules are stacked, and the Ni⋅⋅⋅Ni distance decreases from 3.19 Å at ambient pressure to 2.82 Å at 5.4 GPa. These data are similar to those observed in bis(dimethylglyoximato)nickel(II) over a similar pressure range, though contrary to that system, and in spite of their structural similarity, the salicyloximato does not become conducting at high pressure. Ni-ligand distances also shorten, on average by 0.017 and 0.011 Å for the fluoro and methoxy complexes, respectively. Bond compression is small if the bond in question is directed towards an interstitial void. A band at 620 nm, which occurs in the visible spectrum of each derivative, can be assigned to a transition to an antibonding molecular orbital based on the metal 3d(x(2)-y(2)) orbital. Time-dependent density functional theory calculations show that the energy of this orbital is sensitive to pressure, increasing in energy as the Ni-ligand distances are compressed, and consequently increasing the energy of the transition. The resulting blueshift of the UV-visible band leads to piezochromism, and crystals of both complexes, which are green at ambient pressure, become red at 5 GPa. PMID:22615125

  20. Mare basalts - Crystal chemistry, mineralogy, and petrology

    NASA Technical Reports Server (NTRS)

    Papike, J. J.; Hodges, F. N.; Bence, A. E.; Cameron, M.; Rhodes, J. M.

    1976-01-01

    The paper attempts a synthesis of the major-element chemistry, petrography, mineral chemistry, and crystal chemistry of the mare basalts returned by Apollo and Luna missions. A classification of the mare basalts based on major-element chemistry is given, and textural sequences within each major-element group are identified. The mineral chemistry and crystal chemistry of each mineral group are considered within the framework of the major-element groups and the textural sequences. The various classes of models for the origin of the mare basalts and the nature of their source regions are discussed in the context of the major- and trace-element chemistries and experimental investigations.

  1. Crystal Chemistry of Meteoritic Hibonites

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Burns, V. M.

    1985-01-01

    The characteristics of cation vacancies and site occupancies of natural hibonites in meteors are discussed. Note is taken of the effect of the specific locations of the hibonites in the matrices on the crystal chemistry, electronic stabilities, and spectral features of the metal ions which replace the Al(3+). Hibonites form beta-alumina hexagonal cells with 26 cation sites. Fe cations are found in octahedral, tetrahedral, and five-fold coordinates. Fe(2+) is found in face-shared Al(3) octahedra, a siting explained in terms of ionic radius and crystal field stabilization energy criteria. Spectral colors are attributed to V(3+) and Ti(3+) field transitions at 400 and 700 nm, respectively, although the 700 nm line may arise from transitions of Ti(3+) to Ti(4+) or Fe(2+) to Fe(3+) during heating. Excesses of Mg-26 can be traced to decay of nebular Al-26.

  2. Crystal chemistry of meteoritic hibonites

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Burns, V. M.

    1984-01-01

    The characteristics of cation vacancies and site occupancies of natural hibonites in meteors are discussed. Note is taken of the effect of the specific locations of the hibonites in the matrices on the crystal chemistry, electronic stabilities, and spectral features of the metal ions which replace the Al(3+). Hibonites form beta-alumina hexagonal cells with 26 cation sites. Fe cations are found in octahedral, tetrahedral, and five-fold coordinations. Fe(2+) is found in face-shared Al(3) octahedra, a siting explained in terms of ionic radius and crystal field stabilization energy criteria. Spectral colors are attributed to V(3+) and Ti(3+) field transitions at 400 and 700 nm, respectively, although the 700 nm line may arise from transitions of Ti(3+) to Ti(4+) or Fe(2+) to Fe(3+) during heating. Excesses of Mg-26 can be traced to decay of nebular Al-26.

  3. Crystal chemistry of meteoritic hibonites

    NASA Astrophysics Data System (ADS)

    Burns, R. G.; Burns, V. M.

    1984-11-01

    The characteristics of cation vacancies and site occupancies of natural hibonites in meteors are discussed. Note is taken of the effect of the specific locations of the hibonites in the matrices on the crystal chemistry, electronic stabilities, and spectral features of the metal ions which replace the Al(3+). Hibonites form beta-alumina hexagonal cells with 26 cation sites. Fe cations are found in octahedral, tetrahedral, and five-fold coordinations. Fe(2+) is found in face-shared Al(3) octahedra, a siting explained in terms of ionic radius and crystal field stabilization energy criteria. Spectral colors are attributed to V(3+) and Ti(3+) field transitions at 400 and 700 nm, respectively, although the 700 nm line may arise from transitions of Ti(3+) to Ti(4+) or Fe(2+) to Fe(3+) during heating. Excesses of Mg-26 can be traced to decay of nebular Al-26.

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

    PubMed

    Kilduff, Brandon J; Fredrickson, Daniel C

    2016-07-01

    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

  5. Elasticity of single-crystal olivine at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Mao, Zhu; Fan, Dawei; Lin, Jung-Fu; Yang, Jing; Tkachev, Sergey N.; Zhuravlev, Kirill; Prakapenka, Vitali B.

    2015-09-01

    Elasticity of single-crystal San Carlos olivine has been derived from sound velocity and density measurements at simultaneous high pressure-temperature conditions up to 20 GPa and 900 K using in situ Brillouin spectroscopy and single-crystal X-ray diffraction in externally-heated diamond anvil cells. These experimental results are used to evaluate the combined effect of pressure and temperature on full elastic constants of single-crystal olivine to better understand its velocity profiles and anisotropies in the deep mantle. Analysis of the results shows that the shear moduli display strong concave behaviors as a function of pressure at a given high temperature, while the longitudinal modulus, C11, and the off-diagonal moduli, C12 and C13, exhibit greater temperature dependence at higher pressures than at relatively lower pressures. Using a finite-strain theory and thermal equation of state modeling for a pyrolitic mantle composition along an expected mantle geotherm, our results show that the magnitude of the VP and VS jumps at the 410-km depth are 6% and 6.4%, respectively, which are greater than that found in seismic observations, suggesting a mantle olivine content of 40-50 vol%, which is less than what is expected for the pyrolite model. Our modeled velocity profiles for a metastable olivine wedge in the subduction slabs along a representative cold slab geotherm are 6% and 10% lower than those of wadsleyite and ringwoodite, respectively, at corresponding depths of the normal mantle. Our modeled results also show that metastable olivine in the cold slabs could have strong VP and VS anisotropies. The maximum VP anisotropy is estimated to be 19-22% at transition zone depth, whereas the maximum VS splitting is 13-23% and increases with depth. As a result, the presence of a metastable olivine wedge at the transition zone depth would exhibit a seismic signature of low velocity and strong seismic anisotropy which are consistent with recent seismic observations for

  6. High-pressure synthesis, crystal structure and magnetic properties of TlCrO3 perovskite.

    PubMed

    Yi, Wei; Matsushita, Yoshitaka; Katsuya, Yoshio; Yamaura, Kazunari; Tsujimoto, Yoshihiro; Presniakov, Igor A; Sobolev, Alexey V; Glazkova, Yana S; Lekina, Yuliya O; Tsujii, Naohito; Nimori, Shigeki; Takehana, Kanji; Imanaka, Yasutaka; Belik, Alexei A

    2015-06-21

    TlMO(3) perovskites (M(3+) = transition metals) are exceptional members of trivalent perovskite families because of the strong covalency of Tl(3+)-O bonds. Here we report on the synthesis, crystal structure and properties of TlCrO(3) investigated by Mössbauer spectroscopy, specific heat, dc/ac magnetization and dielectric measurements. TlCrO(3) perovskite is prepared under high pressure (6 GPa) and high temperature (1500 K) conditions. The crystal structure of TlCrO(3) is refined using synchrotron X-ray powder diffraction data: space group Pnma (no. 62), Z = 4 and lattice parameters a = 5.40318(1) Å, b = 7.64699(1) Å and c = 5.30196(1) Å at 293 K. No structural phase transitions are found between 5 and 300 K. TlCrO(3) crystallizes in the GdFeO(3)-type structure similar to other members of the perovskite chromite family, ACrO(3) (A(3+) = Sc, In, Y and La-Lu). The unit cell volume and Cr-O-Cr bond angles of TlCrO(3) are close to those of DyCrO(3); however, the Néel temperature of TlCrO(3) (TN≈ 89 K) is much smaller than that of DyCrO(3) and close to that of InCrO(3). Isothermal magnetization studies show that TlCrO(3) is a fully compensated antiferromagnet similar to ScCrO(3) and InCrO(3), but different from RCrO(3) (R(3+) = Y and La-Lu). Ac and dc magnetization measurements with a fine step of 0.2 K reveal the existence of two Néel temperatures with very close values at T(N2) = 87.0 K and T(N1) = 89.3 K. Magnetic anomalies near T(N2 )are suppressed by static magnetic fields and by 5% iron doping. PMID:25730286

  7. High-Pressure Behavior of U-O-H Materials via Single-Crystal X-ray Diffraction

    NASA Astrophysics Data System (ADS)

    Cahill, C. L.; Budzianowski, A.; Dera, P.

    2002-05-01

    Crystal chemistry of U-O-H (uranyl oxide hydrate) phases has attracted a great deal of attention because of the observation that such materials may form when spent nuclear fuel (UO2) is exposed to the moist, oxidizing conditions of the proposed repository at Yucca Mountain. An expansion of this interest is to investigate the behavior of these phases as a function of both temperature and pressure. Knowledge about stability of U-O-H phases, as well as the eventual phase transformations these materials may undergo during long-term storage may be relevant e.g. for assessing possible radionuclide leakage. In this study, we investigated the high-pressure behavior of a synthetic phase, (UO2)(IO3)2(H2O), [Pbcn, a = 8.504(1)Å, b = 7.734(1)Å, c = 12.398(1)Å] by single-crystal X-ray diffraction in a diamond anvil cell (DAC). The simple topology of the crystal structure, availability of quality single crystals through straight-forward syntheses, and the fact that 129I is one of the long-lived radionuclides found in spent fuel, make (UO2)(IO3)2(H2O) a suitable model for the layered U-O-H phases that are common among oxidation products of spent nuclear fuel. Hydrostatic compression experiments in a Merrill-Bassett DAC were performed to 6.5 GPa using a Bruker 1K CCD diffractometer, and Mo-Kα radiation. Diffraction data sets were collected at 0.1 MPa, 1.0, 2.0, 3.0, 3.5, 4.0, 5.8 and 6.5 GPa. Unit cell refinements indicate an anisotropic compression mechanism: the layers are brought closer together and compressed (a and c directions) whereas the b crystallographic direction remains relatively unchanged. This behavior can be explained by the presence of H-bonding within the layers. Further details of these phenomena, as well as the results of full structure refinements at each pressure will be presented.

  8. 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

  9. 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. PMID:17746396

  10. High-pressure crystal structures of TaAs from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Lu, Mingchun; Guo, Yanan; Zhang, Miao; Liu, Hanyu; Tse, John S.

    2016-08-01

    In this work, we systematically studied the phase transition of TaAs under high pressures and reported three high-pressure structures P-6m2 (hexagonal, stable at 13-32 GPa), P21/c (monoclinic, stable at 32-103 GPa) and Pm-3m (cubic, stable above 103 GPa), by using particle swarm optimization in combination with first principles electronic structure methodology. All predicted structures are dynamically stable, since there is no imaginary mode to be found in the whole Brillouin zone. At high pressures, the TaAs was found to become superconductor with the superconducting critical temperature of ~1 K at about 100 GPa.

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

    NASA Astrophysics Data System (ADS)

    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 were characterized as an ordered double-perovskite structure of space group P21/n with the Ca and Os 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.

  12. 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.

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

    PubMed

    Scott, Carl D; Povitsky, Alexander; Dateo, Christopher; Gökçen, 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. PMID:12908231

  14. Liquids in the Diamond Anvil Cell: High Pressure-Temperature Chemistry of Formic Acid

    NASA Astrophysics Data System (ADS)

    Montgomery, W. B.; Zaug, J. M.; Goncharov, A. F.; Howard, W. M.; Manaa, M. R.; Jeanloz, R.; Young, C. E.; Crowhurst, J. C.

    2003-12-01

    The chemical and physical properties of liquids under high pressures and temperatures are of continuing interest and application to the planetary science community. Using near-simultaneous FTIR and Raman spectroscopy including high-resolution optical video, we have begun to study the behavior of formic acid (HCOOH) at conditions observed on Europa, Ganymede and Callisto. We present a phase diagram, including melting curve, proposed reaction mechanisms and solid-state phase transitions, over a temperature range from 300-550 K and a pressure range from .1 to 9 GPa. Reaction products, including CO2 and amorphous carbons (COOHn) have been identified. Preliminary results from FTIR studies are used to determine reaction rates, and pressure dependent activation energies. We have also employed a detailed kinetic reaction mechanism to study the decomposition of formic acid at extreme conditions by using a fluid exponential-6 equation-of-state for the reacting species. We have used first principles DFT and semi-empirical tight binding methods to predict properties of solid formic acid under isotropic and uniaxial compression. We compare the results of both simulations to our experimental observations.

  15. 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.

  16. 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.

    2016-06-01

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

    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.

  18. 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.

  19. 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.

  20. 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

  1. Promising dissolution enhancement effect of soluplus on crystallized celecoxib obtained through antisolvent precipitation and high pressure homogenization techniques.

    PubMed

    Homayouni, Alireza; Sadeghi, Fatemeh; Varshosaz, Jaleh; Afrasiabi Garekani, Hadi; Nokhodchi, Ali

    2014-10-01

    Poor solubility and dissolution of hydrophobic drugs have become a major challenge in pharmaceutical development. Drug nanoparticles have been widely accepted to overcome this problem. The aim of this study was to manufacture celecoxib nanoparticles using antisolvent precipitation and high pressure homogenization techniques in the presence of varying concentrations of soluplus(®) as a hydrophilic stabilizer. Antisolvent crystallization followed by freeze drying (CRS-FD) and antisolvent crystallization followed by high pressure homogenization and freeze drying (HPH-FD) were used to obtain celecoxib nanoparticles. The obtained nanoparticles were analyzed in terms of particle size, saturation solubility, morphology (optical and scanning electron microscopy), solid state (DSC, XRPD and FT-IR) and dissolution behavior. The results showed that celecoxib nanoparticle can be obtained when soluplus was added to the crystallization medium. In addition, the results showed that the concentration of soluplus and the method used to prepare nanoparticles can control the size and dissolution of celecoxib. Samples obtained in the presence of 5% soluplus through HPH technique showed an excellent dissolution (90%) within 4min. It is interesting to note that celecoxib samples with high crystallinity showed better dissolution than those celecoxib samples with high amorphous content, although they had the same concentration of soluplus. DSC and XRPD proved that samples obtained via HPH technique are more crystalline than the samples obtained through only antisolvent crystallization technique. PMID:25124835

  2. Crystal structure and stability of Tl2CO3 at high pressures.

    PubMed

    Grzechnik, A; Friese, K

    2010-03-01

    The crystal structure of dithallium carbonate, Tl(2)CO(3) (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

  3. 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

  4. Crystal growth of hexagonal boron nitride (hBN) from Mg-B-N solvent system under high pressure

    NASA Astrophysics Data System (ADS)

    Zhigadlo, N. D.

    2014-09-01

    Transparent and colorless hexagonal boron nitride (hBN) single crystals were grown from the Mg-B-N system using high-pressure-high-temperature cubic anvil technique. By varying the synthesis conditions we could determine the sequence of phase transformations occurring in the Mg-B-N system, construct the pressure-temperature (P-T) phase diagram and discuss the possible growth mechanism. The largest plate-like-shaped hBN crystals with sizes up to 2.5 mm in length and up to 10 μm in thickness were grown at 30 kbar and 1900-2100 °C. The hBN crystals exhibited strong, narrow diffraction peaks typical of well-ordered stacking crystal planes, with the c-axis perpendicular to the crystal face. A characteristic Raman peak observed at 1367 cm-1 with a full width at half maximum of 8 cm-1 corresponds to the E2g vibration mode and indicates the high purity and order of hBN crystals grown by this method. From the practical point of view this work can stimulate further explorations of the Mg-B-N solvent system to obtain isotopically-enriched h10BN crystals, which can act as a key element in solid-state neutron detector devices.

  5. 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.

  6. 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.

  7. Crystal lattice and band structure of the intermediate high-pressure phase of PbSe.

    PubMed

    Streltsov, S V; Manakov, A Yu; Vokhmyanin, A P; Ovsyannikov, S V; Shchennikov, V V

    2009-09-23

    In the present paper the results of fitting synchrotron diffraction data are obtained for the intermediate high-pressure phase (9.5 GPa) of the lead selenide based compound Pb(1-x)Sn(x)Se (x = 0.125)-an optoelectronic as well as a thermoelectric material-for two types of lattice symmetries Pnma (space group #62) and Cmcm (space group #63). Both lattice parameters and positions of atoms for the above mentioned structures have been used in calculations of the electron structure of high-pressure phases. The main difference between the electronic properties for Cmcm and Pnma structures established in electronic structure calculations is that in the first one the PbSe compound was found to be a metal, while in the second a small semiconductor gap (E(G) = 0.12 eV) was obtained. Moreover, the forces in the Cmcm structure are an order of magnitude larger than those calculated for the Pnma lattice. In the optimized, Pnma structure within a generalized gradient approximation (GGA), the band gap increases up to E(G) = 0.27 eV. The result coincides with the data on thermoelectric power and electrical resistance data pointing to a semiconductor gap of ∼0.2 eV at ∼9.5 GPa. Thus, the Pmna type of lattice seems to be a preferable version for the intermediate phase compared with the Cmcm one. PMID:21832372

  8. 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.

  9. A device for the high-pressure oxygenation of protein crystals.

    PubMed

    Rutledge, Peter J; Burzlaff, Nicolai I; Elkins, Jonathan M; Pickford, Michael; Baldwin, Jack E; Roach, Peter L

    2002-09-15

    A system has been developed for subjecting protein crystals to hyperbaric pressures of oxygen gas in order to promote enzymatic reaction. Crystals of an oxygenase or oxidase enzyme are grown anaerobically by hanging drop vapor diffusion, under crystallization conditions modified to eliminate combustible materials such as plastic coverslips and grease. The crystalline enzyme:substrate complex can then be exposed to oxygen gas at pressures up to 60 bar using a custom-built device or "bomb." In this way, reaction is initiated synchronously throughout the crystal and subsequent flash freezing allows the trapping of enzyme:product complexes in high occupancy. These complexes can then be structurally characterized by conventional monochromatic X-ray crystallography. The bomb is furnished from naval brass and lubricated with Fomblin RT15 perfluorinated polyether grease in order to ensure compatibility with the highly oxidizing environment. PMID:12419338

  10. Experimental and theoretical evidence for an ionic crystal of ammonia at high pressure

    NASA Astrophysics Data System (ADS)

    Ninet, S.; Datchi, F.; Dumas, P.; Mezouar, M.; Garbarino, G.; Mafety, A.; Pickard, C. J.; Needs, R. J.; Saitta, A. M.

    2014-05-01

    We report experimental and theoretical evidence that solid molecular ammonia becomes unstable at room temperature and high pressures and transforms into an ionic crystalline form. This material has been characterized in both hydrogenated (NH3) and deuterated (ND3) ammonia samples up to about 180 and 200 GPa, respectively, by infrared absorption, Raman spectroscopy, and x-ray diffraction. The presence of a new strong infrared absorption band centered at 2500 cm-1 in NH3 (1900 cm-1 in ND3) is in line with previous theoretical predictions regarding the ionization of ammonia molecules into NH2- and NH4+ ions. The experimental data suggest the coexistence of two crystalline ionic forms, which our ab initio structure searches predict to be the most stable at the relevant pressures. The ionic crystalline form of ammonia appears stable at low temperatures, which contrasts with the behavior of water in which no equivalent crystalline ionic phase has been found.

  11. The EPR study of Mn2+ ion doped DADT single crystal produced under high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Ceylan, Ümit; Tapramaz, Recep

    2016-01-01

    An EPR study on Cu2+ and VO2+ doped di ammonium D-tartrate single crystals has been reported in previous papers, but the same host did not accept Mn2+ ion at the same reaction conditions in previous trials. In this study EPR study of Mn2+ ion doped di ammonium D tartrate single crystal, (DADT) [(NH4)2C4H4O6], produced in a reactor under high pressure and high temperature. The electronic transitions were determined by the optical absorption spectrum. Hyperfine splitting and g values of the Mn2+ ion forming a complex in the lattice were measured from experimental spectra and spin-spin dipolar splitting parameters D and E were found by the spectrum simulation techniques.

  12. High-pressure synthesis, crystal structure and magnetic property of ilmenite-type FeGeO{sub 3}

    SciTech Connect

    Nakatsuka, Daisuke; Yoshino, Takashi; Kano, Jun; Hashimoto, Hideki; Nakanishi, Makoto; Takada, Jun; Fujii, Tatsuo

    2013-02-15

    We synthesized well-crystallized ilmenite-type FeGeO{sub 3} to investigate its structural and magnetic properties. Ilmenite-type FeGeO{sub 3} were synthesized by high-pressure synthesis technique using a Kawai-type multi-anvil apparatus. Their structural and magnetic properties were examined by XRD analysis with Rietveld refinement, transmission electron microscopy, Moessbauer spectroscopy and SQUID-magnetization measurements. The subsequent annealing after the high-pressure synthesis was effective to improve the crystallinity of the ilmenite-type FeGeO{sub 3}. The primary particle size of ilmenite-type FeGeO{sub 3} was {approx}15 nm. Some particles seemed to be covered with non- or poorly crystalline phase even after the annealing, and others showed a lamellar microstructure parallel to the (0 0 1) plane. Theilmenite-type FeGeO{sub 3} showed typical antiferromagnetic behavior with the Neel temperature of 79 K. - Graphical abstract: Crystal structure, transmission electron micrograph and temperature dependent susceptibility of ilmenite-type FeGeO{sub 3}. Highlights: Black-Right-Pointing-Pointer Ilmenite-type FeGeO{sub 3}, a novel polymorphism of FeGeO{sub 3} was successfully synthesized. Black-Right-Pointing-Pointer It was synthesized by using high pressure technique at 23.5 GPa at 500 Degree-Sign C. Black-Right-Pointing-Pointer Subsequent annealing in vacuum was effective to improve the crystallinity. Black-Right-Pointing-Pointer Its primary particle size was {approx}15 nm, and some grains had lamellar microstructure. Black-Right-Pointing-Pointer It showed typical antiferromagnetic behavior with the Neel temperature of 79 K.

  13. Multi feed seed (MFS) high pressure crystallization of 1-2 in GaN

    NASA Astrophysics Data System (ADS)

    Bockowski, M.; Grzegory, I.; Lucznik, B.; Sochacki, T.; Nowak, G.; Sadovyi, B.; Strak, P.; Kamler, G.; Litwin-Staszewska, E.; Porowski, S.

    2012-07-01

    The growth and physical properties of GaN crystallized in a multi feed-seed (MFS) configuration by High Nitrogen Pressure Solution (HNPS) growth method are presented in detail. The conversion of free standing HVPE-GaN crystals to free standing HNPS-GaN is the basis of the MFS configuration. The influence of the experimental conditions (i.e. growth temperature, temperature gradient, etc.), the c-plane bowing of the initial substrate, the electrical properties of HNPS-GaN, and the rate and mode of growth from solution are analyzed. We show that the HNPS-GaN crystals have better structural quality than their HVPE-GaN seeds. The defect density decreases with increasing growth temperature, reaching 5×105 cm-2 for crystals grown at 1420 °C or higher. In contrast, the free carrier concentration in HNPS-GaN increases with increasing growth temperature, reaching 7×1019 cm-3 for samples crystallized at 1440 °C. Thus the possibility to obtain good quality plasmonic GaN substrates for laser diodes can be realized.

  14. Novel high pressure monoclinic Fe2O3 polymorph revealed by single-crystal synchrotron X-ray diffraction studies

    NASA Astrophysics Data System (ADS)

    Bykova, Elena; Bykov, Maxim; Prakapenka, Vitali; Konôpková, Zuzana; Liermann, Hanns-Peter; Dubrovinskaia, Natalia; Dubrovinsky, Leonid

    2013-08-01

    A novel high pressure polymorph of iron sesquioxide, m-Fe2O3, has been identified by means of single-crystal synchrotron X-ray diffraction (XRD). Upon compression of a single crystal of hematite, α-Fe2O3, in a diamond anvil cell, the transition occurs at pressure of about 54 GPa and results in ∼10% volume reduction. The crystal structure of the new phase was solved by the direct method (monoclinic space group P21/n, a=4.588(3), b=4.945(2), c=6.679(7) Å and β=91.31(9)°) and refined to R1 ∼11%. It belongs to the cryolite double-perovskite structure type and consists of corner-linked FeO6 octahedra and FeO6 trigonal prisms filling the free space between the octahedra. Upon compression up to ∼71 GPa at ambient temperature no further phase transitions were observed. Laser heating to ∼ 2100±100 K promotes a transition to the Cmcm CaIrO3-type (post-perovskite (PPv)) phase. The PPv-Fe2O3 crystal structure was refined by means of single-crystal XRD at ∼65 GPa. On decompression the PPv-Fe2O3 phase fully transforms back to hematite at pressures between ∼25 and 15 GPa.

  15. 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.

  16. A rotator for single-crystal neutron diffraction at high pressure.

    PubMed

    Fang, J; Bull, C L; Hamidov, H; Loveday, J S; Gutmann, M J; Nelmes, R J; Kamenev, K V

    2010-11-01

    We present a modified Paris-Edinburgh press which allows rotation of the anvils and the sample under applied load. The device is designed to overcome the problem of having large segments of reciprocal space obscured by the tie rods of the press during single-crystal neutron-scattering experiments. The modified press features custom designed hydraulic bearings and provides controls for precision rotation and positioning. The advantages of using the device for increasing the number of measurable reflections are illustrated with the results of neutron-diffraction experiments on a single crystal of germanium rotated under a load of 70 tonnes. PMID:21133480

  17. 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

  18. Single crystal diffraction studies of phase transition of minerals across Fe high-low spin transition at high pressure

    NASA Astrophysics Data System (ADS)

    Merlini, M.; Hanfland, M.

    2011-12-01

    The spin state of Fe in structure of minerals relevant for the lower mantle mineralogy, is known to undergo a high to low spin state change. This phenomena is often coupled to a remarkable volume contraction and from a structural point of view, often is associated to isosymmetrical phase transition. Recent improvements at X-Ray beamlines for diffraction at extreme conditions at synchrotron facilities allow the possibility to perform single crystal diffraction and determine crystal structure of minerals at extreme conditions, including also structural studies across first or second order phase transition. The accurate knowledge of crystal structure and of phase behaviour at high pressure is a very important step in order to: 1-understand the physical properties; 2- have an accurate experimental constraint on numerical simulation. We report here three examples of structure determination by single crystal X-Ray diffraction at extreme conditions concerning phase transition related to Fe spin state change, measured at ID09A beamline (ESRF, France). CaFe2O4 undergoes a spin transition at 50 GPa. XRD before and after indicate the symmetry and crystal structure is the same. The transition is marked by 10 % volume contraction. The use of He as pressure transmitting media strongly reduced strain induced by pressure and let the crystal survive this transition, allowing for the first time direct determination of Fe-O bond length changes related to variation of spin state. The main structural difference between high and low spin structure is simply a collapse of FeO6 polyhedra. FeCO3 has been also investigated, and the results are also compared with already present in literature. FeCO3 undergoes a transition around 45 GPa, with a remarked hysteresis. In the pressure range 20-45 however an anomalous behaviour is noticed, probably related to a different spin interaction due to reduced Fe-Fe distances. Fe1-xS pyrrhotite has been investigated in two different structure (a

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    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 (Pmax=11.5 GPa) and high-temperature (Tmax=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 MgZn2-type HP-EuPdSn: P63/mmc, a=588.5(2), c=917.0(3) pm, wR2=0.0769, 211 F2 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 RE3+ 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 TN=5.1 K. HP-EuPdSn shows divalent europium and antiferromagnetic ordering at 8.9 K followed by a spin reorientation at 5.7 K.

  20. 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.

  1. 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. PMID:27158503

  2. 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

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

    SciTech Connect

    Hermon, H.; Schieber, M. |; James, R.B.

    1999-06-01

    Sandia National Laboratories (SNL) is leading an effort to evaluate vertical high pressure Bridgman (VHPB) Cd{sub 1{minus}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 and 0.1 {micro}s, respectively, compared to 3--20 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

    Aracne, C. M.; Farber, D. L.; Occelli, F.; Antonangeli, D.; Badro, J.

    2003-12-01

    Measuring the effects of pressure on geomaterials in deep Earth's P-T conditions using the diamond anvil cell (DAC) is essential for understanding the phase transition mechanisms, the mechanical properties (which derives directly from the determination of the elastic constants), and the transport properties of deep-Earth materials. To date, most DAC research has been performed with polycrystalline samples. While these are sufficient for determining orientationally averaged properties of solids (i.e. bulk modulus, P-waves and S-wave aggregate velocities, etc\\ldots), single crystals offer the ability to measure a range of direction dependent properties (i.e. thermal and electrical conductivity, elasticity and plasticity, etc\\ldots). Subsequent comparison of measurements on single-\\ and poly-crystalline materials can, for instance, make it possible to address the effects of pressure on the elastic anisotropy and preferred orientations in deep Earth's conditions. In order to achieve pressures above 1 Mbar, one must produce single crystal samples ˜25 μ m in diameter and less than 10 μ m thick. We have developed procedures to produce extremely high-quality metallic single crystals of this size from commercially available material with millimeter dimensions. Critical to the final product is the preservation of crystallinity during thinning and cutting. Our surface preparation methods include the use of selected abrasives, colloidal silica polishing and chemical etching. Samples are cut to final shape using a laser-ablation facility that can handle both conductive and insulating materials. To date, we have been successful in maintaining an extremely high degree of crystallinity and orientation in the final samples. Presently, 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 minerals, such as zinc, sapphire, and olivine.

  6. Crystal grain growth during room temperature high pressure Martensitic alpha to omega transformation in zirconium

    SciTech Connect

    Velisavljevic, Nenad; Chesnut, Gary N; Stevens, Lewis L; Dattelbaum, Dana M

    2008-01-01

    Systematic increase in transition pressure with increase in interstitial impurities is observed for the martensitic {alpha} {yields} {omega} structural phase transition in Zr. Significant room temperature crystal grain growth is also observed for the two highest purity samples at this transition, while in the case of the lowest purity sample interstitial impurities obstruct grain growth even as the sample is heated to 1279 K. Our results show the importance of impurities in controlling structural phase stability and other mechanical properties associated with the {alpha} {yields} {omega} structural phase transition.

  7. 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).

  8. First-principles study of MoHn (n =1, 2 and 3) crystal structures under high pressure

    NASA Astrophysics Data System (ADS)

    Feng, Xiaolei; Zhang, Jurong; Liu, Hanyu; Wang, Hui

    Hydrogen-rich materials have attracted attention recently, owing to their fascinating chemical bonding and potential high superconducting critical temperatures temperature. Inspired by the recent identification of polyhydrides of d metals and molybdenum hydride molecules with a high H content, we explored the crystal structures of MoHn (n = 1, 2, and 3) under high pressures using particle swarm optimization combined with first-principles electronic structure calculations. Several novel structures of MoH2 and MoH3 are predicted at high pressures. MoH is calculated to be stable at ambient pressure; at P >2.3 GPa the hexagonal phase of MoH2 becomes stable, and at 24 GPa it transforms into an orthorhombic structure, which remains stable up to 100 GPa. All three stable structures show metallic behavior under pressure. The calculated electronic properties suggest that the d-orbitals of the Mo atoms provide the dominant contribution to the density of states at the Fermi level, which is different from the density of states previously predicted for H-rich materials. The present results offer insights in understanding of chemical and physical properties in hydrogen-rich materials, especially in extreme environments.

  9. 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).

  10. High pressure metallization and amorphization of the molecular crystal Sn(IBr){sub 2}

    SciTech Connect

    Machavariani, G.Y.; Rozenberg, G.K.; Pasternak, M.P.; Naaman, O.; Taylor, R.D.

    1998-12-31

    An insulator-to-metal transition concurring with amorphization is found in the cubic (Pa{bar 3}) molecular crystal Sn(IBr){sub 2} at P {approx} 20 GPa. Measurements were carried out with diamond-anvil cells at pressures up to {approximately}30 GPa using resistance measurements, X-ray diffraction (XRD), and {sup 119}Sn Moessbauer spectroscopy (MS). With increasing pressure a new crystalline phase is observed in the 10--23 GPa range; at P {approx} 16 GPa a gradual onset of structural disorder is first observed, and full amorphization takes place at P {ge} 21 GPa. Both electronic properties as measured by R(P,T) and MS data are consistent with a gradual growth of disordered (SnI{sub 2}Br{sub 2}){sub n} polymeric chains, formed by intermolecular I{single_bond}I bonding allowing for electronic delocalization to occur. Upon decompression both XRD and {sup 119}Sn MS show a significant pressure hysteresis.

  11. Single-crystal elasticity of the deep-mantle magnesite at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Yang, Jing; Mao, Zhu; Lin, Jung-Fu; Prakapenka, Vitali B.

    2014-04-01

    Magnesite (MgCO3) is considered to be a major candidate carbon host in the Earth's mantle, and has been found to exist as an accessory mineral in carbonated peridotite and eclogite. Studying the thermal elastic properties of magnesite under relevant pressure-temperature conditions of the upper mantle is thus important for our understanding of the deep-carbon storage in the Earth's interior. Here we have measured the single-crystal elasticity of a natural magnesite using in situ Brillouin spectroscopy and X-ray diffraction in a diamond anvil cell up to 14 GPa at room temperature and up to 750 K at ambient pressure, respectively. Using the third-order Eulerian finite-strain equations to model the elasticity data, we have derived the aggregate adiabatic bulk, KS0, and shear moduli, G0, at ambient conditions: KS0=114.7 (±1.3) GPa and G0=69.9 (±0.6) GPa. The pressure derivatives of the bulk and shear moduli at 300 K are (∂KS/∂P)T=4.82 (±0.10) and (∂G/∂P)T=1.75 (±0.10), respectively, while their temperature derivatives at ambient pressure are (∂Ks/∂T)P=-24.0 (±0.2) MPa/K and (∂G/∂T)P=-14.8 (±0.7) MPa/K. Based on the thermal elastic modeling of the measured elastic constants along an expected normal upper-mantle geotherm and a cold subducting slab, magnesite exhibits compressional wave (VP) anisotropy of approximately 46-49% and shear wave (VS) splitting of 37-41% that are much larger than those of major constituent minerals in the Earth's upper mantle including olivine, pyroxene, and garnet. The modeled aggregate VP and VS velocity in moderately carbonated peridotite and eclogite containing approximately 10 wt.% magnesite (approximately 5 wt.% CO2) show minimal effects of magnesite on the seismic profiles of these rock assemblages at upper mantle conditions, suggesting that the presence of magnesite is likely difficult to be detected seismically. However, due to its unusually high VP and VS anisotropies, magnesite with strong preferred orientations

  12. 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)

  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. Coexistence of monochalocogen and dichalocogen ions in BiSe2 and BiS2 crystals prepared at high pressure.

    PubMed

    Yamamoto, Ayako; Hashizume, Daisuke; Bahramy, Mohammad Saeed; Tokura, Yoshinori

    2015-04-20

    A single crystal of bismuth diselenide, BiSe2, containing both monochalcogen (Se(2-)) and dichalcogen (Se2(2-)) ions, was prepared at a high pressure of 5.5 GPa. Its crystal structure, substitution chemistry, and physical properties were investigated. X-ray analysis showed that BiSe2 is in a monoclinic system (space group C2/m) with the following lattice parameters: a = 16.740(3) Å, b = 4.1410(11) Å, c = 12.027(3) Å, and β = 127.658(13)°. A crystal structure of BiSe2 can be viewed as a layered structure with stacks of neutral BiSe2 blocks along the c-axis, or alternatively as a quasi-one-dimensional structure with double chains of BiSe5 pyramids along the b-axis. Each Bi is coordinated with three Se(2-) ions and two Se2(2-) ions, and the bond valence analysis indicated that Bi was trivalent. BiSe2 and BiS2 form a solid solution in the whole range while retaining the same structure, and the partial substitution of Sb for Bi is also achieved at 10%. All the compounds show a semiconducting property and diamagnetism that can be attributed to the closed-shell ion core. In spite of the compositional analogy with Bi2Se3, BiSe2 is proven by the first-principles calculations not to be a topological insulator. PMID:25856004

  15. 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

  16. 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

  17. 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

  18. 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.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

    Andersson, Ove; Johari, G. P.

