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Sample records for accompanying high-pressure phase

  1. Strength coupling in mixed phases under high pressure

    NASA Astrophysics Data System (ADS)

    Yan, Xiaozhi; Dong, Haini; Sun, Guangai; Ren, Xiangting; He, Duanwei; Yang, Wenge

    2016-10-01

    The strength of a material can be altered by temperature, pressure, grain size, and orientation distributions. At the microscale, neighboring grains often play important roles in the elastic and plastic deformation process. By applying high pressure to a mixture of germanium and gold powder in the vicinity of the germanium phase transition pressure, we found that the deformation behavior of gold largely correlates with that of the surrounding germanium. The deviatoric strain and compressibility of Au behaves anomalously when Ge undergoes a diamond to β-tin structure transition, accompanying a large volume and strength drop. The results demonstrate that the intrinsic strength of a mixed phase could be largely controlled by the other surrounding phase, which is fundamentally important in understanding the deformation mechanism of multiphase materials, especially when one phase undergoes dramatic changes in strength under high pressure conditions.

  2. High-pressure phase transition in ZnSe

    NASA Astrophysics Data System (ADS)

    Köfferlein, M.; Karzel, H.; Potzel, W.; Schiessl, W.; Steiner, M.; Kalvius, G. M.; Mitchell, D. W.; Das, T. P.

    1994-12-01

    A high-pressure Mössbauer spectrometer for the 93.3-keV resonance in67Zn and an X-ray diffractometer of the Guinier type are used to investigate67ZnSe powder at high external pressures. At ˜ 13 GPa, a phase transition from the zinc blende to the fcc (NaCl) structure is observed. The transition is accompanied by a 15.2% decrease of the volume of the unit cell. The Lamb-Mössbauer factor (LMF) increases from f=0.53% at ambient pressure to f=1.07% at 6.1 GPa. It then decreases to f=0.91% as the pressure is further increased to 8.2 GPa. This behavior is investigated by lattice-dynamical calculations using an 11-parameter rigid-ion model. The decrease of the LMF at high pressures is caused by the softening of the TA phonon modes, which occurs already far below the phase transition. The s-electron density ρ(0) at the67Zn nucleus increases with reduced volume. The change of ρ(0) as well as theoretical Hartree-Fock cluster calculations show that covalency of bonding 4s/4p states of Zn and Se plays an essential role and determines the isomer shift.

  3. 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.

  4. 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.

  5. Experimental methods for phase equilibria at high pressures.

    PubMed

    Dohrn, Ralf; Fonseca, José M S; Peper, Stephanie

    2012-01-01

    Knowledge of high-pressure phase equilibria is crucial in many fields, e.g., for the design and optimization of high-pressure chemical and separation processes, carbon capture and storage, hydrate formation, applications of ionic liquids, and geological processes. This review presents the variety of methods to measure phase equilibria at high pressures and, following a classification, discusses the measurement principles, advantages, challenges, and error sources. Examples of application areas are given. A detailed knowledge and understanding of the different methods is fundamental not only for choosing the most suitable method for a certain task but also for the evaluation of experimental data. The discrepancy between the (sometimes low) true accuracy of published experimental data and the (high) accuracy claimed by authors is addressed. Some essential requirements for the generation of valuable experimental results are summarized.

  6. 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.

  7. 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.

  8. Phase transition of La- chalcogenides under high pressure

    SciTech Connect

    Gupta, Dinesh Chandra; Raypuria, Gajendra Singh

    2014-04-24

    The lanthanum compounds have been found to undergo transition from their initial NaCl-type structure to high pressure body centered tetragonal (BCT) structure (distorted CsCl-type P4/mmm) using CTIP model. The calculated values of cohesive energy, lattice constant, phase transition pressure, relative volume collapse agree well with the available measured data and better than those computed by earlier workers.

  9. High pressure phase transition in Pr-monopnictides

    SciTech Connect

    Raypuria, Gajendra Singh E-mail: gsraypuria@gmail.com; Gupta, Dinesh Chandra

    2015-06-24

    The Praseodymium-monopnictides compounds have been found to undergo transition from their initial NaCl-type structure to high pressure body centered tetragonal (BCT) structure (distorted CsCl-type P4/mmm) using CTIP model. The calculated values of cohesive energy, lattice constant, phase transition pressure, relative volume collapse agree well with the available measured data and better than those computed by earlier workers.

  10. High pressure structural phase transitions of PbPo

    NASA Astrophysics Data System (ADS)

    Bencherif, Y.; Boukra, A.; Zaoui, A.; Ferhat, M.

    2012-09-01

    First-principles calculations have been performed to investigate the high pressure phase transitions and dynamical properties of the less known lead polonium compound. The calculated ground state parameters for the NaCl phase show good agreement with the experimental data. The obtained results show that the intermediate phase transition for this compound is the orthorhombic Pnma phase. The PbPo undergoes from the rocksalt to Pnma phase at 4.20 GPa. Further structural phase transition from intermediate to CsCl phase has been found at 8.5 GPa. In addition, phonon dispersion spectra were derived from linear-response to density functional theory. In particular, we show that the dynamical properties of PbPo exhibit some peculiar features compared to other III-V compounds. Finally, thermodynamics properties have been also addressed from quasiharmonic approximation.

  11. 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

  12. High pressure ferroelastic phase transition in SrTiO₃.

    PubMed

    Salje, E K H; Guennou, M; Bouvier, P; Carpenter, M A; Kreisel, J

    2011-07-13

    High pressure measurements of the ferroelastic phase transition of SrTiO₃ (Guennou et al 2010 Phys. Rev. B 81 054115) showed a linear pressure dependence of the transition temperature between the cubic and tetragonal phase. Furthermore, the pressure induced transition becomes second order while the temperature dependent transition is near a tricritical point. The phase transition mechanism is characterized by the elongation and tilt of the TiO₆ octahedra in the tetragonal phase, which leads to strongly nonlinear couplings between the structural order parameter, the volume strain and the applied pressure. The phase diagram is derived from the Clausius-Clapeyron relationship and is directly related to a pressure dependent Landau potential. The nonlinearities of the pressure dependent strains lead to an increase of the fourth order Landau coefficient with increasing pressure and, hence, to a tricritical-second order crossover. This behaviour is reminiscent of the doping related crossover in isostructural KMnF₃.

  13. Phase separation of lanthanum hydride under high pressure

    NASA Astrophysics Data System (ADS)

    Machida, A.; Watanuki, T.; Kawana, D.; Aoki, K.

    2011-02-01

    Structural change of lanthanum dihydride LaH2.3, which has a face-centered-cubic (fcc) metal lattice with tetrahedral interstitial sites fully occupied with hydrogen atoms and partially occupied octahedral sites, has been investigated at high pressures up to 20 GPa at ambient temperature by synchrotron radiation x-ray diffraction. Additional Bragg reflections appear just on higher angle sides of the original ones at ~11 GPa and their peak intensities increase gradually on further compression. The coexistence state of two fcc metal lattices thus observed above 11 GPa is interpreted in terms of phase separation or disproportionation reaction from the dihydride toward a solid solution and trihydride states, in both of which the octahedral interstitial sites are partially occupied with hydrogen atoms. A gradual distortion from the cubic to a tetragonal lattice is observed prior to the phase separation. The coexistence phase goes back to the dihydride fcc phase via the lattice distorted phase with decreasing pressure.

  14. Molecular to atomic phase transition in hydrogen under high pressure.

    PubMed

    McMinis, Jeremy; Clay, Raymond C; Lee, Donghwa; Morales, Miguel A

    2015-03-13

    The metallization of high-pressure hydrogen, together with the associated molecular to atomic transition, is one of the most important problems in the field of high-pressure physics. It is also currently a matter of intense debate due to the existence of conflicting experimental reports on the observation of metallic hydrogen on a diamond-anvil cell. Theoretical calculations have typically relied on a mean-field description of electronic correlation through density functional theory, a theory with well-known limitations in the description of metal-insulator transitions. In fact, the predictions of the pressure-driven dissociation of molecules in high-pressure hydrogen by density functional theory is strongly affected by the chosen exchange-correlation functional. In this Letter, we use quantum Monte Carlo calculations to study the molecular to atomic transition in hydrogen. We obtain a transition pressure of 447(3) GPa, in excellent agreement with the best experimental estimate of the transition 450 GPa based on an extrapolation to zero band gap from experimental measurements. Additionally, we find that C2/c is stable almost up to the molecular to atomic transition, in contrast to previous density functional theory (DFT) and DFT+quantum Monte Carlo studies which predict large stability regimes for intermediary molecular phases.

  15. High-pressure Raman spectroscopy of phase change materials

    SciTech Connect

    Hsieh, Wen-Pin Mao, Wendy L.; Zalden, Peter; Wuttig, Matthias; Lindenberg, Aaron M.

    2013-11-04

    We used high-pressure Raman spectroscopy to study the evolution of vibrational frequencies of the phase change materials (PCMs) Ge{sub 2}Sb{sub 2}Te{sub 5}, GeSb{sub 2}Te{sub 4}, and SnSb{sub 2}Te{sub 4}. We found that the critical pressure for triggering amorphization in the PCMs decreases with increasing vacancy concentration, demonstrating that the presence of vacancies, rather than differences in the atomic covalent radii, is crucial for pressure-induced amorphization in PCMs. Compared to the as-deposited amorphous phase, the pressure-induced amorphous phase has a similar vibrational spectrum but requires much lower laser power to transform into the crystalline phase, suggesting different kinetics of crystallization, which may have implications for applications of PCMs in non-volatile data storage.

  16. 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.

  17. High-pressure phase transition observed in barium hydride

    NASA Astrophysics Data System (ADS)

    Smith, Jesse S.; Desgreniers, Serge; Tse, John S.; Klug, Dennis D.

    2007-08-01

    The pressure-dependent structural and vibrational properties of barium hydride have been studied up to 22 GPa at room temperature by means of powder x-ray diffraction, Raman spectroscopy, and first-principles calculations. At ambient conditions, BaH2 crystallizes in the cotunnite structure (Pnma). A reversible, first-order structural phase transition is observed at 1.6 GPa. The high-pressure phase can be indexed by a hexagonal unit cell with a proposed Ni2In structure (P63/mmc), with the Ba and H atoms in special positions. The experimental volume compression of the high-pressure phase yields an isothermal bulk modulus B0=24(1) GPa (B0' fixed at 4.13). This compares favorably with the results of the first-principles calculations, which reproduce the first-order nature of the transition. The relevance of these results is discussed in the contexts of metal hydrides in particular and ionic AX2(A =metal) compounds in general.

  18. The phase diagram of high-pressure superionic ice

    PubMed Central

    Sun, Jiming; Clark, Bryan K.; Torquato, Salvatore; Car, Roberto

    2015-01-01

    Superionic ice is a special group of ice phases at high temperature and pressure, which may exist in ice-rich planets and exoplanets. In superionic ice liquid hydrogen coexists with a crystalline oxygen sublattice. At high pressures, the properties of superionic ice are largely unknown. Here we report evidence that from 280 GPa to 1.3 TPa, there are several competing phases within the close-packed oxygen sublattice. At even higher pressure, the close-packed structure of the oxygen sublattice becomes unstable to a new unusual superionic phase in which the oxygen sublattice takes the P21/c symmetry. We also discover that higher pressure phases have lower transition temperatures. The diffusive hydrogen in the P21/c superionic phase shows strong anisotropic behaviour and forms a quasi-two-dimensional liquid. The ionic conductivity changes abruptly in the solid to close-packed superionic phase transition, but continuously in the solid to P21/c superionic phase transition. PMID:26315260

  19. Phase changes of CO2 hydrate under high pressure and low temperature.

    PubMed

    Hirai, Hisako; Komatsu, Kazuki; Honda, Mizuho; Kawamura, Taro; Yamamoto, Yoshitaka; Yagi, Takehiko

    2010-09-28

    High pressure and low temperature experiments with CO(2) hydrate were performed using diamond anvil cells and a helium-refrigeration cryostat in the pressure and temperature range of 0.2-3.0 GPa and 280-80 K, respectively. In situ x-ray diffractometry revealed that the phase boundary between CO(2) hydrate and water+CO(2) extended below the 280 K reported previously, toward a higher pressure and low temperature region. The results also showed the existence of a new high pressure phase above approximately 0.6 GPa and below 1.0 GPa at which the hydrate decomposed to dry ice and ice VI. In addition, in the lower temperature region of structure I, a small and abrupt lattice expansion was observed at approximately 210 K with decreasing temperature under fixed pressures. The expansion was accompanied by a release of water content from the sI structure as ice Ih, which indicates an increased cage occupancy. A similar lattice expansion was also described in another clathrate, SiO(2) clathrate, under high pressure. Such expansion with increasing cage occupancy might be a common manner to stabilize the clathrate structures under high pressure and low temperature.

  20. High Pressure Materials Research: Novel Extended Phases of Molecular Triatomics

    SciTech Connect

    Yoo, Choong-Shik

    2006-01-27

    Application of high pressure significantly alters the interatomic distance and thus the nature of intermolecular interaction, chemical bonding, molecular configuration, crystal structure, and stability of solid. With modern advances in high-pressure technologies, it is feasible to achieve a large (often up to a several-fold) compression of lattice, at which condition material can be easily forced into a new physical and chemical configuration. The high-pressure thus offers enhanced opportunities to discover new phases, both stable and metastable ones, and to tune exotic properties in a wide-range of atomistic length scale, substantially greater than (often being several orders of) those achieved by other thermal (varing temperatures) and chemical (varying composition or making alloys) means. Simple molecular solids like H{sub 2}, C, CO{sub 2}, N{sub 2}, O{sub 2}, H{sub 2}O, CO, NH{sub 3}, and CH{sub 4} are bounded by strong covalent intramolecular bonds, yet relatively weak intermolecular bonds of van der Waals and/or hydrogen bonds. The weak intermolecular bonds make these solids highly compressible (i.e., low bulk moduli typically less than 10 GPa), while the strong covalent bonds make them chemically inert at least initially at low pressures. Carboncarbon single bonds, carbon-oxygen double bonds and nitrogen-nitrogen triple bonds, for example, are among the strongest. These molecular forms are, thus, often considered to remain stable in an extended region of high pressures and high temperatures. High stabilities of these covalent molecules are also the basis of which their mixtures are often presumed to be the major detonation products of energetic materials as well as the major constituents of giant planets. However, their physical/chemical stabilities are not truly understood at those extreme pressure-temperature conditions. In fact, an increasing amount of experimental evidences contradict the assumed stability of these materials at high pressures and

  1. High-pressure behavior of fcc phase FeHx

    NASA Astrophysics Data System (ADS)

    Thompson, E. C.; Chidester, B.; Fischer, R. A.; Prakapenka, V.; Bi, W.; Alp, E. E.; Campbell, A. J.

    2015-12-01

    Earth's core is composed of iron with the inclusion of light elements to compensate for the difference between seismically obtained densities and the density of pure Fe at relevant pressure and temperature conditions. As the most abundant and lightest element in the solar system, hydrogen is a plausible contributor to this core density deficit. Nearly stoichiometric iron hydride (FeHx) has been shown to result from the reaction of Fe and hydrous silicates, and is stable up to at least 80 GPa [1]. Iron hydride formation at Earth's surface is unlikely because the equilibrium hydrogen solubility in iron at atmospheric conditions is prohibitively low, yet as hydrogen solubility increases with pressure, so does the likelihood of FeHx formation within the Earth's interior [2]. Recent experimental and ab initio attempts disagree on the equation of state parameters needed to describe the compressional behavior of FeHx [3-5]. The work presented here combines synchrotron x-ray diffraction of laser-heated diamond anvil cell compressed samples with high-pressure, ambient temperature nuclear resonant inelastic scattering (NRIXS) and synchrotron Mössbauer spectroscopy (SMS) to better constrain the behavior of the fcc phase of FeHx at elevated pressures and temperatures. By pairing P-V-T data for iron hydride with the sound velocity information available through high-pressure NRIXS studies, we can better understand the degree to which hydrogen may contribute to the density deficit of Earth's iron core. [1] Antonov et al. (1998) J. Alloys Compd. 264, 214-222 [2] Fukai and Akimoto (1983) Proc. Japan Acad. 59, 158-162 [3] Pépin et al. (2014) Phys. Rev. Lett. 265504, 1-5 [4] Hirao (2004) Geophys. Res. Lett. 31, L06616 [5] Badding et al. (1991) Science. 253, 421-424

  2. Fully Consistent Finite-Strain Landau Theory for High-Pressure Phase Transitions

    NASA Astrophysics Data System (ADS)

    Tröster, A.; Schranz, W.; Karsai, F.; Blaha, P.

    2014-07-01

    Landau theory (LT) is an indispensable cornerstone in the thermodynamic description of phase transitions. As with structural transitions, most applications require one to consistently take into account the role of strain. If temperature drives the transition, the relevant strains are, as a rule, small enough to be treated as infinitesimal, and therefore one can get away with linearized elasticity theory. However, for transitions driven by high pressure, strains may become so large that it is absolutely mandatory to treat them as finite and deal with the nonlinear nature of the accompanying elastic energy. In this paper, we explain how to set up and apply what is, in fact, the only possible consistent Landau theory of high-pressure phase transitions that systematically allows us to take these geometrical and physical nonlinearities into account. We also show how to incorporate available information on the pressure dependence of elastic constants taken from experiment or simulation. We apply our new theory to the example of the high-pressure cubic-tetragonal phase transition in strontium titanate, a model perovskite that has played a central role in the development of the theory of structural phase transitions. Armed with pressure-dependent elastic constants calculated by density-functional theory, we give an accurate description of recent high-precision experimental data and predict a number of elastic transition anomalies accessible to experiments.

  3. High pressure effects on isotropic Nd2Fe14B magnet accompanying change in coercive field

    NASA Astrophysics Data System (ADS)

    Mito, M.; Goto, H.; Nagai, K.; Tsuruta, K.; Deguchi, H.; Tajiri, T.; Konishi, K.

    2015-10-01

    We investigated the effects of hydrostatic pressure on an isotropic Nd2Fe14B magnet (the exact chemical formula is Nd2.0Fe14.1B) consisting of nanocrystals, with the size of approximately 30 nm, by magnetization measurements at pressures (P's) up to 9.3 GPa and structural analyses up to 4.3 GPa. Magnetization curves were measured by using a miniature diamond anvil cell made of Ti alloy with spatially uniform magnetization. The initial value of coercive field Hc at 300 K is 840 kA/m (=10.6 kOe), and Hc initially increases to approximately 1180 kA/m (=15.0 kOe) almost linearly against the pressure. The increase in Hc, however, saturates at around P = 3 GPa. The change in Hc is understood by the decrease in the saturation magnetization Ms within the framework of the constant anisotropy of the single domain phase. The crystalline strain increases for P < 1 GPa. Afterward, the crystalline size (D) starts to decrease with increasing pressure, and the reduction tends to saturate at above approximately 3 GPa. Furthermore, the change in Ms is actually related with both the change in strain and that in D. The data on the temperature dependence of Hc at P = 0, 6.6, and 9.3 GPa exhibit pressure-induced suppression of the Curie temperature. The maximum energy product decreases with increasing pressure over the whole temperature range.

  4. Structural phase transitions of sodium nitride at high pressure

    NASA Astrophysics Data System (ADS)

    Vajenine, G. V.; Wang, X.; Efthimiopoulos, I.; Karmakar, S.; Syassen, K.; Hanfland, M.

    2009-06-01

    The structural evolution of recently characterized sodium nitride Na3N as a function of pressure was investigated at room temperature by the angle-dispersive powder x-ray diffraction in a diamond-anvil cell up to 36 GPa. The rather open cubic anti- ReO3 -type structure stable at ambient pressure is followed by a series of four high-pressure modifications. Along the route, the coordination number for the nitride anion increases from 6 in Na3N-I to 8 in hexagonal Li3N -type Na3N-II , 9 in orthorhombic anti- YF3 -type Na3N-III , 11 in hexagonal Cu3P -type Na3N-IV , and finally 14 in cubic Li3Bi -type Na3N-V structures. The experimental data are compared to the results of total-energy calculations and are discussed with regard to the structural details of the five phases and their equations of state.

  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. High-pressure phase behavior of SrCO3: an experimental and computational Raman scattering study

    NASA Astrophysics Data System (ADS)

    Biedermann, Nicole; Speziale, Sergio; Winkler, Björn; Reichmann, Hans Josef; Koch-Müller, Monika; Heide, Gerhard

    2016-11-01

    The high-pressure phase behavior of strontianite (SrCO3) was both experimentally and theoretically investigated by Raman spectroscopy up to 78 GPa in a diamond anvil cell and density functional theory-based calculations. Our study shows a phase transition between 23.7 and 26.8 GPa during compression from space group Pmcn to post-aragonite SrCO3, which is accompanied by significant changes in the vibrational spectrum. The excellent agreement between the observed and computed Raman frequencies and intensities implies that the high-pressure polymorph has space group Pmmn and contributes to resolving an existing disagreement concerning the correct space group symmetry of this high-pressure polymorph. It is shown that the transition pressure from the aragonite to a post-aragonite phase increases linearly with decreasing cation radius for (Ca, Sr, Ba, Pb) carbonates.

  7. High-pressure phase transition in {gamma}-hexanitrohexaazaisowurtzitane

    SciTech Connect

    Russell, T.P.; Miller, P.J.; Piermarini, G.J.; Block, S.

    1992-06-25

    FTIR, EDXD, and PLM; data for a new high-pressure polymorph, {zeta}-HNIW, which is formed from {gamma}-HNIW at 0.7 +/- 0.05 GPa and room temperature. The {gamma}-{zeta} transformation is rapid and reversible in single crystals in a hydrostatic pressure transmitting medium, but the {zeta} form could not be retrieved to ambient conditions. 12 refs., 6 figs., 2 tabs.