    2016-02-01

    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) κcrystal is 3.6-times the κliquid value at 140 K at 0.1 MPa and 2.2-times at 290 K, and it varies with T according to 138 × T-0.95; (ii) the ratio κliquid (p)/κliquid (0.1 MPa) is 1.45 GPa-1 at 280 K, which, unexpectedly, is about the same as κcrystal (p)/κcrystal (0.1 MPa) of 1.42 GPa-1 at 298 K; (iii) κglass is relatively insensitive to T but sensitive to the applied p (1.38 GPa-1 at 150 K); (iv) κglass-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, κcrystal 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.

  1. High-pressure suppression of crystallization in the metallic supercooled liquid Zr41 Ti14 Cu12.5 Ni10 Be22.5 : Influence of viscosity

    NASA Astrophysics Data System (ADS)

    Wang, W. H.; Wang, Z. X.; Zhao, D. Q.; Tang, M. B.; Utsumi, W.; Wang, X.-L.

    2004-09-01

    The supercooled liquid Zr41Ti14Cu12..5Ni10Be22.5 is studied using a high-pressure (HP) and high-temperature x-ray diffraction technique with synchrotron radiation, which allows us for the first time to in situ monitor the crystallization kinetics of metallic supercooled liquid in both cooling and heating processes under HP. We find that more than 6 GPa can completely suppress the crystallization in the melt at low cooling rate, and distinct crystallization from glassy to melt states during fast heating can be bypassed at 8.3 GPa. HP suppresses the crystallization in the supercooled liquid through increasing its viscosity.

  2. Constraining Oxygen-17 NMR Spectra of High Pressure Crystals and Glasses: New Data for Jadeite, Pyrope, Grossular, and Mullite

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

    17O NMR is a direct way of analyzing the immediate environment around oxygen atoms and can provide information on cation ordering, mixing, and network connectivity in glasses and disordered crystals. Due to overlapping peaks and lack of data on crystalline model compounds, 17O NMR spectra of high pressure glasses have been difficult to interpret. Additionally, data on crystalline model compounds are needed to test the validity of quantum chemical calculations. In this study, 17O NMR spectra were collected for crystalline jadeite, pyrope, grossular, and mullite in order to determine the parameters for oxygen bonded to [6]Al in a variety of environments. Jadeite contains three oxygen sites: oxygen bonded to [4]Si, Na, and two [6]Al atoms (O1), oxygen bonded to [4]Si, Na, and [6]Al atoms (O2), and oxygen bonded to two [4]Si and two Na atoms (O3). The NMR parameters for O1 are CQ = 3.3 MHz, δ = 64 ppm, and ν = 0.9; for O2 are CQ = 4.1 MHz, δ = 59 ppm, and ν = 0.15; and for O3 are CQ = 5.0 MHz, δ = 60 ppm, and ν = 0.15. The parameters for O2 are similar to interpretations of recent data for this kind of site in high pressure sodium aluminosilicate glasses (δ = 59 ppm) and to quantum chemical calculations (Lee et al., 2004, J. Phys. Chem., 108, 5897). Pyrope and grossular each contain one oxygen site, oxygen bonded to [4]Si, [6]Al, and two M2+ cations. The 17O NMR parameters for pyrope are CQ = 3.4 MHz, δ = 84 ppm, and ν = 0.3 and for grossular are CQ = 4.1 MHz, δ = 102 ppm, and ν = 0.4. In grossular, the NMR peak for oxygens bonded to [4]Si, Ca, and high coordinated Al seems to fall between those for "normal" bridging and non bridging oxygens, as reported for high pressure CAS glasses by Allwardt et al. (2005). These data will also be useful to help understand Ca-Mg ordering in the pyrope-grossular solid solutions. Mullite contains four oxygen environments: oxygen bonded to three tetrahedral Al or Si (Oc*), oxygen bonded to two tetrahedral Al or Si (Oc), and

  3. 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.

  4. 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.

  5. 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

  6. 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.

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

    USGS Publications Warehouse

    Evans, H.T., Jr.; 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

  8. Crystal structure of a high-pressure/high-temperature phase of alumina by in situ X-ray diffraction.

    PubMed

    Lin, Jung-Fu; Degtyareva, Olga; Prewitt, Charles T; Dera, Przemyslaw; Sata, Nagayoshi; Gregoryanz, Eugene; Mao, Ho-Kwang; Hemley, Russell J

    2004-06-01

    Alumina (alpha-Al(2)O(3)) has been widely used as a pressure calibrant in static high-pressure experiments and as a window material in dynamic shock-wave experiments; it is also a model material in ceramic science. So understanding its high-pressure stability and physical properties is crucial for interpreting such experimental data, and for testing theoretical calculations. Here we report an in situ X-ray diffraction study of alumina (doped with Cr(3+)) up to 136 GPa and 2,350 K. We observe a phase transformation that occurs above 96 GPa and at high temperatures. Rietveld full-profile refinements show that the high-pressure phase has the Rh(2)O(3) (II) (Pbcn) structure, consistent with theoretical predictions. This phase is structurally related to corundum, but the AlO(6) polyhedra are highly distorted, with the interatomic bond lengths ranging from 1.690 to 1.847 A at 113 GPa. Ruby luminescence spectra from Cr(3+) impurities within the quenched samples under ambient conditions show significant red shifts and broadening, consistent with the different local environments of chromium atoms in the high-pressure structure inferred from diffraction. Our results suggest that the ruby pressure scale needs to be re-examined in the high-pressure phase, and that shock-wave experiments using sapphire windows need to be re-evaluated. PMID:15146173

  9. Structural and elastic anisotropy of crystals at high pressures and temperatures from quantum mechanical methods: The case of Mg2SiO4 forsterite

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    We report accurate ab initio theoretical predictions of the elastic, seismic, and structural anisotropy of the orthorhombic Mg2SiO4 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.

  10. 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

  11. Crystal chemistry of the natural vanadium bronzes

    USGS Publications Warehouse

    Evans, H.T., Jr.; 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

  12. 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. PMID:27163050

  13. 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

  14. 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.

  15. The Crystal Chemistry of the Zippeite Group

    NASA Astrophysics Data System (ADS)

    Burns, P. C.; Deely, K. M.; Hayden, L. A.

    2002-05-01

    Hydrated uranyl sulfates of the zippeite group are relatively widespread, and occur where sulfur is oxidized in the presence of uranium and acidic water. They impact the mobility of uranium in acid-mine drainage. Zippeite-group minerals occur as fine-grained intergrowths, and many uncertainties remain concerning their structures and chemistries. There are at least seven zippeite-group minerals with the general formula My(H2O)z[(UO2)2(SO4)O2-x(OH)x], M = Na, K, Mg, Zn, Ni, Co. Several synthetic zippeite-group materials have also been reported, including those with M = NH4 and Mn. We have used mild hydrothermal techniques to synthesize zippeite-group minerals of suitable size for single-crystal X-ray diffraction analysis. The structures of Na, Zn, Co, two NH4, and two Mg zippeites have been solved and refined. Each has monoclinic symmetry, although the details of the unit cells and space groups differ. Each zippeite-group structure contains a uranyl sulfate sheet. Uranyl square bipyramids share equatorial edges, forming double-wide zigzag chains. Adjacent chains are linked by the sharing of equatorial vertices with sulfate tetrahedra, resulting in sheets of composition [(UO2)2(SO4)O2- x(OH)x], such that all four vertices of the sulfate tetrahedra are shared with different uranyl polyhedra. The interlayer constituents differ significantly within the group. Divalent interlayer cations are octahedrally coordinated by H2O groups and oxygen atoms of the uranyl ions. Monovalent interlayer cations are in large, irregular coordination polyhedra involving H2O groups and uranyl ion oxygen atoms. In most cases there are additional H2O groups that are held in the interlayers by hydrogen bonding only.

  16. High-pressure crystal growth and magnetic and electrical properties of the quasi-one dimensional osmium oxide Na2OsO4

    NASA Astrophysics Data System (ADS)

    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.

    2010-03-01

    Na2OsO4 crystals were grown by a NaCl flux method under high pressure. It was found that Na2OsO4 crystallizes in the Ca2IrO4-type structure, which consists of OsO6 octahedra chains, rather than in the K2NiF4-type. A chain-magnetism was thus expected for the crystal because of the electronic configuration of Os^6+O6 (5d^2, S = 1). However, experimental data suggested the S = 0 state for the crystal rather than the S = 1 state. We carefully investigated the crystal to resolve the contradiction between the expectation and the observation, and found that the absence of the chain-magnetism is likely due to statically uniaxial compression of the OsO6 octahedra, resulting in splitting of the t2g band. The localized 2 electrons per Os are probably paired in the t2g band, forming the S = 0 state. We will discuss details of the issue. This research was supported in part by the WPI Initiative on Materials Nanoarchitectonics from MEXT, Japan, and the Grants-in-Aid for Scientific Research (20360012) from JSPS. Work at Argonne National Laboratory supported under Contract No. DE-AC02- 06CH11357 by UChicago Argonne, LLC, Operator of Argonne National Laboratory, a U.S. Department of Energy Office of Science Laboratory.

  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

    2014-11-01

    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. PMID:25337807

  18. Structural and elastic anisotropy of crystals at high pressures and temperatures from quantum mechanical methods: The case of Mg2SiO4 forsterite.

    PubMed

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

    2015-05-28

    We report accurate ab initio theoretical predictions of the elastic, seismic, and structural anisotropy of the orthorhombic Mg2SiO4 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. PMID:26026453

  19. 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.

  20. 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, M.O.

    2006-05-12

    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.

  1. 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. PMID:19283272

  2. 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…

  3. Deformation of Single Crystal Sample using D-DI Apparatus Coupled with Synchrotron X-rays: Insitu Stress and Strain Measurements at High Pressure and Temperature

    SciTech Connect

    Girard, J.; Chen, J; Raterron, P; Holyoke, C

    2010-01-01

    We present a technique for high pressure and high temperature deformation experiment on single crystals, using the Deformation-DIA apparatus at the X17B2 beamline of the NSLS. While deformation experiments on polycrystalline samples using D-DIA in conjunction with synchrotrons have been previously reported, this technical paper focuses on single crystal application of the technique. Our single crystals are specifically oriented such that only [1 0 0] slip or [0 0 1] slip in (0 1 0) plane is allowed. Constant applied stress (sigma <300 MPa) and specimen strain rates were monitored using in situ time-resolved X-ray diffraction and radiography imaging, respectively. Rheological properties of each activated slip system in the crystals can be revealed using this technique. In this paper, we describe the principle of sample preparation (e.g. [1 1 0]c and [0 1 1]c orientations) to activate specific slip systems (i.e. [1 0 0](0 1 0) and [0 0 1](0 1 0), respectively), stress measurement and procedures of the deformation experiments.

  4. 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

  5. High-pressure single-crystal elasticity study of CO2 across phase I-III transition

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    Sound velocities and elastic moduli of solid single-crystal CO2 were measured at pressures up to 11.7(3) GPa by Brillouin spectroscopy. The aggregate adiabatic bulk modulus (KS), shear modulus (G), and their pressure derivatives for CO2 Phase I are KS0 = 3.4(6) GPa, G0 = 1.8(2) GPa, (dKS/dP)0 = 7.8(3), (dG/dP)0 = 2.5(1), (d2KS/dP2)0 = -0.23(3) GPa-1, and (d2G/dP2)0 = -0.10(1) GPa-1. A small increase of elastic properties was observed between 9.8(1) and 10.5(3) GPa, in agreement with the CO2 I-III transition pressure determined from previous x-ray diffraction experiments. Above the transition pressure PT, we observed a mixture dominated by CO2-I, with minor CO2-III. The CO2-I + III mixture shows slightly increased sound velocities compared to pure CO2-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 PT. Our results coincide with recent X-ray Raman observations, suggesting that a pressure-induced electronic transition is related to local structural and optical changes.

  6. Codetermination of crystal structures at high pressure: Combined application of theory and experiment to the intermetallic compound AuGa2

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

    A combination of x-ray diffraction at high pressures and first-principles calculations reveals the sequence of crystal-structural phase transitions in AuGa2 from cubic (Fm3¯m) to orthorhombic (Pnma) at 10 (±4) GPa and then to monoclinic (P21/n) at 33 (±6) GPa. 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 Fm3¯m→Pnma→P63/mmc transitions predicted for CaF2 and Pnma → P1121/a transition reported for PbCl2 and SnCl2. The combined results from theory and experiment also allow us to constrain the equations of state of the three phases of AuGa2. Calculations on the analog PbCl2 predict a transition to the P21/n phase seen in AuGa2 that could, therefore, be a common high-pressure phase for PbCl2-structured compounds.

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

    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.

  8. 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.

  9. Numerical simulation of the LEC-growth of GaAs crystals with account of high-pressure gas convection

    NASA Astrophysics Data System (ADS)

    Fainberg, J.; Leister, H.-J.; Müller, G.

    1997-10-01

    The influence of the inert gas pressure on the growth of 4 GaAs crystals by the liquid encapsulated Czochralski method (LEC) process is studied for a range of the Ar gas pressure up to 10 bar by using our finite-volume computer code STHAMAS. Up to the pressure of 0.6 bar we are considering laminar convection. For the pressure range from 5 to 10 bar we are using the buoyancy extended standard k-ε turbulence model with wall functions to simulate the gas flow. The numerical results show that the Argon gas pressure has a strong influence on the consumption of heater power in qualitative agreement with our experimental results. The convex curvature of the growth interface and the maximum thermal stress (von Mises criterion) are found to increase with increasing gas pressure both in the laminar and turbulent evaluations.

  10. 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.

  11. Development of a Fluid-Particle Model in Simulating the Motion of External Solidified Crystals and the Evolution of Defect Bands in High-Pressure Die Casting

    NASA Astrophysics Data System (ADS)

    Bi, Cheng; Xiong, Shoumei; Li, Xiaobo; Guo, Zhipeng

    2016-04-01

    A numerical fluid-particle model was developed to simulate the motion of external solidified crystals (ESCs) in the melt during the filling process of high-pressure die casting (HPDC). Simulation results on a tensile bar casting with two types of ingates (semi-circle and circle) revealed that for a long time scale the ESCs tended to distribute in a ring pattern around the specimen center, whereas for a short time scale the ESC distribution changed constantly from the ring pattern to either the center pattern or the ring-center pattern. It was proposed that the defect bands would form at these areas where two solidification fronts met (where solidification shrinkage occurred), including one originating from the skin layer of the specimen and the other from the ESC region. Accordingly, three types of defect band patterns, which were commonly observed in HPDC experiment, could be successfully simulated and explained using this model.

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

    DOE PAGESBeta

    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; et al

    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.

  13. 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

    2016-01-01

    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

  14. 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

  15. 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.

  16. 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.

  17. Algorithmic crystal chemistry: A cellular automata approach

    SciTech Connect

    Krivovichev, S. V.

    2012-01-15

    Atomic-molecular mechanisms of crystal growth can be modeled based on crystallochemical information using cellular automata (a particular case of finite deterministic automata). In particular, the formation of heteropolyhedral layered complexes in uranyl selenates can be modeled applying a one-dimensional three-colored cellular automaton. The use of the theory of calculations (in particular, the theory of automata) in crystallography allows one to interpret crystal growth as a computational process (the realization of an algorithm or program with a finite number of steps).

  18. 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.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    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.

  1. High-Pressure Brillouin Measurements on Single-Crystal Ferropericlase, (Mg0.94Fe0.06)O: Implications for Earth's Lower Mantle

    NASA Astrophysics Data System (ADS)

    Jackson, J. M.; Bass, J. D.; Sinogeikin, S. V.; Jacobsen, S. D.; Reichmann, H.-; Mackwell, S. J.

    2003-12-01

    The determination of accurate compositional models of Earth's interior from observed seismological data requires knowledge of the elastic properties of candidate phases under conditions approaching those of Earth's interior. Ferropericlase, (Mg,Fe)O, is expected to coexist with silicate perovskite in Earth's lower mantle (660 ­C 2900 km depth), and will therefore have a major influence on all properties in this region of the Earth. However, the effect of iron on the single-crystal elasticity of MgO at high-pressures is still poorly constrained. In this contribution, we present the single-crystal elastic properties of ferropericlase, (Mg0.94Fe0.06)O [hereafter referred to as Fe6], measured by Brillouin scattering on a sample compressed to 13.3(4) GPa with a diamond anvil cell. Within the uncertainties, we find that at room-pressure the bulk modulus of Fe6 is unchanged from MgO, but that the shear modulus of Fe6 is about 7% less than that of MgO. Furthermore, the elastic anisotropy of Fe6 is about 10% greater than that of MgO at room-pressure, in excellent agreement with results obtained using gigahertz ultrasonic interferometry on the same sample [1]. Our measurements also allow us to assess the effect of iron on the pressure derivatives of the sound velocities and elastic moduli of MgO. Results indicate that 6 mol% Fe in MgO does not significantly affect the pressure derivatives of the aggregate elastic properties of ferropericlase compared to MgO. At the highest pressure obtained in this experiment, the elastic anisotropy of Fe6 is close to that of MgO. In light of these new high-pressure measurements on Fe6 and other recent measurements on Al-bearing MgSiO3 perovskite [2], implications for the mineralogy of Earth's lower mantle will be discussed. References: [1] S.D. Jacobsen et al. (2002) J. Geophys. Res., 107, 2001JB000490 [2] J.M. Jackson et al. (2003) Geophys. Res. Abstr., 5, EGS-AGU-EUG Joint Assembly, France, EAE03-A-12122.

  2. High-pressure stabilization of argon fluorides.

    PubMed

    Kurzydłowski, Dominik; Zaleski-Ejgierd, Patryk

    2016-01-28

    On account of the rapid development of noble gas chemistry in the past half-century both xenon and krypton compounds can now be isolated in macroscopic quantities. The same does not hold true for the next lighter group 18 element, argon, which forms only isolated molecules stable solely in low temperature matrices or supersonic jet streams. Here we present theoretical investigations into a new high-pressure reaction pathway, which enables synthesis of argon fluorides in bulk and at room temperature. Our hybrid DFT calculations (employing the HSE06 functional) indicate that above 60 GPa ArF2-containing molecular crystals can be obtained by a reaction between argon and molecular fluorine. PMID:26742478

  3. High-Pressure Control of Vanadium Self-Intercalation and Enhanced Metallic Properties in 1T-V1+xS2 Single Crystals.

    PubMed

    Moutaabbid, Hicham; Le Godec, Yann; Taverna, Dario; Baptiste, Benoı̂t; Klein, Yannick; Loupias, Geneviève; Gauzzi, Andrea

    2016-07-01

    By means of high-pressure synthesis in the 4-6 GPa range, we report on the successful growth of high-quality 1T-V1+xS2 single crystals with controlled concentration, x = 0.09-0.17, of self-intercalated V atoms in the van der Waals gap. A systematic X-ray diffraction and energy-dispersive X-ray spectroscopy study unveils a linear decrease of x with the synthesis pressure, dx/dP = -0.042 GPa(-1), suggesting that the stoichiometric (x = 0) phase is stable above 8 GPa. Transmission electron microscopy and electrical resistivity measurements show that, for all x values studied, the system is metallic up to 400 K, with no charge-density-wave order, contrary to the x = 0 composition. This finding clarifies the controversial electronic phase diagram of the 1T-V1+xS2 system and unveils a connection between the charge-density-wave phase observed at x = 0 and the itinerant antiferromagnetic phase stable for x > 0.25. PMID:27300759

  4. LiNbO3-Type Oxide (Tl(1-x)Sc(x))ScO3: High-Pressure Synthesis, Crystal Structure, and Electronic Properties.

    PubMed

    Belik, Alexei A; Yi, Wei; Kumagai, Yu; Katsuya, Yoshio; Tanaka, Masahiko; Oba, Fumiyasu

    2016-02-15

    We investigate the synthesis of a thallium scandate, TlScO3, under high-pressure (6-7.7 GPa) and high-temperature (1373-1773 K) conditions. At 6 GPa, a LiNbO3-type phase appears in a narrow temperature range and in mixtures with other phases. At 7.7 GPa and 1673 K, a new LiNbO3-type oxide is found with a composition of (Tl(1-x)Sc(x))ScO3 and x ≈ 0.26 as determined by structural analysis from X-ray powder diffraction data. It crystallizes in space group R3c (No. 161) with lattice parameters of a = 5.50283(7) Å and c = 14.4606(2) Å. It is stable at least up to 800 K at ambient pressure. The point-charge model gives an electric polarization of 60 μC/cm(2). First-principles calculations show that centrosymmetric ilmenite-type and polar LiNbO3-type structures of stoichiometric TlScO3 have almost the same lowest energy, and the next stable structure is a GdFeO3-type perovskite structure. PMID:26840839

  5. Tunable high pressure lasers

    NASA Technical Reports Server (NTRS)

    Hess, R. V.

    1976-01-01

    Atmospheric transmission of high energy CO2 lasers is considerably improved by high pressure operation which, due to pressure broadening, permits tuning the laser lines off atmospheric absorption lines. Pronounced improvement is shown for horizontal transmission at altitudes above several kilometers and for vertical transmission through the entire atmosphere. Applications of tunable high pressure CO2 lasers to energy transmission and to remote sensing are discussed along with initial efforts in tuning high pressure CO2 lasers.

  6. 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

  7. 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

  8. The crystal chemistry of ferric oxyhydroxyapatite.

    PubMed

    Low, H R; Phonthammachai, N; Maignan, A; Stewart, G A; Bastow, T J; Ma, L L; White, T J

    2008-12-15

    Ferric hydroxyapatites (Fe-HAp) and oxyapatites (Fe-OAp) of nominal composition [Ca(10-x)Fe(x)(3+)][(PO(4))(6)][(OH)(2-x)O(x)] (0 < or = x < or = 0.5) were synthesized from a coprecipitated precursor calcined under flowing nitrogen. The solid solubility of iron was temperature-dependent, varying from x = 0.5 after firing at 600 degrees C to x approximately 0.2 at 1000 degrees C, beyond which Fe-OAp was progressively replaced by tricalcium phosphate (Fe-TCP). Crystal size (13-116 nm) was controlled by iron content and calcination temperature. Ferric iron replaces calcium by two altervalent mechanisms in which carbonate and oxygen are incorporated as counterions. At low iron loadings, carbonate predominantly displaces hydroxyl in the apatite channels (Ca(2+) + OH(-) --> Fe(3+) + CO(3)(2-)), while at higher loadings, "interstitial" oxygen is tenanted in the framework (2Ca(2+) + (vac) --> 2Fe(3+) + O(2+)). Although Fe(3+) is smaller than Ca(2+), the unit cell dilates as iron enters apatite, providing evidence of oxygen injection that converts PO(4) tetrahedra to PO(5) trigonal bipyramids, leading to the crystal chemical formula [Ca(10-x)Fe(x)][(PO(4))(6-x/2)(PO(5))(x/2)][(OH)(2-y)O(2y)] (x < or = 0.5). A discontinuity in unit cell expansion at x approximately 0.2 combined with a substantial reduction of the carbonate FTIR fingerprint shows that oxygen infusion, rather than tunnel hydroxyl displacement, is dominant beyond this loading. This behavior is in contrast to ferrous-fluorapatite where Ca(2+) --> Fe(2+) aliovalent replacement does not require oxygen penetration and the cell volume contracts with iron loading. All of the materials were paramagnetic, but at low iron concentrations, a transition arising from crystallographic modification or a change in spin ordering is observed at 90 K. The excipient behavior of Fe-OAp was superior to that of HAp and may be linked to the crystalline component or mediated by a ubiquitous nondiffracting amorphous phase. Fe-HAp and Fe

  9. Crystal structure and properties of high-pressure-synthesized BiRhO{sub 3}, LuRhO{sub 3}, and NdRhO{sub 3}

    SciTech Connect

    Yi, Wei; Liang, Qifeng; Matsushita, Yoshitaka; Tanaka, Masahiko; Hu, Xiao; Belik, Alexei A.

    2013-04-15

    GdFeO{sub 3}-type orthorhombic perovskite compounds BiRhO{sub 3}, LuRhO{sub 3}, and NdRhO{sub 3} were prepared using a high-pressure and high-temperature technique at 6 GPa and 1300–1600 K. Their crystal structures were investigated using synchrotron X-ray powder diffraction data: a=5.8098(3) Å, b=7.7720(4) Å, and c=5.3510(3) Å for BiRhO{sub 3}; a=5.75519(1) Å, b=7.77218(2) Å, and c=5.37572(1) Å for NdRhO{sub 3}, and a=5.66981(1) Å, b=7.51205(2) Å, and c=5.18520(1) Å for LuRhO{sub 3}. BiRhO{sub 3} crystallizes in the centrosymmetric space group Pnma (No. 62) similar to LuRhO{sub 3} and NdRhO{sub 3} despite the presence of the lone electron pair of Bi{sup 3+} and the non-magnetic ground state of Rh{sup 3+}. BiRhO{sub 3} and LuRhO{sub 3} are non-magnetic, and NdRhO{sub 3} shows paramagnetic behavior from Nd{sup 3+} ions. The specific heat of BiRhO{sub 3}, LuRhO{sub 3}, and NdRhO{sub 3} in different applied magnetic fields was also investigated. An energy gap of BiRhO{sub 3} was estimated to be about 1.3 eV from diffuse reflectance spectra and 0.95 eV from first-principle calculations with U=3.5 eV. - Graphical abstract: A fragment of the crystal structure of BiRhO{sub 3} in the Pnma (along b axis) model, 2×2×2 unit cell. The RhO{sub 6} octahedra are shown in gray. The Bi atoms are shown by big black circles. Highlights: ► BiRhO{sub 3}, LuRhO{sub 3}, and NdRhO{sub 3} were prepared using a high-pressure technique. ► Structure of three compounds was determined: centrosymmetric space group Pnma. ► BiRhO{sub 3} and LuRhO{sub 3} are non-magnetic, and NdRhO{sub 3} shows paramagnetic behavior. ► Specific heat of BiRhO{sub 3}, LuRhO{sub 3}, and NdRhO{sub 3} was investigated. ► BiRhO{sub 3} has an energy gap of about 1.3 eV.

  10. High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

    SciTech Connect

    Bratlie, Kaitlin

    2007-12-19

    Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10{sup -6} Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C{sub 6}H{sub 11}) and {pi}-allyl C{sub 6}H{sub 9}, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, {pi}-allyl C{sub 6}H{sub 9}, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, {pi}-allyl c-C{sub 6}H{sub 9} was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E{sub 2u} mode of free benzene, which leads to catalysis. Linear C{sub 6} (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt(100). Based on spectroscopic signatures

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. High-pressure synthesis, crystal structures, and properties of CdMn7O12 and SrMn7O12 perovskites.

    PubMed

    Glazkova, Yana S; Terada, Noriki; Matsushita, Yoshitaka; Katsuya, Yoshio; Tanaka, Masahiko; Sobolev, Alexey V; Presniakov, Igor A; Belik, Alexei A

    2015-09-21

    We synthesize CdMn7O12 and SrMn7-xFexO12 (x = 0, 0.08, and 0.5) perovskites under high pressure (6 GPa) and high temperature (1373-1573 K) conditions and investigate their structural, magnetic, dielectric, and ferroelectric properties. CdMn7O12 and SrMn7O12 are isostructural with CaMn7O12: space group R3̅ (No. 148), Z = 3, and lattice parameters a = 10.45508(2) Å and c = 6.33131(1) Å for CdMn7O12 and a = 10.49807(1) Å and c = 6.37985(1) Å for SrMn7O12 at 295 K. There is a structural phase transition at 493 K in CdMn7O12 and at 404 K in SrMn7O12 to a cubic structure (space group Im3̅), associated with charge ordering as found by the structural analysis and Mössbauer spectroscopy. SrMn6.5Fe0.5O12 crystallizes in space group Im3̅ at 295 K with a = 7.40766(2) Å and exhibits spin-glass magnetic properties below 34 K. There are two magnetic transitions in CdMn7O12 with the Néel temperatures TN2 = 33 K and TN1 = 88 K, and in SrMn7O12 with TN2 = 63 K and TN1 = 87 K. A field-induced transition is found in CdMn7O12 from about 65 kOe, and TN2 = 58 K at 90 kOe. No dielectric anomalies are found at TN1 and TN2 at 0 Oe in both compound, but CdMn7O12 exhibits small anomalies at TN1 and TN2 at 90 kOe. In pyroelectric current measurements, we observe large and broad peaks around magnetic phase transition temperatures in CdMn7O12, SrMn7O12, and SrMn6.5Fe0.5O12; we assign those peaks to extrinsic effects and compare our results with previously reported results on CaMn7O12. We also discuss general tendencies of the AMn7O12 perovskite family (A = Cd, Ca, Sr, and Pb). PMID:26322969

  20. 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

  1. High-pressure synthesis and single-crystal structure refinement of gadolinium holmium silicate hydroxyapatite Gd{sub 4.33}Ho{sub 4.33}(SiO{sub 4}){sub 6}(OH){sub 2}

    SciTech Connect

    Wang Chao; Liu Xiaoyang . E-mail: liuxy@jlu.edu.cn; Fleet, M.E.; Feng, Shouhua; Xu Ruren

    2006-07-15

    Single crystals of gadolinium holmium silicate hydroxyapatite Gd{sub 4.33}Ho{sub 4.33}(SiO{sub 4}){sub 6}(OH){sub 2} have been synthesized at 2.0GPa and 1450 deg. C using a piston-cylinder-type high-pressure apparatus. The crystal symmetry by single-crystal X-ray diffraction analysis is hexagonal, space group P6{sub 3}/m (No. 176), with a=9.3142(5)A, c=6.7010(4)A, Z=1. Gadolinium and Ho are disordered over the two large cation positions, A(1) and A(2), and charge balance in this silicate apatite is maintained by cation vacancies in A(1). Two other apatite-structure crystals investigated have P3-bar and Imma symmetry, and represent either partially ordered Gd-Ho distributions or crystal strain induced during quenching.

  2. 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

  3. High-Pressure Research in Mineral Physics

    NASA Astrophysics Data System (ADS)

    Hazen, Robert M.

    Advances in high-pressure science and technology have transformed solid Earth geophysics. In the last decade, high-pressure researchers have reproduced the full range of Earth pressure and temperature conditions in the laboratory, and they have synthesized single crystals of dense silicate phases, unknown at the Earth's surface yet suspected to comprise most of the Earth's volume. These and other extraordinary accomplishments are chronicled in High-Pressure Research in Mineral Physics, an outgrowth of the third U.S.-Japan High-Pressure seminar, held in Kahuku, Hawaii, January, 13-16, 1986. The well produced and reasonably priced volume is dedicated to Syun-iti Akimoto, dean of Japanese high-pressure research, who recently retired from the University of Tokyo. Akimoto's fascinating historical account of pressure research at the Institute for Solid State Physics at the University of Tokyo is the leadoff article.

  4. 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. PMID:24377738

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. High pressure gas target

    NASA Astrophysics Data System (ADS)

    Gelbart, W.; Johnson, R. R.; Abeysekera, B.

    2012-12-01

    Compact, high pressure, high current gas target features all metal construction and semi-automatic window assembly change. The unique aspect of this target is the domed-shaped window. The Havar alloy window is electron beam welded to a metal ring, thus forming one, interchangeable assembly. The window assembly is sealed by knife-edges locked by a pneumatic toggle allowing a quick, in situ window change.

  10. Crystal Structure and Crystal Chemistry of Some Common REE Minerals and Nanpingite

    NASA Astrophysics Data System (ADS)

    Ni, Yunxiang

    1995-01-01

    Part I. Crystal structure and crystal chemistry of fluorocarbonate minerals. The crystal structure of bastnasite-(Ce) have been solved in P-62c and refined to R = 0.018. The structure is composed of (001) (CeF) layers interspersed with (CO_3) layers in a 1:1 ratio. The Ce atom is coordinated in rm CeO_6F_3 polyhedra. The atomic arrangement of synchysite-(Ce) has been solved and refined to R = 0.036 with a monoclinic space group C2/c. It possesses a (001) layer structure, with layers of (Ca) and (CeF) separated by layers of carbonate groups. The layers stack in a manner analogous to C2/c muscovite. Polytypism similar to the micas may exist in synchysite. The crystal structures of cordylite-(Ce) have been solved in P6 _3/mmc and refined to R = 0.023. The structure and chemical formula are different from those deduced by Oftedal. The formula is rm MBaCe_2(CO _3)_4F, where M is rm Na^+, Ca^{2+}_{1/2 }+ O_{1/2}, or any solution. The presence of (NaF) layer in the structure is the key difference from the Oftedal's structure. This redefinition of the chemical formula and crystal structure of cordylite will be proposed to IMA-CNMMN. Part II. Crystal structure and crystal chemistry of monazite-xenotime series. Monazite is monoclinic, P2 _1/n, and xenotime is isostructural with zircon (I4_1/amd). Both atomic arrangements are based on (001) chains of intervening phosphate tetrahedra and RE polyhedra, with a REO_8 polyhedron in xenotime that accommodates HRE (Tb - Lu) and a REO_9 polyhedron in monazite that preferentially incorporates LRE (La - Gd). As the structure "transforms" from xenotime to monazite, the crystallographic properties are comparable along the (001) chains, with structural adjustments of 2.2 A along (010) to accommodate the different size RE atoms. Part III. Crystal structure of nanpingite-2M _2, the Cs end-member of muscovite. The crystal structure of nanpingite has been refined to R = 0.058. Compared to K^+ in muscovite, the largest interlayer Cs^+ in

  11. 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.

  12. 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.

  13. Crystal chemistry of Ti-bearing garnets with volcanic origin

    NASA Astrophysics Data System (ADS)

    Scordari, F.; Schingaro, E.; Malitesta, C.; Pedrazzi, G.

    2003-04-01

    The crystal chemistry of Ti-bearing andradites ("melanites") belonging to different pyroclastic units of Albani Hills (Lazio, Italy) has been investigated electron probe microanalysis (EPMA), single crystal X-ray diffraction (SCXRD), Mössbauer spectroscopy (MS) and X-ray Photoelectron Spectroscopy (XPS). The aim is to determine the correct cations distribution over the X(8-fold), Y(6-fold) and Z(4-fold) sites and accurate values of cations site populations. The analysed samples are characterized by a low Ti-content ( TiO_2 in the range 1.76-3.59 wt%) and cell edges in the range 11.996(3)-12.014(1). MS investigation reveald Fe to be present predominantly as Fe3+(Y) and subordinately as Fe2+(X). XPS analysis was accomplished according to the procedure developed by Malitesta et al.(1989). The fitting of Ti2p signals seem to indicate that two (octahedral Ti3+ and Ti4+) or three (octahedral Ti3+ and Ti4+, tetrahedral Ti4+) Ti species may occur in these specimen. From the combination of the results from different techniques the distribution of Al over the Y and Z sites has been deduced. By comparing the Albani Hills samples crystal chemistry with that of melanites from Mt. Vulture (Scordari et al., 1999), it has been found that in the latter samples the Z sites is occupied by Si, Fe3+ and Ti4+, whereas in the former by Si,Ti4+ and Al3+. Substitution mechanisms through which Fe and Ti enter the garnet structure are expected to be related to the geologic environment in which they occurr. It has been recently proposed that in samples from volcanic rocks schorlomite substitution, Ti4+(Y) + Fe3+(Z) leftrightarrow Si4+(Z) + Fe3+(Y) is predominant, associated to a low degree of hydrogarnet component, (SiO_4)4- leftrightarrow (O_4H_4)4-; on the contrary Ti-garnets from metamorphic rocks should be affected by morimotoite substitution Ti4+(Y) + Fe2+(Y) leftrightarrow 2Fe3+(Y) and a high degree of hydrogarnet component (Armbruster et al., 1998). The result obtained in the present

  14. 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 PAGESBeta

    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 onlymore » be understood by probing the structure at the relevant length scales.« less

  15. 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

    DOE PAGESBeta

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

    2016-06-30

    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

  16. High pressure nitriding

    SciTech Connect

    Jung, M.; Hoffmann, F.T.; Mayr, P.; Minarski, P.

    1995-12-31

    The aim of the presented research project is the development of a new high pressure nitriding process, which avoids disadvantages of conventional nitriding processes and allows for new applications. Up to now, a nitriding furnace has been constructed and several investigations have been made in order to characterize the influence of pressure on the nitriding process. In this paper, connections between pressure in the range of 2 to 12 atm and the corresponding nitride layer formation for the steel grades AISI 1045, H11 and a nitriding steel are discussed. Results of the nitride layer formation are presented. For all steel grades, a growth of nitride layers with increasing pressure was obtained. Steels with passive layers, as the warm working steel H11, showed a better nitriding behavior at elevated pressure.

  17. 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.

  18. 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.

  19. 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)

  20. 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).

  1. Analysis of voids in crystal structures: the methods of 'dual' crystal chemistry.

    PubMed

    Blatov, V A; Shevchenko, A P

    2003-01-01

    The theoretical basics of the analysis of voids in crystal structures by means of Voronoi-Dirichlet polyhedra (VDP) and of the graph theory are stated. Topological relations are considered between VDPs and atomic domains in a crystal field. These relations allow the separation of two non-intersecting topological subspaces in a crystal structure, whose connectednesses are defined by two finite 'reduced' graphs. The first, 'direct', subspace includes the atoms (VDP centres) and the network of interatomic bonds (VDP faces), the second, 'dual', one comprises the void centres (VDP vertices) and the system of channels (VDP edges) between them. Computer methods of geometrical-topological analysis of the 'dual' subspace are developed and implemented within the program package TOPOS. They are designed for automatically restoring the system of channels, visualizing and sizing voids and void conglomerates, dimensional analysis of continuous void systems, and comparative topological analysis of 'dual' subspaces for various substances. The methods of analysis of 'dual' and 'direct' subspaces are noted to differ from each other only in some details that allows the term 'dual' crystal chemistry to be introduced. The efficiency of the methods is shown with the analysis of compounds of different chemical nature: simple substances, ionic structures, superionic conductors, zeolites, clathrates, organic supramolecular complexes. PMID:12496460

  2. High-Performance Ferroelectric Bi4Ti3O12 Single Crystals Grown by Top-Seeded Solution Growth Method under High-Pressure Oxygen Atmosphere

    NASA Astrophysics Data System (ADS)

    Kitanaka, Yuuki; Noguchi, Yuji; Miyayama, Masaru

    2010-09-01

    The top-seeded solution growth (TSSG) method under high oxygen pressure (PO2 ) atmosphere has been developed to obtain large high-performance single crystals of ferroelectric Bi4Ti3O12. Crystals grown at 960 °C at a PO2 of 0.9 MPa exhibited well-saturated hysteresis with a remanent polarization of 48 µC/cm2 and a coercive field of 29 kV/cm. The results of piezoresponse force microscopy indicate that polarization switching is accomplished throughout the crystals. Electric-field-induced strain measurements along the a axis yield a piezoelectric constant d11* of 37 pm/V for Bi4Ti3O12.

  3. High-pressure phase transitions of strontianite

    NASA Astrophysics Data System (ADS)

    Speziale, S.; Biedermann, N.; Reichmann, H. J.; Koch-Mueller, M.; Heide, G.

    2015-12-01

    Strontianite (SrCO3) is isostructural to aragonite, a major high-pressure polymorph of calcite. Thus it is a material of interest to investigate the high-pressure phase behavior of aragonite-group minerals. SrCO3 is a common component of natural carbonates and knowing its physical properties at high pressures is necessary to properly model the thermodynamic properties of complex carbonates, which are major crustal minerals but are also present in the deep Earth [Brenker et al., 2007] and control carbon cycling in the Earth's mantle. The few available high-pressure studies of SrCO3 disagree regarding both pressure stability and structure of the post-aragonite phase [Lin & Liu, 1997; Ono et al., 2005; Wang et al. 2015]. To clarify such controversies we investigated the high-pressure behavior of synthetic SrCO3 by Raman spectroscopy. Using a diamond anvil cell we compressed single-crystals or powder of strontianite (synthesized at 4 GPa and 1273 K for 24h in a multi anvil apparatus), and measured Raman scattering up to 78 GPa. SrCO3 presents a complex high-pressure behavior. We observe mode softening above 20 GPa and a phase transition at 25 - 26.9 GPa, which we interpret due to the CO3 groups rotation, in agreement with Lin & Liu [1997]. The lattice modes in the high-pressure phase show dramatic changes which may indicate a change from 9-fold coordinated Sr to a 12-fold-coordination [Ono, 2007]. Our results confirm that the high-pressure phase of strontianite is compatible with Pmmn symmetry. References Brenker, F.E. et al. (2007) Earth and Planet. Sci. Lett., 260, 1; Lin, C.-C. & Liu, L.-G. (1997) J. Phys. Chem. Solids, 58, 977; Ono, S. et al. (2005) Phys. Chem. Minerals, 32, 8; Ono, S. (2007) Phys. Chem. Minerals, 34, 215; Wang, M. et al. (2015) Phys Chem Minerals 42, 517.

  4. [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

  5. High-pressure stability relations, crystal structures, and physical properties of perovskite and post-perovskite of NaNiF{sub 3}

    SciTech Connect

    Shirako, Y.; Shi, Y.G.; Aimi, A.; Mori, D.; Kojitani, H.; Yamaura, K.; Inaguma, Y.; Akaogi, M.

    2012-07-15

    NaNiF{sub 3} perovskite was found to transform to post-perovskite at 16-18 GPa and 1273-1473 K. The equilibrium transition boundary is expressed as P (GPa)=-2.0+0.014 Multiplication-Sign T (K). Structure refinements indicated that NaNiF{sub 3} perovskite and post-perovskite have almost regular NiF{sub 6} octahedra consistent with absence of the first-order Jahn-Teller active ions. Both NaNiF{sub 3} perovskite and post-perovskite are insulators. The perovskite underwent a canted antiferromagnetic transition at 156 K, and the post-perovskite antiferromagnetic transition at 22 K. Magnetic exchange interaction of NaNiF{sub 3} post-perovskite is smaller than that of perovskite, reflecting larger distortion of Ni-F-Ni network and lower dimension of octahedral arrangement in post-perovskite than those in perovskite. - Graphical abstract: Perovskite-post-perovskite transition in NaNiF{sub 3} at high pressure Highlights: Black-Right-Pointing-Pointer NaNiF{sub 3} perovskite (Pv) transforms to post-perovskite (pPv) at 16 GPa and 1300 K. Black-Right-Pointing-Pointer The equilibrium transition boundary is expressed as P (GPa)=-2.0+0.014 T (K). Black-Right-Pointing-Pointer Antiferromagnetic transition occurs at 156 K in Pv and 22 K in pPv.

  6. 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

  7. 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.

  8. Expression, high-pressure refolding, purification, crystallization and preliminary X-ray analysis of a novel single-strand-specific 3′–5′ exonuclease PhoExo I from Pyrococcus horikoshii OT3

    PubMed Central

    Miyazono, Ken-ichi; Tsutsumi, Kanae; Ishino, Yoshizumi; Tanokura, Masaru

    2014-01-01

    PhoExo I is a single-strand-specific 3′–5′ exonuclease from Pyrococcus horikoshii OT3 and is thought to be involved in a Thermococcales-specific DNA-repair pathway. The recombinant PhoExo I protein was produced as inclusion bodies in Escherichia coli cells. Solubilization of the inclusion bodies was performed by the high-pressure refolding method and highly purified protein was subjected to crystallization by the sitting-drop vapour-diffusion method at 20°C. A crystal of PhoExo I was obtained in a reservoir solution consisting of 0.1 M Tris–HCl pH 8.9, 27% PEG 6000 and diffracted X-rays to 1.52 Å resolution. The crystal of PhoExo I belonged to space group H32, with unit-cell parameters a = b = 112.07, c = 202.28 Å. The crystal contained two PhoExo I molecules in the asymmetric unit. PMID:25084386

  9. Expression, high-pressure refolding, purification, crystallization and preliminary X-ray analysis of a novel single-strand-specific 3'-5' exonuclease PhoExo I from Pyrococcus horikoshii OT3.

    PubMed

    Miyazono, Ken-ichi; Tsutsumi, Kanae; Ishino, Yoshizumi; Tanokura, Masaru

    2014-08-01

    PhoExo I is a single-strand-specific 3'-5' exonuclease from Pyrococcus horikoshii OT3 and is thought to be involved in a Thermococcales-specific DNA-repair pathway. The recombinant PhoExo I protein was produced as inclusion bodies in Escherichia coli cells. Solubilization of the inclusion bodies was performed by the high-pressure refolding method and highly purified protein was subjected to crystallization by the sitting-drop vapour-diffusion method at 20°C. A crystal of PhoExo I was obtained in a reservoir solution consisting of 0.1 M Tris-HCl pH 8.9, 27% PEG 6000 and diffracted X-rays to 1.52 Å resolution. The crystal of PhoExo I belonged to space group H32, with unit-cell parameters a = b = 112.07, c = 202.28 Å. The crystal contained two PhoExo I molecules in the asymmetric unit. PMID:25084386

  10. 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.

    2016-04-01

    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.

  11. 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.

  12. 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.

  13. 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

  14. Atomic and electronic structure transformations in SnS2 at high pressures: a joint single crystal X-ray diffraction and DFT study.

    PubMed

    Filsø, M Ø; Eikeland, E; Zhang, J; Madsen, S R; Iversen, B B

    2016-02-18

    The layered semiconductor SnS2 spurs much interest for both intercalation and optoelectronic applications. Despite the wealth of research in the field of metal dichalcogenides, the structure-property relationship of this compound remains unclear. Here we present a thorough study combining single-crystal X-ray diffraction and DFT calculations on SnS2 in the pressure range 0 < p < 20 GPa. The anisotropic compression of the unit cell is clearly linked to the van der Waals interactions between the S-Sn-S sandwich layers, as the compression mainly affects the interlayer distance. This compression behavior is coincidal with the compression of other well-known layered compounds (graphite and boron nitride) but differs significantly from the compression of other MS2 compounds, making it clear that SnS2 presents a unique and interesting case in the field of metal dichalcogenides. The compression leads to a significant increase in SS interlayer interaction which in turn results in a change in the electronic structure, documented through DFT band structure calculations. The calculated narrowing of the band gap is supported by a significant, reversible color change of the single crystal. At 20 GPa, the size of the band gap has decreased from 2.15 to 0.88 eV, and band gap closure is predicted to occur at 33 GPa. PMID:26820716

  15. Hexagonal Ba-ferrite: a good model for the crystal structure of a new high-pressure phase CaAl 4Si 2O 11?

    NASA Astrophysics Data System (ADS)

    Gautron, Laurent; Gerald, John D. Fitz; Kesson, Sue E.; Eggleton, R. Anthony; Irifune, Tetsuo

    1997-07-01

    A new calcium aluminosilicate phase of composition CaAl 4Si 2O 11 has been encountered amongst the transformation products of CaAl 2Si 2O 8 (anorthite composition) at 14 GPa (Gautron et al., 1996). X-ray diffraction (XRD) confirms that its crystal structure is essentially the same as that of a new complex CaAl-silicate (abbreviated CAS phase) first reported by Irifune et al. (1994). The crystal structure of the CAS phase has been investigated by transmission electron microscopy (TEM). It has a hexagonal unit cell with lattice parameters a = 5.4Å and c = 12.7Å, and its space group is either P6 3mc , P overline62c or P6 3/mmc. It is proposed that this CAS phase has a six-layer, close-packed structure so that Z = 2 and density is 3.94 g cm -3, reasonable for a phase stable at transition-zone pressures. The most plausible model for the structure of this phase arises from published refinements of hexagonal Ba-ferrites. This postulated P6 3/mmc structure consists of octahedral layers, 3/4 occupied, separated by 12-coordinate Ca atoms, and by Al and Si in face-shared octahedra and in complex trigonal bipyramidal polyhedra, i.e. some Si would be five-fold coordinated. Observed TEM and XRD data are compared with calculated reflection intensities for this CAS model.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Fundamentals of high pressure adsorption

    SciTech Connect

    Zhou, Y.P.; Zhou, L.

    2009-12-15

    High-pressure adsorption attracts research interests following the world's attention to alternative fuels, and it exerts essential effect on the study of hydrogen/methane storage and the development of novel materials addressing to the storage. However, theoretical puzzles in high-pressure adsorption hindered the progress of application studies. Therefore, the present paper addresses the major theoretical problems that challenged researchers: i.e., how to model the isotherms with maximum observed in high-pressure adsorption; what is the adsorption mechanism at high pressures; how do we determine the quantity of absolute adsorption based on experimental data. Ideology and methods to tackle these problems are elucidated, which lead to new insights into the nature of high-pressure adsorption and progress in application studies, for example, in modeling multicomponent adsorption, hydrogen storage, natural gas storage, and coalbed methane enrichment, was achieved.

  3. 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.

  4. 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

  5. High pressure studies of potassium perchlorate

    NASA Astrophysics Data System (ADS)

    Pravica, Michael; Wang, Yonggang; Sneed, Daniel; Reiser, Sharissa; White, Melanie

    2016-09-01

    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 → hν 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. We present the first direct evidence for O2 crystallization at higher pressures, demonstrating that O2 molecules aggregate at high pressure.

  6. 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.

  7. 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.

  8. High-pressure stability and ambient metastability of marcasite-type rhodium pernitride

    NASA Astrophysics Data System (ADS)

    Niwa, K.; Terabe, T.; Suzuki, K.; Shirako, Y.; Hasegawa, M.

    2016-02-01

    High-pressure stability, ambient metastability, and high-pressure crystal chemistry of chemical bonds of marcasite-type RhN2 have been investigated using a laser-heated diamond-anvil cell up to a pressure of 70.6 GPa. High-pressure in-situ X-ray diffraction and Raman scattering measurements revealed that the marcasite-type RhN2 structure is stable up to 70.6 GPa and exhibited an order of axial compressibility of βc > βb > βa. This indicates that single bonded nitrogen dimer (N-N) plays an important role in the incompressibility of a- and b-axes than in that of the c-axis and stabilizes the marcasite-type structure at high-pressure. Field emission scanning electron microscopic analysis in combination with the energy dispersive X-ray spectroscopic measurements and the result of our previous study indicates that the marcasite-type RhN2 can be quenched to ambient pressure when the grain size is less than 100 nm. Our study together with other previous studies indicates that the ambient metastability of 4d platinum group pernitrides (RuN2, RhN2, and PdN2) decreases from ruthenium to palladium.

  9. High-pressure synthesis, crystal structure, and magnetic properties of KSbO3-type 5d oxides K0.84OsO3 and Bi2.93Os3O11

    NASA Astrophysics Data System (ADS)

    Yuan, Yahua; Feng, Hai L.; Shi, Youguo; Tsujimoto, Yoshihiro; Belik, Alexei A.; Matsushita, Yoshitaka; Arai, Masao; He, Jianfeng; Tanaka, Masahiko; Yamaura, Kazunari

    2014-12-01

    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).

  10. 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. PMID:26634719

  11. High-Pressure Fluorescence Spectroscopy.

    PubMed

    Maeno, Akihiro; Akasaka, Kazuyuki

    2015-01-01

    The combination of fluorescence and pressure perturbation is a widely used technique to study the effect of pressure on a protein system to obtain thermodynamic, structural and kinetic information on proteins. However, we often encounter the situation where the available pressure range up to 400 MPa of most commercial high-pressure fluorescence spectrometers is insufficient for studying highly pressure-stable proteins like inhibitors and allergenic proteins. To overcome the difficulty, we have recently developed a new high-pressure fluorescence system that allows fluorescence measurements up to 700 MPa. Here we describe the basic design of the apparatus and its application to study structural and thermodynamic properties of a couple of highly stable allergenic proteins, hen lysozyme and ovomucoid, using Tryptophan and Tyrosine/Tyrosinate fluorescence, respectively. Finally, we discuss the utility and the limitation of Trp and Tyr fluorescence. We discuss pitfalls of fluorescence technique and importance of simultaneous use of other high-pressure spectroscopy, particularly high-pressure NMR spectroscopy. PMID:26174405

  12. 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. PMID:26634734

  13. 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)

  14. 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.

  15. 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.

  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.

    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.

  17. 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.

  18. 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.

  19. Exotic stable cesium polynitrides at high pressure

    DOE PAGESBeta

    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 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. 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

  1. 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.

  2. 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

  3. 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.

  4. High-pressure well design

    SciTech Connect

    Krus, H.; Prieur, J.M. )

    1991-12-01

    Shell U.K. E and P (Shell Expro), operator in the U.K. North Sea on behalf of Shell and Esso, plans to drill 20 high-pressure oil and gas wells during the next 2 years. This paper reports that the well design is based on new standards developed after the U.K. Dept. of Energy restriction on high-pressure drilling in the autumn of 1988. Studies were carried out to optimize casing design and drilling performance on these wells. Several casing schemes, including a slim-hole option, were analyzed. The material specifications for casing and drillpipe were reviewed to ensure that they met the loads imposed during drilling, well- control, and well-testing operations. The requirement for sour-service material was weighted against possible H{sub 2}S adsorption by the mud film. As a result, a new drillstring and two high-pressure casing schemes have been specified. The high-pressure casing scheme used depends on the maximum expected surface pressure.

  5. 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.

  6. Accurate prediction of lattice energies and structures of molecular crystals with molecular quantum chemistry methods.

    PubMed

    Fang, Tao; Li, Wei; Gu, Fangwei; Li, Shuhua

    2015-01-13

    We extend the generalized energy-based fragmentation (GEBF) approach to molecular crystals under periodic boundary conditions (PBC), and we demonstrate the performance of the method for a variety of molecular crystals. With this approach, the lattice energy of a molecular crystal can be obtained from the energies of a series of embedded subsystems, which can be computed with existing advanced molecular quantum chemistry methods. The use of the field compensation method allows the method to take long-range electrostatic interaction of the infinite crystal environment into account and make the method almost translationally invariant. The computational cost of the present method scales linearly with the number of molecules in the unit cell. Illustrative applications demonstrate that the PBC-GEBF method with explicitly correlated quantum chemistry methods is capable of providing accurate descriptions on the lattice energies and structures for various types of molecular crystals. In addition, this approach can be employed to quantify the contributions of various intermolecular interactions to the theoretical lattice energy. Such qualitative understanding is very useful for rational design of molecular crystals. PMID:26574207

  7. Cold chemistry with electronically excited Ca+ Coulomb crystals.

    PubMed

    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(+) ions and neutral polar molecules (CH(3)F, CH(2)F(2), or CH(3)Cl) have been measured at low collision energies (/k(B)=5-243 K). Low kinetic energy ensembles of (40)Ca(+) 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(+) 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 (40)Ca(+) 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 ((2)S(1/2)) and the combined excited states ((2)D(3/2) and (2)P(1/2)) of (40)Ca(+). 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. PMID:21090857

  8. Cold chemistry with electronically excited Ca+ Coulomb crystals

    NASA Astrophysics Data System (ADS)

    Gingell, Alexander D.; Bell, Martin T.; Oldham, James M.; Softley, Timothy P.; Harvey, Jeremy N.

    2010-11-01

    Rate constants for chemical reactions of laser-cooled Ca+ ions and neutral polar molecules (CH3F, CH2F2, or CH3Cl) have been measured at low collision energies (⟨Ecoll⟩/kB=5-243 K). Low kinetic energy ensembles of C40a+ 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+ 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 C40a+ 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 (S21/2) and the combined excited states (D23/2 and P21/2) of C40a+. 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.

  9. Crystal chemistry of diagenetic zeolites in volcanoclastic deposits of Italy

    NASA Astrophysics Data System (ADS)

    Passaglia, Elio; Vezzalini, Giovanna

    1985-07-01

    Zeolites from the most important volcanoclastic deposits of Italy include: (1) phillipsite and heulandite from the cinerite of the central northern Apennines; (2) chabazite and phillipsite from the phonolitic tephritic ignimbrite with black pumices; (3) phillipsite from the “tufo lionato” of Vulcano Laziale; (4) chabazite and phillipsite from the Campanian ignimbrite; (5) phillipsite from the Neapolitan yellow tuff; and (6) chabazite and phillipsite from the pyroclastics of Monte Vulture. Compared with sedimentary phillipsites and chabazites described in the literature, the chabazites and phillipsites studied here have lower Si/Al ratios and higher K contents. These chemical peculiarities are correlated with both the K-rich vesuvitic-leucititic, latitic-phonolitic, and potassic alkali-trachytic chemistry of the ash from which they were derived and, very likely, with the character of the hydrologically open system environment in which they formed. The zeolite of the heulandite-clinoptilolite group from the cinerite of the central northern Apennines is classified as a true heulandite on the basis of its chemical composition and thermal behavior.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. Partition Coefficients at High Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    Righter, K.; Drake, M. J.

    2003-12-01

    crystallize from a molten mantle, and become entrained in the convecting melt, or eventually settle out at the bottom. The entrainment and settling process has been studied in detail (e.g., Tonks and Melosh, 1990), and is a potential mechanism for differentiation between the deep and shallow parts of Earth's mantle. The lithophile elements, those elements that have D(metal/silicate) <1, fall into many different subclasses and all hold information about the deep mineral structure of the mantle. Rare-earth elements (REEs) have proven to be useful: europium anomalies have helped elucidate the role of plagioclase in lunar crust formation (e.g., Schnetzler and Philpotts, 1971; Weill et al., 1974), and LREE/HREE depletion and enrichment are indicators of partial melting in the presence of garnet in the mantle. High-field-strength elements (HFSEs) - niobium, zirconium, tantalum, and hafnium - are all refractory and hence more resilient to fractionation processes such as volatility or condensation. They also have an affinity for ilmenite and rutile, and can explain differences between lunar and martian samples as well as features of Earth's continental crust ( Taylor and McLennan, 1985). Alkaline-earth and alkaline elements include rubidium, strontium, barium, potassium, caesium, and calcium, some of which are involved in radioactive decay couples, e.g., Rb-Sr and K-Ar. The latter is important in understanding the contribution of radioactive decay to planetary heat production, and potential deep sources of radiogenic argon (see Chapter 2.06). Rubidium and potassium are further useful as tracers of hydrous phases such as mica and amphibole. Possible fractionation of any of these elements from chondritic abundances (see Chapter 2.01) can be assessed with the knowledge of partition coefficients. In this chapter we summarize our understanding of mineral/melt fractionation of minor and trace elements at high pressures and temperatures and discuss the implications for mantle

  15. 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.

  16. High pressure studies of superconductivity

    NASA Astrophysics Data System (ADS)

    Hillier, Narelle Jayne

    Superconductivity has been studied extensively since it was first discovered over 100 years ago. High pressure studies, in particular, have been vital in furthering our understanding of the superconducting state. Pressure allows researchers to enhance the properties of existing superconductors, to find new superconductors, and to test the validity of theoretical models. This thesis presents a series of high pressure measurements performed in both He-gas and diamond anvil cell systems on various superconductors and on materials in which pressure-induced superconductivity has been predicted. Under pressure the alkali metals undergo a radical departure from the nearly-free electron model. In Li this leads to a superconducting transition temperature that is among the highest of the elements. All alkali metals have been predicted to become superconducting under pressure. Pursuant to this, a search for superconductivity has been conducted in the alkali metals Na and K. In addition, the effect of increasing electron concentration on Li1-xMgx alloys has been studied. Metallic hydrogen and hydrogen-rich compounds are believed to be good candidates for high temperature superconductivity. High pressure optical studies of benzene (C6H6) have been performed to 2 Mbar to search for pressure-induced metallization. Finally, cuprate and iron-based materials are considered high-Tc superconductors. These layered compounds exhibit anisotropic behavior under pressure. Precise hydrostatic measurements of dTc/dP on HgBa2CuO 4+delta have been carried out in conjunction with uniaxial pressure experiments by another group. The results obtained provide insight into the effect of each of the lattice parameters on Tc. Finally, a series of hydrostatic and non-hydrostatic measurements on LnFePO (Ln = La, Pr, Nd) reveal startling evidence that the superconducting state in the iron-based superconductors is highly sensitive to lattice strain.

  17. 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.

  18. 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.

  19. 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.

  20. Stable Lithium Argon compounds under high pressure

    NASA Astrophysics Data System (ADS)

    Li, Xiaofeng; Hermann, Andreas; Peng, Feng; Lv, Jian; Wang, Yanchao; Wang, Hui; Ma, Yanming

    2015-11-01

    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.

  1. 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

  2. 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)

  3. 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.

  4. New trends in chemistry and materials science in extremely tight space

    DOE PAGESBeta

    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.

  5. 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.

  6. 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.

  7. New High-Pressure Excitations in Parahydrogen

    SciTech Connect

    Goncharov, A.F.; Hemley, R.J.; Mao, H.; Shu, J.

    1998-01-01

    Raman and infrared spectroscopy of para-H{sub 2} to pressures in excess of 200GPa and to 8K using new ultrapure synthetic diamond anvils reveals numerous new vibrational excitations in the three high-pressure phases. Highly resolved Raman-active librons indicate differences in orientational ordering between phasesII and III, including evidence for changes within phaseII. The librons in phaseIII are strongly pressure dependent and reflect a substantial increase in ordering with pressure. Multiple vibrons in all three phases (I, II, and III) are observed. The results place new bounds on predicted crystal structures and dynamics of the dense molecular solid. {copyright} {ital 1997} {ital The American Physical Society}

  8. Surface chemistry and surface electronic properties of ZnO single crystals and nanorods

    SciTech Connect

    Uhlrich, J. J.; Olson, D. C.; Hsu, J. W. P.; Kuech, T. F.

    2009-03-15

    The surface chemistry of ZnO single crystals of (0001) and (1010) orientations and ZnO nanorods was studied using x-ray and ultraviolet photoelectron spectroscopies. Air drying and UV-ozone preparations were studied in particular as chemical treatments that could be applied to poly(3-hexylthiophene) (P3HT)-ZnO solar cells to enhance performance. The UV-ozone treatment showed negligible effect by photoelectron spectroscopy on the ZnO single crystal surfaces, but brought about electronic shifts consistent with increased upward band bending by {approx}0.25 eV on the ZnO nanorod surface. Modest interface dipoles of {approx}0.15 and {approx}0.25 eV were measured between P3HT and the (1010) and (0001) single crystal orientations, respectively, with the dipole moment pointing from ZnO to the P3HT layer. The sol-gel films showed evidence of forming a small interface dipole in the opposite direction, which illustrates the difference in surface chemistry between the solution-grown ZnO and the ZnO single crystals.

  9. 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.

  10. 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.

  11. Ultra-High-Pressure Water

    NASA Astrophysics Data System (ADS)

    French, Martin; Redmer, Ronald; Mattsson, Thomas R.

    2008-03-01

    We present the first all-electron QMD simulations of water in the ultra-high-pressure regime up to conditions typical for the deep interior of Jupiter and Saturn. We calculate the equation of state and the Hugoniot curve and study the structural properties via pair correlation functions and self-diffusion coefficients. In the ultra-dense superionic phase, we find a continuous transition in the protonic structure. Water at conditions of Jupiter's core (i.e. 20000 K, 50 Mbar, 11 g/cm^3) forms a fluid dense plasma. Supported by the DFG within SFB 652. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States DOE's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  12. Crystal chemistry of layered structures formed by linear rigid silyl-capped molecules

    PubMed Central

    Lumpi, Daniel; Kautny, Paul; Stöger, Berthold; Fröhlich, Johannes

    2015-01-01

    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. PMID:26306200

  13. 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

  14. 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.

  15. The analysis of high pressure experimental data

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert; Ferrante, John

    1991-01-01

    This letter is concerned with the analysis of high pressure experimental data. It is demonstrated that ln H plots based on the Vinet et al. (1988) universal equation of state are a simple sensitive means for identifying anomalous P-V data in high pressure experiments and for detecting structural and phase transitions in solids subjected to high pressure.

  16. 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.

  17. 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. PMID:20950018

  18. 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).

  19. Crystal structure and crystal chemistry of melanovanadite, a natural vanadium bronze.

    USGS Publications Warehouse

    Konnert, J.A.; Evans, H.T., Jr.

    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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Fe 2O 3 single crystals: hydrothermal growth, crystal chemistry and growth morphology

    NASA Astrophysics Data System (ADS)

    Demianets, L. N.; Pouchko, S. V.; Gaynutdinov, R. V.

    2003-11-01

    Hematite single crystals have been grown under hydrothermal conditions. The analysis of atomic structures of the {h k i l} faces has been made, and the sequence of the growth rate change has been explained on the basis of that analysis. Optical and AFM study show two main mechanisms of α-Fe 2O 3 growth. They are layer-by-layer growth and island growth. The morphological characteristics of {1 1 2¯ 0} surfaces are given. Large flat terraces with height h 100-150 nm, width d˜10000 nm are observed of the face surface. Terraces are composed from the steps ( h 15-65, d 100-1200 nm). AFM-images of small steps demonstrate that they consist of globules with rounded or elongated shapes. Typical heights of globules are 0.5-5 nm, and typical lengths are 30-60 nm. These globules are orderly packed on the face, the elongation being along [1 0 1¯ 0] direction.

  6. 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, ??, is generally small (3.1 ??? ?? ??? 4.6??) and decreases with siderophyllite content. As Fe increases, the T1 tetrahedron becomes flatter (112.4 ??? t??1 ??? 110.5??), whereas T2 tetrahedron distortion appears unchanged (110.7 ??? t??T2 ??? 110.9).

  7. 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.

  8. 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

  9. Rare-earth-metal nitridophosphates through high-pressure metathesis.

    PubMed

    Kloss, Simon David; Schnick, Wolfgang

    2015-09-14

    Developing a synthetic method to target an broad spectrum of unknown phases can lead to fascinating discoveries. The preparation of the first rare-earth-metal nitridophosphate LiNdP4 N8 is reported. High-pressure solid-state metathesis between LiPN2 and NdF3 was employed to yield a highly crystalline product. The in situ formed LiF is believed to act both as the thermodynamic driving force and as a flux to aiding single-crystal formation in dimensions suitable for crystal structure analysis. Magnetic properties stemming from Nd(3+) ions were measured by SQUID magnetometry. LiNdP4 N8 serves as a model system for the exploration of rare-earth-metal nitridophosphates that may even be expanded to transition metals. High-pressure metathesis enables the systematic study of these uncharted regions of nitride-based materials with unprecedented properties. PMID:26352033

  10. Crystallographic and magnetic properties of (Cu{sub 1-x}V{sub x})V{sub 2}S{sub 4} (x{approx}0.3) single crystals with the layered defect NiAs structure synthesized under high pressure

    SciTech Connect

    Klein, Y.; Moutaabbid, H.; Soyer, A.; D'Astuto, M.; Rousse, G.; Vigneron, J.; Etcheberry, A.; Gauzzi, A.

    2011-09-15

    We report on the reproducible growth of (Cu{sub 1-x}V{sub x})V{sub 2}S{sub 4} single crystals of sizable dimensions ({approx}0.3 mm) and homogeneous composition (x{approx}0.3) by means of high-pressure synthesis. The refinement of single crystal X-ray diffraction data indicates that the crystal structure is of the monoclinic defect NiAs-type, which consists of a stacking of VS{sub 2} layers with CdI{sub 2}-type structure and chains of edge-sharing (Cu{sub 1-x}V{sub x})S{sub 6} octahedra. Layers and chains form a network of face-sharing octahedra with no Cu-V intra-chain ordering. A combined X-ray photoelectron spectroscopy and bond valence sum analysis indicates that the valence of the V and Cu ions are 3+ and 1+, respectively. Magnetic susceptibility measurements unveil the coexistence of a large Pauli-like and of a small Curie-like paramagnetic contributions, with no evidence of any long range order down to 2 K. This result suggests a picture of predominantly itinerant 3d V electrons with significant electron-electron correlations. - Graphical Abstract: Crystallographic structure of (Cu{sub 0.69}V{sub 0.31})V{sub 2}S{sub 4}. For clarity, the octahedral environment of (Cu{sub 0.69}V{sub 0.31}) site is not shown. Highlights: > Synthesis of new single-crystals in the Cu-V-S system using high pressure and high temperature. > Structural analysis revealed the single-crystals to be of the defect NiAs-type structure. > Bond valence sum analysis combined to X-ray photoemission spectroscopy revealed Cu{sup 1+} and a majority of V{sup 3+}. > Magnetic susceptibility has been measured. > Charge carriers are of two types, localized and itinerant.

  11. Incorporation of iodine into apatite structure: a crystal chemistry approach using Artificial Neural Network

    NASA Astrophysics Data System (ADS)

    Wang, Jianwei

    2015-06-01

    Materials with apatite crystal structure provide a great potential for incorporating the long-lived radioactive iodine isotope (129I) in the form of iodide (I-) from nuclear waste streams. Because of its durability and potentially high iodine content, the apatite waste form can reduce iodine release rate and minimize the waste volume. Crystal structure and composition of apatite was investigated for iodide incorporation into the channel of the structure using Artificial Neural Network. A total of 86 experimentally determined apatite crystal structures of different compositions were compiled from literature, and 46 of them were used to train the networks and 42 were used to test the performance of the trained networks. The results show that the performances of the networks are satisfactory for predictions of unit cell parameters a and c and channel size of the structure. The trained and tested networks were then used to predict unknown compositions of apatite that incorporates iodide. With a crystal chemistry consideration, chemical compositions that lead to matching the size of the structural channel to the size of iodide were then predicted to be able to incorporate iodide in the structural channel. The calculations suggest that combinations of A site cations of Ag+, K+, Sr2+, Pb2+, Ba2+, and Cs+, and X site cations, mostly formed tetrahedron, of Mn5+, As5+, Cr5+, V5+, Mo5+, Si4+, Ge4+, and Re7+ are possible apatite compositions that are able to incorporate iodide. The charge balance of different apatite compositions can be achieved by multiple substitutions at a single site or coupled substitutions at both A and X sites. The results give important clues for designing experiments to synthesize new apatite compositions and also provide a fundamental understanding how iodide is incorporated in the apatite structure. This understanding can provide important insights for apatite waste forms design by optimizing the chemical composition and synthesis procedure.

  12. Basic requirements in experiments under high pressure

    NASA Astrophysics Data System (ADS)

    Singh, Yadunath; Shekhawat, M. S.; Suthar, Bhuvneshwer

    2016-05-01

    The basic requirement for the high pressure and temperature dependent measurements is reviewed in this article, mainly from an experimental aspect. After a brief description of the different types of high pressure cells, techniques for low and high-temperature measurements are presented.

  13. NETL- High-Pressure Combustion Research Facility

    ScienceCinema

    None

    2014-06-26

    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.

  14. 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.

  15. 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.

  16. Phase Transitions of Triflate-Based Ionic Liquids under High Pressure.

    PubMed

    Faria, Luiz F O; Ribeiro, Mauro C C

    2015-11-01

    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 . PMID:26457868

  17. High pressure Raman spectroscopy of H2O-CH3OH mixtures

    NASA Astrophysics Data System (ADS)

    Hsieh, Wen-Pin; Chien, Yu-Hsiang

    2015-02-01

    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.

  18. High pressure Raman spectroscopy of H2O-CH3OH mixtures

    PubMed Central

    Hsieh, Wen-Pin; Chien, Yu-Hsiang

    2015-01-01

    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. PMID:25704667

  19. High pressure Raman spectroscopy of H2O-CH3OH mixtures.

    PubMed

    Hsieh, Wen-Pin; Chien, Yu-Hsiang

    2015-01-01

    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. PMID:25704667

  20. 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.

  1. Nanoscale coherent intergrowthlike defects in a crystal of La1.9Ca1.1Cu2O6+δ made superconducting by high-pressure oxygen annealing

    DOE PAGESBeta

    Hu, Hefei; Zhu, Yimei; Shi, Xiaoya; Li, Qiang; Zhong, Ruidan; Schneeloch, John A.; Gu, Genda; Tranquada, John M.; Billinge, Simon J. L.

    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

  2. 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.

  3. 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. PMID:22663173

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Carbon nanotubes as high-pressure cylinders and nanoextruders.

    PubMed

    Sun, L; Banhart, F; Krasheninnikov, A V; Rodríguez-Manzo, J A; Terrones, M; Ajayan, P M

    2006-05-26

    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. PMID:16728637

  10. High-pressure Raman study of methane hydrate "filled ice"

    NASA Astrophysics Data System (ADS)

    Ohtani, T.; Ohno, Y.; Sasaki, S.; Kume, T.; Shimizu, H.

    2010-03-01

    High-pressure Raman scattering measurements for the high-pressure phase III of methane hydrate (MH-III, filled ice structure) have been performed at pressures up to 25 GPa and at 296 K. We have observed the O-H stretching Raman signal in the MH-III phase by growing the MH-III crystals over several days at 1.9 GPa. The O-H stretching vibrational peak in the MH-III phase shows negative pressure dependence indicative of hydrogen bond and disappears above 14 GPa. The symmetrization pressure of hydrogen bond in the MH-III phase is estimated to be about 45 GPa from the pressure dependence of the O-H stretching Raman frequency, which is consistent with the previous theoretical prediction.

  11. 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.

  12. 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.

  13. 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

  14. High pressure Raman spectroscopy of H2O-CH3OH mixtures

    NASA Astrophysics Data System (ADS)

    Hsieh, Wen-Pin; Chien, Yu-Hsiang

    2015-03-01

    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.

  15. The crystal chemistry of L-Ta 2O 5 and related structures

    NASA Astrophysics Data System (ADS)

    Grey, I. E.; Mumme, W. G.; Roth, R. S.