  8. 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

  9. Collective spin 1 singlet phase in high-pressure oxygen

    PubMed Central

    Crespo, Yanier; Fabrizio, Michele; Scandolo, Sandro; Tosatti, Erio

    2014-01-01

    Oxygen, one of the most common and important elements in nature, has an exceedingly well-explored phase diagram under pressure, up to and beyond 100 GPa. At low temperatures, the low-pressure antiferromagnetic phases below 8 GPa where O2 molecules have spin S = 1 are followed by the broad apparently nonmagnetic ε phase from about 8 to 96 GPa. In this phase, which is our focus, molecules group structurally together to form quartets while switching, as believed by most, to spin S = 0. Here we present theoretical results strongly connecting with existing vibrational and optical evidence, showing that this is true only above 20 GPa, whereas the S = 1 molecular state survives up to about 20 GPa. The ε phase thus breaks up into two: a spinless ε0 (20−96 GPa), and another ε1 (8−20 GPa) where the molecules have S = 1 but possess only short-range antiferromagnetic correlations. A local spin liquid-like singlet ground state akin to some earlier proposals, and whose optical signature we identify in existing data, is proposed for this phase. Our proposed phase diagram thus has a first-order phase transition just above 20 GPa, extending at finite temperature and most likely terminating into a crossover with a critical point near 30 GPa and 200 K. PMID:25002513

  10. Phase transition of solid bismuth under high pressure

    NASA Astrophysics Data System (ADS)

    Chen, Hai-Yan; Xiang, Shi-Kai; Yan, Xiao-Zhen; Zheng, Li-Rong; Zhang, Yi; Liu, Sheng-Gang; Bi, Yan

    2016-10-01

    As a widely used pressure calibrator, the structural phase transitions of bismuth from phase I, to phase II, to phase III, and then to phase V with increasing pressure at 300 K have been widely confirmed. However, there are different structural versions for phase III, most of which are determined by x-ray diffraction (XRD) technology. Using x-ray absorption fine structure (XAFS) measurements combined with ab initio calculations, we show that the proposed incommensurate composite structure of bismuth of the three configurations is the best option. An abnormal continuous increase of the nearest-neighbor distance of phase III with elevated pressure is also observed. The electronic structure transformation from semimetal to metal is responsible for the complex behavior of structure transformation. Project supported by the National Natural Science Foundation of China (Grant Nos. 10904133, 11304294, 11274281, 11404006, and U1230201), the Development Foundation of China Academy of Engineering Physics (Grant Nos. 2015B0101004, 2013B0401062, and 2012A0101001), the Research Foundation of the Laboratory of Shock Wave and Detonation, China (Grant No. 9140C670201140C67282).

  11. New Phase Transition of Solid Bromine under High Pressure

    SciTech Connect

    San-Miguel, A.; Libotte, H.; Gaspard, J.-P.; Gauthier, M.; Aquilanti, G.; Pascarelli, S.

    2007-07-06

    Solid bromine has been studied by x-ray absorption spectroscopy experiments up to a maximum pressure of 75 GPa. The data analysis of the extended fine structure reveals that the intramolecular distance first increases, reaching its maximum value at 25{+-}5 GPa. From this value the intramolecular distance abruptly begins to decrease evidencing a nonpreviously observed phase transformation taking place at 25{+-}5 GPa. A maximum variation of 0.08 A ring is observed at 65{+-}5 GPa where again a phase transition occurs. This last transformation could correspond with the recently observed change to an incommensurate modulated phase. We discuss the possible generalization of the observed new phase transition at 25{+-}5 GPa to the case of the other halogens.

  12. Phase diagram of Mo at high pressure and temperature

    SciTech Connect

    Ross, M

    2008-10-01

    We report values of the Poisson Ratios for shock compressed Mo, calculated from the sound speed measurements, which provide evidence that the 210 GPa ({approx}4100K) transition cannot be a bcc-hcp transition, as originally proposed. Instead, we find the transition is from the bcc to a noncrystalline phase. For pressures above 210 GPa, the Poisson Ratio increases steadily with increasing temperature, approaching the liquid value of 0.5 at 390 GPa({approx}10,000K), suggesting the presence of a noncrystalline solid-liquid mixture. Free energy model calculations were used to show that the low melting slope of Mo, and the phase diagram, can be explained by the presence of local liquid structures. A new phase diagram is proposed for Mo that is constrained by the experimental evidence.

  13. High pressure phase transition and elastic properties of americium telluride

    NASA Astrophysics Data System (ADS)

    Aynyas, Mahendra; Rukmangad, Aditi; Arya, B. S.; Sanyal, S. P.

    2013-06-01

    The structural and elastic properties of Americium Telluride (AmTe) have been investigated by using a modified inter-ionic potential theory (MIPT). This theory is capable of explaining first order phase transition with a crystallographic change NaCl to CsCl structure for this compound. The values of optimized lattice constant, phase transition pressure, zero pressure bulk modulus and second order elastic constants (C11, C44) agree well with their corresponding experimental data. Debye temperature (θD) is also calculated for this compound for the first time.

  14. High pressure phase transition in group III nitrides compounds

    NASA Astrophysics Data System (ADS)

    Soni, Shubhangi; Verma, S.; Kaurav, Netram; Choudhary, K. K.

    2016-05-01

    Using an effective interionic interaction potential (EIOP), the pressure induced structural phase transformation from ZnS-type (B3) to NaCl-type (B1) structure in group III Post-Transition Metal Nitrides [TMN; TM=Ga and Tl] were investigated. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.

  15. Superconducting high-pressure phases composed of hydrogen and iodine

    DOE PAGES

    Shamp, Andrew; Zurek, Eva

    2015-09-25

    Evolutionary structure searches predict three new phases of iodine polyhydrides stable under pressure. Insulating P1-H5I, consisting of zigzag chains of (HI) δ+ and H 2 molecules, is stable between 30-90 GPa. Cmcm-H2I and P6/mmm-H4I are found on the 100, 150 and 200 GPa convex hulls. These two phases are good metals, even at 1 atm, because they consist of monoatomic lattices of iodine. At 100 GPa the superconducting transition temperature, Tc, of H2I and H4I are estimated to be 7.8 and 17.5 K, respectively. Lastly, the increase in Tc relative to elemental iodine results from a larger ωlog from themore » light mass of hydrogen, and an enhanced from modes containing H/I and H/H vibrations.« less

  16. High pressure partially ionic phase of water ice.

    PubMed

    Wang, Yanchao; Liu, Hanyu; Lv, Jian; Zhu, Li; Wang, Hui; Ma, Yanming

    2011-11-29

    Water ice dissociates into a superionic solid at high temperature (>2,000 K) and pressure, where oxygen forms the lattice, but hydrogen diffuses completely. At low temperature, however, the dissociation into an ionic ice of hydronium (H(3)O)(+) hydroxide (OH)(-) is not expected because of the extremely high energy cost (~1.5 eV) of proton transfer between H(2)O molecules. Here we show the pressure-induced formation of a partially ionic phase (monoclinic P2(1) structure) consisting of coupled alternate layers of (OH)(δ-) and (H(3)O)(δ+) (δ=0.62) in water ice predicted by particle-swarm optimization structural search at zero temperature and pressures of >14 Mbar. The occurrence of this ionic phase follows the break-up of the typical O-H covalently bonded tetrahedrons in the hydrogen symmetric atomic phases and is originated from the volume reduction favourable for a denser structure packing.

  17. Rheology of phase A at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Hilairet, N.; Amiguet, E.; Wang, Y.; Merkel, S.

    2013-12-01

    Subduction zones are locations where a tectonic plate slides and bends under another one. Materials there undergo large and heterogeneous deformations and stresses which are released through seismicity, occasionally. Thus plasticity of minerals filling faults and shear zones is a critical parameter for understanding the stress balance of whole subduction zones. We present a deformation study on a hexagonal hydrous phase that can exist in shear zones within subducting slabs, phase A, after dehydration of serpentine into pyroxene + phase A. Pure phase A samples were synthesized at 11 GPa and ca. 1100K, in the multi-anvil facility in Clermont-Ferrand, France, with N. Bolfan and D. Andrault. Three samples were deformed at 11 GPa confining pressure, and 673K or 973K, using a D-DIA apparatus [1] at 13B-MD at GSE-CARS, APS, in uniaxial shortening up to -0.24 strain and at 5.10-5 s-1. Lattice strains (a proxy for macro-stress), texture and strain were measured in-situ, using synchrotron radiation. Results from lattice strain and texture analysis show a decrease in flow stress and a change in deformation mechanisms with temperature, coherent with the findings in transmission electron microscopy on samples recovered in relaxation experiments from [2]. The slip systems involved during deformation were further analyzed using Visco-Plastic Self-Consistent (VPSC) simulations [3]. The model inputs were known slip systems for hexagonal materials, including the ones observed by [2], with tunable strengths, the strain rate, final strain, and either a random texture or the starting experimental texture. The final experimental textures could be reproduced. The slip systems that had to be activated for matching the experimental texture confirm the observations by [2]: at 673K, the most active slip systems are prismatic and pyramidal, with the requirement of a smaller activity on the basal system, and at 973K the basal system is the main slip system activated. [1] Wang et al, Review for

  18. High-pressure synthesis of a pentazolate salt [High-pressure synthesis of condensed-phase pentazolate

    DOE PAGES

    Steele, Brad A.; Stavrou, Elissaios; Crowhurst, Jonathan C.; ...

    2016-12-06

    The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here, we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N5–, which is achieved by compressing and laser heating cesium azide (CsN3) mixed with N2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN5). Electron transfer from Cs atoms tomore » N5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN5 crystal. As a result, this work provides critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species.« less

  19. High-pressure synthesis of a pentazolate salt [High-pressure synthesis of condensed-phase pentazolate

    SciTech Connect

    Steele, Brad A.; Stavrou, Elissaios; Crowhurst, Jonathan C.; Zaug, Joseph M.; Prakapenka, Vitali B.; Oleynik, Ivan I.

    2016-12-06

    The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here, we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N5, which is achieved by compressing and laser heating cesium azide (CsN3) mixed with N2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN5). Electron transfer from Cs atoms to N5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN5 crystal. As a result, this work provides critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species.

  20. Superconducting high-pressure phases composed of hydrogen and iodine

    SciTech Connect

    Shamp, Andrew; Zurek, Eva

    2015-09-25

    Evolutionary structure searches predict three new phases of iodine polyhydrides stable under pressure. Insulating P1-H5I, consisting of zigzag chains of (HI) δ+ and H 2 molecules, is stable between 30-90 GPa. Cmcm-H2I and P6/mmm-H4I are found on the 100, 150 and 200 GPa convex hulls. These two phases are good metals, even at 1 atm, because they consist of monoatomic lattices of iodine. At 100 GPa the superconducting transition temperature, Tc, of H2I and H4I are estimated to be 7.8 and 17.5 K, respectively. Lastly, the increase in Tc relative to elemental iodine results from a larger ωlog from the light mass of hydrogen, and an enhanced from modes containing H/I and H/H vibrations.

  1. Transformation of Hume-Rothery phases under the action of high pressure torsion

    NASA Astrophysics Data System (ADS)

    Straumal, B. B.; Kilmametov, A. R.; Kucheev, Yu. O.; Kolesnikova, K. I.; Korneva, A.; Zieba, P.; Baretzky, B.

    2014-11-01

    It has been revealed experimentally that high-pressure torsion induces phase transformations of certain Hume-Rothery phases (electron compounds) to others. High-pressure torsion induces the ξ → δ + ɛ reaction in copper-tin alloys with the appearance of the δ + ɛ phase mixture as after long-term annealing in the temperature range T eff = 350-589°C. The mass transfer rate driven by high-pressure torsion is 14-18 orders of magnitude higher than the rate of conventional thermal diffusion at the processing temperature T HPT. This phenomenon can be explained by an increased concentration of defects (in particular, vacancies) in the steady state under high-pressure torsion, which is equivalent to an increase in the temperature.

  2. High-Pressure Induced New Phases and Properties in Typical Molecular Systems

    NASA Astrophysics Data System (ADS)

    Cui, Tian

    2013-06-01

    High pressure introduces new phases by the rearrangement of atoms and reconfigurations of electronic states in materials, often with new physical and chemical phenomena. Study of the new phases in typical molecular systems under high pressure is an interesting subject, such as energy storage materials of solid hydrogen and polymeric nitrogen, hydrogen-rich compound with high-Tc superconductivity under high pressure, high pressure induced metallization of hydrogen, etc. High-pressure structures and pressure-induced phase transitions in the typical molecular solids, such as solid iodine, CHBr3, N2/CN, HBr/HCl, hydrogen-rich compounds (H2S, ZrH2, AsH3, BaReH9, etc.), and group IVA hydrides (Si2H6, Ge2H6, Sn2H6, etc.) are investigated extensively by means of first-principles density functional theory and extensive prediction strategies (molecular dynamics simulation, simulated annealing, soft mode phase transition, random structure-searching method and evolutionary methodology etc.). The new structures and new properties derived from pressure-induced phase transitions in these typical molecular systems have been observed. It is showed that high pressure provides a path for producing new materials with new properties.

  3. 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.

  4. 77 FR 3281 - High Pressure Steel Cylinders From China; Scheduling of the Final Phase of Countervailing Duty...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-01-23

    ...-1188 (Final)] High Pressure Steel Cylinders From China; Scheduling of the Final Phase of Countervailing... high pressure steel cylinders, provided for in subheading 7311.00.00 of the Harmonized Tariff Schedule... compressed or liquefied gas (``high pressure steel cylinders''). High pressure steel cylinders are...

  5. Structural phase transitions of SrF2 at high pressure

    NASA Astrophysics Data System (ADS)

    Wang, J. S.; Ma, C. L.; Zhou, D.; Xu, Y. S.; Zhang, M. Z.; Gao, W.; Zhu, H. Y.; Cui, Q. L.

    2012-02-01

    The high-pressure behavior of SrF2 has been investigated by angle-dispersive synchrotron X-ray powder diffraction measurement up to 50.3 GPa at room temperature. Two phase transformations were observed at 6.8 and 29.5 GPa, and the two high pressure phases were identified as orthorhombic (Pnma) phase and hexagonal (P63/mmc) phase by Rietveld refinement. Upon decompression, retransformation was observed and the sample recovered under ambient conditions consisted of a mixture of cubic phase and orthorhombic phase. The compressing characteristics of SrF2 as the pressure increases were discussed, indicating higher incompressibility of SrF2 under high pressure.

  6. First-principles investigation of iron pentacarbonyl molecular solid phases at high pressure

    NASA Astrophysics Data System (ADS)

    Cong, Kien Nguyen; Steele, Brad A.; Landerville, Aaron C.; Oleynik, Ivan I.

    2017-01-01

    The polymeric phases of carbon monoxide (p-CO), an extended non-molecular solid, represent a new class of low-Z energetic materials. The presence of transition metal ions is believed to stabilize polymeric carbon monoxide (p-CO) at ambient conditions. Since p-CO forms at high pressures, it becomes important to investigate the high-pressure behavior of one of the potential precursors, iron pentacarbonyl Fe(CO)5. In this work, a first-principles evolutionary structure search method is used to determine the crystal phases of Fe(CO)5 at high pressure. The calculations predict the crystal structure of Phase I in agreement with experiment. Moreover, the previously unidentified crystal structure of Phase II is found. The calculated pressure-dependent Raman spectra are used to demonstrate that the changes in Raman spectra as a function of pressure observed in recent experiment can be explained without invoking a phase transition to a new phase III.

  7. The new phase of HgF2 at high pressure

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoli; Li, Jianfu

    2013-05-01

    Mercury halides form an amazing number of solid phases and remarkably only the crystal structure of HgF2 at high pressure is not established. We here report a stabilization HgF2 high-pressure phase predicted by the density functional structural searches, which adopts the Pnma symmetric structure (12 atoms/cell, α-PbCl2-type, or cotunnite). The phase transition from the ambient conditions phase Fm-3m (phase I) to the Pnma phase (phase II) was confirmed at 4.7 GPa. The calculated equation of state suggests that this is a first-order phase transition. At this phase transition, the coordination number of Hg2+ increases from eight to nine, similar to the phase transition sequence of CaF2. Furthermore, a thorough CALYPSO structural search up to 100 GPa cannot find any other structure that is more stable than the Pnma structure.

  8. Phase H: A new high pressure phase of dense hydrous magnesium silicates in the lower mantle

    NASA Astrophysics Data System (ADS)

    Tsuchiya, J.; Tsuchiya, T.; Nishi, M.; Mookherjee, M.

    2014-12-01

    It has been believed that water is carried into the deep Earth's interior by hydrous minerals such as the dense hydrous magnesium silicates (DHMSs) in the descending cold plate. Recently, the new high pressure phase of DHMSs is theoretically predicted (Tsuchiya 2013) and experimentally confirmed in lower mantle pressure conditions above ~45 GPa (Nishi et al. 2014). This phase has MgSiO4H2 chemical composition and named as phase H. At the lower mantle pressure conditions, Al and H-bearing SiO2, δ-AlOOH, ɛ-FeOOH and phase H may be the potential hydrous phases in the subducting slabs. Interestingly, the crystal structure of these hydrous phases are almost same and have CaCl2 type structure. This suggests that these hydrous phases may be able to make the wide range of solid solution. Some experimental studies already reported that Al preferentially partitioned into phase H and the stability of phase H drastically increased by incorporation of Al (Nishi et al. 2014, Ohira et al. 2014). The density of subducted MORB is reported to be denser than that of pyrolite in the lower mantle. Therefore, there is a possibility that phase H containing Al and Fe in subducted MORB survive down to the bottom of lower mantle and the melting of phase H at the core mantle boundary may contribute to the cause of ultra-low velocity zones. In this study, we report the effects of Al and Fe on the stability of phase H, elasticity and seismic anisotropy of this new hydrous mineral using first principles calculation techniques and discuss the possible effects of this hydrous phase at the bottom of lower mantle.

  9. Pressure and Temperature effects on the High Pressure Phase Transformation in Zirconium

    SciTech Connect

    Escobedo-Diaz, Juan P.; Cerreta, Ellen K.; Brown, Donald W.; Trujillo, Carl P.; Rigg, Paulo A.; Bronkhorst, Curt A.; Addessio, Francis L.; Lookman, Turab

    2012-06-20

    At high pressure zirconium is known to undergo a phase transformation from the hexagonal close packed (HCP) alpha phase ({alpha}) to the simple hexagonal omega phase ({omega}). Under conditions of shock loading, the high-pressure omega phase is retained upon release. However, the hysteresis in this transformation is not well represented by equilibrium phase diagrams. For this reason, the influence of peak shock pressure and temperature on the retention of omega phase in Zr is explored in this study. In situ VISAR measurements along with post-mortem metallographic and neutron diffraction characterization of soft recovered specimens have been utilized to quantify the volume fraction of retained omega phase, morphology of the shocked alpha and omega phases, and qualitatively understand the kinetics of this transformation. This understanding of the role of peak shock stress will be utilized to address physics to be encoded in our present macro-scale models.

  10. REVIEWS OF TOPICAL PROBLEMS: Properties of high pressure phases in metal-hydrogen systems

    NASA Astrophysics Data System (ADS)

    Ponyatovskiĭ, E. G.; Antonov, Vladimir E.; Belash, I. T.

    1982-08-01

    The development of high-pressure technology has in recent years permitted obtaining extensive new information on the properties of hydrides of group VI-VIII transition metals. In this review, the experimental procedures for compressing macroscopic quantities of hydrogen to record high pressures, phase transitions, and structures of new high-pressure phases in Me-H systems are briefly described. Special attention is devoted to the magnetic properties of solid solutions of hydrogen in 3d metals and their alloys, whose study has yielded definite conclusions concerning the effect of hydrogen on the band structure and exchange interaction in these materials. The role of structural instabilities in the formation of superconducting properties of hydrogen solutions in 4d metal alloys based on palladium is examined.

  11. Vibrational Spectroscopy at High Pressure in CF4: Implications to the Phase Diagram

    SciTech Connect

    Lorenzana, H E; Magnus, J L; Evans, W J; Hemmi, N

    2000-08-15

    The molecular analogue of methane, CF{sub 4} is the most fundamental saturated perfluorocarbon, exhibiting complex optical behavior that is highly unusual for such a simple molecular system. We present Raman measurements in solid CF{sub 4} over a wide range in pressure from 1.6 to over 30 GPa at room temperature. The Raman spectra exhibit polarization-dependent intensity variations and history-dependent absence or presence of high pressure modes. Our results compellingly demonstrate that previously identified phase transitions in CF{sub 4} based on Raman signatures need to be reconsidered. Though our data suggest possible new high-pressure transitions, we do not identify new phases because of spectral complexity. Finally, we used the measured longitudinal and transverse optical mode splitting to estimate the dipole moment derivative at high pressures and find it close to that of gaseous CF{sub 4}.

  12. High-pressure phase of brucite stable at Earth's mantle transition zone and lower mantle conditions

    NASA Astrophysics Data System (ADS)

    Hermann, Andreas; Mookherjee, Mainak

    2016-12-01

    We investigate the high-pressure phase diagram of the hydrous mineral brucite, Mg(OH)2, using structure search algorithms and ab initio simulations. We predict a high-pressure phase stable at pressure and temperature conditions found in cold subducting slabs in Earth’s mantle transition zone and lower mantle. This prediction implies that brucite can play a much more important role in water transport and storage in Earth’s interior than hitherto thought. The predicted high-pressure phase, stable in calculations between 20 and 35 GPa and up to 800 K, features MgO6 octahedral units arranged in the anatase–TiO2 structure. Our findings suggest that brucite will transform from a layered to a compact 3D network structure before eventual decomposition into periclase and ice. We show that the high-pressure phase has unique spectroscopic fingerprints that should allow for straightforward detection in experiments. The phase also has distinct elastic properties that might make its direct detection in the deep Earth possible with geophysical methods.

  13. High-pressure phase transitions of solid HF, HCl, and HBr: An ab initio evolutionary study

    NASA Astrophysics Data System (ADS)

    Zhang, Lijun; Wang, Yanchao; Zhang, Xinxin; Ma, Yanming

    2010-07-01

    Using ab initio evolutionary methodology for structure predictions, we investigated the high-pressure phase diagram for solid-state HF, HCl, and HBr at zero temperature. The ambient-pressure chain-type Cmc21 structure and sequent high-pressure symmetric hydrogen-bonded Cmcm structure were successfully reproduced by structural simulations with the only known information of chemical compositions. We have also presented insight into the underlying mechanism of hydrogen-bond symmetrization at the Cmc21→Cmcm transformation, by analysis of electron localization functions, potential wells, and zone-center phonons with pressure. At higher pressures, it was predicted that HF transforms from the Cmcm phase to another chain-type Pnma structure at ˜143GPa while the post- Cmcm phase of HCl and HBr adopts an intriguing triclinic P1¯ structure at above 108 GPa and 59 GPa, respectively, which consists of nearly planar squares resembling the ambient phase of HI. The newly predicted high-pressure phases of these halides all contain symmetric hydrogen bonds and satisfy lattice dynamical stability. As for the earlier proposed dissociation of HBr, we found that this can only occur at rather high pressures (above 120 GPa) with the formation of monatomic Br and solid H2 .

  14. High-pressure phase transitions of ScPO[subscript 4] and YPO[subscript 4

    SciTech Connect

    Zhang, F.X.; Wang, J.W.; Lang, M.; Zhang, J.M.; Ewing, R.C.; Boatner, L.A.