    2005-11-01

    Single crystals of a new form of L-Ta 2O 5 with a 19× b superstructure have been synthesised by flux growth. The phase is most likely stabilised by the incorporation of a small amount of lithium (0.14 wt% Li) from the flux. The phase has C-centred monoclinic symmetry with a=6.1939(4) Å, b=69.549(5) Å ( =19×3.66 Å), c=3.8895(3) Å, γ=90.00(1)°. The structure was refined in space group C112/m to R1=0.044 for 814 unique reflections with F>4σ(F). The structure can be described as comprising chains of edge-shared TaO 7 pentagonal bipyramids that are regularly folded at (010) planes to give sinusoidal chains along [010]. These chains are interconnected along [100] and [001] by corner sharing, creating inter-chain regions that are occupied by isolated TaO 6 octahedra and pairs of corner-shared octahedra. A comparison with published data for high-quality refinements of related structures has led to the development of a general model that can explain the structural chemistry variations in the known L-Ta 2O 5-related structures. A shorthand notation is presented for representing the structures, based on the sequence along [010] of the interchain octahedra.

  16. 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.

  17. 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.

  18. Single crystal X-ray diffraction study of a mixed-valence gold compound, Cs{sub 2}Au{sup I}Au{sup III}Cl{sub 6} under high pressures up to 18 GPa: Pressure-induced phase transition coupled with gold valence transition

    SciTech Connect

    Matsushita, Nobuyuki Ahsbahs, Hans; Hafner, Stefan S.; Kojima, Norimichi

    2007-04-15

    We performed the single-crystal X-ray diffraction study of a perovskite-type gold mixed-valence compound, Cs{sub 2}Au{sup I}Au{sup III}Cl{sub 6}, under high pressures up to 18 GPa by using a diamond-anvil-cell with helium gas as an ideal hydrostatic pressure-transmitting medium. The lattice parameters and the variable atomic positional parameters were obtained with reasonable accuracy at various pressures. A structural phase transition at ca. 12.5 GPa from I4/mmm to Pm3m was found. The lattice parameters a {sub 0} and c {sub 0}, denoted in the tetragonal cell setting, result in the relationship 2{sup 1/2} a {sub 0}=c {sub 0}, and the superstructure reflections h k l (l is odd), caused by the shift of the Cl ions from the midpoint of the Au ions, disappeared at pressures above the phase transition. Both elongated [Au{sup III}Cl{sub 6}] and compressed [Au{sup I}Cl{sub 6}] octahedra in the low-pressure phase smoothly approach regular octahedra with increasing pressure. Above the structural phase transition at 12.5 GPa, all the [AuCl{sub 6}] octahedra are crystallographically equivalent, which shows that the tetragonal-to-cubic phase transition accompanies the valence transition from the Au{sup I}/Au{sup III} mixed-valence state to the Au{sup II} single-valence state. - Graphical abstract: Single-crystal X-ray diffraction study under high pressures up to 18 GPa by using a diamond-anvil-cell with helium gas as an ideal hydrostatic pressure medium has revealed that a perovskite-type gold mixed-valence compound, Cs{sub 2}Au{sup I}Au{sup III}Cl{sub 6}, exhibits the structural phase transition from tetragonal to cubic at 12.5 GPa accompanying gold valence transition.

  19. 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

  20. Novel Stable Compounds in the C-H-O Ternary System at High Pressure.

    PubMed

    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

  1. High-pressure high-temperature synthesis and crystal structure of the isotypic rare earth (RE)-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu)

    SciTech Connect

    Borna, Marija; Hunger, Jens; Ormeci, Alim; Zahn, Dirk; Burkhardt, Ulrich; Carrillo-Cabrera, Wilder; Cardoso-Gil, Raul; Kniep, Ruediger

    2011-02-15

    Application of high-pressure high-temperature conditions (3.5 GPa at 1673 K for 5 h) to mixtures of the elements (RE:B:S=1:3:6) yielded crystalline samples of the isotypic rare earth-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu), which crystallize in space group P6{sub 3} (Z=2/3) and adopt the Ce{sub 6}Al{sub 3.33}S{sub 14} structure type. The crystal structures were refined from X-ray powder diffraction data by applying the Rietveld method. Dy: a=9.4044(2) A, c=5.8855(3) A; Ho: a=9.3703(1) A, c=5.8826(1) A; Er: a=9.3279(12) A, c=5.8793(8) A; Tm: a=9.2869(3) A, c=5.8781(3) A; Yb: a=9.2514(5) A, c=5.8805(6) A; Lu: a=9.2162(3) A, c=5.8911(3) A. The crystal structure is characterized by the presence of two isolated complex ions [BS{sub 3}]{sup 3-} and [BS{sub 4}]{sup 5-} as well as [{open_square}(S{sup 2-}){sub 3}] units. -- Graphical abstract: Isotypic rare earth-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu) were prepared by application of high-pressure high-temperature conditions to mixtures of the elements. Their crystal structures are characterized by presence of the two isolated complex ions [BS{sub 3}]{sup 3-} and [BS{sub 4}]{sup 5-} as well as [{open_square}(S{sup 2-}){sub 3}] units. Quantum mechanical calculations revealed the arrangement of the intrinsic vacancies. Display Omitted Research Highlights: {yields} Application of high-pressure high-temperature conditions to mixtures of the elements yields crystalline samples of the isotypic rare earth-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu). {yields} RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu) crystallize in space group P6{sub 3} (Z=2/3) and adopt the Ce{sub 6}Al{sub 3.33}S{sub 14} structure type. {yields} The crystal structure of RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu) is characterized by the presence of two isolated complex ions [BS{sub 3

  2. 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.

  3. 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. PMID:27587156

  4. High pressure Moessbauer spectroscopy in diamond anvil cells

    SciTech Connect

    Taylor, R.D. ); Pasternak, M.P. . School of Physics and Astronomy Los Alamos National Lab., NM )

    1991-01-01

    Diamond anvil cells provide a means to obtain near-hydrostatic pressures from the kilobar to the megabar regime. Moessbauer spectroscopy (MS) nicely complements the optical and X-ray measurements usually made. After a brief summary of the techniques applicable to MS, we present several examples of high pressure MS including hysteresis in the {sub {alpha}}-{sub {var epsilon}} transition in Fe, metallization in molecular crystals and the insulator-metal Mott transition in NiI{sub 2} and CoI{sub 2}. 25 refs., 7 figs.

  5. 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.

  6. 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.

  7. 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.

  8. High pressure studies on nanometer sized clusters: Structural, optical, and cooperative properties

    SciTech Connect

    Tolbert, S.H.

    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.

  9. 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.

  10. 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.

  11. High-pressure Raman study of fully deuterated methane hydrate

    NASA Astrophysics Data System (ADS)

    Yabashi, Ryo; Yoshida, Masashi; Kume, Tetsuji; Sasaki, Shigeo

    2013-06-01

    Methane hydrate (MH: CH4- nH2O) crystallizes in a cubic structure I (sI) which consists of hydrogen-bonded water cages which enclathrate methane molecules as guests. With increasing pressure, the initial sI of MH transforms to a hexagonal structure H (sH) at 0.9 GPa, and eventually to an orthorhombic cage-less structure O at 1.9 GPa. The sH consists of three small S1, two small S2, and one large LL water cages in a hexagonal unit cell. The previous high-pressure Raman measurements for C-H stretching vibration of MH-sH indicated that the capacity of methane molecules in the large LL cage abruptly increased at 1.3 GPa, and its occupation number of methane molecule was about 2.5 above 1.3 GPa. However, this result disagrees with the previous high-pressure neutron diffraction experiments for sH of fully deutarated methane hydrate (FDMH: CD4- nD2O). To solve this discrepancy, we have carried out the high pressure Raman measurements for C-D stretching vibration in the sI and sH phases of FDMH. As a result, we have obtained the different Raman spectral patterns between FDMH and MH, which suggests that the occupancy of CD4 in water cages is somewhat different from CH4.

  12. 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. PMID:27389226

  13. Photoexcitations in polythiophene at high pressure

    NASA Astrophysics Data System (ADS)

    Hess, B. C.; Kanner, G. S.; Vardeny, Z.

    1993-01-01

    We report optical-absorption, photoluminescence (PL), and picosecond photoinduced absorption (PA) decay in films of poly-3-hexyl-thiophene at pressures up to 80 kbar. The spectral bands redshift nonlinearly with pressure and the PL intensity decreases markedly. Thermochromic transitions are completely inhibited at pressures as low as 14 kbar. The picosecond recovery of the PA decay at high pressure is similar to that of unpressed polythiophene, but has a power-law exponent consistent with more ordered chains at high pressure. These effects suggest changes with pressure in the chain conformation and in the electronic polarizability; no changes in the interchain transfer integral are observed.

  14. 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.

  15. 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.

  16. 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.

  17. Pr{sub 4}B{sub 10}O{sub 21}: A new composition of rare-earth borates by high-pressure/high-temperature synthesis

    SciTech Connect

    Haberer, Almut; Heymann, Gunter; Huppertz, Hubert

    2007-05-15

    High-pressure chemistry led to the synthesis of the rare-earth borate Pr{sub 4}B{sub 10}O{sub 21} using a Walker-type multianvil apparatus at 3.5 GPa and 1050 deg. C. The tetra-praseodymium(III)-decaborate crystallizes monoclinicly with four formula units in the space group P2{sub 1}/n and lattice parameters of a=710.2(2), b=1948.8(4), c=951.6(2) pm, and {beta}=93.27(3){sup o}. The boron-oxygen network consists of [BO{sub 4}]{sup 5-} tetrahedra and [BO{sub 3}]{sup 3-} groups; however, the [BO{sub 4}]{sup 5-} groups represent the major part (80%) due to the high-pressure conditions during the synthesis. The praseodymium ions are coordinated by 10 and 12 oxygen atoms. Along with a detailed description of the crystal structure, temperature programmed X-ray powder diffraction data are shown, demonstrating the metastable character of this compound. - Graphical abstract: Synthesis of Pr{sub 4}B{sub 10}O{sub 21} via the multianvil high-pressure/high-temperature technique representing a new composition of rare-earth borates.

  18. Studies on synthesis of diamond at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Kailath, Ansu J.

    chapter is a general introduction incorporating the information regarding diamond together with a brief history of diamond synthesis. It also includes the details of the high pressure synthesis of diamond, the uses of diamond grits, the advantages of the synthetic diamond grit over natural grit and an outline to elucidate the reasons which prompted to undertake the present work. The details of the technique used in the present studies for synthesis of diamond grits by high-pressure high-temperature process are included in chapter II. The hydraulic press used for synthesis, the details of the reactant materials, stacking of the high pressure cell and the details of synthesis run have been described together with the separation procedure to isolate diamond grits from the frozen slug. Different analytical and characterization techniques used in the present studies for the analysis and characterization of the reactant materials, synthesized diamonds and the crystallization medium have been illustrated in chapter III. The effect of different synthesizing parameters on synthesized diamond crystals were studied. This study includes: (a) dependence of yield of diamond on temperature and pressure, (b) dependence of crystal size on cook length, (c) effect of variation of the relative amounts of carbonaceous material and catalyst on synthesis, (d) morphological variation and (e) effect of pressure pulse on synthesized crystals. Various observations made during this study and the results obtained have been compiled in chapter IV. The synthesized diamond crystals were characterized by X-ray Powder Diffraction (XRD), Raman Spectroscopy, Scanning Electron Microscopy (SEM) and Optical Microscopy. The results obtained have been compiled in chapter V. In addition to these, the results obtained from the Infrared Spectra and the Electron Paramagnetic Spectra have also been included. Studies of crystallization medium and inclusions in the synthesized diamonds were carried out. This include

  19. The Reticular Chemistry Structure Resource (RCSR) database of, and symbols for, crystal nets.

    PubMed

    O'Keeffe, Michael; Peskov, Maxim A; Ramsden, Stuart J; Yaghi, Omar M

    2008-12-01

    During the past decade, interest has grown tremendously in the design and synthesis of crystalline materials constructed from molecular clusters linked by extended groups of atoms. Most notable are metal-organic frameworks (MOFs), in which polyatomic inorganic metal-containing clusters are joined by polytopic linkers. (Although these materials are sometimes referred to as coordination polymers, we prefer to differentiate them, because MOFs are based on strong linkages that yield robust frameworks.) The realization that MOFs could be designed and synthesized in a rational way from molecular building blocks led to the emergence of a discipline that we call reticular chemistry. MOFs can be represented as a special kind of graph called a periodic net. Such descriptions date back to the earliest crystallographic studies but have become much more common recently because thousands of new structures and hundreds of underlying nets have been reported. In the simplest cases (e.g., the structure of diamond), the atoms in the crystal become the vertices of the net, and bonds are the links (edges) that connect them. In the case of MOFs, polyatomic groups act as the vertices and edges of the net. Because of the explosive growth in this area, a need has arisen for a universal system of nomenclature, classification, identification, and retrieval of these topological structures. We have developed a system of symbols for the identification of three periodic nets of interest, and this system is now in wide use. In this Account, we explain the underlying methodology of assigning symbols and describe the Reticular Chemistry Structure Resource (RCSR), in which about 1600 such nets are collected and illustrated in a database that can be searched by symbol, name, keywords, and attributes. The resource also contains searchable data for polyhedra and layers. The database entries come from systematic enumerations or from known chemical compounds or both. In the latter case, references to

  20. Schorlomite: a discussion of the crystal chemistry, formula, and inter-species boundaries

    NASA Astrophysics Data System (ADS)

    Chakhmouradian, A. R.; McCammon, C. A.

    2005-07-01

    Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe2+ and Mg in the octahedrally coordinated Y site, and Fe3+, Al and Fe2+ in the tetrahedrally coordinated Z site. Substitutions Ti4+Fe3+Fe3+-1Si-1 and Ti4+Al3+Fe3+-1Si-1 are of major significance to the crystal chemistry of schorlomite, whereas Fe2+ enters the Z site in relatively minor quantities (<3% Fe∑). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe2+ contents) for the presence of [6]Ti3+ or [4]Ti4+ in schorlomite. The simplified general formula of schorlomite can be written as Ca3Ti4+2[Si3-x(Fe3+,Al,Fe2+)xO12], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti4+ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe3+, Fe2+ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of [6]Ti4+, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: ([6]Ti4+ [6]Fe2+ [6]Mg2+ [8]Na+)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca3Fe3+2Si3O12), morimotoite (Ca3Fe2+TiSi3O12), and Ca3MgTiSi3O12. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.

  1. High-pressure differential scanning microcalorimeter

    NASA Astrophysics Data System (ADS)

    Senin, A. A.; Dzhavadov, L. N.; Potekhin, S. A.

    2016-03-01

    A differential scanning microcalorimeter for studying thermotropic conformational transitions of biopolymers at high pressure has been designed. The calorimeter allows taking measurements of partial heat capacity of biopolymer solutions vs. temperature at pressures up to 3000 atm. The principles of operation of the device, methods of its calibration, as well as possible applications are discussed.

  2. High-pressure differential scanning microcalorimeter.

    PubMed

    Senin, A A; Dzhavadov, L N; Potekhin, S A

    2016-03-01

    A differential scanning microcalorimeter for studying thermotropic conformational transitions of biopolymers at high pressure has been designed. The calorimeter allows taking measurements of partial heat capacity of biopolymer solutions vs. temperature at pressures up to 3000 atm. The principles of operation of the device, methods of its calibration, as well as possible applications are discussed. PMID:27036806

  3. High Pressure Inactivation of HAV within Mussels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  4. 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.

  5. 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.

  6. High-pressure lubricity at the meso- and nanoscale

    NASA Astrophysics Data System (ADS)

    Vanossi, A.; Benassi, A.; Varini, N.; Tosatti, E.

    2013-01-01

    The increase of sliding friction upon increasing load is a classic in the macroscopic world. Here we discuss the possibility that friction rise might sometimes turn into a drop when, at the mesoscale and nanoscale, a confined lubricant film separating crystalline sliders undergoes strong layering and solidification. Under pressure, transitions from N to N-1 layers may imply a change of lateral periodicity of the crystallized lubricant sufficient to alter the matching of crystal structures, influencing the ensuing friction jump. A pressure-induced friction drop may occur as the shear gradient maximum switches from the lubricant middle, marked by strong stick-slip with or without shear melting, to the crystalline slider-lubricant interface, characterized by smooth superlubric sliding. We present high-pressure sliding simulations to display examples of frictional drops, suggesting their possible relevance to the local behavior in boundary lubrication.

  7. High Pressure Transport Studies of NdIn3

    NASA Astrophysics Data System (ADS)

    Purcell, Kenneth; Graf, David; Ebihara, Takao

    2015-03-01

    NdIn3 is a cubic antiferromagnetic metal that orders with a Neel temperature of 5.9 K and belongs to a family of rare earth intermetallic compounds RIn3 that have a cubic AuCu3-type crystal structure. At 0.5 K and the magnetic field applied in 100 direction, NdIn3 exhibits metamagnetic transitions at 7.8 T and 8.9 T before entering a field induced paramagnetic state at 11.1 T. We report high pressure transport studies of single crystal NdIn3 and the effect that pressure has on the Neel temperature, critical field, and metamagnetic transitions observed in the magnetoresistance. Comparisons to the behavior of the pressure induced superconductor CeIn3 will be discussed.

  8. COMBRESSIBILITY AND HIGH-PRESSURE BRILLOUIN SCATTERING OF NANOMATERIALS

    NASA Astrophysics Data System (ADS)

    Kantor, I.; Prakapenka, V.

    2009-12-01

    Combined Brillouin scattering and X-ray diffraction measurements available at the 13-BMD sector of GSECARS at APS are a perfect method to measure elasticity of a material at high pressures. Brillouin scattering in platelet geometry provides with sound velocities, while X-ray diffraction gives a density of a sample. The power of this technique has been demonstrated before for single-crystal and polycristalline samples. This study presents the results obtained for some nanosized materials, namely magnesium and zinc oxides. The major advantage of using nanosized material is that the probing phonon length is larger than individual crystal. This results in pure averaging of sound velocities and in some sense similar to the real seismological observations. However, due to very small crystallites size, the common theory of phonon dispersion is no longer exact. In particular, measured Vp and Vs of the samples are dramatically lower than is expected for the bulk material.

  9. High pressure x-ray diffraction techniques with synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Jing, Liu

    2016-07-01

    This article summarizes the developments of experimental techniques for high pressure x-ray diffraction (XRD) in diamond anvil cells (DACs) using synchrotron radiation. Basic principles and experimental methods for various diffraction geometry are described, including powder diffraction, single crystal diffraction, radial diffraction, as well as coupling with laser heating system. Resolution in d-spacing of different diffraction modes is discussed. More recent progress, such as extended application of single crystal diffraction for measurements of multigrain and electron density distribution, time-resolved diffraction with dynamic DAC and development of modulated heating techniques are briefly introduced. The current status of the high pressure beamline at BSRF (Beijing Synchrotron Radiation Facility) and some results are also presented. Project supported by the National Natural Science Foundation of China (Grant Nos. 10875142, 11079040, and 11075175). The 4W2 beamline of BSRF was supported by the Chinese Academy of Sciences (Grant Nos. KJCX2-SW-N20, KJCX2-SW-N03, and SYGNS04).

  10. Recent Advances in High Pressure and Temperature Rheological Studies

    SciTech Connect

    Wang, Yanbin; Hilairet, Nadege; Dera, Przemyslaw

    2012-01-20

    Rheological studies at high pressure and temperature using in-situ X-ray diffraction and imaging have made significant progresses in recent years, thanks to a combination of recent developments in several areas: (1) advances in synchrotron X-ray techniques, (2) advances in deformation devices and the abilities to control pressure, temperature, stress, strain and strain rates, (3) theoretical and computational advances in stress determination based on powder and single crystal diffraction, (4) theoretical and computational advances in modeling of grain-level micromechanics based on elasto-plastic and visco-plastic self-consistent formulations. In this article, we briefly introduce the experimental techniques and theoretical background for in-situ high pressure, high temperature rheological studies, and then review recent studies of rheological properties of major mantle materials. Some currently encountered issues have prompted developments in single-crystal quasi-Laue diffraction for complete stress tensor determination and textural evolution of poly-phased composites based on X-ray microtomography. Future prospects are discussed.

  11. Methane and ethane at high pressures: structure and stability

    NASA Astrophysics Data System (ADS)

    Goncharov, A.; Stavrou, E.; Lobanov, S.; Oganov, A. R.; Chanyshev, A.; Litasov, K.; Konopkova, Z.; Prakapenka, V.

    2013-12-01

    Methane is one of the most abundant hydrocarbon molecules in the universe and is expected to be a significant part of the icy giant planets (Uranus and Neptune) and their satellites. Ethane is one of the most predictable products of chemical reactivity of methane at extreme pressures and temperatures. In spite of numerous experimental and theoretical studies, the structure and relative stability of these materials even at room temperature remains controversial. We have performed a combined experimental, using x-ray diffraction and Raman spectroscopy, and theoretical, using the ab-initio evolutionary algorithm, study of both methane and ethane up at high pressures up to 120 GPa at 300 K. In the case of methane we have successfully solved the structure of phase B by determining the space group and the positional parameters of carbon atoms, and by completing these results for the hydrogen positions using the theoretical calculations. The general structural behavior under pressure and the relation between phase B and phases A and pre-B will be also discussed. For ethane we have determined the crystallization point, for room temperature, at 1.7 GPa and also the low pressure crystal structure (Phase I). This crystal structure is orientationally disordered (plastic phase) and deviates from the known crystal structures for ethane at low temperatures. Moreover, a pressure induced phase transition has been indentified, for the first time, at 18 GPa to a monoclinic phase II, the structure of which is solved based on a good agreement of the experimental results and theoretical predictions. We have determined the equations of state of methane and ethane, which provides a solid basis for the discussion of their relative stability at high pressures.

  12. Development of Designer Diamond Technology for High Pressure High Temperature Experiments in Support of Stockpile Stewardship Program

    SciTech Connect

    Vohra, Yogesh, K.

    2009-10-28

    The role of nitrogen in the fabrication of designer diamond was systematically investigated by adding controlled amount of nitrogen in hydrogen/methane/oxygen plasma. This has led to a successful recipe for reproducible fabrication of designer diamond anvils for high-pressure high-temperature research in support of stockpile stewardship program. In the three-year support period, several designer diamonds fabricated with this new growth chemistry were utilized in high-pressure experiments at UAB and Lawrence Livermore National Laboratory. The designer diamond anvils were utilized in high-pressure studies on heavy rare earth metals, high pressure melting studies on metals, and electrical resistance measurements on iron-based layered superconductors under high pressures. The growth chemistry developed under NNSA support can be adapted for commercial production of designer diamonds.

  13. Trace and Minor Elements in Magmas at High Pressure: In Situ Structural Insights on Partitioning at Depth

    NASA Astrophysics Data System (ADS)

    Sanloup, C.; Cochain, B.; de Grouchy, C.; Leroy, C.; Bureau, H.; Schmidt, B.; Konopkova, Z.; Kantor, I.; Irifune, T.; Daisenberg, D.

    2014-12-01

    Trace element partitioning between crystals and silicate melts has been successfully modelled using crystal-chemistry rules [1], although these models do not explicitly include melt's properties. However, melt composition has been shown to strongly influence element partitioning [2], implying a control from the 'melt-chemistry' as well. Additionally, element partitioning can be pressure-dependent, in which case it is a useful marker of depth for planetary processes such as mantle melting, and crust or core formation. To assess the effect of melt structure on partitioning at depth, we have investigated the local structure around trace and minor elements in melts at high pressure using two in situ techniques, high energy x-ray diffraction and EXAFS. X-ray diffraction data, once converted into pair distribution functions, are straightforward to interpret and give access to the full structure although overlaps between different contributions occur. In contrast, EXAFS is a chemically-sensitive probe that describes the local structure around a given element, but is model-dependent. Both methods will be illustrated by results obtained on two types of elements, some volatiles and some lithophiles. References: [1] Blundy JD and Wood BJ, Nature 372:452, 1999. [2] Schmidt MW et al., Science 312:1646, 2006.

  14. Magnetic and Superconducting Materials at High Pressures

    SciTech Connect

    Struzhkin, Viktor V.

    2015-03-24

    The work concentrates on few important tasks in enabling techniques for search of superconducting compressed hydrogen compounds and pure hydrogen, investigation of mechanisms of high-Tc superconductivity, and exploring new superconducting materials. Along that route we performed several challenging tasks, including discovery of new forms of polyhydrides of alkali metal Na at very high pressures. These experiments help us to establish the experimental environment that will provide important information on the high-pressure properties of hydrogen-rich compounds. Our recent progress in RIXS measurements opens a whole field of strongly correlated 3d materials. We have developed a systematic approach to measure major electronic parameters, like Hubbard energy U, and charge transfer energy Δ, as function of pressure. This technique will enable also RIXS studies of magnetic excitations in iridates and other 5d materials at the L edge, which attract a lot of interest recently. We have developed new magnetic sensing technique based on optically detected magnetic resonance from NV centers in diamond. The technique can be applied to study superconductivity in high-TC materials, to search for magnetic transitions in strongly correlated and itinerant magnetic materials under pressure. Summary of Project Activities; development of high-pressure experimentation platform for exploration of new potential superconductors, metal polyhydrides (including newly discovered alkali metal polyhydrides), and already known superconductors at the limit of static high-pressure techniques; investigation of special classes of superconducting compounds (high-Tc superconductors, new superconducting materials), that may provide new fundamental knowledge and may prove important for application as high-temperature/high-critical parameter superconductors; investigation of the pressure dependence of superconductivity and magnetic/phase transformations in 3d transition metal compounds, including

  15. In situ high-temperature high-pressure Raman spectroscopy on single-crystal relaxor ferroelectrics PbSc1/2Ta1/2O3 and PbSc1/2Nb1/2O3

    NASA Astrophysics Data System (ADS)

    Waeselmann, N.; Mihailova, B.; Gospodinov, M.; Bismayer, U.

    2013-04-01

    The effect of temperature on the pressure-induced structural changes in perovskite-type (ABO3) relaxor ferroelectrics is studied by in situ high-temperature high-pressure Raman spectroscopy on single crystals of PbSc1/2Ta1/2O3 (PST) and PbSc1/2Nb1/2O3 (PSN), which allowed us to elucidate the interplay between the polar and antiferrodistortive order coexisting on the mesoscopic scale at ambient conditions. High-pressure experiments were carried out at elevated temperatures below and above the characteristic intermediate temperature T*. The results were compared with those obtained at room temperature, which for PST is just above the paraelectric-ferroelectric phase transition TC, whereas for PSN is below TC. It is shown that the first critical pressure pc1, at which a transition from a relaxor to a non-polar rhombohedral state with antiphase octahedral tilt ordering occurs, decreases at elevated temperatures due to the weakening of the polar coupling, which in turn facilitates the evolution of the preexisting medium-range antiferrodistortive order into a long-range order. The critical pressure pc2 of the second phase transition, involving a change in the type of the antiferrodistortive order, is not affected by temperature, i.e. it is independent of the state of polar coupling and is mainly related to the initial correlation length of antiferrodistortive order. The strong influence of temperature on pc1, which occurs only when the mesoscopic polar order is suppressed, emphasizes the importance of coexisting ferroelectric and antiferrodistortive coupling for the occurrence of the relaxor states.

  16. Deformation twinning of a silver nanocrystal under high pressure. Supplementary materials

    DOE PAGESBeta

    Huang, X. J.; Yang, W. G.; Harder, R.; Sun, Y.; Lu, M.; Chu, Y. S.; Robinson, I. K.; Mao, H. K.

    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. Likewise, 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 also observed amore » 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.« less

  17. Deformation twinning of a silver nanocrystal under high pressure. Supplementary materials

    SciTech Connect

    Huang, X. J.; Yang, W. G.; Harder, R.; Sun, Y.; Lu, M.; Chu, Y. S.; Robinson, I. K.; Mao, H. K.

    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. Likewise, 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 also 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.

  18. High-Pressure Neutron Diffraction Studies for Materials Sciences and Energy Sciences

    NASA Astrophysics Data System (ADS)

    Zhao, Y.; Los Alamos High Pressure Materials Research Team

    2013-05-01

    The development of neutron diffraction under extreme pressure (P) and temperature (T) conditions is highly valuable to condensed matter physics, crystal chemistry, materials sciences, as well as earth and planetary sciences. We have incorporated a 500-ton press TAP-98 into the HiPPO diffractometer at LANSCE to conduct in situ high P-T neutron diffraction experiments. We have worked out a large gem-crystal anvil cell, ZAP, to conduct neutron diffraction experiments at high-P and low-T. The ZAP cell can be used to integrate multiple experimental techniques such as neutron diffraction, laser spectroscopy, and ultrasonic interferometery. Recently, we have developed high-P low-T gas/fluid cells in conjunction with neutron diffraction and inelastic neutron scattering instruments. These techniques enable in-situ and real-time examination of gas uptake/release processes and allow high-resolution time-dependent determination of changes in crystal structure and related reaction kinetics. We have successfully used these techniques to study the equation of state, structural phase transition, and thermo-mechanical properties of metals, ceramics, and minerals. We have conducted researches on the formation of methane and hydrogen clathrates, and hydrogen adsorption of the inclusion compounds such as the recently discovered metal-organic frameworks (MOFs). The aim of our research is to accurately map phase diagram, lattice parameters, thermal parameters, bond lengths, bond angles, neighboring atomic environments, and phase stability in P-T-X space. We are currently developing further high P-T technology with a new "true" triaxial loading press, TAP_6x, to compress cubic sample package to achieve pressures up to 20 GPa and temperatures up to 2000 K in routine experiments. The implementation of TAP_6x300 with high-pressure neutron beamlines is underway for simultaneous high P-T neutron diffraction, ultrasonic, calorimetry, radiography, and tomography studies. Studies based on high-pressure

  19. Design guide for high pressure oxygen systems

    NASA Technical Reports Server (NTRS)

    Bond, A. C.; Pohl, H. O.; Chaffee, N. H.; Guy, W. W.; Allton, C. S.; Johnston, R. L.; Castner, W. L.; Stradling, J. S.

    1983-01-01

    A repository for critical and important detailed design data and information, hitherto unpublished, along with significant data on oxygen reactivity phenomena with metallic and nonmetallic materials in moderate to very high pressure environments is documented. This data and information provide a ready and easy to use reference for the guidance of designers of propulsion, power, and life support systems for use in space flight. The document is also applicable to designs for industrial and civilian uses of high pressure oxygen systems. The information presented herein are derived from data and design practices involving oxygen usage at pressures ranging from about 20 psia to 8000 psia equal with thermal conditions ranging from room temperatures up to 500 F.

  20. Sample injector for high pressure liquid chromatography

    DOEpatents

    Paul, Phillip H.; Arnold, Don W.; Neyer, David W.

    2001-01-01

    Apparatus and method for driving a sample, having a well-defined volume, under pressure into a chromatography column. A conventional high pressure sampling valve is replaced by a sample injector composed of a pair of injector components connected in series to a common junction. The injector components are containers of porous dielectric material constructed so as to provide for electroosmotic flow of a sample into the junction. At an appropriate time, a pressure pulse from a high pressure source, that can be an electrokinetic pump, connected to the common junction, drives a portion of the sample, whose size is determined by the dead volume of the common junction, into the chromatographic column for subsequent separation and analysis. The apparatus can be fabricated on a substrate for microanalytical applications.

  1. Superconducting high-pressure phases of disilane

    PubMed Central

    Jin, Xilian; Meng, Xing; He, Zhi; Ma, Yanming; Liu, Bingbing; Cui, Tian; Zou, Guangtian; Mao, Ho-kwang

    2010-01-01

    High-pressure structures of disilane (Si2H6) are investigated extensively by means of first-principles density functional theory and a random structure-searching method. Three metallic structures with P-1, Pm-3m, and C2/c symmetries are found, which are more stable than those of XY3-type candidates under high pressure. Enthalpy calculations suggest a remarkably wide decomposition (Si and H2) pressure range below 135 GPa, above which three metallic structures are stable. Perturbative linear-response calculations for Pm-3m disilane at 275 GPa show a large electron-phonon coupling parameter λ of 1.397 and the resulting superconducting critical temperature beyond the order of 102 K. PMID:20479272

  2. Combustion of liquid sprays at high pressures

    NASA Technical Reports Server (NTRS)

    Shearer, A. J.; Faeth, G. M.

    1977-01-01

    The combustion of pressure atomized fuel sprays in high pressure stagnant air was studied. Measurements were made of flame and spray boundaries at pressures in the range 0.1-9 MPa for methanol and n-pentane. At the higher test pressure levels, critical phenomena are important. The experiments are compared with theoretical predictions based on a locally homogeneous two-phase flow model. The theory correctly predicted the trends of the data, but underestimates flame and spray boundaries by 30-50 percent, indicating that slip is still important for the present experiments (Sauter mean diameters of 30 microns at atmospheric pressure under cold flow conditions). Since the sprays are shorter at high pressures, slip effects are still important even though the density ratio of the phases approach one another as the droplets heat up. The model indicates the presence of a region where condensed water is present within the spray and provides a convenient means of treating supercritical phenomena.

  3. Superconducting high-pressure phases of disilane.

    PubMed

    Jin, Xilian; Meng, Xing; He, Zhi; Ma, Yanming; Liu, Bingbing; Cui, Tian; Zou, Guangtian; Mao, Ho-Kwang

    2010-06-01

    High-pressure structures of disilane (Si(2)H(6)) are investigated extensively by means of first-principles density functional theory and a random structure-searching method. Three metallic structures with P-1, Pm-3m, and C2/c symmetries are found, which are more stable than those of XY(3)-type candidates under high pressure. Enthalpy calculations suggest a remarkably wide decomposition (Si and H(2)) pressure range below 135 GPa, above which three metallic structures are stable. Perturbative linear-response calculations for Pm-3m disilane at 275 GPa show a large electron-phonon coupling parameter lambda of 1.397 and the resulting superconducting critical temperature beyond the order of 10(2) K. PMID:20479272

  4. High-pressure mechanical instability in rocks

    USGS Publications Warehouse

    Byerlee, J.D.; Brace, W.F.

    1969-01-01

    At a confining pressure of a few kilobars, deformation of many sedimentary rocks, altered mafic rocks, porous volcanic rocks, and sand is ductile, in that instabilities leading to audible elastic shocks are absent. At pressures of 7 to 10 kilobars, however, unstable faulting and stick-slip in certain of these rocks was observed. This high pressure-low temperature instability might be responsible for earthquakes in deeply buried sedimentary or volcanic sequences.

  5. High pressure hydrogen time projection chamber

    SciTech Connect

    Goulianos, K.

    1983-01-01

    We describe a high pressure hydrogen gas time projection chamber which consists of two cylindrical drift regions each 45 cm in diameter and 75 cm long. Typically, at 15 atm of H/sub 2/ with 2 kV/cm drift field and 7 kV on the 35..mu.. sense wires, the drift velocity is about 0.5 cm/..mu..sec and the spatial resolution +-200..mu...

  6. Small, high pressure liquid hydrogen turbopump

    NASA Technical Reports Server (NTRS)

    Csomor, A.; Warren, D. J.

    1980-01-01

    A high pressure, low capacity, liquid hydrogen turbopump was designed, fabricated, and tested. The design configuration of the turbopump is summarized and the results of the analytical and test efforts are presented. Approaches used to pin point the cause of poor suction performance with the original design are described and performance data are included with an axial inlet design which results in excellent suction capability.

  7. Raman spectroscopy of triolein under high pressures

    NASA Astrophysics Data System (ADS)

    Tefelski, D. B.; Jastrzębski, C.; Wierzbicki, M.; Siegoczyński, R. M.; Rostocki, A. J.; Wieja, K.; Kościesza, R.

    2010-03-01

    This article presents results of the high pressure Raman spectroscopy of triolein. Triolein, a triacylglyceride (TAG) of oleic acid, is an unsaturated fat, present in natural oils such as olive oil. As a basic food component and an energy storage molecule, it has considerable importance for food and fuel industries. To generate pressure in the experiment, we used a high-pressure cylindrical chamber with sapphire windows, presented in (R.M. Siegoczyński, R. Kościesza, D.B. Tefelski, and A. Kos, Molecular collapse - modification of the liquid structure induced by pressure in oleic acid, High Press. Res. 29 (2009), pp. 61-66). Pressure up to 750 MPa was applied. A Raman spectrometer in "macro"-configuration was employed. Raman spectroscopy provides information on changes of vibrational modes related to structural changes of triolein under pressure. Interesting changes in the triglyceride C‒H stretching region at 2650-3100 cm-1 were observed under high-pressures. Changes were also observed in the ester carbonyl (C˭ O) stretching region 1700-1780 cm-1 and the C‒C stretching region at 1050-1150 cm-1. The overall luminescence of the sample decreased under pressure, making it possible to set longer spectrum acquisition time and obtain more details of the spectrum. The registered changes suggest that the high-pressure solid phase of triolein is organized as β-polymorphic, as was reported in (C. Akita, T. Kawaguchi, and F. Kaneko, Structural study on polymorphism of cis-unsaturated triacylglycerol: Triolein, J. Phys. Chem. B 110 (2006), pp. 4346-4353; E. Da Silva and D. Rousseau, Molecular order and thermodynamics of the solid-liquid transition in triglycerides via Raman spectroscopy, Phys. Chem. Chem. Phys. 10 (2008), pp. 4606-4613) (with temperature-induced phase transitions). The research has shown that Raman spectroscopy in TAGs under pressure reveals useful information about its structural changes.