    2010-01-12

    ScPO{sub 4} and YPO{sub 4} with the tetragonal zircon-structure were studied at room temperature and pressures up to -50 GPa. Pressure-induced phase transitions to the sheelite structure occur at 30 GPa for ScPO{sub 4} and 16.3 GPa for YPO{sub 4}, respectively. In addition to the scheelite-type high-pressure phase, an intermediate phase with the monoclinic monazite-type structure formed during the phase transition process of YPO{sub 4}. The high-pressure phases of ScPO{sub 4} and YPO{sub 4} are not quenchable on pressure release. The pressure dependence of the total energy of the different phases was calculated using density-functional method, and the results confirm the experimentally observed phase relations under pressure. Structural parameters and compressibility of each phase were determined by refinement of the x-ray diffraction patterns. The high-pressure phase of ScPO{sub 4} has a very large bulk modulus [376(8) GPa].

  15. Phase transition induced strain in ZnO under high pressure

    NASA Astrophysics Data System (ADS)

    Yan, Xiaozhi; Dong, Haini; Li, Yanchun; Lin, Chuanlong; Park, Changyong; He, Duanwei; Yang, Wenge

    2016-05-01

    Under high pressure, the phase transition mechanism and mechanical property of material are supposed to be largely associated with the transformation induced elastic strain. However, the experimental evidences for such strain are scanty. The elastic and plastic properties of ZnO, a leading material for applications in chemical sensor, catalyst, and optical thin coatings, were determined using in situ high pressure synchrotron axial and radial x-ray diffraction. The abnormal elastic behaviors of selected lattice planes of ZnO during phase transition revealed the existence of internal elastic strain, which arise from the lattice misfit between wurtzite and rocksalt phase. Furthermore, the strength decrease of ZnO during phase transition under non-hydrostatic pressure was observed and could be attributed to such internal elastic strain, unveiling the relationship between pressure induced internal strain and mechanical property of material. These findings are of fundamental importance to understanding the mechanism of phase transition and the properties of materials under pressure.

  16. High pressure phase transitions in scheelite structured fluoride: ErLiF{sub 4}

    SciTech Connect

    Garg, Nandini; Mishra, A.K.; Poswal, H.K.; Tyagi, A.K.; Sharma, Surinder M

    2015-09-15

    Our synchrotron based angle dispersive x-ray diffraction studies on scheelite structured ErLiF{sub 4} show that it undergoes two phase transitions, at ~11.5 and ~15.5 GPa to lower symmetry monoclinic phases, before becoming (irreversibly) amorphous at ~28 GPa. The first high pressure phase transformation to the fergusonite structure (space group I2/a) is found to be of thermodynamically second order. The second high pressure phase could be fitted to the P2/c space group, but detailed analysis rules out the wolframite structure (P2/c space group), common to many scheelite compounds under high pressures. We also suggest that despite the ionic character of the LiF{sub 4} tetrahedra, the compressibility of LnLiF{sub 4} (Ln=Eu–Lu) kind of scheelites is more affected by the LnF{sub 8} dodecahedra than the LiF{sub 4} tetrahedra. - Graphical abstract: Volume per formula unit of the scheelite and high pressure phases of ErLiF{sub 4} as a function of pressure. - Highlights: • ErLiF{sub 4} transforms to fergusonite and P2/c phase at high pressure. • Polyhedra of LnF{sub 8} affects compressibility of LnLiF{sub 4} (Ln=Eu–Lu) more than LiF{sub 4}. • Amorphization pressure varies inversely in LnLiF{sub 4} with ionic size of Ln cation. • In ErLiF{sub 4}a/c ratio reduces with pressure in contrast to reported increase in YLiF{sub 4}.

  17. ANALYSIS OF SELECTED PYRETHROID PESTICIDES USING REVERSE PHASE HIGH PRESSURE LIQUID CHROMATOGRAPHY/UV

    EPA Science Inventory

    This research was conducted in cooperation with EPA Region 4 in Athens, GA to develop a method to analyze selected pyrethroid pesticides using Reverse Phase-High Pressure Liquid Chromatography (HPLC). This HPLC method will aid researchers in separating and identifying these py...

  18. Phase field simulations of plastic strain-induced phase transformations under high pressure and large shear

    NASA Astrophysics Data System (ADS)

    Javanbakht, Mahdi; Levitas, Valery I.

    2016-12-01

    Pressure and shear strain-induced phase transformations (PTs) in a nanograined bicrystal at the evolving dislocations pile-up have been studied utilizing a phase field approach (PFA). The complete system of PFA equations for coupled martensitic PT, dislocation evolution, and mechanics at large strains is presented and solved using the finite element method (FEM). The nucleation pressure for the high-pressure phase (HPP) under hydrostatic conditions near a single dislocation was determined to be 15.9 GPa. Under shear, a dislocation pile-up that appears in the left grain creates strong stress concentration near its tip and significantly increases the local thermodynamic driving force for PT, which causes nucleation of HPP even at zero pressure. At pressures of 1.59 and 5 GPa and shear, a major part of a grain transforms to HPP. When dislocations are considered in the transforming grain as well, they relax stresses and lead to a slightly smaller stationary HPP region than without dislocations. However, they strongly suppress nucleation of HPP and require larger shear. Unexpectedly, the stationary HPP morphology is governed by the simplest thermodynamic equilibrium conditions, which do not contain contributions from plasticity and surface energy. These equilibrium conditions are fulfilled either for the majority of points of phase interfaces or (approximately) in terms of stresses averaged over the HPP region or for the entire grain, despite the strong heterogeneity of stress fields. The major part of the driving force for PT in the stationary state is due to deviatoric stresses rather than pressure. While the least number of dislocations in a pile-up to nucleate HPP linearly decreases with increasing applied pressure, the least corresponding shear strain depends on pressure nonmonotonously. Surprisingly, the ratio of kinetic coefficients for PT and dislocations affect the stationary solution and the nanostructure. Consequently, there are multiple stationary solutions

  19. High pressure phase-transformation induced texture evolution and strengthening in zirconium metal: Experiment and modeling

    DOE PAGES

    Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; ...

    2015-07-28

    We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can bemore » attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation.« less

  20. High Pressure Phase-Transformation Induced Texture Evolution and Strengthening in Zirconium Metal: Experiment and Modeling

    PubMed Central

    Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; Vogel, Sven C.; Zhang, Jianzhong; Brown, Donald W.; Wang, Yanbin; Reiche, Helmut M.; Wang, Shanmin; Du, Shiyu; Jin, Changqing; Zhao, Yusheng

    2015-01-01

    We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can be attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation. PMID:26218405

  1. High pressure phase-transformation induced texture evolution and strengthening in zirconium metal: Experiment and modeling

    SciTech Connect

    Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; Vogel, Sven C.; Zhang, Jianzhong; Brown, Donald W.; Wang, Yanbin; Reiche, Helmut M.; Wang, Shanmin; Du, Shiyu; Jin, Changqing; Zhao, Yusheng

    2015-07-28

    We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can be attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation.

  2. Phase changes of filled ice Ih methane hydrate under low temperature and high pressure.

    PubMed

    Tanaka, Takehiko; Hirai, Hisako; Matsuoka, Takahiro; Ohishi, Yasuo; Yagi, Takehiko; Ohtake, Michika; Yamamoto, Yoshitaka; Nakano, Satoshi; Irifune, Tetsuo

    2013-09-14

    Low-temperature and high-pressure experiments were performed with filled ice Ih structure of methane hydrate under 2.0-77.0 GPa and 30-300 K using diamond anvil cells and a helium-refrigeration cryostat. In situ X-ray diffractometry revealed distinct changes in the compressibility of the axial ratios of the host framework with pressure. Raman spectroscopy showed a split in the C-H vibration modes of the guest methane molecules, which was previously explained by the orientational ordering of the guest molecules. The pressure and temperature conditions at the split of the vibration modes agreed well with those of the compressibility change. The results indicate the following: (i) the orientational ordering of the guest methane molecules from an orientationally disordered state occurred at high pressures and low temperatures; and (ii) this guest ordering led to anisotropic contraction in the host framework. Such guest orientational ordering and subsequent anisotropic contraction of the host framework were similar to that reported previously for filled ice Ic hydrogen hydrate. Since phases with different guest-ordering manners were regarded as different phases, existing regions of the guest disordered-phase and the guest ordered-phase were roughly estimated by the X-ray study. In addition, above the pressure of the guest-ordered phase, another high-pressure phase developed in the low-temperature region. The deuterated-water host samples were also examined, and the influence of isotopic effects on guest ordering and phase transformation was observed.

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

    NASA Astrophysics Data System (ADS)

    Zhang, Jin S.; Bass, Jay D.

    2016-08-01

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

  4. High pressure Raman scattering study on the phase stability of LuVO{sub 4}

    SciTech Connect

    Rao, Rekha; Garg, Alka B.; Sakuntala, T.; Achary, S.N.; Tyagi, A.K.

    2009-07-15

    High pressure Raman spectroscopic investigations have been carried out on rare earth orthovanadate LuVO{sub 4} upto 26 GPa. Changes in the Raman spectrum around 8 GPa across the reported zircon to scheelite transition are investigated in detail and compared with those observed in other vanadates. Co-existence of the zircon and scheelite phases is observed over a pressure range of about 8-13 GPa. The zircon to scheelite transition is irreversible upon pressure release. Subtle changes are observed in the Raman spectrum above 16 GPa which could be related to scheelite reversible fergusonite transition. Pressure dependencies of the Raman active modes in the zircon and the scheelite phases are reported. - Graphical abstract: Study of scheelite-fergusonite transition in RVO{sub 4} by Raman spectroscopy is rare. Here we report Raman spectroscopic investigations of LuVO{sub 4} at high pressure to obtain insight into nature of post-scheelite phases.

  5. Magnetic and structural phase transitions in erbium at low temperatures and high pressures

    SciTech Connect

    Thomas, Sarah A.; Tsoi, Georgiy M.; Wenger, Lowell E.; Vohra, Yogesh K.

    2012-02-07

    Electrical resistance and crystal structure measurements have been carried out on polycrystalline erbium (Er) at temperatures down to 10 K and pressures up to 20 GPa. An abrupt change in the slope of the resistance is observed with decreasing temperature below 84 K, which is associated with the c-axis modulated (CAM) antiferromagnetic (AFM) ordering of the Er moments. With increasing pressure the temperature of the resistance slope change and the corresponding AFM ordering temperature decrease until vanishing above 10.6 GPa. The disappearance of the slope change in the resistance occurs at similar pressures where the hcp structural phase of Er is transformed to a nine-layer {alpha}-Sm structural phase, as confirmed by our high-pressure synchrotron x-ray diffraction studies. These results suggest that the disappearance in the AFM ordering of Er moments is strongly correlated to the structural phase transition at high pressures and low temperatures.

  6. Phase equilibria in fluid mixtures at high pressures: The He-CH4 system

    NASA Technical Reports Server (NTRS)

    Streett, W. B.; Erickson, A. L.; Hill, J. L. E.

    1972-01-01

    An experimental study of phase equilibria in the He-CH4 system was carried out over the temperature range 95 to 290 K and at pressures to 10,000 atm. The experimental results consist of equilibrium phase composition for twenty-eight isotherms in the region of coexistence of two fluid phases, together with the pressure-temperature trace of the three-phase boundary at which a CH4-rich solid phase is in equilibrium with the two fluid phases. The system exhibits a fluid-fluid phase separation which persists to temperatures and pressures beyond the range of this experiment. These results, together with those recently obtained for other binary systems, provide information about the form of phase diagrams for binary gas mixtures in the region of pressure induced phase transitions at high pressures. These findings are relevant to problems of deep atmosphere and interior structures in the outer planets.

  7. Phase Stability of Epsilon and Gamma Hniw (CL-20) at High-Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    Gump, Jared C.; Stoltz, Chad A.; Peiris, Suhithi M.

    2007-12-01

    Hexanitrohexaazaisowurtzitane (CL-20) is one of the few ingredients developed since World War II to be considered for transition to military use. Five polymorphs have been identified for CL-20 by FTIR measurements (α, β, γ, ɛ, ζ). As CL-20 is transitioned into munitions it will become necessary to predict its response under conditions of detonation, for performance evaluation. Such predictive modeling requires a phase diagram and basic thermodynamic properties of the various phases at high pressure and temperature. Therefore, the epsilon and gamma phases of CL-20 at static high-pressure and temperature were investigated using synchrotron angle-dispersive x-ray diffraction experiments. The samples were compressed and heated using diamond anvil cells (DAC). Pressures and temperatures achieved were around 5 GPa and 240 °C, respectively. The epsilon phase was stable to 6.3 GPa at ambient temperature. When heated at ambient pressure the epsilon phase was sustained to a temperature of 120 °C then underwent a transition to the gamma phase above 125 °C and then thermal decomposition occurred above 150 °C. Upon compression, the gamma phase underwent a phase transition at both ambient temperature and 140 °C. Pressure—volume data for the epsilon and gamma phase at ambient temperature and the epsilon phase at 75 °C were fit to the Birch-Murnaghan formalism to obtain isothermal equations of state.

  8. Phase transition and metallization of FeO at high pressures and temperatures

    SciTech Connect

    Fischer, Rebecca A.; Campbell, Andrew J.; Lord, Oliver T.; Shofner, Gregory A.; Dera, Przemyslaw; Prakapenka, Vitali B.

    2012-05-10

    Wuestite, Fe{sub 1-x}O, is an important component in the mineralogy of Earth's lower mantle and may also be a component of the core. Therefore its high pressure-temperature behavior, including its electronic structure, is essential to understanding the nature and evolution of Earth's deep interior. We performed X-ray diffraction and radiometric measurements on wuestite in a laser-heated diamond anvil cell, finding an insulator-metal transition at high pressures and temperatures. Our data show a negative slope for this apparently isostructural phase boundary, which is characterized by a volume decrease and emissivity increase. The metallic phase of FeO is stable at conditions of the lower mantle and core, which has implications for the high P-T character of Fe-O bonds, magnetic field propagation, and lower mantle conductivity.

  9. 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.

  10. 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.

  11. High-pressure and high-temperature study of the phase transition in anhydrite

    NASA Astrophysics Data System (ADS)

    Ma, Y. M.; Zhou, Q.; He, Z.; Li, F. F.; Yang, K. F.; Cui, Q. L.; Zou, G. T.

    2007-10-01

    The high-pressure and high-temperature behaviors of anhydrite (CaSO4) are studied up to 53.5 GPa and 1800 K using double-sided laser heating Raman spectroscopy and x-ray diffraction in diamond anvil cells. The evidence of phase transition from an anhydrite structure to the monazite type was observed at about 2 GPa under cold compression. Another phase transition and a change in color of the sample from transparent to black have been also observed at a pressure of 33.2 GPa after laser heating. The new phase after laser heating persists to 53.5 GPa and 1800 K.

  12. Role of relativity in high-pressure phase transitions of thallium

    NASA Astrophysics Data System (ADS)

    Kotmool, Komsilp; Chakraborty, Sudip; Bovornratanaraks, Thiti; Ahuja, Rajeev

    2017-02-01

    We demonstrate the relativistic effects in high-pressure phase transitions of heavy element thallium. The known first phase transition from h.c.p. to f.c.c. is initially investigated by various relativistic levels and exchange-correlation functionals as implemented in FPLO method, as well as scalar relativistic scheme within PAW formalism. The electronic structure calculations are interpreted from the perspective of energetic stability and electronic density of states. The full relativistic scheme (FR) within L(S)DA performs to be the scheme that resembles mostly with experimental results with a transition pressure of 3 GPa. The s-p hybridization and the valence-core overlapping of 6s and 5d states are the primary reasons behind the f.c.c. phase occurrence. A recent proposed phase, i.e., a body-centered tetragonal (b.c.t.) phase, is confirmed with a small distortion from the f.c.c. phase. We have also predicted a reversible b.c.t. → f.c.c. phase transition at 800 GPa. This finding has been suggested that almost all the III-A elements (Ga, In and Tl) exhibit the b.c.t. → f.c.c. phase transition at extremely high pressure.

  13. High-Pressure Phase Transition in Cs 2KMnF 6

    NASA Astrophysics Data System (ADS)

    Xu, Y.; Söderberg, K.; Norrestam, R.

    2000-09-01

    The stability of the cubic high-temperature (HT) form of Cs2KMnF6, with an elpasolite structure, is studied at elevated pressures. The present study shows that the HT form of Cs2KMnF6 undergoes a pressure-induced phase transition at 40 kbar to a more ordered high-pressure (HP) phase of lower symmetry. The space group symmetry of the HP phase, I4/mmm, is the same as that observed for the low-temperature (LT) phase. High-pressure studies performed on the LT phase indicated no transitions up to 50 kbar and gave compressibility features similar to those obtained for the HP phase. Single-crystal X-ray diffraction data for the HP phase were collected at 44 kbar. Refining nine structural parameters against 69 independent significant reflections gave a linear R value of 0.072 (wR=0.086). The values of the positional parameters are in agreement with those observed for the LT phase under ambient conditions. The transition characteristics for the HT form depend on the crystal quality and/or the pressure transmitting media used. With liquid argon, loaded into the pressure cell at low temperature and ambient pressure, the transition pressure became 30 kbar. With methanol:ethanol:water, loaded under ambient conditions, the transition was observed at 40 kbar.

  14. Role of relativity in high-pressure phase transitions of thallium.

    PubMed

    Kotmool, Komsilp; Chakraborty, Sudip; Bovornratanaraks, Thiti; Ahuja, Rajeev

    2017-02-20

    We demonstrate the relativistic effects in high-pressure phase transitions of heavy element thallium. The known first phase transition from h.c.p. to f.c.c. is initially investigated by various relativistic levels and exchange-correlation functionals as implemented in FPLO method, as well as scalar relativistic scheme within PAW formalism. The electronic structure calculations are interpreted from the perspective of energetic stability and electronic density of states. The full relativistic scheme (FR) within L(S)DA performs to be the scheme that resembles mostly with experimental results with a transition pressure of 3 GPa. The s-p hybridization and the valence-core overlapping of 6s and 5d states are the primary reasons behind the f.c.c. phase occurrence. A recent proposed phase, i.e., a body-centered tetragonal (b.c.t.) phase, is confirmed with a small distortion from the f.c.c. phase. We have also predicted a reversible b.c.t. → f.c.c. phase transition at 800 GPa. This finding has been suggested that almost all the III-A elements (Ga, In and Tl) exhibit the b.c.t. → f.c.c. phase transition at extremely high pressure.

  15. Role of relativity in high-pressure phase transitions of thallium

    PubMed Central

    Kotmool, Komsilp; Chakraborty, Sudip; Bovornratanaraks, Thiti; Ahuja, Rajeev

    2017-01-01

    We demonstrate the relativistic effects in high-pressure phase transitions of heavy element thallium. The known first phase transition from h.c.p. to f.c.c. is initially investigated by various relativistic levels and exchange-correlation functionals as implemented in FPLO method, as well as scalar relativistic scheme within PAW formalism. The electronic structure calculations are interpreted from the perspective of energetic stability and electronic density of states. The full relativistic scheme (FR) within L(S)DA performs to be the scheme that resembles mostly with experimental results with a transition pressure of 3 GPa. The s-p hybridization and the valence-core overlapping of 6s and 5d states are the primary reasons behind the f.c.c. phase occurrence. A recent proposed phase, i.e., a body-centered tetragonal (b.c.t.) phase, is confirmed with a small distortion from the f.c.c. phase. We have also predicted a reversible b.c.t. → f.c.c. phase transition at 800 GPa. This finding has been suggested that almost all the III-A elements (Ga, In and Tl) exhibit the b.c.t. → f.c.c. phase transition at extremely high pressure. PMID:28216669

  16. Phase equilibria in molecular hydrogen-helium mixtures at high pressures

    NASA Technical Reports Server (NTRS)

    Streett, W. B.

    1973-01-01

    Experiments on phase behavior in hydrogen-helium mixtures have been carried out at pressures up to 9.3 kilobars, at temperatures from 26 to 100 K. Two distinct fluid phases are shown to exist at supercritical temperatures and high pressures. Both the trend of the experimental results and an analysis based on the van der Waals theory of mixtures suggest that this fluid-fluid phase separation persists at temperatures and pressures beyond the range of these experiments, perhaps even to the limits of stability of the molecular phases. The results confirm earlier predictions concerning the form of the hydrogen-helium phase diagram in the region of pressure-induced solidification of the molecular phases at supercritical temperatures. The implications of this phase diagram for planetary interiors are discussed.

  17. 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.

  18. Pyroxenes and olivines: Structural implications of shock-wave data for high pressure phases

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.; Ahrens, T. J.

    1975-01-01

    The nature of the shock-induced, high-pressure phases of olivine and pyroxene rocks is examined in the light of data for the densities of a new class of perovskite-related silicate structures. Also examined are some new Hugoniot and release adiabat data for bronzite. Reexamining available shock data for magnesian pyroxenes and olivines leads to the conclusion that they define a mixed phase (or disequilibrium) region to about the 100 GPa range, related to the kinetics of phase transformation in these silicates. By recognizing this point, certain discrepancies in previous interpretations of shock data can be explained. A set of theoretical Hugonoits for pyroxene and olivine stoichiometry, perovskite-bearing assemblages was constructed based on their properties deduced from high-pressure work, showing that the shock data is compatible with transformations to perovskites in the 45-7GPa region. Finally, the shock data indicate very similar properties for olivine and pyroxene at high pressures making them both equally likely candidates for the lower mantle.

  19. Structural phase transitions in Bi2Se3 under high pressure

    DOE PAGES

    Yu, Zhenhai; Gu, Genda; Wang, Lin; ...

    2015-11-02

    Raman spectroscopy and angle dispersive X-ray diffraction (XRD) experiments of bismuth selenide (Bi2Se3) have been carried out to pressures of 35.6 and 81.2 GPa, respectively, to explore its pressure-induced phase transformation. The experiments indicate that a progressive structural evolution occurs from an ambient rhombohedra phase (Space group (SG): R-3m) to monoclinic phase (SG: C2/m) and eventually to a high pressure body-centered tetragonal phase (SG: I4/mmm). Evidenced by our XRD data up to 81.2 GPa, the Bi2Se3 crystallizes into body-centered tetragonal structures rather than the recently reported disordered body-centered cubic (BCC) phase. Furthermore, first principles theoretical calculations favor the viewpoint thatmore » the I4/mmm phase Bi2Se3 can be stabilized under high pressure (>30 GPa). Remarkably, the Raman spectra of Bi2Se3 from this work (two independent runs) are still Raman active up to ~35 GPa. Furthermore, it is worthy to note that the disordered BCC phase at 27.8 GPa is not observed here. The remarkable difference in atomic radii of Bi and Se in Bi2Se3 may explain why Bi2Se3 shows different structural behavior than isocompounds Bi2Te3 and Sb2Te3.« less

  20. Structural phase transitions in Bi2Se3 under high pressure

    NASA Astrophysics Data System (ADS)

    Yu, Zhenhai; Wang, Lin; Hu, Qingyang; Zhao, Jinggeng; Yan, Shuai; Yang, Ke; Sinogeikin, Stanislav; Gu, Genda; Mao, Ho-Kwang

    2015-11-01

    Raman spectroscopy and angle dispersive X-ray diffraction (XRD) experiments of bismuth selenide (Bi2Se3) have been carried out to pressures of 35.6 and 81.2 GPa, respectively, to explore its pressure-induced phase transformation. The experiments indicate that a progressive structural evolution occurs from an ambient rhombohedra phase (Space group (SG): R-3m) to monoclinic phase (SG: C2/m) and eventually to a high pressure body-centered tetragonal phase (SG: I4/mmm). Evidenced by our XRD data up to 81.2 GPa, the Bi2Se3 crystallizes into body-centered tetragonal structures rather than the recently reported disordered body-centered cubic (BCC) phase. Furthermore, first principles theoretical calculations favor the viewpoint that the I4/mmm phase Bi2Se3 can be stabilized under high pressure (>30 GPa). Remarkably, the Raman spectra of Bi2Se3 from this work (two independent runs) are still Raman active up to ~35 GPa. It is worthy to note that the disordered BCC phase at 27.8 GPa is not observed here. The remarkable difference in atomic radii of Bi and Se in Bi2Se3 may explain why Bi2Se3 shows different structural behavior than isocompounds Bi2Te3 and Sb2Te3.

  1. Structural phase transitions in Bi2Se3 under high pressure.

    PubMed

    Yu, Zhenhai; Wang, Lin; Hu, Qingyang; Zhao, Jinggeng; Yan, Shuai; Yang, Ke; Sinogeikin, Stanislav; Gu, Genda; Mao, Ho-kwang

    2015-11-02

    Raman spectroscopy and angle dispersive X-ray diffraction (XRD) experiments of bismuth selenide (Bi2Se3) have been carried out to pressures of 35.6 and 81.2 GPa, respectively, to explore its pressure-induced phase transformation. The experiments indicate that a progressive structural evolution occurs from an ambient rhombohedra phase (Space group (SG): R-3m) to monoclinic phase (SG: C2/m) and eventually to a high pressure body-centered tetragonal phase (SG: I4/mmm). Evidenced by our XRD data up to 81.2 GPa, the Bi2Se3 crystallizes into body-centered tetragonal structures rather than the recently reported disordered body-centered cubic (BCC) phase. Furthermore, first principles theoretical calculations favor the viewpoint that the I4/mmm phase Bi2Se3 can be stabilized under high pressure (>30 GPa). Remarkably, the Raman spectra of Bi2Se3 from this work (two independent runs) are still Raman active up to ~35 GPa. It is worthy to note that the disordered BCC phase at 27.8 GPa is not observed here. The remarkable difference in atomic radii of Bi and Se in Bi2Se3 may explain why Bi2Se3 shows different structural behavior than isocompounds Bi2Te3 and Sb2Te3.

  2. Phase transformation of Ho[subscript 2]O[subscript 3] at high pressure

    SciTech Connect

    Jiang, Sheng; Liu, Jing; Li, Xiaodong; Bai, Ligang; Xiao, Wansheng; Zhang, Yufeng; Lin, Chuanlong; Li, Yanchun; Tang, Lingyun

    2012-01-20

    The structural stability of cubic Ho{sub 2}O{sub 3} under high pressure has been investigated by angle-dispersive x-ray diffraction (ADXD) in a diamond anvil cell up to 63.0 GPa at room temperature. The diffraction data reveal two structural transformations on compression. The structural transformation from a cubic to a monoclinic structure starts at 8.9 GPa and is complete at 16.3 GPa with an {approx}8.1% volume collapse. A hexagonal phase begins to appear at {approx}14.8 GPa and becomes dominant at 26.4 GPa. This high-pressure hexagonal phase with a small amount of retained monoclinic phase is stable up to the highest pressure of 63.0 GPa in this study. After release of pressure, the hexagonal phase transforms to a monoclinic structure. A third-order Birch-Murnaghan fit yields zero pressure bulk moduli (B{sub 0}) of 206(3), 200(7) and 204(19) GPa and their pressure derivatives (B'{sub 0}) of 4.8(4), 2.1(4), 3.8(5) for the cubic, monoclinic and hexagonal phases, respectively. Comparing with other rare-earth sesquioxides, it is suggested that the transition pressure from cubic to monoclinic phase, as well as the bulk modulus of the cubic phase, increases with the decreasing of the cation radius of rare-earth sesquioxides.

  3. High-pressure phases of a hydrogen-rich compound: Tetramethylgermane

    NASA Astrophysics Data System (ADS)

    Qin, Zhen-Xing; Zhang, Chao; Tang, Ling-Yun; Zhong, Guo-Hua; Lin, Hai-Qing; Chen, Xiao-Jia

    2012-11-01

    The vibrational and structural properties of a hydrogen-rich group IVa hydride, Ge(CH3)4, are studied by combining Raman spectroscopy and synchrotron x-ray diffraction measurements at room temperature and at pressures up to 30.2 GPa. Both techniques allow the obtaining of complementary information on the high-pressure behaviors and yield consistent phase transitions at 1.4 GPa for the liquid to solid and 3.0, 5.4, and 20.3 GPa for the solid to solid. The four high-pressure solid phases are identified to have the cubic, orthorhombic, monoclinic, and monoclinic crystal structures with space groups of Pa-3 for phase I, Pnma for phase II, P21/c for phase III, and P21 for phase IV, respectively. These transitions are suggested to result from the changes in the inter- and intramolecular bonding of this compound. The softening of some Raman modes on CH3 groups and their sudden disappearance indicate that Ge(CH3)4 might be an ideal compound to realize metallization and even high-temperature superconductivity at modest static pressure for laboratory capability.

  4. A new high-pressure phase transition in natural Fe-bearing orthoenstatite

    SciTech Connect

    Zhang, Jin S.; Dera, Przemyslaw; Bass, Jay D.

    2016-07-29

    Single-crystal X-ray structure refinements have been carried out on natural Fe-bearing orthoenstatite (OEN) at pressures up to 14.53 GPa. We report a new high-pressure phase transition from OEN to a monoclinic phase (HPCEN2) with space group P2{sub 1}/c, with a density change of {approx}1.9(3)%. The HPCEN2 phase is crystallographically different from low-pressure clinoenstatite (LPCEN), which also has P2{sub 1}/c symmetry. Upon release of pressure HPCEN2 reverts to OEN, and the transition pressure is bracketed between 9.96 and 14.26 GPa at room temperature. We find no evidence for a C2/c phase at high pressure. The lattice constants for the new phase at 14.26 GPa are a = 17.87(2), b = 8.526(9), c = 4.9485(10) {angstrom}, {beta} = 92.88(4){sup o} [{rho} = 3.658(9) g/cm{sup 3}]. Refinement of the new structure indicates rotation of tetrahedral chain as the key characteristic of this transition. This experiment points to the possibility of OEN and HPCEN2 as the stable phases in Earth's upper mantle.

  5. Superconducting H5S2 phase in sulfur-hydrogen system under high-pressure

    PubMed Central

    Ishikawa, Takahiro; Nakanishi, Akitaka; Shimizu, Katsuya; Katayama-Yoshida, Hiroshi; Oda, Tatsuki; Suzuki, Naoshi

    2016-01-01

    Recently, hydrogen sulfide was experimentally found to show the high superconducting critical temperature (Tc) under high-pressure. The superconducting Tc shows 30–70 K in pressure range of 100–170 GPa (low-Tc phase) and increases to 203 K, which sets a record for the highest Tc in all materials, for the samples annealed by heating it to room temperature at pressures above 150 GPa (high-Tc phase). Here we present a solid H5S2 phase predicted as the low-Tc phase by the application of the genetic algorithm technique for crystal structure searching and first-principles calculations to sulfur-hydrogen system under high-pressure. The H5S2 phase is thermodynamically stabilized at 110 GPa, in which asymmetric hydrogen bonds are formed between H2S and H3S molecules. Calculated Tc values show 50–70 K in pressure range of 100–150 GPa within the harmonic approximation, which can reproduce the experimentally observed low-Tc phase. These findings give a new aspect of the excellent superconductivity in compressed sulfur-hydrogen system. PMID:26983593

  6. Superconducting H5S2 phase in sulfur-hydrogen system under high-pressure

    NASA Astrophysics Data System (ADS)

    Ishikawa, Takahiro; Nakanishi, Akitaka; Shimizu, Katsuya; Katayama-Yoshida, Hiroshi; Oda, Tatsuki; Suzuki, Naoshi

    2016-03-01

    Recently, hydrogen sulfide was experimentally found to show the high superconducting critical temperature (Tc) under high-pressure. The superconducting Tc shows 30–70 K in pressure range of 100–170 GPa (low-Tc phase) and increases to 203 K, which sets a record for the highest Tc in all materials, for the samples annealed by heating it to room temperature at pressures above 150 GPa (high-Tc phase). Here we present a solid H5S2 phase predicted as the low-Tc phase by the application of the genetic algorithm technique for crystal structure searching and first-principles calculations to sulfur-hydrogen system under high-pressure. The H5S2 phase is thermodynamically stabilized at 110 GPa, in which asymmetric hydrogen bonds are formed between H2S and H3S molecules. Calculated Tc values show 50–70 K in pressure range of 100–150 GPa within the harmonic approximation, which can reproduce the experimentally observed low-Tc phase. These findings give a new aspect of the excellent superconductivity in compressed sulfur-hydrogen system.

  7. Effect of high pressure homogenization on aqueous phase solvent extraction of lipids from Nannochloris Oculata microalgae

    SciTech Connect

    Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.

    2012-12-01

    The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage. Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.

  8. Effect of high pressure homogenization on aqueous phase solvent extraction of lipids from Nannochloris Oculata microalgae

    DOE PAGES

    Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.

    2012-12-01

    The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage.more » Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.« less

  9. High-pressure phase transition and equation of state of CsI

    NASA Technical Reports Server (NTRS)

    Mao, H. K.; Hemley, R. J.; Chen, L. C.; Shu, J. F.; Wu, Y.

    1990-01-01

    Stuructural properties of CsI at high pressure have been investigated by the use of synchrotron X-ray-diffraction techniques with the diamond-anvil cell at 300 K. The results indicate that the material undergoes a continuous distortion from B2 to an hcp-like phase, which is stable to at least 302 GPa. The intermediate orthorhombic phase is geometrically different from previous assignments and about 10 percent denser. With the new structure, the p-V results of static pressure experiments, shock-wave studies, and theoretical calculations are now in good agreement.

  10. Computation of Space Shuttle high-pressure cryogenic turbopump ball bearing two-phase coolant flow

    NASA Technical Reports Server (NTRS)

    Chen, Yen-Sen

    1990-01-01

    A homogeneous two-phase fluid flow model, implemented in a three-dimensional Navier-Stokes solver using computational fluid dynamics methodology is described. The application of the model to the analysis of the pump-end bearing coolant flow of the high-pressure oxygen turbopump of the Space Shuttle main engine is studied. Results indicate large boiling zones and hot spots near the ball/race contact points. The extent of the phase change of the liquid oxygen coolant flow due to the frictional and viscous heat fluxes near the contact areas has been investigated for the given inlet conditions of the coolant.

  11. Phase Transitions in Solids Stimulated by Simultaneous Exposure to High Pressure and Relativistic Heavy Ions

    SciTech Connect

    Glasmacher, Ulrich A.; Lang, Maik; Neumann, Reinhard; Schardt, Dieter; Trautmann, Christina; Keppler, Hans; Langenhorst, Falko; Wagner, Guenther A.

    2006-05-19

    In many solids, heavy ions of high kinetic energy (MeV-GeV) produce long cylindrical damage trails with diameters of order 10 nm. Up to now, no information was available how solids cope with the simultaneous exposure to these energetic projectiles and to high pressure. We report the first experiments where relativistic uranium and gold ions from the SIS heavy-ion synchrotron at GSI were injected through several mm of diamond into solid samples pressurized up to 14 GPa in a diamond anvil cell. In synthetic graphite and natural zircon, the combination of pressure and ion beams triggered drastic structural changes not caused by the applied pressure or the ions alone. The modifications comprise long-range amorphization of graphite rather than individual track formation, and in the case of zircon the decomposition into nanocrystals and nucleation of the high-pressure phase reidite.

  12. Light-induced phase transition in AlD3 at high pressure

    NASA Astrophysics Data System (ADS)

    Besedin, Stanislav P.; Jephcoat, Andrew P.; Irodova, Alla V.

    2011-09-01

    Trivalent aluminum hydride in the rhombohedral α phase (R3¯c space group) was studied at high pressures in a diamond-anvil cell by means of Raman scattering, x-ray diffraction, observation of optical transmission, and the density functional simulations. At P≈53 GPa the heavier isotope AlD3 undergoes a first-order structural phase transition which was found to be stimulated by the laser irradiation used for the Raman-scattering measurements. In the new high-pressure phase Al atoms form a lattice with a monoclinic unit cell (P21/c space group) over which a superstructure is developed when pressure is varied. The superstructure is formed by regular displacements of the Al atoms with the period over three unit cells; the propagation vector is k2=((1)/(3)(1)/(3)(1)/(3)). The undistorted P21/c lattice itself appears as superstructure over the rhombohedral R3¯c one resulting from the displacive structure transformation with the propagation vector k1=((1)/(2)0(1)/(2)). The band gap as given by the density functional calculations and evidenced from the sample transparency behavior at high pressures remains greater than the laser photon energy used (Eph=2.41 eV). That indicates that bond weakening/breaking due to electron excitation across the band gap is not the cause of the phase transition. A likely mechanism of the light action is that structure transformation is driven by phonons, which are excited due to strong electron-phonon coupling in the α phase.

  13. Phase transition induced strain in ZnO under high pressure

    SciTech Connect

    Yan, Xiaozhi; Dong, Haini; Li, Yanchun; Lin, Chuanlong; Park, Changyong; He, Duanwei; Yang, Wenge

    2016-05-13

    Under high pressure, the phase transition mechanism and mechanical property of material are supposed to be largely associated with the transformation induced elastic strain. However, the experimental evidences for such strain are scanty. The elastic and plastic properties of ZnO, a leading material for applications in chemical sensor, catalyst, and optical thin coatings, were determined using in situ high pressure synchrotron axial and radial x-ray diffraction. The abnormal elastic behaviors of selected lattice planes of ZnO during phase transition revealed the existence of internal elastic strain, which arise from the lattice misfit between wurtzite and rocksalt phase. Furthermore, the strength decrease of ZnO during phase transition under non-hydrostatic pressure was observed and could be attributed to such internal elastic strain, unveiling the relationship between pressure induced internal strain and mechanical property of material. Ultimately, these findings are of fundamental importance to understanding the mechanism of phase transition and the properties of materials under pressure.

  14. Phase transition induced strain in ZnO under high pressure

    DOE PAGES

    Yan, Xiaozhi; Dong, Haini; Li, Yanchun; ...

    2016-05-13

    Under high pressure, the phase transition mechanism and mechanical property of material are supposed to be largely associated with the transformation induced elastic strain. However, the experimental evidences for such strain are scanty. The elastic and plastic properties of ZnO, a leading material for applications in chemical sensor, catalyst, and optical thin coatings, were determined using in situ high pressure synchrotron axial and radial x-ray diffraction. The abnormal elastic behaviors of selected lattice planes of ZnO during phase transition revealed the existence of internal elastic strain, which arise from the lattice misfit between wurtzite and rocksalt phase. Furthermore, the strengthmore » decrease of ZnO during phase transition under non-hydrostatic pressure was observed and could be attributed to such internal elastic strain, unveiling the relationship between pressure induced internal strain and mechanical property of material. Ultimately, these findings are of fundamental importance to understanding the mechanism of phase transition and the properties of materials under pressure.« less

  15. Phase transition induced strain in ZnO under high pressure

    PubMed Central

    Yan, Xiaozhi; Dong, Haini; Li, Yanchun; Lin, Chuanlong; Park, Changyong; He, Duanwei; Yang, Wenge

    2016-01-01

    Under high pressure, the phase transition mechanism and mechanical property of material are supposed to be largely associated with the transformation induced elastic strain. However, the experimental evidences for such strain are scanty. The elastic and plastic properties of ZnO, a leading material for applications in chemical sensor, catalyst, and optical thin coatings, were determined using in situ high pressure synchrotron axial and radial x-ray diffraction. The abnormal elastic behaviors of selected lattice planes of ZnO during phase transition revealed the existence of internal elastic strain, which arise from the lattice misfit between wurtzite and rocksalt phase. Furthermore, the strength decrease of ZnO during phase transition under non-hydrostatic pressure was observed and could be attributed to such internal elastic strain, unveiling the relationship between pressure induced internal strain and mechanical property of material. These findings are of fundamental importance to understanding the mechanism of phase transition and the properties of materials under pressure. PMID:27173609

  16. Monitoring Rates and Heterogeneity of High-Pressure Germination of Bacillus Spores by Phase-Contrast Microscopy of Individual Spores

    DTIC Science & Technology

    2014-01-01

    SECURITY CLASSIFICATION OF: The germination of multiple individual Bacillus subtilis spores by a high pressure (HP) of 140-150 (unless noted...public release; distribution is unlimited. Monitoring Rates and Heterogeneity of High-Pressure Germination of Bacillus Spores by Phase-Contrast Microscopy...ADDRESS (ES) U.S. Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 Bacillus , spores, spore germination, high pressure, pressure

  17. High-pressure Sapphire Cell for Phase Equilibria Measurements of CO2/Organic/Water Systems

    PubMed Central

    Pollet, Pamela; Ethier, Amy L.; Senter, James C.; Eckert, Charles A.; Liotta, Charles L.

    2014-01-01

    The high pressure sapphire cell apparatus was constructed to visually determine the composition of multiphase systems without physical sampling. Specifically, the sapphire cell enables visual data collection from multiple loadings to solve a set of material balances to precisely determine phase composition. Ternary phase diagrams can then be established to determine the proportion of each component in each phase at a given condition. In principle, any ternary system can be studied although ternary systems (gas-liquid-liquid) are the specific examples discussed herein. For instance, the ternary THF-Water-CO2 system was studied at 25 and 40 °C and is described herein. Of key importance, this technique does not require sampling. Circumventing the possible disturbance of the system equilibrium upon sampling, inherent measurement errors, and technical difficulties of physically sampling under pressure is a significant benefit of this technique. Perhaps as important, the sapphire cell also enables the direct visual observation of the phase behavior. In fact, as the CO2 pressure is increased, the homogeneous THF-Water solution phase splits at about 2 MPa. With this technique, it was possible to easily and clearly observe the cloud point and determine the composition of the newly formed phases as a function of pressure. The data acquired with the sapphire cell technique can be used for many applications. In our case, we measured swelling and composition for tunable solvents, like gas-expanded liquids, gas-expanded ionic liquids and Organic Aqueous Tunable Systems (OATS)1-4. For the latest system, OATS, the high-pressure sapphire cell enabled the study of (1) phase behavior as a function of pressure and temperature, (2) composition of each phase (gas-liquid-liquid) as a function of pressure and temperature and (3) catalyst partitioning in the two liquid phases as a function of pressure and composition. Finally, the sapphire cell is an especially effective tool to gather

  18. High-pressure sapphire cell for phase equilibria measurements of CO2/organic/water systems.

    PubMed

    Pollet, Pamela; Ethier, Amy L; Senter, James C; Eckert, Charles A; Liotta, Charles L

    2014-01-24

    The high pressure sapphire cell apparatus was constructed to visually determine the composition of multiphase systems without physical sampling. Specifically, the sapphire cell enables visual data collection from multiple loadings to solve a set of material balances to precisely determine phase composition. Ternary phase diagrams can then be established to determine the proportion of each component in each phase at a given condition. In principle, any ternary system can be studied although ternary systems (gas-liquid-liquid) are the specific examples discussed herein. For instance, the ternary THF-Water-CO2 system was studied at 25 and 40 °C and is described herein. Of key importance, this technique does not require sampling. Circumventing the possible disturbance of the system equilibrium upon sampling, inherent measurement errors, and technical difficulties of physically sampling under pressure is a significant benefit of this technique. Perhaps as important, the sapphire cell also enables the direct visual observation of the phase behavior. In fact, as the CO2 pressure is increased, the homogeneous THF-Water solution phase splits at about 2 MPa. With this technique, it was possible to easily and clearly observe the cloud point and determine the composition of the newly formed phases as a function of pressure. The data acquired with the sapphire cell technique can be used for many applications. In our case, we measured swelling and composition for tunable solvents, like gas-expanded liquids, gas-expanded ionic liquids and Organic Aqueous Tunable Systems (OATS)(1-4). For the latest system, OATS, the high-pressure sapphire cell enabled the study of (1) phase behavior as a function of pressure and temperature, (2) composition of each phase (gas-liquid-liquid) as a function of pressure and temperature and (3) catalyst partitioning in the two liquid phases as a function of pressure and composition. Finally, the sapphire cell is an especially effective tool to gather

  19. On the Concordance of Static High Pressure Phase Transformation Data on Minerals With Shock Wave Data

    NASA Astrophysics Data System (ADS)

    de Carli, P. S.; El Goresy, A.; Xie, Z.; Sharp, T. G.

    2006-12-01

    . In other samples, constrained to the same pressure range, long-duration (> 0.1 s) shock pressures are inferred from constant high-pressure mineralogy across wide (>1mm) veins and diaplectic glass is found throughout the meteorite. Evidence for kinetic effects may also be inferred from studies of samples from large impact craters. Pressure estimates based on shock recovery experiments imply post-shock temperatures that are too high for the survival of metastable high-pressure phases, such as stishovite, present in the samples. Release adiabat measurements on quartz also account for the presence of coesite in association with stishovite and diaplectic glass. Release wave velocitie slow below about 7 GPa, providing a relatively long period for the growth of coesite in its stability field from shock heated silica. Studies of high-pressure phases of olivine and pyroxene in meteorites are also concordant with both static high pressure data and inferences from Hugoniot and release measurements. These phases are not found in microsecond duration shock recovery experiments. Finally experiments on the shock synthesis of diamond are in complete accord with evidence for shock synthesized diamond in large impact craters and with static high pressure data on the direct uncatalyzed transition of graphite to diamond.