  8. (High-pressure structural studies of promethium)

    SciTech Connect

    Haire, R.G.

    1988-11-15

    The primary object of the foreign travel was to carry out collaborative high-pressure structural studies at the European Institute for Transuranium Elements (EITU), Karlsruhe, Federal Republic of Germany. These studies reestablished previous collaborative investigations by ORNL and EITU that have been very productive scientifically during the past few years. The study during the present travel period was limited to a structural study of promethium metal under pressure.

  9. Efficient High-Pressure State Equations

    NASA Technical Reports Server (NTRS)

    Harstad, Kenneth G.; Miller, Richard S.; Bellan, Josette

    1997-01-01

    A method is presented for a relatively accurate, noniterative, computationally efficient calculation of high-pressure fluid-mixture equations of state, especially targeted to gas turbines and rocket engines. Pressures above I bar and temperatures above 100 K are addressed The method is based on curve fitting an effective reference state relative to departure functions formed using the Peng-Robinson cubic state equation Fit parameters for H2, O2, N2, propane, methane, n-heptane, and methanol are given.

  10. Apparatus for testing high pressure injector elements

    NASA Technical Reports Server (NTRS)

    Myers, William Neill (Inventor); Scott, Ewell M. (Inventor); Forbes, John C. (Inventor); Shadoan, Michael D. (Inventor)

    1995-01-01

    An apparatus for testing and evaluating the spray pattern of high pressure fuel injector elements for use in supplying fuel to combustion engines is presented. Prior art fuel injector elements were normally tested by use of low pressure apparatuses which did not provide a purge to prevent mist from obscuring the injector element or to prevent frosting of the view windows; could utilize only one fluid during each test; and had their viewing ports positioned one hundred eighty (180 deg) apart, thus preventing optimum use of laser diagnostics. The high pressure fluid injector test apparatus includes an upper hub, an upper weldment or housing, a first clamp and stud/nut assembly for securing the upper hub to the upper weldment, a standoff assembly within the upper weldment, a pair of window housings having view glasses within the upper weldment, an injector block assembly and purge plate within the upper weldment for holding an injector element to be tested and evaluated, a lower weldment or housing, a second clamp and stud/nut assembly for securing the lower weldment to the upper hub, a third clamp and stud/nut assembly for securing the lower hub to the lower weldment, mechanisms for introducing fluid under high pressure for testing an injector element, and mechanisms for purging the apparatus to prevent frosting of view glasses within the window housings and to permit unobstructed viewing of the injector element.

  11. [The high pressure life of piezophiles].

    PubMed

    Oger, Philippe; Cario, Anaïs

    2014-01-01

    The deep biosphere is composed of very different biotopes located in the depth of the oceans, the ocean crust or the lithosphere. Although very different, deep biosphere biotopes share one common feature, high hydrostatic pressure. The deep biosphere is colonized by specific organisms, called piezophiles, that are able to grow under high hydrostatic pressure. Bacterial piezophiles are mainly psychrophiles belonging to five genera of γ-proteobacteria, Photobacterium, Shewanella, Colwellia, Psychromonas and Moritella, while piezophilic Archaea are mostly (hyper)thermophiles from the Thermococcales. None of these genera are specific for the deep biosphere. High pressure deeply impacts the activity of cells and cellular components, and reduces the activity of numerous key processes, eventually leading to cell death of piezosensitive organisms. Biochemical and genomic studies yield a fragmented view on the adaptive mechanisms in piezophiles. It is yet unclear whether piezophilic adaptation requires the modification of a few genes, or metabolic pathways, or a more profound reorganization of the genome, the fine tuning of gene expression to compensate the pressure-induced loss of activity of the proteins most affected by high pressure, or a stress-like physiological cell response. In contrast to what has been seen for thermophily or halophily, the adaptation to high pressure is diffuse in the genome and may concern only a small fraction of the genes. PMID:25474000

  12. Apparatus for testing high pressure injector elements

    NASA Astrophysics Data System (ADS)

    Myers, William Neill; Scott, Ewell M.; Forbes, John C.; Shadoan, Michael D.

    1993-09-01

    An apparatus for testing and evaluating the spray pattern of high pressure fuel injector elements for use in supplying fuel to combustion engines is presented. Prior art fuel injector elements were normally tested by use of low pressure apparatuses which did not provide a purge to prevent mist from obscuring the injector element or to prevent frosting of the view windows; could utilize only one fluid during each test; and had their viewing ports positioned one hundred eighty (180 deg) apart, thus preventing optimum use of laser diagnostics. The high pressure fluid injector test apparatus includes an upper hub, an upper weldment or housing, a first clamp and stud/nut assembly for securing the upper hub to the upper weldment, a standoff assembly within the upper weldment, a pair of window housings having view glasses within the upper weldment, an injector block assembly and purge plate within the upper weldment for holding an injector element to be tested and evaluated, a lower weldment or housing, a second clamp and stud/nut assembly for securing the lower weldment to the upper weldment, a lower hub, a third clamp and stud/nut assembly for securing the lower hub to the lower weldment, mechanisms for introducing fluid under high pressure for testing an injector element, and mechanisms for purging the apparatus to prevent frosting of view glasses within the window housings and to permit unobstructed viewing of the injector element.

  13. Apparatus for testing high pressure injector elements

    NASA Astrophysics Data System (ADS)

    Myers, William Neill; Scott, Ewell M.; Forbes, John C.; Shadoan, Michael D.

    1995-05-01

    An apparatus for testing and evaluating the spray pattern of high pressure fuel injector elements for use in supplying fuel to combustion engines is presented. Prior art fuel injector elements were normally tested by use of low pressure apparatuses which did not provide a purge to prevent mist from obscuring the injector element or to prevent frosting of the view windows; could utilize only one fluid during each test; and had their viewing ports positioned one hundred eighty (180 deg) apart, thus preventing optimum use of laser diagnostics. The high pressure fluid injector test apparatus includes an upper hub, an upper weldment or housing, a first clamp and stud/nut assembly for securing the upper hub to the upper weldment, a standoff assembly within the upper weldment, a pair of window housings having view glasses within the upper weldment, an injector block assembly and purge plate within the upper weldment for holding an injector element to be tested and evaluated, a lower weldment or housing, a second clamp and stud/nut assembly for securing the lower weldment to the upper hub, a third clamp and stud/nut assembly for securing the lower hub to the lower weldment, mechanisms for introducing fluid under high pressure for testing an injector element, and mechanisms for purging the apparatus to prevent frosting of view glasses within the window housings and to permit unobstructed viewing of the injector element.

  14. Introduction to High-Pressure Science

    NASA Astrophysics Data System (ADS)

    Dera, Przemyslaw

    To a common person pressure is just one of the parameters that describe a thermodynamic state. We all hear about it in everyday weather forecasts, and most of us do not associate it with anything particularly unique. Probably the most intuitive idea of the effect of high-pressure comes from movies, where submarine sinking to the bottom of the ocean is gradually crushed by the surrounding water, until its hull implodes. Why, then hundreds of scientists throughout the world spent their lifelong careers studying high-pressure phenomena? Despite all the developments in experimental technologies and instrumentation, modern scientist has very few tools that allow him or her to "grab" two atoms and bring them, in a very controllable way, closer together. Being able to achieve this task means the ability to directly probe interatomic interaction potentials and can cause transformations as dramatic as turning of a common gas into solid metal. Before the reader delves into more advanced topics described later in this book, this introductory chapter aims to explain several elementary, but extremely important concepts in high-pressure science. We will start with a brief discussion of laboratory devices used to produce pressure, address the issue of hydrostaticity, elastic and plastic compression, and will conclude with a short discussion of unique effects of anisotropic stress.

  15. Phase transitions at high pressure in tetracyanoethylene

    NASA Astrophysics Data System (ADS)

    Mukhopadhyay, R.; Deb, S. K.; Das, Amitabh; Chaplot, S. L.

    2009-11-01

    We report in situ x-ray diffraction studies in tetracyanoethylene (TCNE) at high pressure using diamond anvil cell (DAC) at Elettra synchrotron source, Trieste, Italy. Experiments were performed with both the polymorphic phases (monoclinic and cubic) of TCNE as the starting phase. While starting with monoclinic (the high temperature stable) TCNE, it was found that the Bragg peaks get broadened with increase of pressure and above 5 GPa only few broad peaks remained to be observed. On release of pressure from 6.4 GPa, when the sample started turning black, the diffraction pattern at ambient pressure corresponds to cubic, the other crystalline phase of TCNE. Results reconfirm the monoclinic to cubic transition at high pressure but via an intermediate 'disordered' phase. This settles a number of conflicting issues. TCNE represents only system, which undergoes transition from one crystalline to another crystalline phase via a 'disordered' metastable phase at high pressure. When the starting phase was cubic (the low temperature stable) no apparent phase transition was observed up to 10.8 GPa.

  16. Single Molecule Raman Spectroscopy Under High Pressure

    NASA Astrophysics Data System (ADS)

    Fu, Yuanxi; Dlott, Dana

    2014-06-01

    Pressure effects on surface-enhanced Raman scattering spectra of Rhdoamine 6G adsorbed on silver nanoparticle surfaces was studied using a confocal Raman microscope. Colloidal silver nanoparticles were treated with Rhodamine 6G (R6G) and its isotopically substituted partner, R6G-d4. Mixed isotopomers let us identify single-molecule spectra, since multiple-molecule spectra would show vibrational transitions from both species. The nanoparticles were embedded into a poly vinyl alcohol film, and loaded into a diamond anvil cell for the high-pressure Raman scattering measurement. Argon was the pressure medium. Ambient pressure Raman scattering spectra showed few single-molecule spectra. At moderately high pressure ( 1GPa), a surprising effect was observed. The number of sites with observable spectra decreased dramatically, and most of the spectra that could be observed were due to single molecules. The effects of high pressure suppressed the multiple-molecule Raman sites, leaving only the single-molecule sites to be observed.

  17. Apparatus for testing high pressure injector elements

    NASA Technical Reports Server (NTRS)

    Myers, William Neill (Inventor); Scott, Ewell M. (Inventor); Forbes, John C. (Inventor); Shadoan, Michael D. (Inventor)

    1993-01-01

    An apparatus for testing and evaluating the spray pattern of high pressure fuel injector elements for use in supplying fuel to combustion engines is presented. Prior art fuel injector elements were normally tested by use of low pressure apparatuses which did not provide a purge to prevent mist from obscuring the injector element or to prevent frosting of the view windows; could utilize only one fluid during each test; and had their viewing ports positioned one hundred eighty (180 deg) apart, thus preventing optimum use of laser diagnostics. The high pressure fluid injector test apparatus includes an upper hub, an upper weldment or housing, a first clamp and stud/nut assembly for securing the upper hub to the upper weldment, a standoff assembly within the upper weldment, a pair of window housings having view glasses within the upper weldment, an injector block assembly and purge plate within the upper weldment for holding an injector element to be tested and evaluated, a lower weldment or housing, a second clamp and stud/nut assembly for securing the lower weldment to the upper weldment, a lower hub, a third clamp and stud/nut assembly for securing the lower hub to the lower weldment, mechanisms for introducing fluid under high pressure for testing an injector element, and mechanisms for purging the apparatus to prevent frosting of view glasses within the window housings and to permit unobstructed viewing of the injector element.

  18. Raman study of opal at high pressure

    NASA Astrophysics Data System (ADS)

    Farfan, G.; Wang, S.; Mao, W. L.

    2011-12-01

    More commonly known for their beauty and lore as gemstones, opals are also intriguing geological materials which may have potential for materials science applications. Opal lacks a definite crystalline structure, and is composed of an amorphous packing of hydrated silica (SiO2) spheroids, which provides us with a unique nano-scaled mineraloid with properties unlike those of other amorphous materials like glass. Opals from different localities were studied at high pressure using a diamond anvil cell to apply pressure and Raman spectroscopy to look at changes in bonding as pressure was increased. We first tested different samples from Virgin Valley, NV, Spencer, ID, Juniper Ridge, OR, and Australia, which contain varying amounts of water at ambient conditions, using Raman spectroscopy to determine if they were opal-CT (semicrystalline cristobalite-trydimite volcanic origin) or opal-A (amorphous sedimentary origin). We then used x-ray diffraction and Raman spectroscopy in a diamond anvil cell to see how their bonding and structure changed under compression and to determine what effect water content had on their high pressure behavior. Comparison of our results on opal to other high pressure studies of amorphous materials like glass has implications from a geological and materials science standpoint.

  19. A Laboratory Experiment in Pharmaceutical Analysis: Analysis of Diazepam Tablets by High Pressure Liquid Chromatography

    ERIC Educational Resources Information Center

    Bailey, Leonard

    1978-01-01

    The experiment described was developed for the third-year course in inorganic and analytical pharmaceutical chemistry to provide students with "hands-on" experience with high pressure liquid chromatography. Assay procedures are given along with experimental parameters and student results. (LBH)

  20. Soft chemistry synthesis and crystal structure of Mg{sub x}Cu{sub 3-x}V{sub 2}O{sub 6}(OH){sub 4}.2H{sub 2}O

    SciTech Connect

    Melghit, Khaled

    2009-04-02

    Mg{sub x}Cu{sub 3-x}V{sub 2}O{sub 6}(OH){sub 4}.2H{sub 2}O (x {approx} 1), with similar crystal structure as volborthite Cu{sub 3}V{sub 2}O{sub 7}(OH){sub 2}.2H{sub 2}O, was successfully prepared by a soft chemistry technique. The method consists of mixing magnesium nitrate and copper nitrate with a boiling solution of vanadium oxide (obtained by reacting V{sub 2}O{sub 5} with few mL of 30 vol.% H{sub 2}O{sub 2} followed by addition of distilled water). When ammonium hydroxide NH{sub 4}OH 10% was added (pH 7.8), a green yellowish precipitate was obtained. Using X-ray powder diffraction data, its crystal structure has been determined by Rietveld refinement. Compared to volborthite, the vanadium coordination changes from tetrahedral VO{sub 4} to trigonal bipyramidal VO{sub 5}, and magnesium replaces copper, preferably, in the less distorted octahedron. At 300 deg. C, the phase formed is similar to the high pressure (HP) monoclinic Cu{sub 3}V{sub 2}O{sub 8} phase. However at higher temperature, 600 deg. C, the phase obtained is different from known Cu{sub 3}V{sub 2}O{sub 8} phases.

  1. Proton delocalization under extreme conditions of high pressure and temperature

    SciTech Connect

    Goncharov, Alexander F.; Crowhurst, Jonathan

    2008-10-02

    Knowledge of the behaviour of light hydrogen-containing molecules under extreme conditions of high pressure and temperature is crucial to a comprehensive understanding of the fundamental physics and chemistry that is relevant under such conditions. It is also vital for interpreting the results of planetary observations, in particular those of the gas giants, and also for various materials science applications. On a fundamental level, increasing pressure causes the redistribution of the electronic density, which results in a modification of the interatomic potentials followed by a consequent qualitative change in the character of the associated bonding. Ultimately, at sufficiently high pressure, one may anticipate a transformation to a homogeneously bonded material possessing unusual physical properties (e.g. a quantum fluid). As temperature increases so does the concentration of ionised species leading ultimately to a plasma. Considerable improvements have recently been made in both the corresponding experimental and theoretical investigations. Here we review recent results for hydrogen and water that reveal unexpected routes of transformation to nonmolecular materials. We stress the importance of quantum effects, which remain significant even at high temperatures.

  2. Fracture strength of glass chips for high-pressure microfluidics

    NASA Astrophysics Data System (ADS)

    Andersson, Martin; Hjort, Klas; Klintberg, Lena

    2016-09-01

    High-pressure microfluidics exposes new areas in chemistry. In this paper, the reliability of transparent borosilicate glass chips is investigated. Two designs of circular cavities are used for fracture strength tests, either 1.6 mm wide with rounded corners to the fluid inlets, or 2.0 mm wide with sharp inlet corners. Two kinds of tests are done, either short-term, e.g. pressurization to fracture at room temperature, or long-term, with fracture at constant pressurization for up to one week, in the temperature region 11–125 °C. The speed of crack fronts is measured using a high-speed camera. Results show fracture stresses in the range of 129 and 254 MPa for short-term measurements. Long-term measurements conclude the presences of a temperature and stress dependent delayed fracture. For a reliability of one week at 11–38 °C, a pressure limit is found at the lower end of the short-term measurements, or 15% lower than the average. At 80 °C, this pressure limit is 45% lower. Crack speeds are measured to be 10‑5 m s‑1 during short-term fracture. These measurements are comparable with estimations based on slow crack growth and show that the growth affects the reliability of glass chips. This effect is strongly affected by high temperatures, thus lowers the operating window of high-pressure glass microfluidic devices.

  3. Equation of state of unreacted high explosives at high pressures

    SciTech Connect

    Yoo, C-S

    1998-08-14

    Isotherms of unreacted high explosives (HMX, RDX, and PETN) have been determined to quasi-hydrostatic high pressures below 45 GPa, by using a diamond-anvil cell angle-resolved synchrotron x-ray diffraction method. The equation-of-state parameters (bulk modulus Bo, and its derivatives B' ) are presented for the 3rd-order Birch-Murnaghan formula based on the measured isotherms. The results are also used to retrieve unreacted Hugoniots in these high explosives and to develop the equations of state and kinetic models for composite high explolsivcs such as XTX-8003 and LX-04. The evidence of shear-induced chemistry of HMX in non-hydrostatic conditions is also presented.

  4. 7 CFR 58.219 - High pressure pumps and lines.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 3 2013-01-01 2013-01-01 false High pressure pumps and lines. 58.219 Section 58.219....219 High pressure pumps and lines. High pressure lines may be cleaned-in-place and shall be of such construction that dead ends, valves and the high pressure pumps can be disassembled for hand cleaning. The...

  5. 7 CFR 58.219 - High pressure pumps and lines.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 3 2010-01-01 2010-01-01 false High pressure pumps and lines. 58.219 Section 58.219....219 High pressure pumps and lines. High pressure lines may be cleaned-in-place and shall be of such construction that dead ends, valves and the high pressure pumps can be disassembled for hand cleaning. The...

  6. 7 CFR 58.219 - High pressure pumps and lines.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 3 2012-01-01 2012-01-01 false High pressure pumps and lines. 58.219 Section 58.219....219 High pressure pumps and lines. High pressure lines may be cleaned-in-place and shall be of such construction that dead ends, valves and the high pressure pumps can be disassembled for hand cleaning. The...

  7. 7 CFR 58.219 - High pressure pumps and lines.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 3 2011-01-01 2011-01-01 false High pressure pumps and lines. 58.219 Section 58.219....219 High pressure pumps and lines. High pressure lines may be cleaned-in-place and shall be of such construction that dead ends, valves and the high pressure pumps can be disassembled for hand cleaning. The...

  8. 7 CFR 58.219 - High pressure pumps and lines.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 3 2014-01-01 2014-01-01 false High pressure pumps and lines. 58.219 Section 58.219....219 High pressure pumps and lines. High pressure lines may be cleaned-in-place and shall be of such construction that dead ends, valves and the high pressure pumps can be disassembled for hand cleaning. The...

  9. Silicon Framework-Based Lithium Silicides at High Pressures.

    PubMed

    Zhang, Shoutao; Wang, Yanchao; Yang, Guochun; Ma, Yanming

    2016-07-01

    The bandgap and optical properties of diamond silicon (Si) are not suitable for many advanced applications such as thin-film photovoltaic devices and light-emitting diodes. Thus, finding new Si allotropes with better bandgap and optical properties is desirable. Recently, a Si allotrope with a desirable bandgap of ∼1.3 eV was obtained by leaching Na from NaSi6 that was synthesized under high pressure [Nat. Mater. 2015, 14, 169], paving the way to finding new Si allotropes. Li is isoelectronic with Na, with a smaller atomic core and comparable electronegativity. It is unknown whether Li silicides share similar properties, but it is of considerable interest. Here, a swarm intelligence-based structural prediction is used in combination with first-principles calculations to investigate the chemical reactions between Si and Li at high pressures, where seven new compositions (LiSi4, LiSi3, LiSi2, Li2Si3, Li2Si, Li3Si, and Li4Si) become stable above 8.4 GPa. The Si-Si bonding patterns in these compounds evolve with increasing Li content sequentially from frameworks to layers, linear chains, and eventually isolated Si ions. Nearest-neighbor Si atoms, in Cmmm-structured LiSi4, form covalent open channels hosting one-dimensional Li atom chains, which have similar structural features to NaSi6. The analysis of integrated crystal orbital Hamilton populations reveals that the Si-Si interactions are mainly responsible for the structural stability. Moreover, this structure is dynamically stable even at ambient pressure. Our results are also important for understanding the structures and electronic properties of Li-Si binary compounds at high pressures. PMID:27302244

  10. Electronic Transitions in f-electron Metals at High Pressures:

    SciTech Connect

    Yoo, C; Maddox, B; Lazicki, A; Iota, V; Klepeis, J P; McMahan, A

    2007-02-08

    This study was to investigate unusual phase transitions driven by electron correlation effects that occur in many f-band transition metals and are often accompanied by large volume changes: {approx}20% at the {delta}-{alpha} transition in Pu and 5-15% for analogous transitions in Ce, Pr, and Gd. The exact nature of these transitions has not been well understood, including the short-range correlation effects themselves, their relation to long-range crystalline order, the possible existence of remnants of the transitions in the liquid, the role of magnetic moments and order, the critical behavior, and dynamics of the transitions, among other issues. Many of these questions represent forefront physics challenges central to Stockpile materials and are also important in understanding the high-pressure behavior of other f- and d-band transition metal compounds including 3d-magnetic transition monoxide (TMO, TM=Mn, Fe, Co, Ni). The overarching goal of this study was, therefore, to understand the relationships between crystal structure and electronic structure of transition metals at high pressures, by using the nation's brightest third-generation synchrotron x-ray at the Advanced Photon Source (APS). Significant progresses have been made, including new discoveries of the Mott transition in MnO at 105 GPa and Kondo-like 4f-electron dehybridization and new developments of high-pressure resonance inelastic x-ray spectroscopy and x-ray emission spectroscopy. These scientific discoveries and technology developments provide new insights and enabling tools to understand scientific challenges in stockpile materials. The project has broader impacts in training two SEGRF graduate students and developing an university collaboration (funded through SSAAP).

  11. Dissolution rates and surface chemistry of feldspar glass and crystal. Final technical report, June 15, 1995 - August 14, 2001

    SciTech Connect

    Brantley, S.; Pantano, C.

    2002-06-11

    Final report summarizing the completed work of the project entitled 'Dissolution of Feldspar in the Field and Laboratory.' One of the highly debated questions today in low-temperature geochemical kinetics centers upon the rate and mechanism of dissolution of feldspar, the most common mineral in the crust. In this project, the mechanisms of feldspar dissolution were investigated by emphasizing experiments with feldspar glass and crystal while comparing surface and solution chemistry. Specifically, laboratory work focused on the structure of altered surface layers on feldspars, the rate of dissolution of feldspar crystal and glass, and the presence of porosity and surface coatings on feldspars. In a complementary field project, the use of Sr concentrations and isotopic ratios were used to calculate feldspar dissolution rates.

  12. Structural investigation of ribonuclease A conformational preferences using high pressure protein crystallography

    NASA Astrophysics Data System (ADS)

    Kurpiewska, Katarzyna; Dziubek, Kamil; Katrusiak, Andrzej; Font, Josep; Ribò, Marc; Vilanova, Maria; Lewiński, Krzysztof

    2016-04-01

    Hydrostatic pressure in range 0.1-1.5 GPa is used to modify biological system behaviour mostly in biophysical studies of proteins in solution. Due to specific influence on the system equilibrium high pressure can act as a filter that enables to identify and investigate higher energy protein conformers. The idea of the presented experiments is to examine the behaviour of RNase A molecule under high pressure before and after introduction of destabilizing mutation. For the first time crystal structures of wild-type bovine pancreatic ribonuclease A and its markedly less stable variant modified at position Ile106 were determined at different pressures. X-ray diffraction experiments at high pressure showed that the secondary structure of RNase A is well preserved even beyond 0.67 GPa at room temperature. Detailed structural analysis of ribonuclease A conformation observed under high pressure revealed that pressure influences hydrogen bonds pattern, cavity size and packing of molecule.

  13. Very high-pressure orogenic garnet peridotites

    PubMed Central

    Liou, J. G.; Zhang, R. Y.; Ernst, W. G.

    2007-01-01

    Mantle-derived garnet peridotites are a minor component in many very high-pressure metamorphic terranes that formed during continental subduction and collision. Some of these mantle rocks contain trace amounts of zircon and micrometer-sized inclusions. The constituent minerals exhibit pre- and postsubduction microstructures, including polymorphic transformation and mineral exsolution. Experimental, mineralogical, petrochemical, and geochronological characterizations using novel techniques with high spatial, temporal, and energy resolutions are resulting in unexpected discoveries of new phases, providing better constraints on deep mantle processes. PMID:17519341

  14. Very high-pressure orogenic garnet peridotites.

    PubMed

    Liou, J G; Zhang, R Y; Ernst, W G

    2007-05-29

    Mantle-derived garnet peridotites are a minor component in many very high-pressure metamorphic terranes that formed during continental subduction and collision. Some of these mantle rocks contain trace amounts of zircon and micrometer-sized inclusions. The constituent minerals exhibit pre- and postsubduction microstructures, including polymorphic transformation and mineral exsolution. Experimental, mineralogical, petrochemical, and geochronological characterizations using novel techniques with high spatial, temporal, and energy resolutions are resulting in unexpected discoveries of new phases, providing better constraints on deep mantle processes. PMID:17519341

  15. High-Pressure Synthesis of Materials

    NASA Astrophysics Data System (ADS)

    McMillan, Paul F.

    High pressure-high temperature techniques are used to synthesise new solid state compounds and materials that can be developed for technological applications. Laboratory and synchrotron x-ray diffraction and optical spectroscopy are combined with ab initio calculations to determine the structures and properties of new materials. We describe recent work on major classes of new materials including boron-rich solids, transition metal nitride superconductors, nitride spinels and light element solids based in the C-N-H system using examples from our own work.

  16. High-pressure liquid chromatographic gradient mixer

    DOEpatents

    Daughton, C.G.; Sakaji, R.H.

    1982-09-08

    A gradient mixer effects the continuous mixing of any two miscible solvents without excessive decay or dispersion of the resultant isocratic effluent or of a linear or exponential gradient. The two solvents are fed under low or high pressure by means of two high performance liquid chromatographic pumps. The mixer comprises a series of ultra-low dead volume stainless steel tubes and low dead volume chambers. The two solvent streams impinge head-on at high fluxes. This initial nonhomogeneous mixture is then passed through a chamber packed with spirally-wound wires which cause turbulent mixing thereby homogenizing the mixture with minimum band-broadening.

  17. High pressure liquid chromatographic gradient mixer

    DOEpatents

    Daughton, Christian G.; Sakaji, Richard H.

    1985-01-01

    A gradient mixer which effects the continuous mixing of any two miscible solvents without excessive decay or dispersion of the resultant isocratic effluent or of a linear or exponential gradient. The two solvents are fed under low or high pressure by means of two high performance liquid chromatographic pumps. The mixer comprises a series of ultra-low dead volume stainless steel tubes and low dead volume chambers. The two solvent streams impinge head-on at high fluxes. This initial nonhomogeneous mixture is then passed through a chamber packed with spirally-wound wires which cause turbulent mixing thereby homogenizing the mixture with minimum "band-broadening".

  18. HIGH PRESSURE COAL COMBUSTON KINETICS PROJECT

    SciTech Connect

    Stefano Orsino

    2005-03-30

    As part of the U.S. Department of Energy (DoE) initiative to improve the efficiency of coal-fired power plants and reduce the pollution generated by these facilities, DOE has funded the High-Pressure Coal Combustion Kinetics (HPCCK) Projects. A series of laboratory experiments were conducted on selected pulverized coals at elevated pressures with the specific goals to provide new data for pressurized coal combustion that will help extend to high pressure and validate models for burnout, pollutant formation, and generate samples of solid combustion products for analyses to fill crucial gaps in knowledge of char morphology and fly ash formation. Two series of high-pressure coal combustion experiments were performed using SRI's pressurized radiant coal flow reactor. The first series of tests characterized the near burner flame zone (NBFZ). Three coals were tested, two high volatile bituminous (Pittsburgh No.8 and Illinois No.6), and one sub-bituminous (Powder River Basin), at pressures of 1, 2, and 3 MPa (10, 20, and 30 atm). The second series of experiments, which covered high-pressure burnout (HPBO) conditions, utilized a range of substantially longer combustion residence times to produce char burnout levels from 50% to 100%. The same three coals were tested at 1, 2, and 3 MPa, as well as at 0.2 MPa. Tests were also conducted on Pittsburgh No.8 coal in CO2 entrainment gas at 0.2, 1, and 2 MPa to begin establishing a database of experiments relevant to carbon sequestration techniques. The HPBO test series included use of an impactor-type particle sampler to measure the particle size distribution of fly ash produced under complete burnout conditions. The collected data have been interpreted with the help of CFD and detailed kinetics simulation to extend and validate devolatilization, char combustion and pollutant model at elevated pressure. A global NOX production sub-model has been proposed. The submodel reproduces the performance of the detailed chemical reaction

  19. Polymerization of formic acid under high pressure

    SciTech Connect

    Goncharov, A.F.; Manaa, M.R.; Zaug, J.M.; Gee, R.H.; Fried, L.E.; Montgomery, W.B.

    2010-07-19

    We report Raman, infrared, and x-ray diffraction (XRD) measurements, along with ab initio calculations on formic acid (FA) under pressure up to 50 GPa. We find an infinite chain Pna2{sub 1} structure to be a high-pressure phase at room temperature. Our data indicate the symmetrization and a partially covalent character of the intrachain hydrogen bonds above approximately 20 GPa. Raman spectra and XRD patterns indicate a loss of long-range order at pressures above 40 GPa, with a large hysteresis upon decompression. We attribute this behavior to a three-dimensional polymerization of FA.

  20. High pressure structural phase transitions of TiO2 nanomaterials

    NASA Astrophysics Data System (ADS)

    Quan-Jun, Li; Bing-Bing, Liu

    2016-07-01

    Recently, the high pressure study on the TiO2 nanomaterials has attracted considerable attention due to the typical crystal structure and the fascinating properties of TiO2 with nanoscale sizes. In this paper, we briefly review the recent progress in the high pressure phase transitions of TiO2 nanomaterials. We discuss the size effects and morphology effects on the high pressure phase transitions of TiO2 nanomaterials with different particle sizes, morphologies, and microstructures. Several typical pressure-induced structural phase transitions in TiO2 nanomaterials are presented, including size-dependent phase transition selectivity in nanoparticles, morphology-tuned phase transition in nanowires, nanosheets, and nanoporous materials, and pressure-induced amorphization (PIA) and polyamorphism in ultrafine nanoparticles and TiO2-B nanoribbons. Various TiO2 nanostructural materials with high pressure structures are prepared successfully by high pressure treatment of the corresponding crystal nanomaterials, such as amorphous TiO2 nanoribbons, α-PbO2-type TiO2 nanowires, nanosheets, and nanoporous materials. These studies suggest that the high pressure phase transitions of TiO2 nanomaterials depend on the nanosize, morphology, interface energy, and microstructure. The diversity of high pressure behaviors of TiO2 nanomaterials provides a new insight into the properties of nanomaterials, and paves a way for preparing new nanomaterials with novel high pressure structures and properties for various applications. Project supported by the National Basic Research Program of China (Grant No. 2011CB808200), the National Natural Science Foundation of China (Grant Nos. 11374120, 11004075, 10979001, 51025206, 51032001, and 21073071), and the Cheung Kong Scholars Programme of China.

  1. High-pressure layered structure of carbon disulfide

    NASA Astrophysics Data System (ADS)

    Naghavi, S. Shahab; Crespo, Yanier; MartoÅák, Roman; Tosatti, Erio

    2015-06-01

    Solid CS2 is superficially similar to CO2, with the same C m c a molecular crystal structure at low pressures, which has suggested similar phases also at high pressures. We carried out an extensive first-principles evolutionary search in order to identify the zero-temperature lowest-enthalpy structures of CS2 for increasing pressure up to 200 GPa. Surprisingly, the molecular C m c a phase does not evolve into β -cristobalite as in CO2 but transforms instead into phases HP2 and HP1, both recently described in high-pressure SiS2. HP1 in particular, with a wide stability range, is a layered P 21/c structure characterized by pairs of edge-sharing tetrahedra and is theoretically more robust than all other CS2 phases discussed so far. Its predicted Raman spectrum and pair correlation function agree with experiment better than those of β -cristobalite, and further differences are predicted between their respective IR spectra. The band gap of HP1-CS2 is calculated to close under pressure, yielding an insulator-metal transition near 50 GPa, in agreement with experimental observations. However, the metallic density of states remains modest above this pressure, suggesting a different origin for the reported superconductivity.

  2. Nonmetallization and band inversion in beryllium dicarbide at high pressure

    PubMed Central

    Du, Henan; Feng, Wanxiang; Li, Fei; Wang, Dashuai; Zhou, Dan; Liu, Yanhui

    2016-01-01

    Carbides have attracted much attention owing to their interesting physical and chemical properties. Here, we systematically investigated global energetically stable structures of BeC2 in the pressure range of 0–100 GPa using a first-principles structural search. A transition from the ambient-pressure α-phase to the high-pressure β-phase was theoretically predicted. Chemical bonding analysis revealed that the predicted phase transition is associated with the transformation from sp2 to sp3 C-C hybridization. The electrical conductivity of the high-pressure phase changed from a metal (α-phase) to a narrow bandgap semiconductor (β-phase), and the β-phase had an inverted band structure with positive pressure dependence. Interestingly, the β-phase was a topological insulator with the metallic surface states protected by the time-reversal symmetry of the crystal. The results indicate that pressure modulates the electronic band structure of BeC2, which is an important finding for fundamental physics and for a wide range of potential applications in electronic devices. PMID:27198492

  3. Fabrication of Bulk Glassy Alloy Foams by High Pressure Hydrogen

    NASA Astrophysics Data System (ADS)

    Wada, Takeshi; Inoue, Akihisa

    Porous Pd42.5Cu30Ni7.5P20 bulk glassy alloy rods with porosities of up to 70% were successfully prepared by high pressure hydrogen of 15 MPa. The melt of Pd42.5Cu30Ni7.5P20 alloy kept under high pressure hydrogen absorbs hydrogen and subsequent water quenching of the melt causes the homogeneous dispersion of hydrogen bubbles, which was resulted from the decrease of hydrogen solubility with decrease of pressure. Annealing the hydrogen bubble containing sample at a supercooled liquid state under vacuum, the bubbles are allowed to expand due to the decrease of viscosity of metallic glass matrix. Pores expansion continues until glassy matrix crystallizes or the equilibration among pressure of the pores, pressure of the atmosphere and surface tension is achieved. By utilizing these phenomena, pores up to 80 m in diameters are homogeneously distributed over the whole cross-sectional area of a fully glassy matrix. Under compressive deformation, the porous alloys with porosities exceeding 40% did not show macroscopic fracture in a wide compressive strain range up to 0.6 whereas the non-porous alloy fractures instantly after elastic limit of about 0.02. Porous bulk glassy alloys exhibit higher plateau stress, lower Young‧s modulus and higher energy absorption capacity compared with the conventional crystalline metal foams.

  4. High-pressure electrides: the chemical nature of interstitial quasiatoms.

    PubMed

    Miao, Mao-sheng; Hoffmann, Roald

    2015-03-18

    Building on our previous chemical and physical model of high-pressure electrides (HPEs), we explore the effects of interaction of electrons confined in crystals but off the atoms, under conditions of extreme pressure. Electrons in the quantized energy levels of voids or vacancies, interstitial quasiatoms (ISQs), effectively interact with each or with other atoms, in ways that are quite chemical. With the well-characterized Na HPE as an example, we explore the ionic limit, ISQs behaving as anions. A detailed comparison with known ionic compounds points to high ISQ charge density. ISQs may also form what appear to be covalent bonds with neighboring ISQs or real atoms, similarly confined. Our study looks specifically at quasimolecular model systems (two ISQs, a Li atom and a one-electron ISQ, a Mg atom and two ISQs), in a compression chamber made of He atoms. The electronic density due to the formation of bonding and antibonding molecular orbitals of the compressed entities is recognizable, and a bonding stabilization, which increases with pressure, is estimated. Finally, we use the computed Mg electride to understand metallic bonding in one class of electrides. In general, the space confined between atoms in a high pressure environment offers up quantized states to electrons. These ISQs, even as they lack centering nuclei, in their interactions with each other and neighboring atoms may show anionic, covalent, or metallic bonding, all the chemical features of an atom. PMID:25706033

  5. Nonmetallization and band inversion in beryllium dicarbide at high pressure

    NASA Astrophysics Data System (ADS)

    Du, Henan; Feng, Wanxiang; Li, Fei; Wang, Dashuai; Zhou, Dan; Liu, Yanhui

    2016-05-01

    Carbides have attracted much attention owing to their interesting physical and chemical properties. Here, we systematically investigated global energetically stable structures of BeC2 in the pressure range of 0–100 GPa using a first-principles structural search. A transition from the ambient-pressure α-phase to the high-pressure β-phase was theoretically predicted. Chemical bonding analysis revealed that the predicted phase transition is associated with the transformation from sp2 to sp3 C-C hybridization. The electrical conductivity of the high-pressure phase changed from a metal (α-phase) to a narrow bandgap semiconductor (β-phase), and the β-phase had an inverted band structure with positive pressure dependence. Interestingly, the β-phase was a topological insulator with the metallic surface states protected by the time-reversal symmetry of the crystal. The results indicate that pressure modulates the electronic band structure of BeC2, which is an important finding for fundamental physics and for a wide range of potential applications in electronic devices.