  20. High pressure-induced distortion in face-centered cubic phase of thallium

    NASA Astrophysics Data System (ADS)

    Kotmool, Komsilp; Li, Bing; Chakraborty, Sudip; Bovornratanaraks, Thiti; Luo, Wei; Mao, Ho-kwang; Ahuja, Rajeev

    2016-10-01

    The complex and unusual high-pressure phase transition of III-A (i.e. Al, Ga, and In) metals have been investigated in the last several decades because of their interesting periodic table position between the elements having metallic and covalent bonding. Our present first principles-based electronic structure calculations and experimental investigation have revealed the unusual distortion in face-centered cubic (f.c.c.) phase of the heavy element thallium (Tl) induced by the high pressure. We have predicted body-centered tetragonal (b.c.t) phase at 83 GPa using an evolutionary algorithm coupled with ab initio calculations, and this prediction has been confirmed with a slightly distorted parameter (2 × a - c)/c lowered by 1% using an angle-dispersive X-ray diffraction technique. The density functional theory (DFT)-based calculations suggest that s-p mixing states and the valence-core overlapping of 6s and 5d states play the most important roles for the phase transitions along the pathway h.c.p→b.c.t.

  1. Phase transformation and fluorescent enhancement of ErF3 at high pressure

    NASA Astrophysics Data System (ADS)

    Li, Wentao; Ren, Xiangting; Huang, Yanwei; Yu, Zhenhai; Mi, Zhongying; Tamura, Nobumichi; Li, Xiaodong; Peng, Fang; Wang, Lin

    2016-09-01

    Pressure-induced phase transformation and fluorescent properties of ErF3 were investigated here using in-situ synchrotron X-ray diffraction and photoluminescence up to 32.1 GPa at room temperature. Results showed that ErF3 underwent a reversible pressure-induced phase transition from the β-YF3-type to the fluocerite LaF3-type at 9.8 GPa. The bulk moduli B0 for low- and high-pressure phases were determined to be 130 and 208 GPa, respectively. Photoluminescencent studies showed that new emission lines belonging to the transition of 2H11/2→4I15/2, 4S3/2→4I15/2, and 4F9/2→4I15/2 appeared during phase transition, suggesting pressure-induced electronic band splitting. Remarkably, significant pressure-induced enhancement of photoluminescence was observed, which was attributed to lattice distortion of the material under high pressure.

  2. High pressure-induced distortion in face-centered cubic phase of thallium.

    PubMed

    Kotmool, Komsilp; Li, Bing; Chakraborty, Sudip; Bovornratanaraks, Thiti; Luo, Wei; Mao, Ho-Kwang; Ahuja, Rajeev

    2016-10-04

    The complex and unusual high-pressure phase transition of III-A (i.e. Al, Ga, and In) metals have been investigated in the last several decades because of their interesting periodic table position between the elements having metallic and covalent bonding. Our present first principles-based electronic structure calculations and experimental investigation have revealed the unusual distortion in face-centered cubic (f.c.c.) phase of the heavy element thallium (Tl) induced by the high pressure. We have predicted body-centered tetragonal (b.c.t) phase at 83 GPa using an evolutionary algorithm coupled with ab initio calculations, and this prediction has been confirmed with a slightly distorted parameter ([Formula: see text] × a - c)/c lowered by 1% using an angle-dispersive X-ray diffraction technique. The density functional theory (DFT)-based calculations suggest that s-p mixing states and the valence-core overlapping of 6s and 5d states play the most important roles for the phase transitions along the pathway h.c.p[Formula: see text]f.c.c.[Formula: see text]b.c.t.

  3. Successive disorder to disorder phase transitions in ionic liquid [HMIM][BF4] under high pressure

    NASA Astrophysics Data System (ADS)

    Zhu, Xiang; Yuan, Chaosheng; Li, Haining; Zhu, Pinwen; Su, Lei; Yang, Kun; Wu, Jie; Yang, Guoqiang; Liu, Jing

    2016-02-01

    In situ high-pressure Raman spectroscopy and synchrotron X-ray diffraction have been employed to investigate the phase behavior of ionic liquid, 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][BF4]) under high pressure up to 20 GPa at room temperature. With increasing pressure, some characteristic bands of [HMIM][BF4] disappear, and some characteristic bands of [HMIM][BF4] display non-monotonic pressure-induced frequency shift and non-monotonic variation of full width at half-maximum. Two successive phase transitions at ˜1.7 GPa and 7.3 GPa have been corroborated by the results above. The glass transition pressure (Pg) of [HMIM][BF4] at ˜7.3 GPa has been obtained by ruby R1 line broadening measurements and analysis of synchrotron X-ray diffraction patterns, and its glass transition mechanism is also analyzed in detail. These facts are suggestive of two successive disorder to disorder phase transitions induced by compression, that is, [HMIM][BF4] serves as a superpressurized glass under the pressure above 7.3 GPa, which is similar to the glassy state at low temperature, and a compression-induced liquid to liquid phase transition in [HMIM][BF4] occurs at ˜1.7 GPa. Besides, the conformational equilibrium of the GAAA conformer and AAAA conformer was converted easily in liquid [HMIM][BF4], while it was difficult to be influenced in glassy state.

  4. High pressure-induced distortion in face-centered cubic phase of thallium

    PubMed Central

    Kotmool, Komsilp; Li, Bing; Chakraborty, Sudip; Bovornratanaraks, Thiti; Luo, Wei; Mao, Ho-kwang; Ahuja, Rajeev

    2016-01-01

    The complex and unusual high-pressure phase transition of III-A (i.e. Al, Ga, and In) metals have been investigated in the last several decades because of their interesting periodic table position between the elements having metallic and covalent bonding. Our present first principles-based electronic structure calculations and experimental investigation have revealed the unusual distortion in face-centered cubic (f.c.c.) phase of the heavy element thallium (Tl) induced by the high pressure. We have predicted body-centered tetragonal (b.c.t) phase at 83 GPa using an evolutionary algorithm coupled with ab initio calculations, and this prediction has been confirmed with a slightly distorted parameter (2 × a − c)/c lowered by 1% using an angle-dispersive X-ray diffraction technique. The density functional theory (DFT)-based calculations suggest that s–p mixing states and the valence-core overlapping of 6s and 5d states play the most important roles for the phase transitions along the pathway h.c.p→f.c.c.→b.c.t. PMID:27655891

  5. On the high-pressure phase stability and elastic properties of β-titanium alloys

    NASA Astrophysics Data System (ADS)

    Smith, D.; Joris, O. P. J.; Sankaran, A.; Weekes, H. E.; Bull, D. J.; Prior, T. J.; Dye, D.; Errandonea, D.; Proctor, J. E.

    2017-04-01

    We have studied the compressibility and stability of different β-titanium alloys at high pressure, including binary Ti–Mo, Ti–24Nb–4Zr–8Sn (Ti2448) and Ti–36Nb–2Ta–0.3O (gum metal). We observed stability of the β phase in these alloys to 40 GPa, well into the ω phase region in the P–T diagram of pure titanium. Gum metal was pressurised above 70 GPa and forms a phase with a crystal structure similar to the η phase of pure Ti. The bulk moduli determined for the different alloys range from 97  ±  3 GPa (Ti2448) to 124  ±  6 GPa (Ti–16.8Mo–0.13O).

  6. On the high-pressure phase stability and elastic properties of β-titanium alloys.

    PubMed

    Smith, D; Joris, O P J; Sankaran, A; Weekes, H E; Bull, D J; Prior, T J; Dye, D; Errandonea, D; Proctor, J E

    2017-04-20

    We have studied the compressibility and stability of different β-titanium alloys at high pressure, including binary Ti-Mo, Ti-24Nb-4Zr-8Sn (Ti2448) and Ti-36Nb-2Ta-0.3O (gum metal). We observed stability of the β phase in these alloys to 40 GPa, well into the ω phase region in the P-T diagram of pure titanium. Gum metal was pressurised above 70 GPa and forms a phase with a crystal structure similar to the η phase of pure Ti. The bulk moduli determined for the different alloys range from 97  ±  3 GPa (Ti2448) to 124  ±  6 GPa (Ti-16.8Mo-0.13O).

  7. Superconductivity in metastable phases of phosphorus-hydride compounds under high pressure

    NASA Astrophysics Data System (ADS)

    Flores Livas, Jose; Amsler, Maximilian; Sanna, Antonio; Heil, Christoph; Boeri, Lilia; Profeta, Gianni; Wolverton, Crhis; Goedecker, Stefan; Gross, E. K. U.

    Recently, compressed phosphine was reported to metallize at pressures above 45 GPa, reaching a superconducting transition temperature (Tc) of 100 K at 200 GPa. However, neither the exact composition nor the crystal structure of the superconducting phase have been conclusively determined. In this work the phase diagram of PHn (n = 1 , 2 , 3 , 4 , 5 , 6) was extensively explored by means of ab initio crystal structure prediction methods. The results do not support the existence of thermodynamically stable PHn compounds, which exhibit a tendency for elemental decomposition at high pressure even when vibrational contributions to the free energies are taken into account. Although the lowest energy phases of PH1 , 2 , 3 display Tc's comparable to experiments, it remains questionable if the measured values of Tc can be fully attributed to a phase-pure compound of PHn. This work was done within the NCCR MARVEL project.

  8. High-Pressure Measurements of Hydrogen Phase IV Using Synchrotron Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zha, Chang-sheng; Liu, Zhenxian; Ahart, Muhtar; Boehler, Reinhard; Hemley, Russell J.

    2013-05-01

    Phase IV of dense solid hydrogen has been identified by its infrared spectrum using high-pressure synchrotron radiation techniques. The spectrum exhibits a sharp vibron band at higher frequency and lower intensity than that for phase III, indicating the stability of molecular H2 with decreased intermolecular interactions and charge transfer between molecules. A low-frequency vibron having a strong negative pressure shift indicative of strongly interacting molecules is also observed. The character of the spectrum is consistent with an anisotropic, mixed layer structure related to those recently predicted theoretically. Phase IV was found to be stable from 220 GPa (300 K) to at least 340 GPa (near 200 K), with the I-III-IV triple point located. Infrared transmission observed to the lowest photon energies measured places constraints on the electronic properties of the phase.

  9. The Effect of High Pressure on Phase Relationships and Some Properties of Ti and Its alloys.

    DTIC Science & Technology

    1981-05-01

    A. Rabinkin and E. (;ut:i.’ana. May 1981 Final Technical Report prepared for EUROPEAN RESEARCH OFFICE, UNITED STATES ARMY 223 Old Marylebone Road...Address 12° Report Da _l..jMay 181 I Eropean Research Office, US Army ----- 223 Old Marylebone Road Lond on 1, 1t E l n 3. Number of Pages 82 L ~ndon N 5th...related to this research (Appendix 1 and 2) were published. #7-9 Key Words Ti alloys, high pressure, phase transformations 2 ’hi report summarizes a

  10. Observation of a high-pressure cinnabar phase in CdTe

    NASA Astrophysics Data System (ADS)

    Nelmes, R. J.; McMahon, M. I.; Wright, N. G.; Allan, D. R.

    1993-07-01

    Angle-dispersive powder-diffraction techniques with an image-plate area detector and synchrotron radiation have been used to reexamine the high-pressure behavior of cadmium telluride. We find that the well-known structural phase transition at ~3.5 GPa from the zinc-blende to NaCl structure actually involves two closely spaced transitions-zinc blende to cinnabar, and cinnabar to NaCl. This is the example of the cinnabar structure outside the mercury chalcogenides. The Cd and Te atoms are site ordered, and the coordination of the structure is closer to fourfold than is found in HgS cinnabar.

  11. Superconductivity of high-pressure phases of S and Se to 230 GPa

    NASA Astrophysics Data System (ADS)

    Struzhkin, Viktor; Gregoryanz, Eugene; Timofeev, Yuri; Eremets, Mikhail; Mao, Ho-Kwang; Hemley, Russell

    2000-03-01

    We have investigated in detail the superconducting state of sulfur in its β-Po phase from 160 to 230 GPa. The superconducting Tc is close to 17 K from 160 to 200 GPa, and drops to 15 K at 230 GPa. Similar behavior was predicted recently [1] from ab initio LDA calculations. The high value of Tc in the β-Po phase is consistent with electon-phonon coupling mechanism with reasonably strong electron-phonon coupling (λ=0.76), and with the standard value of the Morel-Anderson pseudopotential μ^*=0.11 [1]. Our measurements in Se at high pressures indicate superconductivity from 17 to 23 GPa, which apparently has not been previously reported. We relate this behavior to the occurence of new metastable phase in Se which can be observed on decompression from 30 GPa at low temperatures. The results for Tc in Se at higher pressures will be also presented. We will also discuss the similiarities in high-pressure induced superconductivity of chalcogen family members: S, Se, and Te. ^1 Sven P. Rudin and Amy Y. Liu, Phys. Rev. Lett. 83, 3049 (1999).

  12. Phase transformations in amorphous fullerite C60 under high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Borisova, P. A.; Blanter, M. S.; Brazhkin, V. V.; Somenkov, V. A.; Filonenko, V. P.

    2015-08-01

    First phase transformations of amorphous fullerite C60 at high temperatures (up to 1800 K) and high pressures (up to 8 GPa) have been investigated and compared with the previous studies on the crystalline fullerite. The study was conducted using neutron diffraction and Raman spectroscopy. The amorphous fullerite was obtained by ball-milling. We have shown that under thermobaric treatment no crystallization of amorphous fullerite into С60 molecular modification is observed, and it transforms into amorphous-like or crystalline graphite. A kinetic diagram of phase transformation of amorphous fullerite in temperature-pressure coordinates was constructed for the first time. Unlike in crystalline fullerite, no crystalline polymerized phases were formed under thermobaric treatment on amorphous fullerite. We found that amorphous fullerite turned out to be less resistant to thermobaric treatment, and amorphous-like or crystalline graphite were formed at lower temperatures than in crystalline fullerite.

  13. Shear wave measurements in shock-induced, high-pressure phases

    SciTech Connect

    Aidun, J.B.

    1993-01-01

    Structural phase transformations under shock loading are of considerable interest for understanding the response of solids under nonhydrostatic stresses and at high strain-rates. Examining shock-induced transformations from continuum level measurements is fundamentally constrained by the inability to directly identify microscopic processes, and also by the limited number of material properties that can be directly measured. ne latter limitation can be reduced by measuring both shear and compression waves using Lagrangian gauges in combined, compression and shear loading. The shear wave serves as an important, real-time probe of the shocked state and unloading response. Using results from a recent study of CaCO[sub 3], the unique information obtained from the shear wave speed and the detailed structure of the shear wave are shown to be useful for distinguishing the effects of phase transformations from yielding, as well as in characterizing the high-pressure phases and the yielding process under shock loading.

  14. Shear wave measurements in shock-induced, high-pressure phases

    SciTech Connect

    Aidun, J.B.

    1993-07-01

    Structural phase transformations under shock loading are of considerable interest for understanding the response of solids under nonhydrostatic stresses and at high strain-rates. Examining shock-induced transformations from continuum level measurements is fundamentally constrained by the inability to directly identify microscopic processes, and also by the limited number of material properties that can be directly measured. ne latter limitation can be reduced by measuring both shear and compression waves using Lagrangian gauges in combined, compression and shear loading. The shear wave serves as an important, real-time probe of the shocked state and unloading response. Using results from a recent study of CaCO{sub 3}, the unique information obtained from the shear wave speed and the detailed structure of the shear wave are shown to be useful for distinguishing the effects of phase transformations from yielding, as well as in characterizing the high-pressure phases and the yielding process under shock loading.

  15. Equation of state and phase diagram of ammonia at high pressures from ab initio simulations.

    PubMed

    Bethkenhagen, Mandy; French, Martin; Redmer, Ronald

    2013-06-21

    We present an equation of state as well as a phase diagram of ammonia at high pressures and high temperatures derived from ab initio molecular dynamics simulations. The predicted phases of ammonia are characterized by analyzing diffusion coefficients and structural properties. Both the phase diagram and the subsequently computed Hugoniot curves are compared to experimental results. Furthermore, we discuss two methods that allow us to take into account nuclear quantum effects, which are of considerable importance in molecular fluids. Our data cover pressures up to 330 GPa and a temperature range from 500 K to 10,000 K. This regime is of great interest for interior models of the giant planets Uranus and Neptune, which contain, besides water and methane, significant amounts of ammonia.

  16. Modeling high-pressure and high-temperature phase changes in bulk carbon

    SciTech Connect

    Glosi, J N; Ree, F H

    1999-07-01

    The phase diagram of carbon is not experimentally well known at high pressure and/or high temperature. We have determined the phase diagram of carbon by means of Monte Carlo and molecular dynamics simulations methods using the Brenner bond order potential. The melting line of diamond was found to have a positive slope with the graphite-diamond-liquid triple point in agreement with an estimated value based on experiment. The present calculation predicts a first-order phase transition in liquid carbon terminated by a critical point and by a triple point on the graphite melting line. The low-density liquid is predominantly sp bonded with little sp{sup 3} character. The high-density liquid is mostly sp{sup 3} bonded with little sp character.

  17. Hybrid functional study rationalizes the simple cubic phase of calcium at high pressures.

    PubMed

    Liu, Hanyu; Cui, Wenwen; Ma, Yanming

    2012-11-14

    Simple cubic (SC) phase has been long experimentally determined as the high-pressure phase III of elemental calcium (Ca) since 1984. However, recent density functional calculations within semi-local approximation showed that this SC phase is structurally unstable by exhibiting severely imaginary phonons, and is energetically unstable with respect to a theoretical body-centered tetragonal I4(1)/amd structure over the pressure range of phase III. These calculations generated extensive debates on the validity of SC phase. Here we have re-examined the SC structure by performing more precise density functional calculations within hybrid functionals of Heyd-Scuseria-Erhzerhof and PBE0. Our calculations were able to rationalize fundamentally the phase stability of SC structure over all other known phases by evidence of its actual energetic stability above 33 GPa and its intrinsically dynamical stability without showing any imaginary phonons in the entire pressure range studied. We further established that the long-thought theoretical I4(1)/amd structure remains stable in a narrow pressure range before entering SC phase and is actually the structure of experimental Ca-III(') synthesized recently at low temperature 14 K as supported by the excellent agreement between our simulated x-ray diffraction patterns and the experimental data. Our results shed strong light on the crucial role played by the precise electron exchange energy in a proper description of the potential energy of Ca.

  18. Nanosecond Ultrasonics to Study Phase Transitions in Solid and Liquid Systems at High Pressure and Temperature

    SciTech Connect

    Bonner, B P; Berge, P A; Carlson, S C; Farber, D L; Akella, J

    2007-03-21

    This report describes the development of a high-frequency ultrasonic measurement capability for application to the study of phase transitions at elevated pressure and temperature. We combined expertise in various aspects of static high-pressure technique with recent advances in wave propagation modeling, ultrasonic transducer development, electronic methods and broadband instrumentation to accomplish the goals of this project. The transduction and electronic systems have a demonstrated bandwidth of 400 MHz, allowing investigations of phenomena with characteristic times as short as 2.5 nS. A compact, pneumatically driven moissanite anvil cell was developed and constructed for this project. This device generates a high-pressure environment for mm dimension samples to pressures of 3 GPa. Ultrasonic measurements were conducted in the moissanite cell, an LLNL multi-anvil device and in a modified piston cylinder device. Measurements for water, and elemental tantalum, tin and cerium demonstrate the success of the methods. The {gamma}-{alpha} phase transition in cerium was clearly detected at {approx}0.7 GPa with 75 MHz longitudinal waves. These results have direct application to important problems in LLNL programs, as well as seismology and planetary science.

  19. Phase relations in the Fe-FeSi system at high pressures and temperatures

    SciTech Connect

    Fischer, Rebecca A.; Campbell, Andrew J.; Reaman, Daniel M.; Miller, Noah A.; Heinz, Dion L.; Dera, Przymyslaw; Prakapenka, Vitali B.

    2016-07-29

    The Earth's core is comprised mostly of iron and nickel, but it also contains several weight percent of one or more unknown light elements, which may include silicon. Therefore it is important to understand the high pressure, high temperature properties and behavior of alloys in the Fe–FeSi system, such as their phase diagrams. We determined melting temperatures and subsolidus phase relations of Fe–9 wt% Si and stoichiometric FeSi using synchrotron X-ray diffraction at high pressures and temperatures, up to ~200 GPa and ~145 GPa, respectively. Combining this data with that of previous studies, we generated phase diagrams in pressure–temperature, temperature–composition, and pressure–composition space. We find the B2 crystal structure in Fe–9Si where previous studies reported the less ordered bcc structure, and a shallower slope for the hcp+B2 to fcc+B2 boundary than previously reported. In stoichiometric FeSi, we report a wide B2+B20 two-phase field, with complete conversion to the B2 structure at ~42 GPa. The minimum temperature of an Fe–Si outer core is 4380 K, based on the eutectic melting point of Fe–9Si, and silicon is shown to be less efficient at depressing the melting point of iron at core conditions than oxygen or sulfur. At the highest pressures reached, only the hcp and B2 structures are seen in the Fe–FeSi system. We predict that alloys containing more than ~4–8 wt% silicon will convert to an hcp+B2 mixture and later to the hcp structure with increasing pressure, and that an iron–silicon alloy in the Earth's inner core would most likely be a mixture of hcp and B2 phases.

  20. [Raman characterization of rutile phase transitions under high-pressure and high-temperature].

    PubMed

    Xiao, Wan-Sheng; Zhang, Hong; Tan, Da-Yong; Weng, Ke-Nan; Li, Yan-Chun; Luo, Chong-Ju; Liu, Jing; Xie, Hong-Sen

    2007-07-01

    The pressure-induced phase transition of rutile-structured TiO2 was investigated by in-situ Raman spectrum method in a laser-heated diamond anvil cell (DAC). The experiment was conducted at 35 GPa under quasihydrostatic conditions using argon as medium. At room temperature, the rutile-type TiO2 begins to transform to baddeleyite-type phase at 13.4 GPa and completes at 21 GPa, and this new high-pressure structure retains up to 35 GPa, the upmost pressure used in this study. At the pressure of 29.4 GPa the sample of baddeleyite-type TiO2 was heated by an YAG laser to about 1 000-1500 degrees C, and then the baddeleyite phase transformed to a Pbca phase. The Pbca phase was heated again at 35.0 GPa and it was still stable. The sample then began to be decompressed, and the Pbca phase of TiO2 transformed to baddeleyite structure at 26.3 GPa, which stayed stable to 11.4 GPa. The formation of Pbca phase from baddeleyite phase needs the condition of high temperature, it transforms back to badde-leyite structure completely at pressure of a little below that on its formation, which suggests the boundary of the two phases can be determined at about 28 GPa. At 7. 6 GPa, and the Raman spectrum shows the characteristics of the mixture of two phases of baddeleyite-type and alpha-PbO2-type, which indicates that the baddeleyite phase transforms to alpha-PbO2 phase at about 7 GPa. The alpha-PbO2-type TiO2 is metastable under ambient condition.

  1. Observations of a high-pressure phase creation in oleic acid

    NASA Astrophysics Data System (ADS)

    Kościesza, R.; Kulisiewicz, L.; Delgado, A.

    2010-03-01

    Oleic acid is one of the unsaturated fatty acids which frequently appears in food products such as edible fats and oils. A molecule of oleic acid possesses a double carbon bond, C=C, which is responsible for a transition to a new phase when pressure is applied. This work presents the results of optical observations of such a transition. The observations were made in two cases, the first being static p-T conditions under 60 MPa at 20°C and the other the dynamic application of the pressure up to 350 MPa. The obtained visualization reveals differences in the creation of the phase and in its further appearance. Some crystal forms may be recognized. These results tend to be of interest for food engineers due to increasing interest in high-pressure food preservation among nutritionists and medical scientists concerned with fatty acids.

  2. Phase transitions, mechanical properties and electronic structures of novel boron phases under high-pressure: A first-principles study

    PubMed Central

    Fan, Changzeng; Li, Jian; Wang, Limin

    2014-01-01

    We have explored the mechanical properties, electronic structures and phase transition behaviors of three designed new phases for element boron from ambient condition to high-pressure of 120 GPa including (1) a C2/c symmetric structure (m-B16); (2) a symmetric structure (c-B56) and (3) a Pmna symmetric structure (o-B24). The calculation of the elastic constants and phonon dispersions shows that the phases are of mechanical and dynamic stability. The m-B16 phase is found to transform into another new phase (the o-B16 phase) when pressure exceeds 68 GPa. This might offer a new synthesis strategy for o-B16 from the metastable m-B16 at low temperature under high pressure, bypassing the thermodynamically stable γ-B28. The enthalpies of the c-B56 and o-B24 phases are observed to increase with pressure. The hardness of m-B16 and o-B16 is calculated to be about 56 GPa and 61 GPa, approaching to the highest value of 61 GPa recorded for α-Ga-B among all available Boron phases. The electronic structures and bonding characters are analyzed according to the difference charge-density and crystal orbital Hamilton population (COHP), revealing the metallic nature of the three phases. PMID:25345910

  3. High-pressure structural phase transitions in CuWO[subscript 4

    SciTech Connect

    Ruiz-Fuertes, J.; Errandonea, D.; Lacomba-Perales, R.; Segura, A.; González, J.; Rodríguez, F.; Manjón, F.J.; Ray, S.; Rodríguez-Hernández, P.; Muñoz, A.; Zhu, Zh.; Tu, C.Y.

    2010-07-23

    We study the effects of pressure on the structural, vibrational, and magnetic behavior of cuproscheelite. We performed powder x-ray diffraction and Raman spectroscopy experiments up to 27 GPa as well as ab initio total-energy and lattice-dynamics calculations. Experiments provide evidence that a structural phase transition takes place at 10 GPa from the low-pressure triclinic phase (P1{sup -}) to a monoclinic wolframite-type structure (P2/c). Calculations confirmed this finding and indicate that the phase transformation involves a change in the magnetic order. In addition, the equation of state for the triclinic phase is determined: V{sub 0} = 132.8(2) {angstrom}{sup 3}, B{sub 0} = 139(6) GPa, and B{prime}{sub 0} = 4. Furthermore, experiments under different stress conditions show that nonhydrostatic stresses induce a second phase transition at 17 GPa and reduce the compressibility of CuWO{sub 4}, B{sub 0} = 171(6) GPa. The pressure dependence of all Raman modes of the triclinic and high-pressure phases is also reported and discussed.

  4. Phase stability and magnetic behavior of hexagonal phase of N2-O2 system with kagome lattice under high pressure and low temperature

    NASA Astrophysics Data System (ADS)

    Akahama, Y.; Ishihara, D.; Yamashita, H.; Fujihisa, H.; Hirao, N.; Ohishi, Y.

    2016-08-01

    The pressure-temperature (P -T ) phase diagram of N2-O2 mixture with a composition of N2-48 mol % O2 has been investigated using x-ray diffraction and the phase stability of a hexagonal phase (space group: P 6 /mmm), with the kagome lattice examined under high-pressure and low-temperature conditions. While the phase appears as a low-temperature phase of the cubic phase (P m 3 n ) with the structure of γ -O2 or δ -N2 and is stable in a wide range of pressures and temperatures, it transforms to lower symmetry monoclinic or orthorhombic phases at lower temperature, accompanied with a distortion of the kagome lattice. Based on Rietveld refinements, the monoclinic and orthorhombic phases are found to be in the P 21/a and Cmmm space groups, respectively. In magnetization measurements, a magnetic transition is observed with a relatively large drop of magnetization, corresponding to the cubic-to-hexagonal phase transition. This suggests that the hexagonal phase has a certain magnetic ordered state that arises from the molecular magnetic moment of O2.

  5. High-pressure phases of Mg2Si from first principles

    NASA Astrophysics Data System (ADS)

    Huan, Tran Doan; Tuoc, Vu Ngoc; Le, Nam Ba; Minh, Nguyen Viet; Woods, Lilia M.

    2016-03-01

    First-principles calculations are presented to resolve the possible pressure-dependent phases of Mg2Si . Although previous reports show that Mg2Si is characterized by the cubic antifluorite F m 3 ¯m structure at low pressures, the situation at higher pressures is less clear with many contradicting results. Here we utilize several methods to examine the stability, electron, phonon, and transport properties of this material as a function of pressure and temperature. We find that Mg2Si is thermodynamically stable at low and high pressures. Between 6 and 24 GPa, Mg2Si can transform into Mg9Si5 , a defected compound, and vice versa, without energy cost. Perhaps this result is related to the aforementioned inconsistency in the structures reported for Mg2Si within this pressure range. Focusing solely on Mg2Si , we find a new monoclinic C 2 /m structure of Mg2Si , which is stable at high pressures within thermodynamical considerations. The calculated electrical conductivity and Seebeck coefficient taking into account results from the electronic structure calculations help us understand better how transport can be affected in this material by modulating pressure and temperature.

  6. Exploring the Phase Diagram SiO2-CO2 at High Pressures and Temperatures

    NASA Astrophysics Data System (ADS)

    Kavner, A.

    2015-12-01

    CO2 is an important volatile system relevant for planetary sciences and fundamental chemistry. Molecular CO2 has doubly bonded O=C=O units but high pressure-high temperature (HP-HT) studies have recently shown its transformation into a three-dimensional network of corner-linked [CO4] units analogous to the silica mineral polymorphs, through intermediate non-molecular phases. Here, we report P-V-T data on CO2-IV ice from time-of-flight neutron diffraction experiments, which allow determining the compressibility and thermal expansivity of this intermediate molecular-to-non-molecular phase.1 Aditionally, we have explored the SiO2-CO2 phase diagram and the potential formation of silicon carbonate compounds. New data obtained by laser-heating diamond-anvil experiments in CO2-filled microporous silica polymorphs will be shown. In particular, these HP-HT experiments explore the existence of potential CO2/SiO2 compounds with tetrahedrally-coordinated C/Si atoms by oxygens, which are predicted to be stable (or metastable) by state-of-the-art ab initio simulations.2,3 These theoretical predictions were supported by a recent study that reports the formation of a cristobalite-type Si0.4C0.6O2 solid solution at high-pressures and temperatures, which can be retained as a metastable solid down to ambient conditions.4 Entirely new families of structures could exist based on [CO4]4- units in various degrees of polymerisation, giving rise to a range of chain, sheet and framework solids like those found in silicate chemistry. References[1] S. Palaich et al., Am. Mineral. Submitted (2015) [2] A. Morales-Garcia et al., Theor. Chem. Acc. 132, 1308 (2013) [3] R. Zhou et al., Phys. Rev. X, 4, 011030 (2014) [4] M. Santoro et al. Nature Commun. 5, 3761 (2014)

  7. New high-pressure phases of MoSe2 and MoTe2

    NASA Astrophysics Data System (ADS)

    Kohulák, Oto; MartoÅák, Roman

    2017-02-01

    Three Mo-based transition-metal dichalcogenides MoS2,MoSe2, and MoTe2 share at ambient conditions the same structure 2 Hc , consisting of layers where Mo atoms are surrounded by six chalcogen atoms in trigonal prism coordination. The knowledge of their high-pressure behavior is, however, limited, particularly in case of MoSe2 and MoTe2. The latter materials do not undergo a layer-sliding transition 2 Hc→ 2 Ha known in MoS2 and currently no other stable phase aside from 2 Hc is known in these systems at room temperature. Employing evolutionary crystal structure prediction in combination with ab initio calculations, we study the zero-temperature phase diagram of both materials up to Mbar pressures. We find a tetragonal phase with space group P4/mmm, previously predicted in MoS2, to become stable in MoSe2 at 118 GPa. In MoTe2, we predict at 50 GPa a transition to a new layered tetragonal structure with space group I4/mmm, similar to CaC2, where Mo atoms are surrounded by eight Te atoms. The phase is metallic already at the transition pressure and becomes a good metal beyond 1 Mbar. We discuss chemical trends in the family of Mo-based transition-metal dichalcogenides and suggest that MoTe2 likely offers the easiest route towards the post-2 H phases.

  8. High-pressure phase behavior of binary mixtures of octacosane and carbon dioxide

    SciTech Connect

    McHugh, M.A.; Seckner, A.J.; Yogan, T.J.

    1984-11-01

    The high-pressure fluid phase behavior of binary mixtures of octacosane and CO/sub 2/ is experimentally investigated. Solubilities of octacosane in supercritical CO/sub 2/ and mixture molar volumes are determined for isotherms of 34.7, 45.4, 50.2, and 52.0/sup 0/C over a range of pressures from 80 to 325 atm. The solubility data are obtained by two different experimental techniques. The pressure-temperature projection of the two branches of the three-phase solid-liquid-gas freezing point depression curve is also determined. The octacosane-CO/sub 2/ LCEP is determined as 32.2/sup 0/ C and 72.6 atm. The UCEP, which is at a pressure greater than 650 atm, could not be determined due to the pressure limitation of the experimental apparatus. Phase diagram constructions are used qualitatively to explain the observed phase behavior and to provide information on the expected phase behavior of the octacosane-CO/sub 2/ system at pressures higher than those experimentally investigated.

  9. Study on objective functions for the slow shot phase in high-pressure die casting

    NASA Astrophysics Data System (ADS)

    Frings, Markus; Behr, Marek; Elgeti, Stefanie

    2016-10-01

    High-pressure die casting is an important process in the field of aluminum processing. Especially during the slow shot phase, the process parameters immensely influence the cast part quality. At the current state of the art, the appropriate process parameters are identified based on running-in trials and significant experience. To translate this experience into a mathematical framework is the aim of this work. The idea is to shift the running-in trials to the computer—now in the form of a numerical optimization. In view of the optimization, this paper presents a selection of objective functions. These are assessed with the respect to (1) their suitability as an overall quality measure of the casting process and (2) the extent to which they reflect the goals of the casting process.

  10. Isotope effect in the superconducting high-pressure simple cubic phase of calcium from first principles

    NASA Astrophysics Data System (ADS)

    Errea, Ion; Rousseau, Bruno; Bergara, Aitor

    2012-06-01

    It has been recently shown [I. Errea, B. Rousseau, and A. Bergara, Phys. Rev. Lett. 106, 165501 (2011)] that the phonons of the high-pressure simple cubic phase of calcium are stabilized by strong quantum anharmonic effects. This was obtained by a fully ab initio implementation of the self-consistent harmonic approximation including explicitly anharmonic coefficients up to fourth order. The renormalized anharmonic phonons make possible to estimate the superconducting transition temperature in this system, and a sharp agreement with experiments is found. In this work, this analysis is extended in order to study the effect of anharmonicity in the isotope effect. According to our calculations, despite the huge anharmonicity in the system, the isotope coefficient is predicted to be 0.45, close to the 0.5 value expected for a harmonic BCS superconductor.

  11. Phase transitions in Group III-V and II-VI semiconductors at high pressure

    NASA Technical Reports Server (NTRS)

    Yu, S. C.; Liu, C. Y.; Spain, I. L.; Skelton, E. F.

    1979-01-01

    The structures and transition pressures of Group III-V and II-VI semiconductors and of a pseudobinary system (Ga/x/In/1-x/Sb) have been investigated. Results indicate that GaP, InSb, GaSb, GaAs and possible AlP assume Metallic structures at high pressures; a tetragonal, beta-Sn-like structure is adopted by only InSb and GaSb. The rocksalt phase is preferred in InP, InAs, AlSb, ZnO and ZnS. The model of Van Vechten (1973) gives transition pressures which are in good agreement with measured values, but must be refined to account for the occurrence of the ionic rocksalt structure in some compounds. In addition, discrepancies between the theoretical scaling values for volume changes at the semiconductor-to-metal transitions are observed.

  12. High pressure induced phase transition and superdiffusion in anomalous fluid confined in flexible nanopores

    SciTech Connect

    Bordin, José Rafael; Krott, Leandro B. Barbosa, Marcia C.

    2014-10-14

    The behavior of a confined spherical symmetric anomalous fluid under high external pressure was studied with Molecular Dynamics simulations. The fluid is modeled by a core-softened potential with two characteristic length scales, which in bulk reproduces the dynamical, thermodynamical, and structural anomalous behavior observed for water and other anomalous fluids. Our findings show that this system has a superdiffusion regime for sufficient high pressure and low temperature. As well, our results indicate that this superdiffusive regime is strongly related with the fluid structural properties and the superdiffusion to diffusion transition is a first order phase transition. We show how the simulation time and statistics are important to obtain the correct dynamical behavior of the confined fluid. Our results are discussed on the basis of the two length scales.

  13. High-pressure phases of group-II difluorides: Polymorphism and superionicity

    NASA Astrophysics Data System (ADS)

    Nelson, Joseph R.; Needs, Richard J.; Pickard, Chris J.

    2017-02-01

    We investigate the high-pressure behavior of beryllium, magnesium, and calcium difluorides using ab initio random structure searching and density functional theory (DFT) calculations, over the pressure range 0 -70 GPa. Beryllium fluoride exhibits extensive polymorphism at low pressures, and we find two new phases for this compound—the silica moganite and CaCl2 structures—which are stable over the wide pressure range 12 -57 GPa. For magnesium fluoride, our searching results show that the orthorhombic "O-I" TiO2 structure (P b c a ,Z =8 ) is stable for this compound between 40 and 44 GPa. Our searches find no new phases at the static-lattice level for calcium difluoride between 0 and 70 GPa; however, a phase with P 6 ¯2 m symmetry is close to stability over this pressure range, and our calculations predict that this phase is stabilized at high temperature. The P 6 ¯2 m structure exhibits an unstable phonon mode at large volumes which may signal a transition to a superionic state at high temperatures. The group-II difluorides are isoelectronic to a number of other AB2-type compounds such as SiO2 and TiO2, and we discuss our results in light of these similarities.

  14. Chromatographic behaviour of synthetic high pressure high temperature diamond in aqueous normal phase chromatography.

    PubMed

    Peristyy, Anton; Paull, Brett; Nesterenko, Pavel N

    2016-10-28

    The chromatographic properties of high pressure high temperature synthesised diamond (HPHT) are investigated under the conditions of hydrophilic interaction liquid chromatography (HILIC). A 50×4.6mm ID stainless steel column packed with HPHT particles of mean diameter 1.6μm and specific surface area 5.1m(2)g(-1) is used. According to the results of acid-base titration with NaOH the purified HPHT batch contains 4.59μeqg(-1) of protogenic, mainly carboxyl- and hydroxyl-, groups, which make this polar adsorbent suitable for use as a stationary phase in HILIC. The retention behaviour of several classes of polar compounds including benzoic and benzenesulfonic acids, nitro- and chlorophenols, various organic bases, and quaternary ammonium compounds are studied using acetonitrile and methanol based mobile phases containing 5-30v/v% of water. The effects of the buffer pH and concentration, column temperature and organic solvent content on retention of model compounds are also investigated. It is shown that both pH and acetonitrile/methanol ratio in the mobile phase can be used to vary the separation selectivity. Molecular adsorption mechanism (related to aqueous normal phase mode), rather than partitioning is established to be responsible for the retention.

  15. Atomic ordering in cubic bismuth telluride alloy phases at high pressure

    NASA Astrophysics Data System (ADS)

    Loa, I.; Bos, J.-W. G.; Downie, R. A.; Syassen, K.

    2016-06-01

    Pressure-induced transitions from ordered intermetallic phases to substitutional alloys to semi-ordered phases were studied in a series of bismuth tellurides. By using angle-dispersive x-ray diffraction, the compounds Bi4Te5 , BiTe, and Bi2Te were observed to form alloys with the disordered body-centered cubic (bcc) crystal structure upon compression to above 14-19 GPa at room temperature. The BiTe and Bi2Te alloys and the previously discovered high-pressure alloys of Bi2Te3 and Bi4Te3 were all found to show atomic ordering after gentle annealing at very moderate temperatures of ˜100 ∘C . Upon annealing, BiTe transforms from bcc to the B2 (CsCl) crystal-structure type, and the other phases adopt semi-disordered variants thereof, featuring substitutional disorder on one of the two crystallographic sites. The transition pressures and atomic volumes of the alloy phases show systematic variations across the BimTen series including the end members Bi and Te. First-principles calculations were performed to characterize the electronic structure and chemical bonding properties of B2-type BiTe and to identify the driving forces of the ordering transition. The calculated Fermi surface of B2-type BiTe has an intricate structure and is predicted to undergo three topological changes between 20 and 60 GPa.

  16. An ab initio molecular dynamics study of iron phases at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Belonoshko, A. B.; Arapan, S.; Rosengren, A.

    2011-12-01

    The crystal structure of iron, the major component of the Earth’s inner core (IC), is unknown for the IC high pressure (P; 3.3-3.6 Mbar) and temperature (T; 5000-7000 K). There is mounting evidence that the hexagonal close-packed (hcp) phase of iron, stable at the high P of the IC and a low T, might be unstable under the IC conditions due to the impact of high T and impurities. Experiments at the IC P and T are difficult and do not provide a conclusive answer as regards the iron stability at the pressure of the IC and temperatures close to the iron melting curve. Recent theory provides contradictory results regarding the nature of the stable Fe phase. We investigated the possibility of body-centered cubic (bcc) phase stabilization at the P and T in the vicinity of the Fe melting curve by using ab initio molecular dynamics. Thermodynamic calculations, relying on the model of uncorrelated harmonic oscillators, provide nearly identical free energies within the error bars of our calculations. However, direct simulation of iron crystallization demonstrates that liquid iron freezes in the bcc structure at the P of the IC and T = 6000 K. All attempts to grow the hcp phase from the liquid failed. The mechanism of bcc stabilization is explained. This resolves most of the earlier confusion.

  17. Superconductivity in metastable phases of phosphorus-hydride compounds under high pressure

    NASA Astrophysics Data System (ADS)

    Flores-Livas, José A.; Amsler, Maximilian; Heil, Christoph; Sanna, Antonio; Boeri, Lilia; Profeta, Gianni; Wolverton, Chris; Goedecker, Stefan; Gross, E. K. U.

    2016-01-01

    Hydrogen-rich compounds have been extensively studied both theoretically and experimentally in the quest for novel high-temperature superconductors. Reports on sulfur hydride attaining metallicity under pressure and exhibiting superconductivity at temperatures as high as 200 K have spurred an intense search for room-temperature superconductors in hydride materials. Recently, compressed phosphine was reported to metallize at pressures above 45 GPa, reaching a superconducting transition temperature (TC) of 100 K at 200 GPa. However, neither the exact composition nor the crystal structure of the superconducting phase have been conclusively determined. In this work, the phase diagram of PHn (n =1 ,2 ,3 ,4 ,5 ,6 ) was extensively explored by means of ab initio crystal structure predictions using the minima hopping method (MHM). The results do not support the existence of thermodynamically stable PHn compounds, which exhibit a tendency for elemental decomposition at high pressure even when vibrational contributions to the free energies are taken into account. Although the lowest energy phases of PH1 ,2 ,3 display TC's comparable to experiments, it remains uncertain if the measured values of TC can be fully attributed to a phase-pure compound of PHn.

  18. Inelastic neutron scattering, lattice dynamics, and high-pressure phase stability of zircon-structured lanthanide orthophosphates

    SciTech Connect

    Bose, Preyoshi P.; Mittal, R; Chaplot, S L; Loong, C. K.; Boatner, Lynn A

    2010-01-01

    Inelastic neutron-scattering experiments and lattice-dynamical calculations are reported on a series of rareearth orthophosphates RPO4 R=Tm, Er, Ho, and Tb. The experimental phonon spectra for the compounds are in good agreement with our model calculations. The lattice-dynamical model is found useful for the calculation of various thermodynamic properties such as the lattice specific heat, thermal expansion, and equation of state of these compounds. The RPO4 compounds are known to transform to the scheelite body-centered tetragonal, I41 /a or monoclinic phase P21 /n at high pressures. Our calculations show that while the scheelite phase stabilizes at high pressure due to its lower volume, the monoclinic phase may occur as an intermediate phase depending on the ionic size of the R atom. The latter phase is stabilized at higher temperature at high pressure due to its high vibrational entropy. A pressure-temperature phase diagram is proposed.

  19. Phase transition of iron doped MgO under high pressure by first-principles study

    NASA Astrophysics Data System (ADS)

    Yang, K. S.; Li, S. L.; Zhang, J.; Zeng, Z.; Qin, X. Y.; Zhou, X. M.

    2015-07-01

    The (Mg, Fe)O solid solution is one of the major lower mantle minerals, and studying its properties and structures under high pressure is a fundamental step toward understanding Earth's deep interior. Here within the framework of density functional theory, we first discuss the relationship between the total energy and iron doped positions of (Mg, Fe)O, and find that the doped iron favors to be dispersive. Then the pressure-induced phase transitions of (Mg, Fe)O from NaCl-type (B1) to CsCl-type (B2) are probed. It is found that the phase transition pressure of (Mg, Fe)O decreases with damped oscillation, as the increase of iron concentration. This phenomenon is essentially determined by the iron concentration as well as iron doped positions. The electronic structures of MgO and (Mg0.75Fe0.25)O at 436 GPa are calculated, and the results show that the doped irons play a crucial role in the metallicity of (Mg0.75Fe0.25)O. Our results are in agreement with the experimental counterparts. This study would provide some useful information for understanding the behavior of pressure-induced phase transition and geoscience.