  6. Nonmetallization and band inversion in beryllium dicarbide at high pressure.

    PubMed

    Du, Henan; Feng, Wanxiang; Li, Fei; Wang, Dashuai; Zhou, Dan; Liu, Yanhui

    2016-01-01

    Carbides have attracted much attention owing to their interesting physical and chemical properties. Here, we systematically investigated global energetically stable structures of BeC2 in the pressure range of 0-100 GPa using a first-principles structural search. A transition from the ambient-pressure α-phase to the high-pressure β-phase was theoretically predicted. Chemical bonding analysis revealed that the predicted phase transition is associated with the transformation from sp(2) to sp(3) C-C hybridization. The electrical conductivity of the high-pressure phase changed from a metal (α-phase) to a narrow bandgap semiconductor (β-phase), and the β-phase had an inverted band structure with positive pressure dependence. Interestingly, the β-phase was a topological insulator with the metallic surface states protected by the time-reversal symmetry of the crystal. The results indicate that pressure modulates the electronic band structure of BeC2, which is an important finding for fundamental physics and for a wide range of potential applications in electronic devices. PMID:27198492

  7. Phase relations of iron alloys at high pressure (Invited)

    NASA Astrophysics Data System (ADS)

    Kuwayama, Y.; Hirose, K.; Sata, N.; Ohishi, Y.

    2009-12-01

    The Earth's core is believed to be composed of iron-nickel alloy with a small amount of one or more light elements (such as H, C, O, Si and S). Phase relations and crystal structures of iron alloys at high pressures are essential for understanding the seismic observations and the nature of the solid inner core. For recent years, we have developed experimental techniques of the high P-T generation using a laser-heated diamond-anvil cell (LH-DAC) and studied the phase relations of various iron alloys at high pressure and high temperature. For example, phase relations of iron and iron-nickel alloys were investigated up to 300 GPa and 2000 K (Kuwayama et al. EPSL, 2008). Iron-silicon alloys and iron-sulfur alloys were also studied up to more than 200 GPa, based on in-situ x-ray diffraction measurements along with chemical analysis of the quenched samples using a field-emission electron microprobe (FE-EPMA)(Kuwayama et al. PCM, 2009). In this talk, I will present recent experimental results on iron alloys and discuss the structure and composition of the Earth's inner core.

  8. Stable Calcium Nitrides at Ambient and High Pressures.

    PubMed

    Zhu, Shuangshuang; Peng, Feng; Liu, Hanyu; Majumdar, Arnab; Gao, Tao; Yao, Yansun

    2016-08-01

    The knowledge of stoichiometries of alkaline-earth metal nitrides, where nitrogen can exist in polynitrogen forms, is of significant interest for understanding nitrogen bonding and its applications in energy storage. For calcium nitrides, there were three known crystalline forms, CaN2, Ca2N, and Ca3N2, at ambient conditions. In the present study, we demonstrated that there are more stable forms of calcium nitrides than what is already known to exist at ambient and high pressures. Using a global structure searching method, we theoretically explored the phase diagram of CaNx and discovered a series of new compounds in this family. In particular, we found a new CaN phase that is thermodynamically stable at ambient conditions, which may be synthesized using CaN2 and Ca2N. Four other stoichiometries, namely, Ca2N3, CaN3, CaN4, and CaN5, were shown to be stable under high pressure. The predicted CaNx compounds contain a rich variety of polynitrogen forms ranging from small molecules (N2, N4, N5, and N6) to extended chains (N∞). Because of the large energy difference between the single and triple nitrogen bonds, dissociation of the CaNx crystals with polynitrogens is expected to be highly exothermic, making them as potential high-energy-density materials. PMID:27428707

  9. The effect of in-situ high-temperature high-pressure on the structural changes of single-crystal relaxor ferroelectrics PbSc1/2Ta1/2O3 (PST) and PbSc1/2Nb1/2O3 (PSN)

    NASA Astrophysics Data System (ADS)

    Waeselmann, Naemi; Mihailova, Boriana; Gospodinov, Marin; Bismayer, Ullrich

    2013-06-01

    Relaxor ferroelectrics (relaxor) of the perovskite structure (ABO3) have remarkably high dielectric permittivity dependent on temperature and frequency as well as remarkable piezoelectric and electro-optic coefficients. These structurally heterogeneous materials undergo a sequence of structural changes on the mesoscopic scale associated with characteristic temperatures resulting from the development of polar order on temperature decrease. Pressure increase on the other hand favors antiferrodistortive order at room temperature. To explore the importance of the antiferrodistortive coupling on the development of polar order simultaneous high-temperature high-pressure Raman studies were undertaken on single crystals of PST and PSN from 400-600 K over pressures extending to 9 GPa. We find that the first pressure-induced transition pc1 decreases with temperature while the second transition pc2 is relatively temperature independent. The behavior of pc1 is interpreted as a weakening of the polar coupling, which in turn facilitates the evolution of the preexisting medium-range antiferodistortive order into a long-range order. The near constant value of pc2 suggests that it is independent of the state of polar coupling and is mainly related to the initial correlation length of antiferrodistortive order. Thus the coexistence of both polar order and antiferrodistortive order is required for the occurrence of the relaxor state. Now at: University of Washington.

  10. Crystal structure of a new high-pressure phase, K{sub 0.82}Mg{sub 1.68}(Cr{sub 2.84}Fe{sub 0.84}Ti{sub 2.11}Zr{sub 0.08})O{sub 12}, with one-dimensional tunnels

    SciTech Connect

    Yang Hexiong . E-mail: yang@fiu.edu; Konzett, Juergen

    2004-12-01

    The crystal structure of a new complex Ti-Cr oxide phase, K{sub 0.82}Mg{sub 1.68}(Cr{sub 2.84}Fe{sub 0.84}Ti{sub 2.11}Zr{sub 0.08})O{sub 12}, synthesized at 13GPa and 1400{sup o}C, has been determined with single-crystal X-ray diffraction. It has a hexagonal symmetry with the space group P6{sub 3}/m and unit-cell parameters a=9.1763(13) and c=2.8790(6)A, V=209.89(8)A3, Z=1. The structure is characterized by the hollandite-type double chains of edge-shared M2 octahedra occupied by trivalent and tetravalent cations (Ti+Cr+Fe+Zr); these double chains are linked to one another through shared octahedral apexes to form a framework structure containing two types of tunnels running parallel to the c-axis. One type of tunnels has a hexagonal cross-section and is occupied by large K{sup +}, whereas the other has a triangular cross-section and is occupied by Mg{sup 2+}. The K{sup +} cation is disordered between two crystallographically equivalent (2a) sites in the tunnels and displays a U33 displacement parameter that is significantly greater than U11. The new high-pressure phase reported in this study possesses many structural features similar to those for the hollandite compounds, making it a candidate for the 1-D fast ionic conductors.

  11. Crystal Chemistry of Lead Oxide Hydroxide Nitrates. III. The Crystal Structure of Pb 3O 2(OH)(NO 3)

    NASA Astrophysics Data System (ADS)

    Krivovichev, Sergey V.; Li, Yaping; Burns, Peter C.

    2001-04-01

    The lead oxide hydroxide nitrate, Pb3O2(OH)(NO3), has been synthesized by hydrothermal methods. The crystal structure has been determined by single-crystal X-ray diffraction and refined to R1=0.044. The compound is orthorhombic, space group Pca21, a=14.149(2) Å, b=8.7668(12) Å, c=5.7124(8) Å, V=708.6(2) Å3, Z=4. The structure is based on [O2Pb3] chains of edge-sharing (OPb4) tetrahedra that are parallel to the c axis. The chains are linked by (OH)Pb2 dimers to [Pb3O2](OH) sheets that are parallel to (100). (NO3) triangles are parallel to the (001) plane. The Pb coordination polyhedra are strongly distorted due to the influence of lone pair electrons.

  12. Unusual electronic and mechanical properties of sodium chlorides at high pressures

    NASA Astrophysics Data System (ADS)

    Bu, Hongxia; Zhao, Mingwen; Zhou, Hongcai; Du, Yanling

    2016-04-01

    Using first-principles calculations, we performed systematic investigation on the electronic and mechanical properties of sodium chlorides with different stoichiometries at high pressures. It was found that most of the phases are metallic except the Pnma-NaCl3 with a gap of 2.155 eV. The extended Cl (or Na) sublattice at Cl-rich (or Na-rich) conditions contributes to the metallization. Accompanied by metallization, the NamCln crystals exhibit good ductility in contrast to the brittle NaCl crystal, due to the changes of binding features induced by high pressure. These results are expected to be useful for understanding the exotic properties of NaCl at high pressures.

  13. Elasticity of Hydrogen at High Pressures

    NASA Astrophysics Data System (ADS)

    Goncharov, A. F.; Decremps, F.; Gauthier, M.; Ayrinhac, S.; Antonangeli, D.; Freiman, Y. A.; Grechnev, A.; Tretyak, S. M.

    2015-12-01

    High-pressure elastic properties of hydrogen give insight into anisotropy, equation of state, thermodynamic properties, and intermolecular potentials of this material providing an important link to ultrahigh pressure behavior approaching transformation to metallic monatomic or molecular state. Here we present picosecond acoustics measurements of compressional sound velocities [1] combined with optical interferometry and Raman spectroscopy of H2 and D2 at 295 K up to 55 GPa. Using the equation of state determined previously [2], we deduced the transverse sound velocities and the Poisson's ratio up to 55 GPa. The latter shows a broad minimum near 45 GPa (c.f. Ref. [3]) providing a new experimentally proven insight into lattice dynamics of hydrogen at high pressure that can be compared to theoretical calculations of various levels [4]. [1] F. Decremps, M. Gauthier, S. Ayrinhac, L. Bove, L. Belliard, B. Perrin, M. Morand, G. Le Marchand, F. Bergame, J. Philippe, Ultrasonics, 56 (2015) 129-140. [2] P. Loubeyre, R. LeToullec, D. Hausermann, M. Hanfland, R.J. Hemley, H.K. Mao, L.W. Finger, Nature, 383 (1996) 702-704. [3] C.-s. Zha, T.S. Duffy, H.-k. Mao, R.J. Hemley, Phys. Rev. B, 48 (1993) 9246-9255. [4] Y.A. Freiman, A. Grechnev, S.M. Tretyak, A.F. Goncharov, E. Gregoryanz, Fizika Nizkikh Temperatur, 41 (2015) 571.

  14. A picosecond high pressure gas switch

    SciTech Connect

    Cravey, W.R.; Poulsen, P.P.; Pincosy, P.A.

    1992-06-01

    Work is being done to develop a high pressure gas switch (HPGS) with picosecond risetimes for UWB applications. Pulse risetimes on the order of 200 picoseconds have been observed at 1 kHz prf and 1 atmosphere. Calculations show that switching closure times on the order of tens of picoseconds can be achieved at high pressures and higher electric fields. A voltage hold-off of 1 MV/cm has been measured at 10 atmospheres and several MV/cm appears possible with the HPGS. With these high electric field levels, energy storage of tens of Joules in a reasonably sized package is achievable. Initial HPGS performance has been characterized on the WASP pulse generator at LLNL. A detailed description of the switch used for initial testing is given. Switch recovery times of 1-ms have been measured at 1 atmosphere. Data on the switching uniformity, voltage hold-off recovery, and pulse repeatability, is presented. In addition, a physics switch model is described and results are compared with lab data.

  15. High-pressure droplet combustion studies

    NASA Technical Reports Server (NTRS)

    Mikami, Masato; Kono, M.; Sato, Junichi; Dietrich, Daniel L.; Williams, Forman A.

    1993-01-01

    This is a joint research program, pursued by investigators at the University of Tokyo, UCSD, and NASA Lewis Research Center. The focus is on high-pressure combustion of miscible binary fuel droplets. It involves construction of an experimental apparatus in Tokyo, mating of the apparatus to a NASA-Lewis 2.2-second drop-tower frame in San Diego, and performing experiments in the 2.2-second tower in Cleveland, with experimental results analyzed jointly by the Tokyo, UCSD, and NASA investigators. The project was initiated in December, 1990 and has now involved three periods of drop-tower testing by Mikami at Lewis. The research accomplished thus far concerns the combustion of individual fiber-supported droplets of mixtures of n-heptane and n-hexadecane, initially about 1 mm diameter, under free-fall microgravity conditions. Ambient pressures ranged up to 3.0 MPa, extending above the critical pressures of both pure fuels, in room-temperature nitrogen-oxygen atmospheres having oxygen mole fractions X of 0.12 and 0.13. The general objective is to study near-critical and super-critical combustion of these droplets and to see whether three-stage burning, observed at normal gravity, persists at high pressures in microgravity. Results of these investigations will be summarized here; a more complete account soon will be published.

  16. Sounding experiments of high pressure gas discharge

    SciTech Connect

    Biele, Joachim K.

    1998-07-10

    A high pressure discharge experiment (200 MPa, 5{center_dot}10{sup 21} molecules/cm{sup 3}, 3000 K) has been set up to study electrically induced shock waves. The apparatus consists of the combustion chamber (4.2 cm{sup 3}) to produce high pressure gas by burning solid propellant grains to fill the electrical pump chamber (2.5 cm{sup 3}) containing an insulated coaxial electrode. Electrical pump energy up to 7.8 kJ at 10 kV, which is roughly three times of the gas energy in the pump chamber, was delivered by a capacitor bank. From the current-voltage relationship the discharge develops at rapidly decreasing voltage. Pressure at the combustion chamber indicating significant underpressure as well as overpressure peaks is followed by an increase of static pressure level. These data are not yet completely understood. However, Lorentz forces are believed to generate pinching with subsequent pinch heating, resulting in fast pressure variations to be propagated as rarefaction and shock waves, respectively. Utilizing pure axisymmetric electrode initiation rather than often used exploding wire technology in the pump chamber, repeatable experiments were achieved.

  17. X-ray microtomography at high pressure

    NASA Astrophysics Data System (ADS)

    Lesher, C. E.; Wang, Y.; Gaudio, S.; Clark, A.; Yamada, A.; Sanehira, T.; Rivers, M.

    2009-05-01

    X-ray microtomography at high pressure is now possible with the rotating anvil apparatus (RAA) on the 13-BM- D beamline at the Advanced Photon Source (Argonne National Lab). The high-pressure X-ray tomography microscope (HPXTM) can be used to determine densities of amorphous materials (glasses and melts) and in situ characterization of 3D microstructure of multiphase materials subject to temperature and shear deformation [1, 2]. Densities may be obtained directly by volume rendering or from X-ray absorption. The rotating anvil apparatus is compressed by a 250-ton hydraulic press between concentric thrust bearings. Toroidal and truncated cylindrical (Drickamer) anvils can be accommodated. The latter anvils perform well up to 11.5 GPa and 1873K, using boron epoxy/diamond epoxy gaskets and X-ray transparent aluminum or polytherimide plastic containment rings. Differential rotation allows for controlled sample deformation. Pressure is determined by energy dispersive diffraction of an internal standard by convenient switching from monochromatic and polychromatic radiation. In-situ calibrations of linear attenuation coefficient permit bracketing of natural basalt density to better than 1 percent relative, while [2] used volume rendering to determine the compressibility of magnesium silicate glasses and supercooled liquid. The utility of the RRA to characterize microstructural evolution will be discussed. [1] Wang et al., Rev. Sci. Instrum., 76, 073709, 2005. [2] Lesher et al., PEPI, in press, DOI: 10.1016/j.pepi.2008.10.023, 2009

  18. Phonon triggered rhombohedral lattice distortion in vanadium at high pressure

    PubMed Central

    Antonangeli, Daniele; Farber, Daniel L.; Bosak, Alexei; Aracne, Chantel M.; Ruddle, David G.; Krisch, Michael

    2016-01-01

    In spite of the simple body-centered-cubic crystal structure, the elements of group V, vanadium, niobium and tantalum, show strong interactions between the electronic properties and lattice dynamics. Further, these interactions can be tuned by external parameters, such as pressure and temperature. We used inelastic x-ray scattering to probe the phonon dispersion of single-crystalline vanadium as a function of pressure to 45 GPa. Our measurements show an anomalous high-pressure behavior of the transverse acoustic mode along the (100) direction and a softening of the elastic modulus C44 that triggers a rhombohedral lattice distortion occurring between 34 and 39 GPa. Our results provide the missing experimental confirmation of the theoretically predicted shear instability arising from the progressive intra-band nesting of the Fermi surface with increasing pressure, a scenario common to all transition metals of group V. PMID:27539662

  19. Phonon triggered rhombohedral lattice distortion in vanadium at high pressure.

    PubMed

    Antonangeli, Daniele; Farber, Daniel L; Bosak, Alexei; Aracne, Chantel M; Ruddle, David G; Krisch, Michael

    2016-01-01

    In spite of the simple body-centered-cubic crystal structure, the elements of group V, vanadium, niobium and tantalum, show strong interactions between the electronic properties and lattice dynamics. Further, these interactions can be tuned by external parameters, such as pressure and temperature. We used inelastic x-ray scattering to probe the phonon dispersion of single-crystalline vanadium as a function of pressure to 45 GPa. Our measurements show an anomalous high-pressure behavior of the transverse acoustic mode along the (100) direction and a softening of the elastic modulus C44 that triggers a rhombohedral lattice distortion occurring between 34 and 39 GPa. Our results provide the missing experimental confirmation of the theoretically predicted shear instability arising from the progressive intra-band nesting of the Fermi surface with increasing pressure, a scenario common to all transition metals of group V. PMID:27539662

  20. Electronic Structure of Crystalline 4He at High Pressures

    SciTech Connect

    Mao, Ho Kwang; Shirley, Eric L.; Ding, Yang; Eng, Peter; Cai, Yong Q.; Chow, Paul; Xiao, Yuming; Jinfu Shu, A=Kao, Chi-Chang; Hemley, Russell J.; Kao, Chichang; Mao, Wendy L.; /Stanford U., Geo. Environ. Sci. /SLAC

    2011-01-10

    Using inelastic X-ray scattering techniques, we have succeeded in probing the high-pressure electronic structure of helium crystal at 300 K which has the widest known electronic energy bandgap of all materials, that was previously inaccessible to measurements due to the extreme energy and pressure range. We observed rich electron excitation spectrum, including a cut-off edge above 23 eV, a sharp exciton peak showing linear volume dependence, and a series of excitations and continuum at 26 to 45 eV. We determined electronic dispersion along the {Gamma}-M direction over two Brillouin zones, and provided a quantitative picture of the helium exciton beyond the simplified Wannier-Frenkel description.

  1. High pressure x-ray diffraction studies on nanocrystalline materials

    NASA Astrophysics Data System (ADS)

    Palosz, B.; Stel'makh, S.; Grzanka, E.; Gierlotka, S.; Pielaszek, R.; Bismayer, U.; Werner, S.; Palosz, W.

    2004-02-01

    Application of the in situ high pressure powder diffraction technique for examination of specific structural properties of nanocrystals based on the experimental data of SiC nanocrystalline powders of 2-30 nm in diameter is presented. Limitations and capabilities of the experimental techniques themselves and methods of diffraction data elaboration applied to nanocrystals with very small dimensions (<30 nm) are discussed. It is shown that a unique value of the lattice parameter cannot be determined for such small crystals using a standard powder diffraction experiment. It is also shown that, due to the complex structure constituting a two-phase, core/surface shell system, no unique compressibility coefficient can satisfactorily describe the behaviour of nanocrystalline powders under pressure. We offer a tentative interpretation of the distribution of macro- and micro-strains in nanoparticles of different grain size.

  2. Water in Olivine and its High-Pressure Polymorphs

    NASA Astrophysics Data System (ADS)

    Thomas, S. M.; Jacobsen, S. D.; Bina, C. R.; Reichart, P.; Moser, M.; Dollinger, G.; Hauri, E. H.

    2014-12-01

    Theory and high-pressure experiments imply a significant water storage capacity of nominally anhydrous minerals (NAMs), such as olivine, wadsleyite and ringwoodite, composing the Earth's upper mantle and transition zone to a depth of 660 km. The presence of water, dissolved as OH into such nominally anhydrous high-pressure silicates, notably influences phase relations, melting behavior, conductivity, elasticity, viscosity and rheology. The first direct evidence for hydration of the transition zone has recently been reported by Pearson et al. (2014) and Schmandt et al. (2014). Knowledge of absolute water contents in NAMs is essential for modeling the Earth's interior water cycle. To take advantage of IR spectroscopy as highly sensitive water quantification tool, mineral-specific absorption coefficients are required. Such calibration constants can be derived from hydrogen concentrations determined by independent techniques, such as secondary ion mass spectrometry (SIMS), Raman spectroscopy or proton-proton(pp)-scattering. Broad beam pp-scattering has been performed on double-polished mm-sized mineral platelets (Thomas et al. 2008), but until recently analysis was not feasible for smaller samples synthetized in high-pressure apparati. Here we present first results from pp-scattering microscopy studies on μm-sized single crystals of hydrous olivine, wadsleyite and ringwoodite, which were synthesized at various pressure-temperature conditions in a multi-anvil press. The method allows us to quantify 3D distributions of atomic hydrogen in μm dimensions. These self-calibrating measurements were carried out at the nuclear microprobe SNAKE at the Munich tandem accelerator lab using a 25 MeV proton microbeam. We provide hydrogen depth-profiles, hydrogen maps and H2O concentrations. Pp-scattering data and results from independent Raman and SIMS analyses are in good agreement. Water contents for a set of high-pressure polymorphs with varying Fe-concentrations range from 0

  3. High Pressure X-Ray Diffraction Studies of Nanocrystalline Materials

    NASA Technical Reports Server (NTRS)

    Palosz, B.; Stel'makh, S.; Grzanka, E.; Gierlotka, S.; Palosz, W.

    2004-01-01

    Experimental evidence obtained for a variety of nanocrystalline materials suggest that the crystallographic structure of a very small size particle deviates from that in the bulk crystals. In this paper we show the effect of the surface of nanocrystals on their structure by the analysis of generation and distribution of macro- and micro-strains at high pressures and their dependence on the grain size in nanocrystalline powders of Sic. We studied the structure of Sic nanocrystals by in-situ high-pressure powder diffraction technique using synchrotron and neutron sources and hydrostatic or isostatic pressure conditions. The diffraction measurements were done in HASYLAB at DESY using a Diamond Anvil Cell (DAC) in the energy dispersive geometry in the diffraction vector range up to 3.5 - 4/A and under pressures up to 50 GPa at room temperature. In-situ high pressure neutron diffraction measurements were done at LANSCE in Los Alamos National Laboratory using the HIPD and HIPPO diffractometers with the Paris-Edinburgh and TAP-98 cells, respectively, in the diffraction vector range up to 26 Examination of the response of the material to external stresses requires nonstandard methodology of the materials characterization and description. Although every diffraction pattern contains a complete information on macro- and micro-strains, a high pressure experiment can reveal only those factors which contribute to the characteristic diffraction patterns of the crystalline phases present in the sample. The elastic properties of powders with the grain size from several nm to micrometers were examined using three methodologies: (l), the analysis of positions and widths of individual Bragg reflections (used for calculating macro- and micro-strains generated during densification) [I], (2). the analysis of the dependence of the experimental apparent lattice parameter, alp, on the diffraction vector Q [2], and (3), the atomic Pair Distribution Function (PDF) technique [3]. The results

  4. Toward a Role of Light Absorption in Initiation Chemistry of Shocked HMX single Crystals and Crystalline High Explosives

    NASA Astrophysics Data System (ADS)

    Plaksin, Igor; Rodrigues, L.

    2013-06-01

    Question which mechanism is driving radiation-induced reactions, thermal or athermal becomes a subject of conflicting discussions. Major challenge of this work is to identify at micro- (sub-granular), meso- (grain level) and macro-scale roles of these two mechanisms in triggering initiation chemistry in HMX-based HEs. Four acceptor-patterns were tested at 20 GPa input pressure: single HMX crystal-in-water, HMX/water-slurry, PBX(HMX/HTPB) & inert PBX-simulant (HMX-particles replaced by crystalline sucrose). Scenario of reaction onset-localizations-dissipation was spatially resolved using Multi-Channel Optical Analyzer MCOA-UC (96 channels, 100um-spatial accuracy, 0.2ns-timeresolution, 450-850 nm-spectral range) through real-time panoramic recording emitted reaction light and shock field in standard optic monitor. Experiments reveal a dual nature of initiation chemistry: athermal and thermal. Single-crystal tests disclose origination of photo-induced reactions downstream of emitting reaction spot due to intensified radiation absorption in surface micro-defects. Polycrystalline samples reveal cyclic reproducibility of radiation-induced thermal precursors in which radiation absorption causes thermal expansion/phase-changes of HMX-grains resulting in oscillating detonation. Work was supported by the Office of Naval Research under the ONR and ONR Global Grants N00014-12-1-0477 and N62909-12-1-7131 with Drs. Cliff Bedford and Shawn Thorne Program Managers.

  5. High pressure studies on extended phases of CO2

    NASA Astrophysics Data System (ADS)

    Montoya, Javier A.; Lee, Mal-Soon; Scandolo, Sandro

    2010-03-01

    Recent findings have shown that the chemistry of CO2 at high pressure and temperature is richer than previously thought and that the activation of the C=O bond that can give origin to different forms of non-molecular CO2. Such findings may have important implications for the understanding of the Earth's deep carbon cycle and CO2 sequestration technologies. First principles simulations of CO2's electronic properties under different pressure and temperature conditions can constrain the thermodynamic phase diagram of CO2 and explore P-T conditions necessary for the C=O bond activation. We have shown that at about 50 GPa molecular CO2 can transform to a metastable amorphous form characterized by an almost equal proportion of three- and four-fold coordinated carbon atoms [1], while higher carbon coordination does not take place up to at least 900 GPa [2-3]. We have also found that doping with transition metals can reduce the activation barrier and transition pressure for the C=O bond activation in CO2 [4]. Our results suggest that pressure can radically alter the oxidation chemistry of carbon. [1] J. A. Montoya et al., PRL 100, 163002 (2008) [2] J. Sun et al., PNAS 106, 6077 (2009) [3] M-S. Lee, J. A. Montoya and S. Scandolo, PRB 79, 144102 (2009) [4] J. A. Montoya, R. Rousseau, and S. Scandolo, unpublished.

  6. (Ultra) High Pressure Homogenization for Continuous High Pressure Sterilization of Pumpable Foods – A Review

    PubMed Central

    Georget, Erika; Miller, Brittany; Callanan, Michael; Heinz, Volker; Mathys, Alexander

    2014-01-01

    Bacterial spores have a strong resistance to both chemical and physical hurdles and create a risk for the food industry, which has been tackled by applying high thermal intensity treatments to sterilize food. These strong thermal treatments lead to a reduction of the organoleptic and nutritional properties of food and alternatives are actively searched for. Innovative hurdles offer an alternative to inactivate bacterial spores. In particular, recent technological developments have enabled a new generation of high pressure homogenizer working at pressures up to 400 MPa and thus, opening new opportunities for high pressure sterilization of foods. In this short review, we summarize the work conducted on (ultra) high pressure homogenization (U)HPH to inactivate endospores in model and food systems. Specific attention is given to process parameters (pressure, inlet, and valve temperatures). This review gathers the current state of the art and underlines the potential of UHPH sterilization of pumpable foods while highlighting the needs for future work. PMID:25988118

  7. Impulsive Stimulated Light Scattering at High Pressure - Precise Determination of Elastic Constants of Opaque Materials

    SciTech Connect

    Crowhurst, J C; Zaug, J M; Abramson, E H; Brown, J M; Ahre, D W

    2002-08-22

    Impulsive stimulated light scattering has been used to measure interfacial wave propagation speeds and elastic constants under conditions of high pressure. Data obtained from single-crystal Ge and Fe, and from polycrystalline Ta is presented. The method is complementary to other techniques for obtaining this type of information. There appears no fundamental reason why it cannot be extended to the 1 Mbar regime.

  8. Sealed rotors for in situ high temperature high pressure MAS NMR.

    PubMed

    Hu, Jian Zhi; Hu, Mary Y; Zhao, Zhenchao; Xu, Suochang; Vjunov, Aleksei; Shi, Hui; Camaioni, Donald M; Peden, Charles H F; Lercher, Johannes A

    2015-09-11

    Here we present the design of reusable and perfectly sealed all-zirconia MAS rotors. The rotors are used to study AlPO4-5 molecular sieve crystallization under hydrothermal conditions, high temperature high pressure cyclohexanol dehydration reaction, and low temperature metabolomics of intact biological tissue. PMID:26171928

  9. Sealed Rotors for In Situ High Temperature High Pressure MAS NMR†

    PubMed Central

    Hu, Jian Zhi; Hu, Mary Y.; Zhao, Zhenchao; Xu, Suochang; Vjunov, Aleksei; Shi, Hui; Camaioni, Donald M.; Peden, Charles H. F.; Lercher, Johannes A.

    2015-01-01

    Here we present the design of reusable and perfectly-sealed all-zircornia MAS rotors. The rotors are used to study AlPO4-5 molecular sieve crystallization under hydrothermal conditions, high temperature high pressure cyclohexanol dehydration reaction, and low temperature metabolomics of intact biological tissue. PMID:26171928

  10. New developments in high pressure x-ray spectroscopy beamline at High Pressure Collaborative Access Team

    SciTech Connect

    Xiao, Y. M. Chow, P.; Boman, G.; Bai, L. G.; Rod, E.; Bommannavar, A.; Kenney-Benson, C.; Sinogeikin, S.; Shen, G. Y.

    2015-07-15

    The 16 ID-D (Insertion Device - D station) beamline of the High Pressure Collaborative Access Team at the Advanced Photon Source is dedicated to high pressure research using X-ray spectroscopy techniques typically integrated with diamond anvil cells. The beamline provides X-rays of 4.5-37 keV, and current available techniques include X-ray emission spectroscopy, inelastic X-ray scattering, and nuclear resonant scattering. The recent developments include a canted undulator upgrade, 17-element analyzer array for inelastic X-ray scattering, and an emission spectrometer using a polycapillary half-lens. Recent development projects and future prospects are also discussed.

  11. TOPICAL REVIEW: High-pressure synthesis, crystal growth, phase diagrams, structural and magnetic properties of Y2Ba4CunO2n+x, HgBa2Can- 1CunO2n+2+delta and quasi-one-dimensional cuprates

    NASA Astrophysics Data System (ADS)

    Karpinski, J.; Meijer, G. I.; Schwer, H.; Molinski, R.; Kopnin, E.; Conder, K.; Angst, M.; Jun, J.; Kazakov, S.; Wisniewski, A.; Puzniak, R.; Hofer, J.; Alyoshin, V.; Sin, A.

    1999-09-01

    In this paper we present a review of high-gas-pressure single crystal growth studies of YBa2Cu4O8 and Y2Ba4Cu7O15-x performed in oxygen pressure up to 3000 bar and Hg1-xMxBa2Can- 1CunO2n+2+icons/Journals/Common/delta" ALT="delta" ALIGN="MIDDLE"/> (M = Pb, Re; n = 1-7) compounds in argon pressure up 11 000 bar at temperature up to 1200 °C. Chain compounds A1-xCuO2 (A = Sr, Ca, Ba) have been synthesized at high oxygen pressure up to 2000 bar. High-pressure phase diagram studies of the investigated systems are also discussed. Structure analyses of Y2Ba4CunO2n+x (n = 6-8), Hg1-xMxBa2Can- 1CunO2n+2+icons/Journals/Common/delta" ALT="delta" ALIGN="MIDDLE"/> (M = Pb, Re; n = 1-8), Sr0.73CuO2 and (Sr,Ca)4Cu6O10 single crystals have been performed. The effects of substitutions and trends in bondlengths are discussed. The vortex state properties of HgBa2Ca2Cu3O8+icons/Journals/Common/delta" ALT="delta" ALIGN="MIDDLE"/> and YBa2Cu4O8 single crystals are compared. For Hg-based compounds, the influence of oxygen content, chemical substitutions and radiation defects on vortex pinning were determined. The quasi-one-dimensional cuprates Ca0.83CuO2 and Sr0.73CuO2 show an antiferromagnetically ordered state of long-range 3D character at T < 10 K. The spin dynamics of Sr0.73CuO2, measured by inelastic neutron scattering, indicate that this ordered state coexists with a dimerized singlet ground state.

  12. Synthesis of sodium polyhydrides at high pressures

    PubMed Central

    Struzhkin, Viktor V.; Kim, Duck Young; Stavrou, Elissaios; Muramatsu, Takaki; Mao, Ho-kwang; Pickard, Chris J.; Needs, Richard J.; Prakapenka, Vitali B.; Goncharov, Alexander F.

    2016-01-01

    The only known compound of sodium and hydrogen is archetypal ionic NaH. Application of high pressure is known to promote states with higher atomic coordination, but extensive searches for polyhydrides with unusual stoichiometry have had only limited success in spite of several theoretical predictions. Here we report the first observation of the formation of polyhydrides of Na (NaH3 and NaH7) above 40 GPa and 2,000 K. We combine synchrotron X-ray diffraction and Raman spectroscopy in a laser-heated diamond anvil cell and theoretical random structure searching, which both agree on the stable structures and compositions. Our results support the formation of multicenter bonding in a material with unusual stoichiometry. These results are applicable to the design of new energetic solids and high-temperature superconductors based on hydrogen-rich materials. PMID:27464650

  13. High pressure and high temperature apparatus

    DOEpatents

    Voronov, Oleg A.

    2005-09-13

    A design for high pressure/high temperature apparatus and reaction cell to achieve .about.30 GPa pressure in .about.1 cm volume and .about.100 GPa pressure in .about.1 mm volumes and 20-5000.degree. C. temperatures in a static regime. The device includes profiled anvils (28) action on a reaction cell (14, 16) containing the material (26) to be processed. The reaction cell includes a heater (18) surrounded by insulating layers and screens. Surrounding the anvils are cylindrical inserts and supporting rings (30-48) whose hardness increases towards the reaction cell. These volumes may be increased considerably if applications require it, making use of presses that have larger loading force capability, larger frames and using larger anvils.

  14. Synthesis of sodium polyhydrides at high pressures.

    PubMed

    Struzhkin, Viktor V; Kim, Duck Young; Stavrou, Elissaios; Muramatsu, Takaki; Mao, Ho-Kwang; Pickard, Chris J; Needs, Richard J; Prakapenka, Vitali B; Goncharov, Alexander F

    2016-01-01

    The only known compound of sodium and hydrogen is archetypal ionic NaH. Application of high pressure is known to promote states with higher atomic coordination, but extensive searches for polyhydrides with unusual stoichiometry have had only limited success in spite of several theoretical predictions. Here we report the first observation of the formation of polyhydrides of Na (NaH3 and NaH7) above 40 GPa and 2,000 K. We combine synchrotron X-ray diffraction and Raman spectroscopy in a laser-heated diamond anvil cell and theoretical random structure searching, which both agree on the stable structures and compositions. Our results support the formation of multicenter bonding in a material with unusual stoichiometry. These results are applicable to the design of new energetic solids and high-temperature superconductors based on hydrogen-rich materials. PMID:27464650

  15. Small, high-pressure liquid oxygen turbopump

    NASA Technical Reports Server (NTRS)

    Csomor, A.; Sutton, R.

    1977-01-01

    A small, high-pressure, liquid oxygen turbopump was designed, fabricated, and tested. The pump was of a single-stage, centrifugal type; power to the pump was supplied by a single-stage, partial emission, axial-impulse turbine. Design conditions included an operating speed of 70,000 rpm, pump discharge pressure of 2977 N/sq cm (4318 psia), and a pump flowrate of 16.4 kg/s (36.21 lb/sec). The turbine was propelled by LO2/LH2 combustion products at 1041 K (1874 R) inlet temperature, and at a design pressure ratio of 1.424. The approaches used in the detail 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.

  16. Small, high-pressure, liquid oxygen turbopump

    NASA Technical Reports Server (NTRS)

    Csomor, A.

    1978-01-01

    A small, high-pressure, LOX turbopump was designed, fabricated, and tested. The pump was of a single-stage, centrifugal type; power to the pump was supplied by a single-stage, partial-admission, axial-impulse turbine. Design conditions included an operating speed of 7330 rad/sec (70,000 rpm) pump discharge pressure of 2977 N/sq cm (4318 psia), and a pump flowrate of 16.4 kg/s (36.21 lb/sec). The turbine was propelled by LOX/LH2 combustion products at 1041 K (1874 R) inlet temperature, and at a design pressure ratio of 1.424. Test data obtained with the turbopump are presented and mechanical performance is discussed.

  17. Polymerization of Formic Acid under High Pressure

    SciTech Connect

    Goncharov, A F; Manaa, M R; Zaug, J M; Fried, L E; Montgomery, W B

    2004-08-23

    We report combined Raman, infrared (IR) and x-ray diffraction (XRD) measurements, along with ab initio calculations on formic acid under pressure up to 50 GPa. Contrary to the report of Allan and Clark (PRL 82, 3464 (1999)), we find an infinite chain low-temperature Pna2{sub 1} structure consisting of trans molecules to be a high-pressure phase at room temperature. Our data indicate the symmetrization and a partially covalent character of the intra-chain hydrogen bonds above approximately 20 GPa. Raman spectra and XRD patterns indicate a loss of the long-range order at pressures above 40 GPa with a large hysteresis at decompression. We attribute this behavior to a three-dimensional polymerization of formic acid.

  18. Synthesis of sodium polyhydrides at high pressures

    NASA Astrophysics Data System (ADS)

    Struzhkin, Viktor V.; Kim, Duck Young; Stavrou, Elissaios; Muramatsu, Takaki; Mao, Ho-Kwang; Pickard, Chris J.; Needs, Richard J.; Prakapenka, Vitali B.; Goncharov, Alexander F.

    2016-07-01

    The only known compound of sodium and hydrogen is archetypal ionic NaH. Application of high pressure is known to promote states with higher atomic coordination, but extensive searches for polyhydrides with unusual stoichiometry have had only limited success in spite of several theoretical predictions. Here we report the first observation of the formation of polyhydrides of Na (NaH3 and NaH7) above 40 GPa and 2,000 K. We combine synchrotron X-ray diffraction and Raman spectroscopy in a laser-heated diamond anvil cell and theoretical random structure searching, which both agree on the stable structures and compositions. Our results support the formation of multicenter bonding in a material with unusual stoichiometry. These results are applicable to the design of new energetic solids and high-temperature superconductors based on hydrogen-rich materials.

  19. Low energy high pressure miniature screw valve

    DOEpatents

    Fischer, Gary J.; Spletzer, Barry L.

    2006-12-12

    A low energy high pressure screw valve having a valve body having an upper portion and a lower portion, said lower portion of said valve body defining an inlet flow passage and an outlet flow passage traversing said valve body to a valve seat, said upper portion of said valve body defining a cavity at said valve seat, a diaphragm restricting flow between said upper portion of said valve body and said lower portion, said diaphragm capable of engaging said valve seat to restrict fluid communication between said inlet passage and said outlet passage, a plunger within said cavity supporting said diaphragm, said plunger being capable of engaging said diaphragm with said valve seat at said inlet and outlet fluid passages, said plunger being in point contact with a drive screw having threads engaged with opposing threads within said upper portion of said valve body such engagement allowing motion of said drive screw within said valve body.

  20. Safety improvements in high pressure thermal machines

    SciTech Connect

    Otters, J.L.

    1988-02-09

    In a thermal machine of the type including a machine body having a main axis extending between a thermal end and a work end, a working fluid at relatively high pressure in a working fluid chamber defined in the body and a displacer element reciprocable within the chamber for subjecting the fluid to a thermodynamic cycle in cooperation with a reciprocable work piston, the improvement is described comprising outer shell means enclosing the machine body for maintaining a substantially sealed atmosphere about the machine body, and diffuser means arranged between the machine body and the outer shell means for diffusing a shock wave traveling towards the outer shell means resulting from explosive failure of the machine body and for shielding the outer shell means against fragments projected upon such failure.

  1. Synthesis of sodium polyhydrides at high pressures

    DOE PAGESBeta

    Struzhkin, Viktor V.; Kim, Duck Young; Stavrou, Elissaios; Muramatsu, Takaki; Mao, Ho-kwang; Pickard, Chris J.; Needs, Richard J.; Prakapenka, Vitali B.; Goncharov, Alexander F.

    2016-07-28

    Archetypal ionic NaH is the only known compound of sodium and hydrogen. Application of high pressure is known to promote states with higher atomic coordination, but extensive searches for polyhydrides with unusual stoichiometry have had only limited success in spite of several theoretical predictions. Here we report the first observation of the formation of polyhydrides of Na (NaH3 and NaH7) above 40 GPa and 2,000 K. Moreover, we combine synchrotron X-ray diffraction and Raman spectroscopy in a laser-heated diamond anvil cell and theoretical random structure searching, which both agree on the stable structures and compositions. Our results support the formationmore » of multicenter bonding in a material with unusual stoichiometry. These results are applicable to the design of new energetic solids and high-temperature superconductors based on hydrogen-rich materials.« less

  2. Structural behaviour of YGa under high pressure

    SciTech Connect

    Sekar, M. Shekar, N. V. Chandra Sahu, P. Ch.; Babu, R.

    2014-04-24

    High pressure X-ray diffraction studies on rare-earth gallide YGa was carried up to a pressure of ∼ 33 GPa using rotating anode x-ray source in an angle dispersive mode. YGa exhibits CrB (B33) type orthorhombic structure (space group Cmcm) at ambient pressure. It undergoes a reversible structural phase transition from orthorhombic to tetragonal structure at ∼ 8.8 GPa. Both the phases coexist up to the highest pressure studied. The zero pressure bulk modulus and its derivative for parent phase have been estimated to be B{sub o} = 60 ± 3 GPa, B{sub o}' = 4.6 ± 1.5.

  3. Urea and deuterium mixtures at high pressures

    SciTech Connect

    Donnelly, M. Husband, R. J.; Frantzana, A. D.; Loveday, J. S.; Bull, C. L.; Klotz, S.

    2015-03-28

    Urea, like many network forming compounds, has long been known to form inclusion (guest-host) compounds. Unlike other network formers like water, urea is not known to form such inclusion compounds with simple molecules like hydrogen. Such compounds if they existed would be of interest both for the fundamental insight they provide into molecular bonding and as potential gas storage systems. Urea has been proposed as a potential hydrogen storage material [T. A. Strobel et al., Chem. Phys. Lett. 478, 97 (2009)]. Here, we report the results of high-pressure neutron diffraction studies of urea and D{sub 2} mixtures that indicate no inclusion compound forms up to 3.7 GPa.

  4. Ceramic high pressure gas path seal

    NASA Technical Reports Server (NTRS)

    Liotta, G. C.

    1987-01-01

    Stage 1 ceramic shrouds (high pressure turbine gas path seal) were developed for the GE T700 turbine helicopter engine under the Army/NASA Contract NAS3-23174. This contract successfully proved the viability and benefits of a Stage 1 ceramic shroud for production application. Stage 1 ceramic shrouds were proven by extensive component and engine testing. This Stage 1 ceramic shroud, plasma sprayed ceramic (ZrOs-BY2O3) and bond coating (NiCrAlY) onto a cast metal backing, offers significant engine performance improvement. Due to the ceramic coating, the amount of cooling air required is reduced 20% resulting in a 0.5% increase in horsepower and a 0.3% decrease in specific fuel consumption. This is accomplished with a component which is lower in cost than the current production shroud. Stage 1 ceramic shrouds will be introduced into field service in late 1987.

  5. High Pressure Quick Disconnect Particle Impact Tests

    NASA Technical Reports Server (NTRS)

    Rosales, Keisa R.; Stoltzfus, Joel M.

    2009-01-01

    NASA Johnson Space Center White Sands Test Facility (WSTF) performed particle impact testing to determine whether there is a particle impact ignition hazard in the quick disconnects (QDs) in the Environmental Control and Life Support System (ECLSS) on the International Space Station (ISS). Testing included standard supersonic and subsonic particle impact tests on 15-5 PH stainless steel, as well as tests performed on a QD simulator. This paper summarizes the particle impact tests completed at WSTF. Although there was an ignition in Test Series 4, it was determined the ignition was caused by the presence of a machining imperfection. The sum of all the test results indicates that there is no particle impact ignition hazard in the ISS ECLSS QDs. KEYWORDS: quick disconnect, high pressure, particle impact testing, stainless steel

  6. High pressure study of acetophenone azine

    NASA Astrophysics Data System (ADS)

    Tang, X. D.; Ding, Z. J.; Zhang, Z. M.

    2009-02-01

    High pressure Raman spectra of acetophenone azine (APA) have been measured up to 17.7 GPa with a diamond anvil cell. Two crystalline-to-crystalline phase transformations are found at pressures about 3.6 and 5.8 GPa. A disappearance of external modes and the C-H vibration at pressures higher than 8.7 GPa suggests that the sample undergoes a phase transition to amorphous or orientationally disordered (plastic) state, and the amorphization was completed at about 12.1 GPa. The disordered state is unstable and, then, a polymerization transformation reaction occurs with a further pressure increase. After the pressure has been released, the polymerization state can remain at the ambient condition, indicating that the virgin crystalline state is not recovered. The results show that the phenomenon underlying the pressure induced phase transition of APA may involve profound changes in the coordination environments of the symmetric aromatic azine.

  7. High-Pressure Research Applications Seminar

    NASA Astrophysics Data System (ADS)

    Manghnani, Murli H.; Akimoto, Syun-iti; Ahrens, Thomas J.; Syono, Yasuhiko; Jeanloz, Raymond; Yagi, Takehiko

    The United States-Japan seminar on “High-Pressure Research Applications in Geophysics and Geochemistry” was held in Honolulu, Hawaii, January 13-16, 1986, under the auspices of the National Science Foundation (NSF) and the Japan Society for the Promotion of Science (JSPS). The seminar, the third in a series, was cocovened by Murli H. Manghnani (University of Hawaii, Honolulu) and Syun-iti Akimoto (University of Tokyo). Coming together for this symposium were 25 researchers from Japan, 22 from the United States, and four others, from Australia, the People's Republic of China, the Netherlands, and the Federal Republic of Germany. Of the 52 papers presented, 38 were presented orally at seven scientific sessions, and the rest were displayed at a poster session.

  8. High-pressure coal fuel processor development

    SciTech Connect

    Greenhalgh, M.L.

    1992-11-01

    The objective of Subtask 1.1 Engine Feasibility was to conduct research needed to establish the technical feasibility of ignition and stable combustion of directly injected, 3,000 psi, low-Btu gas with glow plug ignition assist at diesel engine compression ratios. This objective was accomplished by designing, fabricating, testing and analyzing the combustion performance of synthesized low-Btu coal gas in a single-cylinder test engine combustion rig located at the Caterpillar Technical Center engine lab in Mossville, Illinois. The objective of Subtask 1.2 Fuel Processor Feasibility was to conduct research needed to establish the technical feasibility of air-blown, fixed-bed, high-pressure coal fuel processing at up to 3,000 psi operating pressure, incorporating in-bed sulfur and particulate capture. This objective was accomplished by designing, fabricating, testing and analyzing the performance of bench-scale processors located at Coal Technology Corporation (subcontractor) facilities in Bristol, Virginia. These two subtasks were carried out at widely separated locations and will be discussed in separate sections of this report. They were, however, independent in that the composition of the synthetic coal gas used to fuel the combustion rig was adjusted to reflect the range of exit gas compositions being produced on the fuel processor rig. Two major conclusions resulted from this task. First, direct injected, ignition assisted Diesel cycle engine combustion systems can be suitably modified to efficiently utilize these low-Btu gas fuels. Second, high pressure gasification of selected run-of-the-mine coals in batch-loaded fuel processors is feasible. These two findings, taken together, significantly reduce the perceived technical risks associated with the further development of the proposed coal gas fueled Diesel cycle power plant concept.

  9. Yield strength of molybdenum at high pressures.

    PubMed

    Jing, Qiumin; Bi, Yan; Wu, Qiang; Jing, Fuqian; Wang, Zhigang; Xu, Jian; Jiang, Sheng

    2007-07-01

    In the diamond anvil cell technology, the pressure gradient approach is one of the three major methods in determining the yield strength for various materials at high pressures. In the present work, by in situ measuring the thickness of the sample foil, we have improved the traditional technique in this method. Based on this modification, the yield strength of molybdenum at pressures has been measured. Our main experimental conclusions are as follows: (1) The measured yield strength data for three samples with different initial thickness (100, 250, and 500 microm) are in good agreement above a peak pressure of 10 GPa. (2) The measured yield strength can be fitted into a linear formula Y=0.48(+/-0.19)+0.14(+/-0.01)P (Y and P denote the yield strength and local pressure, respectively, both of them are in gigapascals) in the local pressure range of 8-21 GPa. This result is in good agreement with both Y=0.46+0.13P determined in the pressure range of 5-24 GPa measured by the radial x-ray diffraction technique and the previous shock wave data below 10 GPa. (3) The zero-pressure yield strength of Mo is 0.5 GPa when we extrapolate our experimental data into the ambient pressure. It is close to the tensile strength of 0.7 GPa determined by Bridgman [Phys. Rev. 48, 825 (1934)] previously. The modified method described in this article therefore provides the confidence in determination of the yield strength at high pressures. PMID:17672772

  10. Crystal chemistry and stability of "Li7La3Zr2O12" garnet: a fast lithium-ion conductor.

    PubMed

    Geiger, Charles A; Alekseev, Evgeny; Lazic, Biljana; Fisch, Martin; Armbruster, Thomas; Langner, Ramona; Fechtelkord, Michael; Kim, Namjun; Pettke, Thomas; Weppner, Werner

    2011-02-01

    Recent research has shown that certain Li-oxide garnets with high mechanical, thermal, chemical, and electrochemical stability are excellent fast Li-ion conductors. However, the detailed crystal chemistry of Li-oxide garnets is not well understood, nor is the relationship between crystal chemistry and conduction behavior. An investigation was undertaken to understand the crystal chemical and structural properties, as well as the stability relations, of Li(7)La(3)Zr(2)O(12) garnet, which is the best conducting Li-oxide garnet discovered to date. Two different sintering methods produced Li-oxide garnet but with slightly different compositions and different grain sizes. The first sintering method, involving ceramic crucibles in initial synthesis steps and later sealed Pt capsules, produced single crystals up to roughly 100 μm in size. Electron microprobe and laser ablation inductively coupled plasma mass spectrometry (ICP-MS) measurements show small amounts of Al in the garnet, probably originating from the crucibles. The crystal structure of this phase was determined using X-ray single-crystal diffraction every 100 K from 100 K up to 500 K. The crystals are cubic with space group Ia3̅d at all temperatures. The atomic displacement parameters and Li-site occupancies were measured. Li atoms could be located on at least two structural sites that are partially occupied, while other Li atoms in the structure appear to be delocalized. (27)Al NMR spectra show two main resonances that are interpreted as indicating that minor Al occurs on the two different Li sites. Li NMR spectra show a single narrow resonance at 1.2-1.3 ppm indicating fast Li-ion diffusion at room temperature. The chemical shift value indicates that the Li atoms spend most of their time at the tetrahedrally coordinated C (24d) site. The second synthesis method, using solely Pt crucibles during sintering, produced fine-grained Li(7)La(3)Zr(2)O(12) crystals. This material was studied by X-ray powder

  11. Novel high-pressure phase of ZrO{sub 2}: An ab initio prediction

    SciTech Connect

    Durandurdu, Murat

    2015-10-15

    The high-pressure behavior of the orthorhombic cotunnite type ZrO{sub 2} is explored using an ab initio constant pressure technique. For the first time, a novel hexagonal phase (Ni{sub 2}In type) within P6{sub 3}/mmc symmetry is predicted through the simulation. The Ni{sub 2}In type crystal is the densest high-pressure phase of ZrO{sub 2} proposed so far and has not been observed in other metal dioxides at high pressure before. The phase transformation is accompanied by a small volume drop and likely to occur around 380 GPa in experiment. - Graphical abstract: Post-cotunnite Ni{sub 2}In type hexagonal phase forms in zirconia at high pressure. - Highlights: • A post-cotunnite phase is predicted for ZrO{sub 2} through an ab initio simulation. • Cotunnite ZrO{sub 2} adopts the Ni{sub 2}In type structure at high pressure. • The Ni{sub 2}In type structure is the densest high-pressure phase of ZrO{sub 2} proposed so far. • The preferred mechanism in ZrO{sub 2} differs from the other metal dioxides.

  12. The high-pressure dimension in earth and planetary science

    SciTech Connect

    Mao, Ho-kwang; Hemley, Russell J.

    2008-06-17

    The bulk of our planet is hidden from view, within the earth, under high pressures and temperatures. The behavior of this material dictates the formation, evolution, and present state of the solid earth. Recent geophysical and geochemical studies of the planet present us with a rich array of large-scale processes and phenomena that are not fully understood. These range from the fate of deeply subducted slabs and the origin of plumes, to the nature of the core-mantle boundary; the differentiation of materials to form the present-day crust, mantle, and core; the distribution of trace elements; and the uptake and recycling of volatiles throughout earth's history. Addressing these questions experimentally has a long history, but it is only recently that the entire range of pressures that prevail within the earth could be produced in the laboratory and the materials probed with the necessary tools. Experiments have demonstrated that, under these extreme conditions, the physical and chemical behavior of materials can be profoundly altered, causing new and unforeseen reactions and giving rise to structural, elastic, electronic, and magnetic transitions not observed in rocks and minerals in the near-surface environment. Resolving new issues that have arisen requires an integrated approach involving subfields that include seismology, geochemistry, petrology, and geodynamics, as well as theoretical and experimental high-pressure mineral sciences. The collection of feature articles that follows, which were presented at a recent symposium, highlights an array of new developments in high-pressure geoscience. In ultrahigh-pressure metamorphic rocks, solid and fluid inclusions in phenocrysts contain rich information on deep-mantle processes. The structure, texture, strain, chemistry, and exsolution of these micrometer- to nanometer-sized inclusions indicate the formation environment of these rocks and contain rich information about the relevant physical and chemical processes

  13. High pressure/high temperature thermogravimetric apparatus. Final report

    SciTech Connect

    Calo, J.M.; Suuberg, E.M.

    1999-12-01

    The purpose of this instrumentation grant was to acquire a state-of-the-art, high pressure, high temperature thermogravimetric apparatus (HP/HT TGA) system for the study of the interactions between gases and carbonaceous solids for the purpose of solving problems related to coal utilization and applications of carbon materials. The instrument that we identified for this purpose was manufactured by DMT (Deutsche Montan Technologies)--Institute of Cokemaking and Coal Chemistry of Essen, Germany. Particular features of note include: Two reactors: a standard TGA reactor, capable of 1100 C at 100 bar; and a high temperature (HT) reactor, capable of operation at 1600 C and 100 bar; A steam generator capable of generating steam to 100 bar; Flow controllers and gas mixing system for up to three reaction gases, plus a separate circuit for steam, and another for purge gas; and An automated software system for data acquisition and control. The HP/TP DMT-TGA apparatus was purchased in 1996 and installed and commissioned during the summer of 1996. The apparatus was located in Room 128 of the Prince Engineering Building at Brown University. A hydrogen alarm and vent system were added for safety considerations. The system has been interfaced to an Ametek quadruple mass spectrometer (MA 100), pumped by a Varian V250 turbomolecular pump, as provided for in the original proposed. With this capability, a number of gas phase species of interest can be monitored in a near-simultaneous fashion. The MS can be used in a few different modes. During high pressure, steady-state gasification experiments, it is used to sample, measure, and monitor the reactant/product gases. It can also be used to monitor gas phase species during nonisothermal temperature programmed reaction (TPR) or temperature programmed desorption (TPD) experiments.

  14. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1981

    1981-01-01

    Describes 13 activities, experiments and demonstrations, including the preparation of iron (III) chloride, simple alpha-helix model, investigating camping gas, redox reactions of some organic compounds, a liquid crystal thermometer, and the oxidation number concept in organic chemistry. (JN)

  15. 30 CFR 57.13021 - High-pressure hose connections.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false High-pressure hose connections. 57.13021... Air and Boilers § 57.13021 High-pressure hose connections. Except where automatic shutoff valves are...-pressure hose lines of 3/4-inch inside diameter or larger, and between high-pressure hose lines of...

  16. 30 CFR 57.13021 - High-pressure hose connections.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false High-pressure hose connections. 57.13021... Air and Boilers § 57.13021 High-pressure hose connections. Except where automatic shutoff valves are...-pressure hose lines of 3/4-inch inside diameter or larger, and between high-pressure hose lines of...

  17. 30 CFR 57.13021 - High-pressure hose connections.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false High-pressure hose connections. 57.13021... Air and Boilers § 57.13021 High-pressure hose connections. Except where automatic shutoff valves are...-pressure hose lines of 3/4-inch inside diameter or larger, and between high-pressure hose lines of...

  18. 30 CFR 57.13021 - High-pressure hose connections.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false High-pressure hose connections. 57.13021... Air and Boilers § 57.13021 High-pressure hose connections. Except where automatic shutoff valves are...-pressure hose lines of 3/4-inch inside diameter or larger, and between high-pressure hose lines of...

  19. 30 CFR 57.13021 - High-pressure hose connections.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false High-pressure hose connections. 57.13021... Air and Boilers § 57.13021 High-pressure hose connections. Except where automatic shutoff valves are...-pressure hose lines of 3/4-inch inside diameter or larger, and between high-pressure hose lines of...

  20. Structural chemistry and number theory amalgamized: crystal structure of Na11Hg52.

    PubMed

    Hornfeck, Wolfgang; Hoch, Constantin

    2015-12-01

    The recently elucidated crystal structure of the technologically important amalgam Na11Hg52 is described by means of a method employing some fundamental concept of number theory, namely modular arithmetical (congruence) relations observed between a slightly idealized set of atomic coordinates. In combination with well known ideas from group theory, regarding lattice-sublattice transformations, these allow for a deeper mutual understanding of both and provide the structural chemist with a slightly different kind of spectacles, thus enabling a distinct viw on complex crystal structures in general. PMID:26634733

  1. A study of the influence of riming of ice crystals on snow chemistry during different seasons in precipitating continental clouds

    NASA Astrophysics Data System (ADS)

    Kalina, M. F.; Puxbaum, H.

    During three field campaigns at Mt Sonnblick—SBO—(3106 m a.s.l.), Salzburg, Austria, in winter 1991, spring and summer 1992, a comprehensive study of cloud water and precipitation chemistry was performed including a microscopic study of form, size and degree of riming of precipitating ice crystals. The surface weighted average of the degree of riming of precipitating snow showed large fluctuations during all seasons studied with a range of 0.5-4.5 The average degree of riming was around 2 during the November and June campaigns and 2.6 in March. The attachment of cloud droplets to precipitating ice crystals was found to be the predominant process determining the final composition of a snowflake. This process was found to be active during all seasons studied. The strong seasonality of the sulfate concentration in precipitation at SBO with very low values during winter and high values during summer could be attributed primarily to the corresponding fluctuation of the sulfate concentration in the cloud water while the extent of riming was rather similar at least during the periods of our winter and summer campaigns. There are indications that the extent of riming is higher during the spring season as compared to winter or summer conditions which might help to explain the spring maximum of sulfate observed in continental precipitation. the amount of cloud water being attached to the ice crystals in relation to the amount of unrimed ice phase in the riming process was estimated to be around 30% during November and June and around 70% in March. The ice crystal shapes and size distributions observed during different cloud temperatures were according to the scheme of Magono and Lee ( Journal of the Faculty of Science of Hokkaido University, Series VII, 1966, 2, 321-335).

  2. High-Pressure Equation of State for Partially Ionic Solids

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert; Ferrante, John

    1993-01-01

    Recently, we showed that the cohesive energy of partially ionic solids may be characterized by a two-term energy relationship consisting of a Coulomb term arising from the valence-charge transfer delta Z between the atoms, and a scaled universal energy function E(sup *)(a(sup *)), which accounts for the partially covalent character of the bond and for the repulsion between the atomic cores for small R; a(sup *) is a scaled length. Normalized cohesive-energy curves of alkali halide crystals and of Ti and Ag halide crystals were obtained, and the cohesive-energy-curve parameters were used to generate theoretical equation-of-state (EOS) curves for the Li, Na, K, Cs, and Ag halides. Good agreement was obtained with the experimental isothermal compression curves over a wide pressure range (0-90 kbar). In this paper we verify that the cohesive-energy relationship is valid for divalent partially ionic solids; physically reasonable charge-transfer values (1.80 less than delta Z less than 2.0) are obtained for MgO, CaO, and CaS. Next, EOS curves for LiF, NaF, Nal, CsCl, Csl, MgO, CaO, and CaS are generated in terms of the cohesive-energy parameters. These EOS's yield excellent fits to experimental isothermal-compression data and to shock-wave data to very high pressures (P(sub max)= 250-1350 kbar).

  3. High-Pressure Polymorph of NaBiO3.

    PubMed

    Naa, Octavianti; Kumada, Nobuhiro; Miura, Akira; Takei, Takahiro; Azuma, Masaki; Kusano, Yoshihiro; Oka, Kengo

    2016-06-20

    A new high-pressure polymorph of NaBiO3 (hereafter β-NaBiO3) was synthesized under the conditions of 6 GPa and 600 °C. The powder X-ray diffraction pattern of this new phase was indexed with a hexagonal cell of a = 9.968(1) Å and c = 3.2933(4) Å. Crystal structure refinement using synchrotron powder X-ray diffraction data led to RWP = 8.53% and RP = 5.55%, and the crystal structure was closely related with that of Ba2SrY6O12. No photocatalytic activity for phenol decomposition was observed under visible-light irradiation in spite of a good performance for its mother compound, NaBiO3. The optical band-gap energy of β-NaBiO3 was narrower than that of NaBiO3, which was confirmed with density of states curves simulated by first-principles density functional theory calculation. PMID:27243818

  4. New High-Pressure Phase in Fe2O3

    NASA Astrophysics Data System (ADS)

    Tsuchiya, T.; Nishiyama, N.; Yusa, H.; Tsuchiya, J.; Funakoshi, K.

    2009-12-01

    Hematite Fe2O3, a prototype of trivalent transition metal oxides, crystallizes in the antiferromagnetic (AFM) insulating phase with the corundum structure at ambient conditions. Extensive studies have been carried out to clarify its structural, magnetic, and electronic evolutions under high pressure due to the broad interests in hematite from condensed matter physics to geosciences. The high-pressure phase relation in Fe2O3 is also substantial to understand geophysically important MgSiO3-Fe2O3 phase equilibria. Those are however still yet to be clarified as for example, some in situ X-ray diffraction measurements using the diamond anvil cell (DAC) reported a phase change from Rh2O3(II) (or orthorhombic Pv) to the CaIrO3-type structure over 60 GPa, while an experiment using the Kawai-type apparatus with sintered diamond (SD) anvils suggested to stabilize a different phase with an unidentified orthorhombic structure at much lower pressure of 40~45 GPa. On the other hand, recent theoretical and experimental investigations of non-magnetic sesquioxide compounds have revealed an emerging systematics of their high-pressure phase sequence (Tsuchiya et al., 2005; Tsuchiya et al., 2007; Yusa et al., 2008; Yusa et al., 2009). While the CaIrO3-type phase with six and eight disproportionate coordination polyhedra was found to stabilize in Al2O3 and Ga2O3 at megabar pressure, several other compounds such as In2O3 and Sc2O3 were reported to transform directly to a further denser phase with the α-Gd2S3 structure composed only of high eight-fold coordination polyhedra at much lower pressure. Similarly to these studies, we searched for a stable form of Fe2O3 under pressure theoretically by means of the density-functional structurally consistent LDA+U method and succeeded to discover a new phase transformation from Rh2O3(II) at the pressure fairly close to that reported by the SD experiment. The high-pressure phase however has different lattice constants suggested experimentally and

  5. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1981

    1981-01-01

    Outlines laboratory procedures, demonstrations, teaching suggestions, and content information related to chemistry. Topics include polarizing power; calorimetry and momentum; microcomputers in school chemistry; a constant-volume dispenser for liquids, floating magnets, and crystal lattices; preparation of chromium; and solvent polarity and…

  6. High-pressure powder x-ray diffraction study of EuVO{sub 4}

    SciTech Connect

    Garg, Alka B.; Errandonea, D.

    2015-03-15

    The high-pressure structural behavior of europium orthovanadate has been studied using in-situ, synchrotron based, high-pressure x-ray powder diffraction technique. Angle-dispersive x-ray diffraction measurements were carried out at room temperature up to 34.7 GPa using a diamond-anvil cell, extending the pressure range reported in previous experiments. We confirmed the occurrence of zircon–scheelite phase transition at 6.8 GPa and the coexistence of low- and high-pressure phases up to 10.1 GPa. In addition, clear evidence of a scheelite–fregusonite transition is found at 23.4 GPa. The fergusonite structure remains stable up to 34.7 GPa, the highest pressure reached in the present measurements. A partial decomposition of EuVO{sub 4} was also observed from 8.1 to 12.8 GPa; however, this fact did not preclude the identification of the different crystal structures of EuVO{sub 4}. The crystal structures of the different phases have been Rietveld refined and their equations of state (EOS) have been determined. The results are compared with the previous experimental data and theoretical calculations. - Graphical abstract: The high-pressure structural sequence of EuVO{sub 4}. - Highlights: • EuVO{sub 4} is studied under pressure up to 35 GPa using synchrotron XRD. • The zircón–scheelite–fergusonite structural sequence is observed. • Crystal structures are refined and equations of state determined.

  7. Crystal chemistry of merrillite from Martian meteorites: Mineralogical recorders of magmatic processes and planetary differentiation

    NASA Astrophysics Data System (ADS)

    Shearer, C. K.; Burger, P. V.; Papike, J. J.; McCubbin, F. M.; Bell, A. S.

    2015-04-01

    Merrillite is a ubiquitous accessory phase in a variety of Martian meteorite lithologies. The Martian merrillites exhibit a positive correlation between Mg# and Na and a negative correlation between Mg# and both Mn and vacancies in the octahedral Na-site. Their REE patterns are varied and range from LREE-depleted to LREE-enriched. The dominant cation substitutions in the Martian merrillites are Fe2+VI Mg-site⇔Mg2+VI Mg-site and Ca2+VI Na-site + □VI Na-site⇔2Na+VI Na-site. The REE substitution into the 8-fold coordinated Ca-site is accommodated by the coupled substitution CaVIII Ca-site + (Na)VI Na-site ⇔(Y3+ + REE3+)VIII Ca-site + □VI Na-site. The REE substitution is significantly more prevalent in lunar merrillite and can be used as a "fingerprint" to distinguish lunar from Martian meteorites. The substitution of OH- (whitlockite) and/or F- (bobdownsite) for O2- on one of the phosphate tetrahedrons appears to be rather insignificant. The correlations among Na, Mg#, Mn, and Na-site vacancies are linked to the premerrillite crystallization history of the melt and the crystal chemical behavior of the Mg- and Na-sites. The former reflects the sequence and extent of plagioclase and pyroxene crystallization. The differences in REE pattern shapes among the merrillites reflect source regions for the Martian basalts and the shapes are not greatly perturbed by the crystallization history. The occurrence of merrillite does not imply low-volatile component in the Martian magmas. However, the low whitlockite and bobdownsite contents suggest that these samples were not altered by hydrothermal fluids and therefore not reset owing to aqueous fluid interactions. Consequently, the young ages of the shergottites are probably true igneous crystallization ages.

  8. Robert Boyle's chiral crystal chemistry: computational re-evaluation of enantioselective adsorption on quartz.

    PubMed

    Kahr, Bart; Chittenden, Brianne; Rohl, Andrew

    2006-02-01

    While searching for early examples of interactions of organic chromophores with minerals in the context of a systematic study of the process of dyeing crystals, we came across Robert Boyle's description of an experiment that may have been evidence of the enantioselective adsorption of a natural product, carminic acid (7-beta-D-glucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1-methyl-9,10-dioxo-2-anthracenecarboxylic acid), to the chiral surfaces of alpha-quartz, three centuries before such interactions became the subject of active chemical investigations. In order to determine whether Boyle did indeed observe enantioselective adsorption--albeit unbeknownst to him--we attempted to dye quartz with carminic acid according to his recipe. Quartz adsorbs carminic acid only because on heating it develops a network of microfissures that adsorb dye. This process depends on capillarity, not on specific non-covalent interactions; there is no evidence of enantioselectivity adsorption to heated crystals or enantioselective epitaxy to unheated crystals. These failures changed the focus of our inquiry: Why have almost all attempts to demonstrate the enantioselective adsorption of additives to quartz crystal surfaces been generally confounding and equivocal? In order to answer this question, we complement our experimental historical re-investigation with contemporary computational techniques for modeling crystal surface structure and the adsorption of additives. Minimizations of the energies associated with the adsorption of carminic acid to relaxed, hydrated d- and l-quartz {10(-)0} surfaces are analyzed in light of quartz's abysmal record as an enantioselective stationary phase. PMID:16385623

  9. High pressure electrides: a predictive chemical and physical theory.

    PubMed

    Miao, Mao-Sheng; Hoffmann, Roald

    2014-04-15

    Electrides, in which electrons occupy interstitial regions in the crystal and behave as anions, appear as new phases for many elements (and compounds) under high pressure. We propose a unified theory of high pressure electrides (HPEs) by treating electrons in the interstitial sites as filling the quantized orbitals of the interstitial space enclosed by the surrounding atom cores, generating what we call an interstitial quasi-atom, ISQ. With increasing pressure, the energies of the valence orbitals of atoms increase more significantly than the ISQ levels, due to repulsion, exclusion by the atom cores, effectively giving the valence electrons less room in which to move. At a high enough pressure, which depends on the element and its orbitals, the frontier atomic electron may become higher in energy than the ISQ, resulting in electron transfer to the interstitial space and the formation of an HPE. By using a He lattice model to compress (with minimal orbital interaction at moderate pressures between the surrounding He and the contained atoms or molecules) atoms and an interstitial space, we are able to semiquantitatively explain and predict the propensity of various elements to form HPEs. The slopes in energy of various orbitals with pressure (s > p > d) are essential for identifying trends across the entire Periodic Table. We predict that the elements forming HPEs under 500 GPa will be Li, Na (both already known to do so), Al, and, near the high end of this pressure range, Mg, Si, Tl, In, and Pb. Ferromagnetic electrides for the heavier alkali metals, suggested by Pickard and Needs, potentially compete with transformation to d-group metals. PMID:24702165

  10. Raman Scattering from Solid and Fluid Helium at High Pressure

    NASA Astrophysics Data System (ADS)

    Watson, George Henry, Jr.

    Raman spectra were measured in solid helium at two molar volumes: 7.74 cm('3) ("10 kbar") and 9.06 cm('3) ("5 kbar"). The Raman-active E(,2g) phonon has been observed in the hcp phase of each crystal. The volume dependence measured for this phonon frequency is well represented by the mode Gruneisen parameter (gamma) = 1.06 + 0.097 V. Conventional lattice dynamics, using modern helium potentials, predicts a frequency and volume dependence for the E(,2g) phonon in good agreement with the measurements over this range of volume. Temperature dependence of the E(,2g) phonon frequency and linewidth was measured under isochoric conditions. Over the limited range of temperature in which the hcp phase exists, the thermal shift of frequency was measured to be negative by an amount no more than 1 cm('-1). The phonon linewidth was observed to be non-zero at 0 K, increasing in width with increasing temperature. The temperature dependence is compatible with a strong interaction between the E(,2g) phonon and zone-edge phonons, where the optical phonon combines with a transverse acoustic phonon to create a longitudinal acoustic phonon. In addition, second-order Raman spectra were collected for both high-pressure solid phases, hcp and fcc. Structure has been observed in the two-phonon portion of the solid helium spectra and is remarkably similar in both phases. Significant intensity extends beyond the expected cut-off for two-phonon processes, though to a decreasing extent with increasing pressure. Thus multi-phonon processes remain important in helium even at high pressure. Raman scattering from dense fluid helium shows clear departure from the behavior of collision-induced scattering from the more classical fluids. Even at room temperature, a departure from the usual roughly-exponential behavior is observed at low frequency in helium at high pressure. The departure becomes even more pronounced near the freezing temperature, with a dramatic reduction in low-frequency intensity

  11. High-pressure promoted combustion chamber

    NASA Technical Reports Server (NTRS)

    Rucker, Michelle A. (Inventor); Stoltzfus, Joel M. (Inventor)

    1991-01-01

    In the preferred embodiment of the promoted combusiton chamber disclosed herein, a thick-walled tubular body that is capable of withstanding extreme pressures is arranged with removable upper and lower end closures to provide access to the chamber for dependently supporting a test sample of a material being evaluated in the chamber. To facilitate the real-time analysis of a test sample, several pressure-tight viewing ports capable of withstanding the simulated environmental conditions are arranged in the walls of the tubular body for observing the test sample during the course of the test. A replaceable heat-resistant tubular member and replaceable flame-resistant internal liners are arranged to be fitted inside of the chamber for protecting the interior wall surfaces of the combustion chamber during the evaluation tests. Inlet and outlet ports are provided for admitting high-pressure gases into the chamber as needed for performing dynamic analyses of the test sample during the course of an evaluation test.