  20. Phase transition of iron doped MgO under high pressure by first-principles study

    NASA Astrophysics Data System (ADS)

    Yang, K. S.; Li, S. L.; Zhang, J.; Zeng, Z.; Qin, X. Y.; Zhou, X. M.

    2014-07-01

    The (Mg, Fe)O solid solution is one of the major lower mantle minerals, and studying its properties and structures under high pressure is a fundamental step toward understanding Earth's deep interior. Here within the framework of density functional theory, we first discuss the relationship between the total energy and iron doped positions of (Mg, Fe)O, and find that the doped iron favors to be dispersive. Then the pressure-induced phase transitions of (Mg, Fe)O from NaCl-type (B1) to CsCl-type (B2) are probed. It is found that the phase transition pressure of (Mg, Fe)O decreases with damped oscillation, as the increase of iron concentration. This phenomenon is essentially determined by the iron concentration as well as iron doped positions. The electronic structures of MgO and (Mg0.75Fe0.25)O at 436 GPa are calculated, and the results show that the doped irons play a crucial role in the metallicity of (Mg0.75Fe0.25)O. Our results are in agreement with the experimental counterparts. This study would provide some useful information for understanding the behavior of pressure-induced phase transition and geoscience.

  1. Serpentines, talc, chlorites, and their high-pressure phase transitions: a Raman spectroscopic study

    NASA Astrophysics Data System (ADS)

    Reynard, Bruno; Bezacier, Lucile; Caracas, Razvan

    2015-09-01

    Raman spectra of magnesian phyllosilicates belonging to the serpentine, talc, and chlorite groups have been obtained at ambient conditions, and at high pressures and up to 200 °C in order to study high-pressure transformations in the 10 GPa range. The complex and distinct Raman spectra of these minerals allow straightforward identification, which may otherwise be difficult from optical microscopy. High-pressure measurements are in good agreement with DFT calculations for talc and lizardite. Pressure-induced displacive modifications are identified in lizardite and antigorite serpentines, and in chlorite at ~4, 7 and 8 GPa, respectively, while talc shows no transition up to ~11 GPa. At high temperature, the high-pressure distortions of serpentines shift to higher pressures. Given the stability limits of these minerals, and the natural range of P-T conditions, none of the high-pressure distortions observed at high pressure are likely to occur at depth in the Earth.

  2. Kinematics and thermodynamics of a growing rim of high-pressure phase

    NASA Astrophysics Data System (ADS)

    Morris, S. J. S.

    2014-03-01

    We have reanalysed the problem of growth of a dense product rim on a sphere of parent phase. To decouple the problem of calculating deformation from rheology, we assume spherical symmetry, and incompressible phases. Within the product, the radial deviatoric strain and its time-derivative prove to be of opposite sign: strain is compressive, but the strain rate is tensile. Further, the radial deviatoric strain in the new product adjacent to the interface is invariant in time. Propagation of the phase interface is determined by a competition between two mechanisms: as an element of material is transformed, its shear strain energy is increased; and the core pressure performs work compressing it. For elastic phases, this competition results in metastability. Within a certain pressure range, either phase can occur alone, but the two phases can not coexist. Because this result is inconsistent with experiments by Kawazoe et al. (2010) in which a rim of high-pressure phase (wadsleyite) coexists with a central core of low-pressure phase (olivine), we then incorporate plastic flow. Assuming perfect plasticity, we show that for a given applied pressure exceeding the coexistence pressure, a rim of product can now nucleate if the excess pressure Δp exceeds a critical value depending on yield stress. Increasing Δp above this value allows product to grow into the parent phase. There are now two possibilities, depending on the value of Δp. Growth may eventually cease to produce a state in which the product rim is in equilibrium with a parent core; or growth may follow a more complicated path: within a range of excess pressures, the growth rate can decrease strongly from its initial value to produce a quasi-equilibrium state, before increasing again to a rate similar to that at which transformation began. We interpret these results to mean that if Δp is increased slowly in a series of experiments with constant yield stress, the sample passes through a series of equilibria until

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

    PubMed

    Faria, Luiz F O; Ribeiro, Mauro C C

    2015-11-05

    Raman spectroscopy has been used to study phase transitions of ionic liquids based on the triflate anion, [TfO](-), as a function of pressure or temperature. Raman spectra of ionic liquids containing the cations 1-butyl-3-methylimidazolium, [C4C1Im](+), 1-octyl-3-methylimidazolium, [C8C1Im](+), 1-butyl-2,3-dimethylimidazolium, [C4C1C1Im](+), and 1-butyl-1-methylpyrrolidinium, [C4C1Pyr](+), were compared. Vibrational frequencies and binding energy of ionic pairs were calculated by quantum chemistry methods. The ionic liquids [C4C1Im][TfO] and [C4C1Pyr][TfO] crystallize at 1.0 GPa when the pressure is increased in steps of ∼ 0.2 GPa from the atmospheric pressure, whereas [C8C1Im][TfO] and [C4C1C1Im][TfO] do not crystallize up to 2.3 GPa of applied pressure. The low-frequency range of the Raman spectrum of [C4C1Im][TfO] indicates that the system undergoes glass transition, rather than crystallization, when the pressure applied on the liquid has been increased above 2.0 GPa in a single step. Strong hysteresis of spectral features (frequency shift and bandwidth) of the high-pressure crystalline phase when the pressure was released stepwise back to the atmospheric pressure has been found .

  4. Incommensurate atomic density waves in the high-pressure IVb phase of barium

    PubMed Central

    Arakcheeva, Alla; Bykov, Maxim; Bykova, Elena; Dubrovinsky, Leonid; Pattison, Phil; Dmitriev, Vladimir; Chapuis, Gervais

    2017-01-01

    The host–guest structures of elements at high pressure discovered a decade ago still leave many open questions due to the lack of precise models based on full exploitation of the diffraction data. This concerns in particular Ba IV, which is stable in the range 12–45 GPa. With the example of phase Ba IVb, which is characterized here for the first time, a systematic analysis is presented of possible host–guest structure models based on high-quality single-crystal diffraction data obtained with synchrotron radiation at six different pressures between 16.5 and 19.6 GPa. It is shown that a new incommensurately modulated (IM) structure model better fits the experimental data. Unlike the composite models which are commonly reported for the Ba IV phases, the IM model reveals a density wave and its pressure-dependent evolution. The crucial role played by the selected model in the interpretation of structure evolution under pressure is discussed. The findings give a new experimental basis for a better understanding of the nature of host–guest structures. PMID:28250954

  5. Structures of the metallic and superconducting high pressure phases of solid CS2

    PubMed Central

    Zarifi, Niloofar; Liu, Hanyu; Tse, John S.

    2015-01-01

    First principles structural prediction and molecular dynamics (MD) calculations have been performed to examine the structures responsible for the recently reported metallic and superconducting phases of highly compressed CS2. The low pressure experimental molecular crystal structure was found to be metastable and transformed into a disordered structure above 10 GPa. At 60 GPa, the predicted low energy structures show molecular CS2 is separated into C and S dominant regions. A crystalline structure with the P21/m symmetry was found to be most stable from 60 to 120 GPa. The structure is formed from alternate layers of hexagonal C rings and S 2D-square-nets linked by C-S bonds. A non-crystalline structure with similar features structure is also predicted by MD calculations. Electron-phonon coupling calculations show this crystalline phase is superconductive. Contrary to the suggestions made from the experiments, no magnetism was found in all predicted low enthalpy high pressure structures. Moreover, the theoretical results do not support the proposal on the existence of hypervalent 6-coordinated carbon at 120 GPa. PMID:25982346

  6. Incommensurate atomic density waves in the high-pressure IVb phase of barium.

    PubMed

    Arakcheeva, Alla; Bykov, Maxim; Bykova, Elena; Dubrovinsky, Leonid; Pattison, Phil; Dmitriev, Vladimir; Chapuis, Gervais

    2017-03-01

    The host-guest structures of elements at high pressure discovered a decade ago still leave many open questions due to the lack of precise models based on full exploitation of the diffraction data. This concerns in particular Ba IV, which is stable in the range 12-45 GPa. With the example of phase Ba IVb, which is characterized here for the first time, a systematic analysis is presented of possible host-guest structure models based on high-quality single-crystal diffraction data obtained with synchrotron radiation at six different pressures between 16.5 and 19.6 GPa. It is shown that a new incommensurately modulated (IM) structure model better fits the experimental data. Unlike the composite models which are commonly reported for the Ba IV phases, the IM model reveals a density wave and its pressure-dependent evolution. The crucial role played by the selected model in the interpretation of structure evolution under pressure is discussed. The findings give a new experimental basis for a better understanding of the nature of host-guest structures.

  7. Structures of the metallic and superconducting high pressure phases of solid CS2.

    PubMed

    Zarifi, Niloofar; Liu, Hanyu; Tse, John S

    2015-05-18

    First principles structural prediction and molecular dynamics (MD) calculations have been performed to examine the structures responsible for the recently reported metallic and superconducting phases of highly compressed CS2. The low pressure experimental molecular crystal structure was found to be metastable and transformed into a disordered structure above 10 GPa. At 60 GPa, the predicted low energy structures show molecular CS2 is separated into C and S dominant regions. A crystalline structure with the P21/m symmetry was found to be most stable from 60 to 120 GPa. The structure is formed from alternate layers of hexagonal C rings and S 2D-square-nets linked by C-S bonds. A non-crystalline structure with similar features structure is also predicted by MD calculations. Electron-phonon coupling calculations show this crystalline phase is superconductive. Contrary to the suggestions made from the experiments, no magnetism was found in all predicted low enthalpy high pressure structures. Moreover, the theoretical results do not support the proposal on the existence of hypervalent 6-coordinated carbon at 120 GPa.

  8. Titanium-scaffolded organic-monolithic stationary phases for ultra-high-pressure liquid chromatography.

    PubMed

    Vonk, Rudy J; Vaast, Axel; Eeltink, Sebastiaan; Schoenmakers, Peter J

    2014-09-12

    Organic-polymer monoliths with overall dimensions larger than one millimetre are prone to rupture - either within the monolith itself or between the monoliths and the containing wall - due to the inevitable shrinkage accompanying the formation of a cross-linked polymeric network. This problem has been addressed by creating titanium-scaffolded poly(styrene-co-divinylbenzene) (S-co-DVB) monoliths. Titanium-scaffolded monoliths were successfully used in liquid chromatography at very high pressures (up to 80MPa) and using gradients spanning the full range of water-acetonitrile compositions (0 to 100%). The kinetic-performance of (50-mm long) titanium-scaffolded monoliths was compared to that of similar monolith created in 1-mm i.d. glass-lined tubing at pressures up to 50MPa. The peak capacities obtained with the titanium-scaffolded column was about 30% lower. An increased Eddy-diffusion, due to the pillar-structure, and a decreased permeability are thought to be the main reasons for this reduced kinetic-performance. No decrease in performance was observed when the titanium-scaffolded columns were operated at pressures of 80MPa for up to 12h. The column-to-column repeatability (n=5) was acceptable in terms of observed peak widths at half heights (RSD ca. 10%) The run-to-run repeatability (n=135) in terms of retention times and peak widths at half height were found to be good. Titanium-scaffolded columns coupled in series up to a combined length of (200mm) were used for the analyses of a complex Escherichia coli protein sample. Our experiments demonstrate that columns based on titanium-scaffolded organic-polymer monolith can be operated under strenuous conditions without loss in performance. The titanium-scaffolded approach makes it feasible to create organic-polymer monoliths in wide-bore columns with accurate temperature control.

  9. The role of equilibrium volume and magnetism on the stability of iron phases at high pressures.

    PubMed

    Alnemrat, S; Hooper, J P; Vasiliev, I; Kiefer, B

    2014-01-29

    The present study provides new insights into the pressure dependence of magnetism by tracking the hybridization between crystal orbitals for pressures up to 600 GPa in the known hcp, bcc and fcc iron. The Birch-Murnaghan equation of state parameters are; bcc: V0 = 11.759 A(3)/atom, K0 = 177.72 GPa; hcp: V0 = 10.525 A(3)/atom, K0 = 295.16 GPa; and fcc: V0 = 10.682 A(3)/atom, K0 = 274.57 GPa. These parameters compare favorably with previous studies. Consistent with previous studies we find that the close-packed hcp and fcc phases are non-magnetic at pressures above 50 GPa and 60 GPa, respectively. The principal features of magnetism in iron are predicted to be invariant, at least up to ∼6% overextension of the equilibrium volume. Our results predict that magnetism for overextended fcc iron disappears via an intermediate spin state. This feature suggests that overextended lattices can be used to stabilize particular magnetic states. The analysis of the orbital hybridization shows that the magnetic bcc structure at high pressures is stabilized by splitting the majority and minority spin bands. The bcc phase is found to be magnetic at least up to 600 GPa; however, magnetism is insufficient to stabilize the bcc phase itself, at least at low temperatures. Finally, the analysis of the orbital contributions to the total energy provides evidence that non-magnetic hcp and fcc phases are likely more stable than bcc at core earth pressures.

  10. Investigation of high pressure phase transition and electronic properties of Lutetium Nitride

    NASA Astrophysics Data System (ADS)

    Singh, Sanjay Kumar; Verma, U. P.

    2015-09-01

    In the present manuscript we have investigated the structural, electronic and phase transition properties of the heaviest lanthanide lutetium nitride (LuN) compound using an ab initio calculations based on the density functional theory with Perdrew, Burke and Ernzerhof generalized gradient approximation (PBE-GGA) and Engel-Vosko(EV)-GGA as implemented in WIEN2k code. The basic ground state properties viz., lattice constants (a), bulk modulus (B0) and its pressure derivative (B0’) and total energy (E0) are calculated. The calculated values of lattice constant is 4.76 Å which is in good agreement with experimental value a= 4.76 A and other theoretical value. The relative stabilities of LuN at high pressures in the NaCl (B1), CsCl (B2), zinc blende (B3) and body centred tetragonal (BCT) structures are analysed. At compressed volumes, this compound is found to favour the CsCl phase rather the body centred tetragonal phase and zinc blende as observed in other lanthanum pnictides, which has been predicted by the total energy minimization. Under compression LuN undergoes a transition from NaCl to CsCl type structure at around 250.81 GPa with a volume collapse of 3.75%. To see the effect of functional we have also computed the band structure in B1 and B2 structure. Obtained result on band structure shows that LuN are semimetal by GGA while depicts semiconducting behaviour by EV-GGA. It shows metallic nature in B2 phase.

  11. Review of high pressure phases of calcium by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Ishikawa, T.; Nagara, H.; Suzuki, N.; Tsuchiya, J.; Tsuchiya, T.

    2010-03-01

    We review high pressure phases of calcium which have obtained by recent experimental and first-principles studies. In this study, we investigated the face-centered cubic (fcc) structure, the body-centered cubic (bcc) structure, the simple cubic (sc) structure, a tetragonal P43212 [Ishikawa T et al. 2008 Phys. Rev. B 77 020101(R)], an orthorhombic Cmca [Ishikawa T et al. 2008 Phys. Rev. B 77 020101(R)], an orthorhombic Cmcm [Teweldeberhan A M and Bonev S A 2008 Phys. Rev. B 78 140101(R)], an orthorhombic Pnma [Yao Y et al. 2008 Phys. Rev. B 78 054506] and a tetragonal I4/mcm(00) [Arapan S et al. 2008 Proc. Natl. Acad. Sci. USA 105 20627]. We compared the enthalpies among the structures up to 200 GPa and theoretically determined the phase diagram of calcium. The sequence of the structural transitions is fcc (0- 3.5 GPa) → bcc (3.5 - 35.7 GPa) → Cmcm (35.7- 52GPa) → P43212 (52-109 GPa) → Cmca (109-117.4GPa) → Pnma (117.4-134.6GPa) → I4/mcm(00) (134.6 GPa -). The sc phase is experimentally observed in the pressure range from 32 to 113 GPa but, in our calculation, there is no pressure region where the sc phase is the most stable. In addition, we found that the enthalpy of the hexagonal close-packed (hcp) structure is lower than that of I4/mcm(00) above 495 GPa.

  12. A Novel High-Density Phase and Amorphization of Nitrogen-Rich 1H-Tetrazole (CH2N4) under High Pressure

    NASA Astrophysics Data System (ADS)

    Li, Wenbo; Huang, Xiaoli; Bao, Kuo; Zhao, Zhonglong; Huang, Yanping; Wang, Lu; Wu, Gang; Zhou, Bo; Duan, Defang; Li, Fangfei; Zhou, Qiang; Liu, Bingbing; Cui, Tian

    2017-02-01

    The high-pressure behaviors of nitrogen-rich 1H-tetrazole (CH2N4) have been investigated by in situ synchrotron X-ray diffraction (XRD) and Raman scattering up to 75 GPa. A first crystalline-to-crystalline phase transition is observed and identified above ~3 GPa with a large volume collapse (∼18% at 4.4 GPa) from phase I to phase II. The new phase II forms a dimer-like structure, belonging to P1 space group. Then, a crystalline-to-amorphous phase transition takes place over a large pressure range of 13.8 to 50 GPa, which is accompanied by an interphase region approaching paracrystalline state. When decompression from 75 GPa to ambient conditions, the final product keeps an irreversible amorphous state. Our ultraviolet (UV) absorption spectrum suggests the final product exhibits an increase in molecular conjugation.

  13. A Novel High-Density Phase and Amorphization of Nitrogen-Rich 1H-Tetrazole (CH2N4) under High Pressure

    PubMed Central

    Li, Wenbo; Huang, Xiaoli; Bao, Kuo; Zhao, Zhonglong; Huang, Yanping; Wang, Lu; Wu, Gang; Zhou, Bo; Duan, Defang; Li, Fangfei; Zhou, Qiang; Liu, Bingbing; Cui, Tian

    2017-01-01

    The high-pressure behaviors of nitrogen-rich 1H-tetrazole (CH2N4) have been investigated by in situ synchrotron X-ray diffraction (XRD) and Raman scattering up to 75 GPa. A first crystalline-to-crystalline phase transition is observed and identified above ~3 GPa with a large volume collapse (∼18% at 4.4 GPa) from phase I to phase II. The new phase II forms a dimer-like structure, belonging to P1 space group. Then, a crystalline-to-amorphous phase transition takes place over a large pressure range of 13.8 to 50 GPa, which is accompanied by an interphase region approaching paracrystalline state. When decompression from 75 GPa to ambient conditions, the final product keeps an irreversible amorphous state. Our ultraviolet (UV) absorption spectrum suggests the final product exhibits an increase in molecular conjugation. PMID:28218236

  14. Elastic Softening of Peridotite Due to the Presence of Melt Phases at High Pressure

    SciTech Connect

    Li, L.; Wang, L; Vaughan, M

    2008-01-01

    Here we report an observation of softening of Young's modulus of a sample of KLB-1 peridotite as a metallic Ni melt intruded into it at 2.5 GPa and about 1500 C. A uniaxial oscillation of stress was applied to the sample with frequency of 0.01-0.02 Hz and an amplitude up to 500 MPa. The Young's modulus is measured as the amplitude ratio between the sample and a reference material, while the attenuation is determined by the phase angle delays. The Ni intrusion was captured by in situ X-ray radiography. A planar intrusion occurred gradually, but advanced only during the extension; eventually, the Ni melt dissected the sample on a plane normal to the extension axis. Accompanied softening of Young's modulus was observed after the Ni intrusion was completed. This study suggests that percolation of a liquid metallic phase is possible within a partially melted mantle rock in the presence of a differential stress field.

  15. The high-pressure stability of zoisite and phase relationships of zoisite-bearing assemblages

    NASA Astrophysics Data System (ADS)

    Poli, S.; Schmidt, M. W.

    The fluid-absent reaction 12 zoisite=3 lawsonite+7 grossular+8 kyanite+1 coesite was experimentally reversed in the model system CaO-Al2O3-SiO2-H2O (CASH) using a multi-anvil apparatus. The upper pressure stability limit for zoisite was found to extend to 5.0GPa at 700°C and to 6.6GPa at 950°C. Additional experiments both in the H2O-SiO2-saturated and in the H2O-Al2O3-saturated portions of CASH provide further constraints on high pressure phase relationships of lawsonite, zoisite, grossular, kyanite, coesite, and an aqueous fluid. Consistency of the present experiments with the H2O-saturated breakdown of lawsonite is demonstrated by thermodynamic analysis using linear programming techniques. Two sets of data consistent with databases of Berman (1988) and Holland and Powell (1990) were retrieved combining experimental phase relationships, calorimetric constraints, and recently measured elastic properties of solid phases. The best fits result in Gf,1,298∘,zoisite=-6,499,400 J and S1,298∘,zoisite=302 J/K, and Gf,1,298∘,lawsonite=-4,514,600 J and S1,298∘,lawsonite=220 J/K for the dataset of Holland and Powell, and Gf,1,298∘,zoisite=-6,492,120 J and S1,298∘,zoisite=304 J/K, and Gf,1,298∘,lawsonite=-4,513,000 J and S1,298∘,lawsonite= 218 J/K for the dataset of Berman. Examples of the usage of zoisite as a geohygrometer and as a geobarometer in rocks metamorphosed at eclogite facies conditions are worked, profiting from the thermodynamic properties retrieved here.

  16. Extraction of Lipids from Chlorella saccharophila Using High-Pressure Homogenization Followed by Three Phase Partitioning.

    PubMed

    Mulchandani, Ketan; Kar, Jayaranjan R; Singhal, Rekha S

    2015-07-01

    Commercial exploitation of microalgae for biofuel and food ingredients is hindered due to laborious extraction protocols and use of hazardous chemicals. Production of lipids in the microalga grown in modified BG11 medium was evaluated to arrive at the appropriate harvesting conditions. The use of three phase partitioning (TPP) as a green approach for extraction of lipids from Chlorella saccharophila was investigated. Cells disrupted by probe sonication were used for separation of lipids by TPP. The TPP-optimized conditions of 30 % ammonium sulfate, using slurry/t-butanol of 1:0.75 for 60 min at 25 to 35 °C, showed a lipid recovery of 69.05 ± 3.12 % (w/w) as against 100 % (w/w) by using chloroform-methanol extraction. Subsequently, parameters of high-pressure homogenization for cell disruption were optimized for maximum recovery of lipids by TPP. A final recovery of 89.91 ± 3.69 % (w/w) lipids was obtained along with ∼1.26 % w/w carotenoids of dry biomass in the t-butanol layer and protein content of ∼12 % w/w of dry biomass in the middle protein layer due to ammonium sulfate precipitation, after performing TPP under the optimized conditions.