  12. Stable magnesium peroxide at high pressure.

    PubMed

    Lobanov, Sergey S; Zhu, Qiang; Holtgrewe, Nicholas; Prescher, Clemens; Prakapenka, Vitali B; Oganov, Artem R; Goncharov, Alexander F

    2015-01-01

    Rocky planets are thought to comprise compounds of Mg and O as these are among the most abundant elements, but knowledge of their stable phases may be incomplete. MgO is known to be remarkably stable to very high pressure and chemically inert under reduced condition of the Earth's lower mantle. However, in exoplanets oxygen may be a more abundant constituent. Here, using synchrotron x-ray diffraction in laser-heated diamond anvil cells, we show that MgO and oxygen react at pressures above 96 GPa and T = 2150 K with the formation of I4/mcm MgO2. Raman spectroscopy detects the presence of a peroxide ion (O2(2-)) in the synthesized material as well as in the recovered specimen. Likewise, energy-dispersive x-ray spectroscopy confirms that the recovered sample has higher oxygen content than pure MgO. Our finding suggests that MgO2 may be present together or instead of MgO in rocky mantles and rocky planetary cores under highly oxidized conditions. PMID:26323635

  13. Picosecond High Pressure Gas Switch experiment

    SciTech Connect

    Cravey, W.R.; Freytag, E.K.; Goerz, D.A.; Poulsen, P.; Pincosy, P.A.

    1993-08-01

    A high Pressure Gas Switch has been developed and tested at LLNL. Risetimes on the order of 200 picoseconds have been observed at 1 kHz prf and 1 atmosphere pressures. Calculations show that switching closure times on the order of tens of picoseconds can be achieved at higher pressures and electric fields. A voltage hold-off of 1 MV/cm has been measured at 10 atmospheres and several MV/cm appears possible with the HPGS. With such high electric field levels, energy storage of tens of Joules in a reasonably sized package is achievable. Initial HPGS performance has been characterized using the WASP pulse generator at LLNL. A detailed description of the switch used for initial testing is given. Switch recovery times of 1-ms have been measured at 1 atmosphere. Data on the switching uniformity, voltage hold-off recovery, and pulse repeatability, is presented. In addition, a physics switch model is described and results are compared with experimental data. Modifications made to the WASP HV pulser in order to drive the HPGS will also be discussed. Recovery times of less than 1 ms were recorded without gas flow in the switch chambers. Low pressure synthetic air was used as the switch dielectric. Longer recovery times were required when it was necessary to over-voltage the switch.

  14. High-pressure structural properties of tetramethylsilane

    NASA Astrophysics Data System (ADS)

    Zhen-Xing, Qin; Xiao-Jia, Chen

    2016-02-01

    High-pressure structural properties of tetramethylsilane are investigated by synchrotron powder x-ray diffraction at pressures up to 31.1 GPa and room temperature. A phase with the space group of Pnma is found to appear at 4.2 GPa. Upon compression, the compound transforms to two following phases: the phase with space groups of P21/c at 9.9 GPa and the phase with P2/m at 18.2 GPa successively via a transitional phase. The unique structural character of P21/c supports the phase stability of tetramethylsilane without possible decomposition upon heavy compression. The appearance of the P2/m phase suggests the possible realization of metallization for this material at higher pressure. Project supported by the Cultivation Fund of the Key Scientific and Technical Innovation Project from Ministry of Education of China (Grant No. 708070), the Fundamental Research Funds for the Central Universities, South China University of Technology (Grant No. 2014ZZ0069), the National Natural Science Foundation of China (Grant No. 51502189), and the Doctoral Project of Taiyuan University of Science and Technology, China (Grant No. 20132010).

  15. Raman Study of SWNT Under High Pressure

    NASA Astrophysics Data System (ADS)

    Venkateswaran, U.; Rao, A. M.; Richter, E.; Eklund, P. C.; Smalley, R. E.

    1998-03-01

    A gasketed Merrill-Bassett-type diamond anvil cell was used for high pressure Raman measurements at room temperature. A 4:1 methanol-ethanol mixture served as the pressure transmitting medium. The radial mode (denoted as R, occuring at 186 cm-1 at 1 bar) and tangential modes (designated T_1, T_2, and T_3, located, respectively, at 1550, 1567, and 1593 cm-1 at 1 bar) were recorded for several representative pressures. With increasing pressure, both the R and T modes shift to higher frequencies with gradual weakening of intensity and broadening of linewidth. The radial mode disappears around ~ 2 GPa whereas the tangential modes, albeit weak in intensity, persist until 5.2 GPa. The decrease in Raman intensity under pressure can be attributed to a loss of resonance, since the strong Raman signals observed at ambient pressure have been interpreted as due a resonance with the electronic bands [1]. The R and T mode frequencies are fit to quadratic function of pressure i.e., ω=ω(0)+aP+bP^2 where `a' represents the linear pressure shift of the mode frequency which is proportional to the mode Gruneisen parameter. The linear pressure coefficient for the R mode is found to be nearly twice that of the high frequency T mode. A. M. Rao et al., Science 275, 187, 1997

  16. Amorphous boron nitride at high pressure

    NASA Astrophysics Data System (ADS)

    Durandurdu, Murat

    2016-06-01

    The pressure-induced phase transformation in hexagonal boron nitrite and amorphous boron nitrite is studied using ab initio molecular dynamics simulations. The hexagonal-to-wurtzite phase transformation is successfully reproduced in the simulation with a transformation mechanism similar to one suggested in experiment. Amorphous boron nitrite, on the other hand, gradually transforms to a high-density amorphous phase with the application of pressure. This phase transformation is irreversible because a densified amorphous state having both sp3 and sp2 bonds is recovered upon pressure release. The high-density amorphous state mainly consists of sp3 bonds and its local structure is quite similar to recently proposed intermediate boron nitrite phases, in particular tetragonal structure (P42/mnm), rather than the known the wurtzite or cubic boron nitrite due to the existence of four membered rings and edge sharing connectivity. On the basis of this finding we propose that amorphous boron nitrite might be best candidate as a starting structure to synthesize the intermediate phase(s) at high pressure and temperature (probably below 800 °C) conditions.

  17. Stable xenon nitride at high pressures

    NASA Astrophysics Data System (ADS)

    Peng, Feng; Wang, Yanchao; Wang, Hui; Zhang, Yunwei; Ma, Yanming

    2015-09-01

    Nitrides in many ways are fascinating since they often appear as superconductors, high-energy density, and hard materials. Though there exist a large variety of nitrides, noble gas nitrides are missing in nature. Pursuit of noble gas nitrides has therefore become the subject of topical interests, but remains as a great challenge since molecular nitrogen (N2, a major form of nitrogen) and noble gases are both inert systems and do not interact at normal conditions. We show through a first-principles swarm-structure search that high pressure enables a direct interaction of N2 and xenon (Xe) above 146 GPa. The resultant Xe nitride has a peculiar stoichiometry of XeN6, possessing a high-energy density of approximately 2.4 kJg -1, rivaling that of the modern explosives. Structurally, XeN6 is intriguing with the appearance of chaired N6 hexagons and unusually high 12-coordination of Xe bonded with N. Our work opens up the possibility of achieving Xe nitride with superior high-energy density whose formation is long sought as impossible.

  18. Diffusion creep of enstatite at high pressures

    NASA Astrophysics Data System (ADS)

    Zhang, G.; Mei, S.; Kohlstedt, D. L.

    2014-12-01

    Deformation behavior of fine-grained enstatite (g.s. ~ 8 μm) was investigated with triaxial compressive creep experiments at high pressures (4.2 - 6.9 GPa) and high temperatures (1373 - 1573 K) using a deformation-DIA apparatus. Experiments were carried out under anhydrous conditions. In each experiment, a sample column composed of a sample and alumina pistons was assembled with a boron nitride sleeve and graphite resistance heater into a 6.2-mm edge length cubic pressure medium. Experiments were carried out at the National Synchrotron Light Source at Brookhaven National Laboratory. In a run, differential stress and sample displacement were monitored in-situ using synchrotron x-ray diffraction and radiography, respectively. Based on results from this study, the deformation behavior of enstatite under anhydrous conditions has been quantitatively presented in the form of a flow law that describes the dependence of deformation rate on stress, temperature, and pressure. Specifically, data fitting yields the dependence of creep rate on stress with an exponent of n ≈ 1; indicating samples were deformed in the regime of diffusion creep. Experimental results also yield the dependences of creep rate on temperature and pressure with an activation energy of ~250 kJ/mol and activation volume of ~3.5×10-6 m3/mol, respectively. The flow laws for enstatite, one important constituent component for the upper mantle, quantified from this study provides a necessary constraint for modeling the dynamic activities occurring within Earth's interior.

  19. High-pressure transformations in xenon hydrates

    PubMed Central

    Sanloup, Chrystèle; Mao, Ho-kwang; Hemley, Russell J.

    2002-01-01

    A high-pressure investigation of the Xe⋅H2O chemical system was conducted by using diamond-anvil cell techniques combined with in situ Raman spectroscopy, synchrotron x-ray diffraction, and laser heating. Structure I xenon clathrate was observed to be stable up to 1.8 GPa, at which pressure it transforms to a new Xe clathrate phase stable up to 2.5 GPa before breaking down to ice VII plus solid xenon. The bulk modulus and structure of both phases were determined: 9 ± 1 GPa for Xe clathrate A with structure I (cubic, a = 11.595 ± 0.003 Å, V = 1,558.9 ± 1.2 Å3 at 1.1 GPa) and 45 ± 5 GPa for Xe clathrate B (tetragonal, a = 8.320 ± 0.004 Å, c = 10.287 ± 0.007 Å, V = 712.1 ± 1.2 Å3 at 2.2 GPa). The extended pressure stability field of Xe clathrate structure I (A) and the discovery of a second Xe clathrate (B) above 1.8 GPa have implications for xenon in terrestrial and planetary interiors. PMID:11756690

  20. Stable magnesium peroxide at high pressure

    PubMed Central

    Lobanov, Sergey S.; Zhu, Qiang; Holtgrewe, Nicholas; Prescher, Clemens; Prakapenka, Vitali B.; Oganov, Artem R.; Goncharov, Alexander F.

    2015-01-01

    Rocky planets are thought to comprise compounds of Mg and O as these are among the most abundant elements, but knowledge of their stable phases may be incomplete. MgO is known to be remarkably stable to very high pressure and chemically inert under reduced condition of the Earth’s lower mantle. However, in exoplanets oxygen may be a more abundant constituent. Here, using synchrotron x-ray diffraction in laser-heated diamond anvil cells, we show that MgO and oxygen react at pressures above 96 GPa and T = 2150 K with the formation of I4/mcm MgO2. Raman spectroscopy detects the presence of a peroxide ion (O22−) in the synthesized material as well as in the recovered specimen. Likewise, energy-dispersive x-ray spectroscopy confirms that the recovered sample has higher oxygen content than pure MgO. Our finding suggests that MgO2 may be present together or instead of MgO in rocky mantles and rocky planetary cores under highly oxidized conditions. PMID:26323635

  1. Structures of xenon oxides at high pressures

    NASA Astrophysics Data System (ADS)

    Worth, Nicholas; Pickard, Chris; Needs, Richard; Dewaele, Agnes; Loubeyre, Paul; Mezouar, Mohamed

    2014-03-01

    For many years, it was believed that noble gases such as xenon were entirely inert. It was only in 1962 that Bartlett first synthesized a compound of xenon. Since then, a number of other xenon compounds, including oxides, have been synthesized. Xenon oxides are unstable under ambient conditions but have been predicted to stabilize under high pressure. Here we present the results of a combined theoretical and experimental study of xenon oxides at pressures of 80-100 GPa. We have synthesized new xenon oxides at these pressures and they have been characterized with X-ray diffraction and Raman spectroscopy. Calculations were performed with a density-functional theory framework. We have used the ab-initio random structure searching (AIRSS) method together with a data-mining technique to determine the stable compounds in the xenon-oxygen system in this pressure range. We have calculated structural and optical properties of these phases, and a good match between theoretical and experimental results has been obtained. Funding for computational research provided by the engineering and physical sciences research council (EPSRC; UK). Computing resources provided by Cambridge HPC and HECToR. X-ray diffraction experiments performed at ESRF.

  2. Biomolecular interactions and tools for their recognition: focus on the quartz crystal microbalance and its diverse surface chemistries and applications.

    PubMed

    Cheng, Cathy I; Chang, Yi-Pin; Chu, Yen-Ho

    2012-03-01

    Interactions between molecules are ubiquitous and occur in our bodies, the food we eat, the air we breathe, and myriad additional contexts. Although numerous tools are available for the recognition of biomolecular interactions, such tools are often limited in their sensitivity, expensive, and difficult to modify for various uses. In contrast, the quartz crystal microbalance (QCM) has sub-nanogram detection capabilities, is label-free, is inexpensive to create, and can be readily modified with a number of diverse surface chemistries to detect and characterize diverse interactions. To maximize the versatility of the QCM, scientists need to know available methods by which QCM surfaces can be modified. Therefore, in addition to summarizing the various tools currently used for biomolecular recognition, explicating the fundamental principles of the QCM as a tool for biomolecular recognition, and comparing the QCM with other acoustic sensors, we systematically review the numerous types of surface chemistries-including hydrophobic bonds, ionic bonds, hydrogen bonds, self-assembled monolayers, plasma-polymerized films, photochemistry, and sensing ionic liquids-used to functionalize QCMs for various purposes. We also review the QCM's diverse applications, which include the detection of gaseous species, detection of carbohydrates, detection of nucleic acids, detection of non-enzymatic proteins, characterization of enzymatic activity, detection of antigens and antibodies, detection of cells, and detection of drugs. Finally, we discuss the ultimate goals of and potential barriers to the development of future QCMs. PMID:22158962

  3. A New Scanning Tunneling Microscope Reactor Used for High Pressure and High Temperature Catalysis Studies

    SciTech Connect

    Tao, Feng; Tang, David C.; Salmeron, Miquel; Somorjai, Gabor A.

    2008-05-12

    We present the design and performance of a home-built high-pressure and high-temperature reactor equipped with a high-resolution scanning tunneling microscope (STM) for catalytic studies. In this design, the STM body, sample, and tip are placed in a small high pressure reactor ({approx}19 cm{sup 3}) located within an ultrahigh vacuum (UHV) chamber. A sealable port on the wall of the reactor separates the high pressure environment in the reactor from the vacuum environment of the STM chamber and permits sample transfer and tip change in UHV. A combination of a sample transfer arm, wobble stick, and sample load-lock system allows fast transfer of samples and tips between the preparation chamber, high pressure reactor, and ambient environment. This STM reactor can work as a batch or flowing reactor at a pressure range of 10{sup -13} to several bars and a temperature range of 300-700 K. Experiments performed on two samples both in vacuum and in high pressure conditions demonstrate the capability of in situ investigations of heterogeneous catalysis and surface chemistry at atomic resolution at a wide pressure range from UHV to a pressure higher than 1 atm.

  4. High-pressure synthesis of new materials via formation of new bonding patterns and unusual stoichiometries

    NASA Astrophysics Data System (ADS)

    Goncharov, Alexander

    2013-06-01

    The search for new materials synthesized under extreme conditions of high pressure and high pressure is currently actively pursued. There are multiple theoretical predictions for superior material properties, such as ultra-hardness, superior transport properties such as electrical and thermal conductivity, high energy-density, high-temperature superconductivity, ability to storage hydrogen, etc. Synthesis of new materials at high pressures is based on changes in the equilibrium chemical bonding. Moreover, materials with ``unusual'' stoichiometries have been predicted to become thermodynamically stable at high pressures. Implications of this novel extreme chemistry for synthesis of new materials for practical applications remain challenging because high-pressure bonding patterns are often thermodynamically unstable at ambient pressure. Search for a recovery mechanisms or attempts of synthesis in nominally metastable conditions require detailed knowledge of the energy landscape; extensive collaborative efforts of experiment and theory are needed for its determination. Here, I emphasize the importance for this task of in situ fast diagnostic methods. I will present new results on synthesis of materials with new bonding patterns and unusual stoichiometries containing hydrogen, nitrogen, carbon, and halogens. This work has been performed in collaboration with M. Somayazulu, V. V. Struzhkin, V. Prakapenka, E. Stavrou, T. Muramatsu,A. Oganov, W. Zhang, Q. Zhu, S. E. Boulfelfel, A. O. Lyakhov, Z. Konopkova, H.-P. Liermann, D.-Y. Kim. I acknowledge the support of NSF, EFRee (DOE), DARPA, Army Research Office, Deep Carbon Observatory.

  5. The Incorporation of Single Crystal X-Ray Diffraction into the Undergraduate Chemistry Curriculum Using Internet-Facilitated Remote Diffractometer Control

    ERIC Educational Resources Information Center

    Szalay, P. S.; Hunter, A. D.; Zeller, M.

    2005-01-01

    The benefits of integrating single crystal X-ray diffraction into the curricula of the disciplines of science such as chemistry, biology, biochemistry physics, and many more are addressed. The results showed that students were able to complete all report requirements with the aid of handouts and instructor inputs, and remote control of the…

  6. High-Pressure Optical Studies of Doped Yttrium Aluminum Garnet

    NASA Astrophysics Data System (ADS)

    Wamsley, Paula

    This thesis demonstrates the application of high pressure spectroscopy to the study of doped insulator laser materials. We investigated transition metal ion and rare -earth ion doped yttrium aluminum garnet (YAG) crystals. Our goal was to explore the relationship between the local bonding environment of the dopant ion and the bulk optical properties of the crystals. Pressure is a useful probe for this type of investigation because pressure changes the local bonding environment of the dopant ion. We conducted laser induced fluorescence experiments and time-resolved laser induced fluorescence experiments on samples in modified Merrill-Basset style diamond anvil cells. We measured the effect of pressure on the laser induced emission of Cr^{3+} and Tm^{3+} in Cr ^{3+}:YAG and Tm^ {3+}:YAG. These experiments provided information about the energy level structure of Cr ^{3+} and Tm^{3+ } as a function of the crystal field strength. In Cr^{3+}:YAG we were able to correlate changes in the emission spectrum to pressure induced changes in the local site-symmetry of the Cr ^{3+} ions. In Tm^ {3+}:YAG we determined that several emission features were incorrectly assigned and observed previously unreported Tm^{3+} emission features. We also measured the time-resolved laser induced emission of Cr^{3+} in Cr^{3+}:YAG and Cr ^{3+}:Tm^{3+ }:YAG. With these measurements we were able to determine the effect of thermal and spin-orbit coupling on the fluorescence properties of Cr^{3+ }. In addition we determined that the fluorescence properties of Cr^{3+} strongly influence the rate of energy transfer and the efficiency of energy transfer from Cr^{3+ } to Tm^{3+} in Cr^{3+}:Tm ^{3+}:YAG.

  7. Molecular docking study of conformational polymorph: building block of crystal chemistry.

    PubMed

    Dubey, Rashmi; Tewari, Ashish Kumar; Singh, Ved Prakash; Singh, Praveen; Dangi, Jawahar Singh; Puerta, Carmen; Valerga, Pedro; Kant, Rajni

    2013-01-01

    Two conformational polymorphs of novel 2-[2-(3-cyano-4,6-dimethyl-2-oxo-2H-pyridin-1-yl)-ethoxy]-4,6-dimethyl nicotinonitrile have been developed. The crystal structure of both polymorphs (1a and 1b) seems to be stabilized by weak interactions. A difference was observed in the packing of both polymorphs. Polymorph 1b has a better binding affinity with the cyclooxygenase (COX-2) receptor than the standard (Nimesulide). PMID:24250264

  8. Crystal Chemistry of Cement-Clinker Minerals and Melt Differentiation Reaction of Interstitial Melt

    NASA Astrophysics Data System (ADS)

    Fukuda, Koichiro

    Microtextures of belite induced by polymorphic phase transitions and a remelting reaction have been reviewed, together with the melt differentiation reaction of interstitial melt. In the α-to-α'H phase transition, the α'H-phase nucleates as lamellae within the parent α-phase so as to realize a good lattice matching across the interface. The remelting reaction, in which the α-phase belite decomposes into a liquid and the α'H-phase during cooling, is necessarily preceded by the α-to-α'H phase transition. The lamella boundaries provide heterogeneous nucleation sites for the exsolving liquid. A variety of microtextures results depending on the surface tension between belite lamellae and exsolved liquid as well as on the cooling rate. As the simultaneous crystallization of zoned ferrite and belite proceeds during the cooling process of clinkers, the coexisting melt progressively increases the Al2O3/Fe2O3 ratio. After the termination of the ferrite crystallization, the aluminete and belite crystallize out of the differentiated melt.

  9. Toxicity of TiO2 nanoparticles to Escherichia coli: effects of particle size, crystal phase and water chemistry.

    PubMed

    Lin, Xiuchun; Li, Jingyi; Ma, Si; Liu, Gesheng; Yang, Kun; Tong, Meiping; Lin, Daohui

    2014-01-01

    Controversial and inconsistent results on the eco-toxicity of TiO2 nanoparticles (NPs) are commonly found in recorded studies and more experimental works are therefore warranted to elucidate the nanotoxicity and its underlying precise mechanisms. Toxicities of five types of TiO2 NPs with different particle sizes (10∼50 nm) and crystal phases were investigated using Escherichia coli as a test organism. The effect of water chemistry on the nanotoxicity was also examined. The antibacterial effects of TiO2 NPs as revealed by dose-effect experiments decreased with increasing particle size and rutile content of the TiO2 NPs. More bacteria could survive at higher solution pH (5.0-10.0) and ionic strength (50-200 mg L(-1) NaCl) as affected by the anatase TiO2 NPs. The TiO2 NPs with anatase crystal structure and smaller particle size produced higher content of intracellular reactive oxygen species and malondialdehyde, in line with their greater antibacterial effect. Transmission electron microscopic observations showed the concentration buildup of the anatase TiO2 NPs especially those with smaller particle sizes on the cell surfaces, leading to membrane damage and internalization. These research results will shed new light on the understanding of ecological effects of TiO2 NPs. PMID:25310452

  10. Toxicity of TiO2 Nanoparticles to Escherichia coli: Effects of Particle Size, Crystal Phase and Water Chemistry

    PubMed Central

    Lin, Xiuchun; Li, Jingyi; Ma, Si; Liu, Gesheng; Yang, Kun; Tong, Meiping; Lin, Daohui

    2014-01-01

    Controversial and inconsistent results on the eco-toxicity of TiO2 nanoparticles (NPs) are commonly found in recorded studies and more experimental works are therefore warranted to elucidate the nanotoxicity and its underlying precise mechanisms. Toxicities of five types of TiO2 NPs with different particle sizes (10∼50 nm) and crystal phases were investigated using Escherichia coli as a test organism. The effect of water chemistry on the nanotoxicity was also examined. The antibacterial effects of TiO2 NPs as revealed by dose-effect experiments decreased with increasing particle size and rutile content of the TiO2 NPs. More bacteria could survive at higher solution pH (5.0–10.0) and ionic strength (50–200 mg L−1 NaCl) as affected by the anatase TiO2 NPs. The TiO2 NPs with anatase crystal structure and smaller particle size produced higher content of intracellular reactive oxygen species and malondialdehyde, in line with their greater antibacterial effect. Transmission electron microscopic observations showed the concentration buildup of the anatase TiO2 NPs especially those with smaller particle sizes on the cell surfaces, leading to membrane damage and internalization. These research results will shed new light on the understanding of ecological effects of TiO2 NPs. PMID:25310452

  11. Better Actuation Through Chemistry: Using Surface Coatings to Create Uniform Director Fields in Nematic Liquid Crystal Elastomers.

    PubMed

    Xia, Yu; Lee, Elaine; Hu, Hao; Gharbi, Mohamed Amine; Beller, Daniel A; Fleischmann, Eva-Kristina; Kamien, Randall D; Zentel, Rudolf; Yang, Shu

    2016-05-18

    Controlling the molecular alignment of liquid crystal monomers (LCMs) within nano- and microstructures is essential in manipulating the actuation behavior of nematic liquid crystal elastomers (NLCEs). Here, we study how to induce uniformly vertical alignment of nematic LCMs within a micropillar array to maximize the macroscopic shape change using surface chemistry. Landau-de Gennes numerical modeling suggests that it is difficult to perfectly align LCMs vertically in every pore within a poly(dimethylsiloxane) (PDMS) mold with porous channels during soft lithography. In an untreated PDMS mold that provides homeotropic anchoring of LCMs, a radially escaped configuration of LCMs is observed. Vertically aligned LCMs, a preferred configuration for actuation, are only observed when using a PDMS mold with planar anchoring. Guided by the numerical modeling, we coat the PDMS mold with a thin layer of poly(2-hydroxyethyl methacrylate) (PHEMA), leading to planar anchoring of LCM. Confirmed by polarized optical microscopy, we observe monodomains of vertically aligned LCMs within the mold, in agreement with modeling. After curing and peeling off the mold, the resulting NLCE micropillars showed a relatively large and reversible radial strain (∼30%) when heated above the nematic to isotropic transition temperature. PMID:27152975

  12. Distortions and Stabilization of Simple Cubic Calcium at High Pressure and Low Temperature

    SciTech Connect

    Veith, Alison A.

    2012-04-18

    Ca-III, the first superconducting calcium phase under pressure, was identified as simple-cubic (sc) by previous X-ray diffraction (XRD) experiments. In contrast, all previous theoretical calculations showed that sc had a higher enthalpy than many proposed structures and had an imaginary (unstable) phonon branch. By using our newly developed submicrometer high-pressure single-crystal XRD, cryogenic high-pressure XRD, and theoretical calculations, we demonstrate that Ca-III is neither exactly sc nor any of the lower-enthalpy phases, but sustains the sc-like, primitive unit by a rhombohedral distortion at 300 K and a monoclinic distortion below 30 K. This surprising discovery reveals a scenario that the high-pressure structure of calcium does not go to the zero-temperature global enthalpy minimum but is dictated by high-temperature anharmonicity and low-temperature metastability fine-tuned with phonon stability at the local minimum.

  13. Distortions and stabilization of simple-cubic calcium at high pressure and low temperature

    SciTech Connect

    Mao, Wendy L.; Wang, Lin; Ding, Yang; Yang, Wenge; Liu, Wenjun; Kim, Duck Young; Luo, Wei; Ahuja, R.; Meng, Yue; Sinogeikin, Stanislav V.; Shu, Jinfu; Mao, Ho-kwang

    2010-06-01

    Ca-III, the first superconducting calcium phase under pressure, was identified as simple-cubic (sc) by previous X-ray diffraction (XRD) experiments. In contrast, all previous theoretical calculations showed that sc had a higher enthalpy than many proposed structures and had an imaginary (unstable) phonon branch. By using our newly developed submicrometer high-pressure single-crystal XRD, cryogenic high-pressure XRD, and theoretical calculations, we demonstrate that Ca-III is neither exactly sc nor any of the lower-enthalpy phases, but sustains the sc-like, primitive unit by a rhombohedral distortion at 300 K and a monoclinic distortion below 30 K. This surprising discovery reveals a scenario that the high-pressure structure of calcium does not go to the zero-temperature global enthalpy minimum but is dictated by high-temperature anharmonicity and low-temperature metastability fine-tuned with phonon stability at the local minimum.

  14. First principle investigation of iron pentacarbonyl energetic solid at high pressure

    NASA Astrophysics Data System (ADS)

    Nguyen Cong, Kien; Steele, Brad; Landerville, Aaron; Oleynik, Ivan

    2015-06-01

    Polymeric phase of carbon mono-oxide (p-CO), an extended non-molecular solid, is extremely energetic, and therefore represents a new class of low-Z energetic materials. Recently, iron penta-carbonyl Fe(CO)5 has been experimentally investigated as a p-CO precursor: the presence of transition metal ions is believed to stabilize p-CO at ambient conditions. Since p-CO forms at high pressures, it becomes important to investigate the high-pressure behavior of Fe(CO)5 as well. In this work, first-principles evolutionary structure search method is used to predict the crystal phases of Fe(CO)5 at high pressure. Known experimental structure of phase I is confirmed. Moreover, previously unknown structure of phase II is predicted. The Raman spectra, calculated as a function of pressure, were used to demonstrate that the phase III, predicted by a recent experiment, is identical to phase II.

  15. Pressure Dome for High-Pressure Electrolyzer

    NASA Technical Reports Server (NTRS)

    Norman, Timothy; Schmitt, Edwin

    2012-01-01

    A high-strength, low-weight pressure vessel dome was designed specifically to house a high-pressure [2,000 psi (approx. = 13.8 MPa)] electrolyzer. In operation, the dome is filled with an inert gas pressurized to roughly 100 psi (approx. = 690 kPa) above the high, balanced pressure product oxygen and hydrogen gas streams. The inert gas acts to reduce the clamping load on electrolyzer stack tie bolts since the dome pressure acting axially inward helps offset the outward axial forces from the stack gas pressure. Likewise, radial and circumferential stresses on electrolyzer frames are minimized. Because the dome is operated at a higher pressure than the electrolyzer product gas, any external electrolyzer leak prevents oxygen or hydrogen from leaking into the dome. Instead the affected stack gas stream pressure rises detectably, thereby enabling a system shutdown. All electrical and fluid connections to the stack are made inside the pressure dome and require special plumbing and electrical dome interfaces for this to be accomplished. Further benefits of the dome are that it can act as a containment shield in the unlikely event of a catastrophic failure. Studies indicate that, for a given active area (and hence, cell ID), frame outside diameter must become ever larger to support stresses at higher operating pressures. This can lead to a large footprint and increased costs associated with thicker and/or larger diameter end-plates, tie-rods, and the frames themselves. One solution is to employ rings that fit snugly around the frame. This complicates stack assembly and is sometimes difficult to achieve in practice, as its success is strongly dependent on frame and ring tolerances, gas pressure, and operating temperature. A pressure dome permits an otherwise low-pressure stack to operate at higher pressures without growing the electrolyzer hardware. The pressure dome consists of two machined segments. An O-ring is placed in an O-ring groove in the flange of the bottom

  16. Useful microscopic concepts for high pressure phenomena

    NASA Astrophysics Data System (ADS)

    Recio, J.; Menéndez, J.; Álvarez-Uría, Ruth; Marqués, Miriam; Ouahrani, Tarik; Baonza, Valentín

    2013-06-01

    A better understanding of the macroscopic behavior of crystalline solids under pressure can be achieved introducing microscopic concepts as the local compressibility (κi = -1/V∂V/∂p ) and the local pressure (pi = -∂E/∂Vi ). Both are derived from topological analysis of crystalline electron densities. This formalism allows for a partition of the unit cell volume (V) into disjoint atomic-like regions such that V = ∑iVi , i runs over all different atomic constituents. Using this topological partition, the compressibility of the crystal is recovered: κ = ∑iVi/Vκi . Although local pressures are not additive, their reciprocals are: 1/p = ∑i1/pi , where p is the thermodynamic pressure. This fact leads to the interpretation of the atomic constituents of crystals as parallel mechanical resistors when pressure is applied. Consequently, atomic-like mechanical resistances and mechanical conductances can be defined. After extensive first principles calculations, computed results of these local properties reveal systematic trends for crystal families under pressure, as we illustrate for II-VI binary semiconductors and oxide spinels. Funded by Spanish MINECO and MICINN through CSD2007-00045 and CTQ2012-38599 projects.

  17. Cobalt ferrite nanoparticles under high pressure

    SciTech Connect

    Saccone, F. D.; Ferrari, S.; Grinblat, F.; Bilovol, V.; Errandonea, D.

    2015-08-21

    We report by the first time a high pressure X-ray diffraction and Raman spectroscopy study of cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles carried out at room temperature up to 17 GPa. In contrast with previous studies of nanoparticles, which proposed the transition pressure to be reduced from 20–27 GPa to 7.5–12.5 GPa (depending on particle size), we found that cobalt ferrite nanoparticles remain in the spinel structure up to the highest pressure covered by our experiments. In addition, we report the pressure dependence of the unit-cell parameter and Raman modes of the studied sample. We found that under quasi-hydrostatic conditions, the bulk modulus of the nanoparticles (B{sub 0} = 204 GPa) is considerably larger than the value previously reported for bulk CoFe{sub 2}O{sub 4} (B{sub 0} = 172 GPa). In addition, when the pressure medium becomes non-hydrostatic and deviatoric stresses affect the experiments, there is a noticeable decrease of the compressibility of the studied sample (B{sub 0} = 284 GPa). After decompression, the cobalt ferrite lattice parameter does not revert to its initial value, evidencing a unit cell contraction after pressure was removed. Finally, Raman spectroscopy provides information on the pressure dependence of all Raman-active modes and evidences that cation inversion is enhanced by pressure under non-hydrostatic conditions, being this effect not fully reversible.

  18. High-pressure inactivation of dried microorganisms.

    PubMed

    Espinasse, V; Perrier-Cornet, J-M; Marecat, A; Gervais, P

    2008-01-01

    Dried microorganisms are particularly resistant to high hydrostatic pressure effects. In this study, the survival of Saccharomyces cerevisiae was studied under pressure applied in different ways. Original processes and devices were purposely developed in our laboratory for long-term pressurization. Dried and wet yeast powders were submitted to high-pressure treatments (100-150 MPa for 24-144 h at 25 degrees C) through liquid media or inert gas. These powders were also pressurized after being vacuum-packed. In the case of wet yeasts, the pressurization procedure had little influence on the inactivation rate. In this case, inactivations were mainly due to hydrostatic pressure effects. Conversely, in the case of dried yeasts, inactivation was highly dependent on the treatment scheme. No mortality was observed when dried cells were pressurized in a non-aqueous liquid medium, but when nitrogen gas was used as the pressure-transmitting fluid, the inactivation rate was found to be between 1.5 and 2 log for the same pressure level and holding time. Several hypotheses were formulated to explain this phenomenon: the thermal effects induced by the pressure variations, the drying resulting from the gas pressure release and the sorption and desorption of the gas in cells. The highest inactivation rates were obtained with vacuum-packed dried yeasts. In this case, cell death occurred during the pressurization step and was induced by shear forces. Our results show that the mechanisms at the origin of cell death under pressure are strongly dependent on the nature of the pressure-transmitting medium and the hydration of microorganisms. PMID:17573691

  19. Origins of life and biochemistry under high-pressure conditions.

    PubMed

    Daniel, Isabelle; Oger, Philippe; Winter, Roland

    2006-10-01

    Life on Earth can be traced back to as far as 3.8 billion years (Ga) ago. The catastrophic meteoritic bombardment ended between 4.2 and 3.9 Ga ago. Therefore, if life emerged, and we know it did, it must have emerged from nothingness in less than 400 million years. The most recent scenarios of Earth accretion predict some very unstable physico-chemical conditions at the surface of Earth, which, in such a short time period, would impede the emergence of life from a proto-biotic soup. A possible alternative would be that life originated in the depth of the proto-ocean of the Hadean Earth, under high hydrostatic pressure. The large body of water would filter harmful radiation and buffer physico-chemical variations, and therefore would provide a more stable radiation-free environment for pre-biotic chemistry. After a short introduction to Earth history, the current tutorial review presents biological and physico-chemical arguments in support of high-pressure origin for life on Earth. PMID:17003893

  20. The Future of High-Pressure Mineral Physics

    NASA Astrophysics Data System (ADS)

    Liebermann, Robert C.

    2005-10-01

    Research in mineral physics is essential in interpreting observational data from many other disciplines in the Earth sciences, including geodynamics, seismology, geochemistry, petrology, geomagnetism, and planetary science, as well as materials science and climate studies, as illustrated in Figure 1. The field of high-pressure mineral physics is highly interdisciplinary and fundamentally multidisciplinary. Mineral physicists do not always study minerals or use only physics; they study the science of materials that compose the Earth and other planets, and employ concepts and techniques from chemistry, physics, materials science, and biology. A dramatic example of this interdisciplinarity in action occurred during the past year. The experimental discovery and theoretical confirmation in 2004 of a new phase of magnesium metasilicate (MgSiO3) stable only at pressures above 100 Gigapascals (and termed the postperovskite phase) has had an immediate and profound impact on multidisciplinary studies of the deep mantle of the Earth (see article by Lay et al. in the 4 January 2005 issue of Eos).