  17. High-pressure displacive phase transition of a natural Mg-rich pigeonite

    NASA Astrophysics Data System (ADS)

    Alvaro, Matteo; Nestola, Fabrizio; Cámara, Fernando; Domeneghetti, M. Chiara; Tazzoli, Vittorio

    2011-05-01

    A high-pressure single-crystal X-ray diffraction study has been carried out on a P21/ c natural Mg-rich pigeonite sample with composition ca. Wo6En76Fs18 using a diamond anvil-cell. The unit-cell parameters were determined at 14 different pressures to 7.14 GPa. The sudden disappearance of the b-type reflections ( h + k = odd) and a strong discontinuity (about 2.8%) in the unit-cell volume indicated a first-order P21/ c- C2/ c phase transition between 4.66 and 4.88 GPa. The P( V) data of the P21/ c phase were fitted to 4.66 GPa by a third-order Birch-Murnaghan equation of state (BM3 EoS), whereas the limited number of experimental data collected within the C2/ c phase between 4.88 and 7.14 GPa were fitted using the same equation of state but with K' constrained to the value obtained for the P21/ c fitting. The equation of state coefficients are V 0 = 424.66(6) Å3, K T0 = 104(2) GPa and K' = 8(1) for the P21/ c phase, and V 0 = 423.6(1) Å3, K T0 = 112.4(8) GPa, and K' fixed to 8(1) for the C2/ c phase. The axial moduli for a, b, and c for the P21/ c phase were obtained using also a BM3-EoS, while for the C2/ c phase only a linear calculation could be performed, and therefore the same approach was applied for comparison also to the P21/ c phase. In general the C2/ c phase exhibits axial compressibilities ( β c > β a >> β b) lower than those of the P21/ c phase ( β b > β c ≈ β a; similar to those found in previous studies in clinopyroxenes and orthopyroxenes). The lower compressibility of the C2/ c phase compared with that of the P21/ c could be ascribed to the greater stiffness along the b direction. A previously published relationship between P c and M2 average cation radius (i.r.) has been updated using all the literature data on P21/ c clinopyroxene containing large cations at M2 site and our new data. The following weighted regression was obtained: P c (GPa) = 26(4) - 28(5) × i.r (Å), R 2 = 0.97. This improved equation can be used to predict the

  18. Strength and structural phase transitions of gadolinium at high pressure from radial X-ray diffraction

    SciTech Connect

    Xiong, Lun Liu, Jing; Bai, Ligang; Li, Xiaodong; Lin, Chuanlong; Lin, Jung-Fu

    2014-12-28

    Lattice strength and structural phase transitions of gadolinium (Gd) were determined under nonhydrostatic compression up to 55 GPa using an angle-dispersive radial x-ray diffraction technique in a diamond-anvil cell at room temperature. Three new phases of fcc structure, dfcc structure, and new monoclinic structure were observed at 25 GPa, 34 GPa, and 53 GPa, respectively. The radial x-ray diffraction data yield a bulk modulus K{sub 0} = 36(1) GPa with its pressure derivate K{sub 0}′ = 3.8(1) at the azimuthal angle between the diamond cell loading axis and the diffraction plane normal and diffraction plane ψ = 54.7°. With K{sub 0}′ fixed at 4, the derived K{sub 0} is 34(1) GPa. In addition, analysis of diffraction data with lattice strain theory indicates that the ratio of differential stress to shear modulus (t/G) ranges from 0.011 to 0.014 at pressures of 12–55 GPa. Together with estimated high-pressure shear moduli, our results show that Gd can support a maximum differential stress of 0.41 GPa, while it starts to yield to plastic deformation at 16 GPa under uniaxial compression. The yield strength of Gd remains approximately a constant with increasing pressure, and reaches 0.46 GPa at 55 GPa.

  19. Structure and compressibility of the high-pressure molecular phase II of carbon dioxide

    NASA Astrophysics Data System (ADS)

    Datchi, Frédéric; Mallick, Bidyut; Salamat, Ashkan; Rousse, Gwenaëlle; Ninet, Sandra; Garbarino, Gaston; Bouvier, Pierre; Mezouar, Mohamed

    2014-04-01

    The structure and equation of state of the crystalline molecular phase II of carbon dioxide have been investigated at room temperature from 15.5 to 57.5 GPa using synchrotron x-ray diffraction methods. The CO2 samples were embedded in neon pressure medium in order to provide quasihydrostatic conditions. The x-ray diffraction patterns of phase II are best described by a tetragonal structure, with space group P42/mnm and 2 molecules per unit cell, in accordance with a previous study [Yoo et al., Phys. Rev. B 65, 104103 (2002), 10.1103/PhysRevB.65.104103]. There is however a large (15%) difference in the intramolecular C=O bond length between the present study, 1.14(3) Å, and the latter work (1.329-1.366 Å). The present value is similar to that of the free molecule and is in very good agreement with predictions based on density functional theory. The compressibility of CO2-II determined here also disagrees with the previous study: our value for the zero-pressure bulk modulus, B0=8.5(3) GPa [with B0'=(∂B/∂P)0=6.29], is 15.5 times smaller. These findings oppose the view that CO2-II is an intermediate state between the low-pressure molecular phases and the high-pressure nonmolecular forms, consistent with our previous results for phase IV [Datchi et al., Phys. Rev. Lett. 103, 185701 (2009), 10.1103/PhysRevLett.103.185701]. The x-ray diffraction patterns of CO2-II above 15 GPa indicate the presence of a large orthorhombic microstrain. Carrying out density functional theory calculations of the elastic tensor and stress-strain relation, we interpret this as due to the softness of the crystal against deviatoric stress in the [110] and symmetry-related directions. Unlike the other dioxides of the group-14 elements, there is however no mechanical or dynamical instability of the P42/mnm structure in CO2 up to 57.5 GPa at 295 K, and therefore no symmetry lowering to Pnnm.

  20. Effect of pressure on the selectivity of polymeric C18 and C30 stationary phases in reversed-phase liquid chromatography. Increased separation of isomeric fatty acid methyl esters, triacylglycerols, and tocopherols at high pressure.

    PubMed

    Okusa, Kensuke; Iwasaki, Yuki; Kuroda, Ikuma; Miwa, Shohei; Ohira, Masayoshi; Nagai, Toshiharu; Mizobe, Hoyo; Gotoh, Naohiro; Ikegami, Tohru; McCalley, David V; Tanaka, Nobuo

    2014-04-25

    A high-density, polymeric C18 stationary phase (Inertsil ODS-P) or a polymeric C30 phase (Inertsil C30) provided improved resolution of the isomeric fatty acids (FAs), FA methyl esters (FAMEs), triacylglycerols (TAGs), and tocopherols with an increase in pressure of 20-70MPa in reversed-phase HPLC. With respect to isomeric C18 FAMEs with one cis-double bond, ODS-P phase was effective for recognizing the position of a double bond among petroselinic (methyl 6Z-octadecenoate), oleic (methyl 9Z-octadecenoate), and cis-vaccenic (methyl 11Z-octadecenoate), especially at high pressure, but the differentiation between oleic and cis-vaccenic was not achieved by C30 phase regardless of the pressure. A monomeric C18 phase (InertSustain C18) was not effective for recognizing the position of the double bond in monounsaturated FAME, while the separation of cis- and trans-isomers was achieved by any of the stationary phases. The ODS-P and C30 phases provided increased separation for TAGs and β- and γ-tocopherols at high pressure. The transfer of FA, FAME, or TAG molecules from the mobile phase to the ODS-P stationary phase was accompanied by large volume reduction (-30∼-90mL/mol) resulting in a large increase in retention (up to 100% for an increase of 50MPa) and improved isomer separation at high pressure. For some isomer pairs, the ODS-P and C30 provided the opposite elution order, and in each case higher pressure improved the separation. The two stationary phases showed selectivity for the isomers having rigid structures, but only the ODS-P was effective for differentiating the position of a double bond in monounsaturated FAMEs. The results indicate that the improved isomer separation was provided by the increased dispersion interactions between the solute and the binding site of the stationary phase at high pressure.

  1. Quenching ilmenite with a high-temperature and high-pressure phase using super-high-energy ball milling.

    PubMed

    Hashishin, Takeshi; Tan, Zhenquan; Yamamoto, Kazuhiro; Qiu, Nan; Kim, Jungeum; Numako, Chiya; Naka, Takashi; Valmalette, Jean Christophe; Ohara, Satoshi

    2014-04-25

    The mass production of highly dense oxides with high-temperature and high-pressure phases allows us to discover functional properties that have never been developed. To date, the quenching of highly dense materials at the gramme-level at ambient atmosphere has never been achieved. Here, we provide evidence of the formation of orthorhombic Fe2TiO4 from trigonal FeTiO3 as a result of the high-temperature (>1250 K) and high-pressure (>23 GPa) condition induced by the high collision energy of 150 gravity generated between steel balls. Ilmenite was steeply quenched by the surrounding atmosphere, when iron-rich ilmenite (Fe2TiO4) with a high-temperature and high-pressure phase was formed by planetary collisions and was released from the collision points between the balls. Our finding allows us to infer that such intense planetary collisions induced by high-energy ball milling contribute to the mass production of a high-temperature and high-pressure phase.

  2. Quenching ilmenite with a high-temperature and high-pressure phase using super-high-energy ball milling

    PubMed Central

    Hashishin, Takeshi; Tan, Zhenquan; Yamamoto, Kazuhiro; Qiu, Nan; Kim, Jungeum; Numako, Chiya; Naka, Takashi; Valmalette, Jean Christophe; Ohara, Satoshi

    2014-01-01

    The mass production of highly dense oxides with high-temperature and high-pressure phases allows us to discover functional properties that have never been developed. To date, the quenching of highly dense materials at the gramme-level at ambient atmosphere has never been achieved. Here, we provide evidence of the formation of orthorhombic Fe2TiO4 from trigonal FeTiO3 as a result of the high-temperature (>1250 K) and high-pressure (>23 GPa) condition induced by the high collision energy of 150 gravity generated between steel balls. Ilmenite was steeply quenched by the surrounding atmosphere, when iron-rich ilmenite (Fe2TiO4) with a high-temperature and high-pressure phase was formed by planetary collisions and was released from the collision points between the balls. Our finding allows us to infer that such intense planetary collisions induced by high-energy ball milling contribute to the mass production of a high-temperature and high-pressure phase. PMID:24763088

  3. Mechanical behaviors and phase transition of Ho{sub 2}O{sub 3} nanocrystals under high pressure

    SciTech Connect

    Yan, Xiaozhi; Ren, Xiangting; He, Duanwei E-mail: yangwg@hpstar.ac.cn; Chen, Bin; Yang, Wenge E-mail: yangwg@hpstar.ac.cn

    2014-07-21

    Mechanical properties and phase transition often show quite large crystal size dependent behavior, especially at nanoscale under high pressure. Here, we have investigated Ho{sub 2}O{sub 3} nanocrystals with in-situ x-ray diffraction and Raman spectroscopy under high pressure up to 33.5 GPa. When compared to the structural transition routine cubic -> monoclinic -> hexagonal phase in bulk Ho{sub 2}O{sub 3} under high pressure, the nano-sized Ho{sub 2}O{sub 3} shows a much higher onset transition pressure from cubic to monoclinic structure and followed by a pressure-induced-amorphization under compression. The detailed analysis on the Q (Q = 2π/d) dependent bulk moduli reveals the nanosized Ho{sub 2}O{sub 3} particles consist of a clear higher compressible shell and a less compressible core. Insight into these phenomena shed lights on micro-mechanism studies of the mechanical behavior and phase evolution for nanomaterials under high pressure, in general.

  4. In Situ Observations of Thermoreversible Gelation and Phase Separation of Agarose and Methylcellulose Solutions under High Pressure.

    PubMed

    Kometani, Noritsugu; Tanabe, Masahiro; Su, Lei; Yang, Kun; Nishinari, Katsuyoshi

    2015-06-04

    Thermoreversible sol-gel transitions of agarose and methylcellulose (MC) aqueous solutions on isobaric cooling or heating under high pressure up to 400 MPa have been investigated by in situ observations of optical transmittance and falling-ball experiments. For agarose, which undergoes the gelation on cooling, the application of pressure caused a gradual rise in the cloud-point temperature over the whole pressure range examined, which is almost consistent with the pressure dependence of gelling temperature estimated by falling-ball experiments, suggesting that agarose gel is stabilized by compression and that the gelation occurs nearly in parallel with phase separation under ambient and high-pressure conditions. For MC, which undergoes the gelation on heating, the cloud-point temperature showed a slight rise with an initial elevation of pressure up to ∼150 MPa, whereas it showed a marked depression above 200 MPa. In contrast, the gelling temperature of MC, which is nearly identical to the cloud-point temperature at ambient pressure, showed a monotonous rise with increasing pressure up to 350 MPa, which means that MC undergoes phase separation prior to gelation on heating under high pressure above 200 MPa. Similar results were obtained for the melting process of MC gel on cooling. The unique behavior of the sol-gel transition of MC under high pressure has been interpreted in terms of the destruction of hydrophobic hydration by compression.

  5. A new phase of ThC at high pressure predicted from a first-principles study

    NASA Astrophysics Data System (ADS)

    Guo, Yongliang; Qiu, Wujie; Ke, Xuezhi; Huai, Ping; Cheng, Cheng; Han, Han; Ren, Cuilan; Zhu, Zhiyuan

    2015-08-01

    The phase transition of thorium monocarbide (ThC) at high pressure has been studied by means of density functional theory. Through structure search, a new phase with space group P 4 / nmm has been predicted. The calculated phonons demonstrate that this new phase and the previous B2 phase are dynamically stable as the external pressure is greater than 60 GPa and 120 GPa, respectively. The transformation from B1 to P 4 / nmm is predicted to be a first-order transition, while that from P 4 / nmm to B2 is found to be a second-order transition.

  6. Li-Ion Conductivity and Phase Stability of Ca-Doped LiBH4 under High Pressure.

    PubMed

    Mezaki, Takeya; Kuronuma, Yota; Oikawa, Itaru; Kamegawa, Atsunori; Takamura, Hitoshi

    2016-10-17

    The effect of Ca doping on the Li-ion conductivity and phase stability of the rock-salt-type LiBH4 phase emerging under high pressures in the range of gigapascals has been investigated. In situ electrochemical measurements under high pressure were performed using a cubic-anvil-type apparatus. Ca doping drastically enhanced the ionic conductivity of the rock-salt-type phase: the ionic conductivity of undoped and 5 mol %Ca-doped LiBH4 was 2.2 × 10(-4) and 1.4 × 10(-2) S·cm(-1) under 4.0 GPa at 220 °C, respectively. The activation volume of LiBH4-5 mol %Ca(BH4)2, at 3.2 cm(3)·mol(-1), was comparable to that of other fast ionic conductors, such as lithium titanate and NASICONs. Moreover, Ca-doped LiBH4 showed lithium plating-stripping behavior in a cyclic voltammogram. These results indicate that the conductivity enhancement by Ca doping can be attributed to the formation of a LiBH4-Ca(BH4)2 solid solution; however, the solid solution decomposed into the orthorhombic LiBH4 phase and the orthorhombic Ca(BH4)2 phase after unloading the high pressure.

  7. Thermodynamics of the ferromagnetic phase transition in nearly half metallic CoS2 at high pressures

    SciTech Connect

    Elkin, F. S.; Zibrov, I. P.; Novikov, A. P.; Khasanov, S. S.; Sidorov, V. A.; Petrova, A. E.; Lograsso, Thomas A.; Thompson, J. D.; Stishov, S. M.

    2013-12-06

    The volume change and heat capacity at the ferromagnetic phase transition in COS2 were measured at high pressures using X-rays generated by the Argonne synchrotron light source and by ac-calorimetry, respectively. The transition entropy, calculated on the basis of these experimental data, drops along the transition line due to quantum degradation, as required by Nernst's law. The volume change increases strongly along the transition line, which is explained by specifics of the compressibility difference of coexisting phases that results from nearly half metallic nature of the ferromagnetic phase of COS2. (C) 2013 Elsevier Ltd. All rights reserved.

  8. Development and testing of a high-pressure downhole pump for jet-assist drilling. Topical report, Phase II

    SciTech Connect

    1997-10-01

    The goal of jet-assisted drilling is to increase the rate of penetration (ROP) in deeper gas and oil wells, where the rocks become harder and more difficult to drill. Increasing the ROP can result in fewer drilling days, and therefore, lower drilling cost. In late 1993, FlowDril and the Gas Research Institute (GRI) began a three-year development of a down hole pump (DHP{reg_sign}) capable of producing 30,000 psi out pressure to provide the high-pressure flow for high-pressure jet-assist of the drill bit. The U.S. Department of Energy (DOE) through its Morgantown, WV (DOE-Morgantown) field office, joined with GRI and FlowDril to develop and test a second prototype designed for drilling in 7-7/8 inch holes. This project, {open_quotes}Development and Testing of a High-Pressure Down Hole Pump for Jet-Assist Drilling,{close_quotes} is for the development and testing of the second prototype. It was planned in two phases. Phase I included an update of a market analysis, a design, fabrication, and an initial laboratory test of the second prototype. Phase II is continued iterative laboratory and field developmental testing. This report summarizes the results of Phase II. In the downhole pump approach shown in the following figure, conventional drill pipe and drill collars are used, with the DHP as the last component of the bottom hole assembly next to the bit. The DHP is a reciprocating double ended, intensifier style positive displacement, high-pressure pump. The drive fluid and the high-pressure output fluid are both derived from the same source, the abrasive drilling mud pumped downhole through the drill string. Approximately seven percent of the stream is pressurized to 30,000 psi and directed through a high-pressure nozzle on the drill bit to produce the high speed jet and assist the mechanical action of the bit to make it drill faster.

  9. Melting and phase relations in the Fe-C-S-O system at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Fei, Yingwei

    2010-05-01

    The physical state of the core (liquid outer core and solid inner core) could provide tight constraint on the core temperature if melting temperature of core materials is precisely determined at high pressure. On the other hand, the density of the Earth's core is significantly lower than that of pure iron measured experimentally at high pressure and temperature. The density deficit in the core (both liquid outer core and solid inner core) provides inside into the chemistry of the core, suggesting that the core must contain several weight percent of one or more light elements (lighter than iron) in addition to Fe-Ni alloy. Sulfur (S), carbon (C), and oxygen (O) are the prominent candidates among the proposed light elements, because of their high solar abundance and strong chemical affinity for Fe. Determining the effect of pressure on melting relations in the Fe-S, Fe-C, and Fe-O binary systems and multi-component system is crucial for understanding the chemistry, temperature, and evolution of planetary cores. There has been significant progress in determining the melting relations in the system Fe-FeS at high pressure, using multi-anvil apparatus and laser-heating diamond-anvil cell. These studies have revealed new iron-sulfur compounds (Fe3S2, Fe2S, and Fe3S) stable at high pressures, change of melting relations, and pressure effect on eutectic temperature and composition. The behaviors of the Fe-C and Fe-O systems have also been experimentally investigated recently. Experimental data in the Fe-C-S-O system at high pressure have just emerged. In parallel, there are high-quality data on density measurements of solid and liquid phases at high pressure and temperature. In this study, I present recent advances in experimental techniques and melting relations in the Fe-C-S-O system. The emphasis will be on the need to develop thermodynamic models by synthesis of thermochemical, thermophysical, and phase equilibrium data. The systematic approach provides a better

  10. Entropic phase transitions and accompanying anomalous thermodynamics of matter

    NASA Astrophysics Data System (ADS)

    Iosilevskiy, I. L.

    2015-11-01

    Thermodynamic consequences of subdivision for all first-order phase transitions (PT) into enthalpy- and entropy-driven ones (H-PT and S-PT), proposed previously [arXiv:1403.8053], are under discussions. Key-value for proposed discrimination is main benefit (decreasing) in enthalpy or (nega)entropy in spontaneous phase decomposition, i.e. the sign of latent heat of PT and consequent slope of its P(T)-dependence. The main driving mechanism for many isostructural S-PT is the decay (delocalization) of some kind of bound complexes, e.g. atoms, molecules etc. Thermodynamic features of H-PT and S-PT differ significantly. Entropic PT are always the part of more general thermodynamic anomaly—domain where great number of usually positive second cross derivatives (e.g. Grüneisen parameter, thermal pressure coefficient etc.) became negative simultaneously. This domain is restricted (in the case of isostructural S-PT) by remarkable bound, where all mentioned second derivatives are equal to zero. Isostructural S-PT has more complicated topology of stable, metastable and unstable states and their boundaries—binodals and spinodals in comparison with ordinary enthalpic PTs. Two new thermodynamic objects accompany isostructural S-PT: (i) appearance of third (additional) region of metastable states with positive compressibility, isolated from the regions of stable states; (ii) appearance of new additional spinodal, topped with a new singular point, separating metastable and unstable states. These additional spinodal and singular point obey to relation (∂P/∂V)T = ∞. All thermodynamic anomalies of entropic PTs correspond to conclusive and transparent geometrical feature of such PTs: multilayered structure of thermodynamic surfaces for temperature, entropy and internal energy as pressure- density functions U(P, V), S(P, V) and T(P, V).

  11. Series of Phase Transitions in Cesium Azide Under High Pressure Studied by in situ X-ray Diffraction

    SciTech Connect

    D Hou; F Zhang; C Ji; T Hannon; H Zhu; J Wu; Y Ma

    2011-12-31

    In situ x-ray diffraction measurements of cesium azide (CsN{sub 3}) were performed at high pressures of up to 55.4 GPa at room temperature. Three phase transitions were revealed as follows: tetragonal (I4/mcm, Phase II) {yields} monoclinic (C2/m, Phase III) {yields} monoclinic (P2{sub 1}/m or P2{sub 1}, Phase IV) {yields} triclinic (P1 or P1{sup -}, Phase V), at 0.5, 4.4, and 15.4 GPa, respectively. During the II-III phase transition, CsN{sub 3} keeps its layered structure and the azide anions rotate obviously. The compressibility of Phase II is dominated by the repulsions between azide anions. The deformation of unit cell is isotropic in Phases II and IV and anisotropic in Phase III. With increasing pressures, the monoclinic angle increases in Phase III and then becomes stable in Phase IV. The bulk moduli of Phases II, III, IV, and V are determined to be 18 {+-} 4, 20 {+-} 1, 27 {+-} 1 and 34 {+-} 1 GPa, respectively. The ionic character of alkali azides is found to play a key role in their pressure-induced phase transitions.

  12. Structural and magnetic phase transitions in gadolinium under high pressures and low temperatures

    SciTech Connect

    Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; Vohra, Yogesh K.

    2014-11-07

    High pressure structural transition studies have been carried out on rare earth metal gadolinium in a diamond anvil cell at room temperature to 169 GPa. Gadolinium has been compressed to 38% of its initial volume at this pressure. With increasing pressure, a crystal structure sequence of hcp → Smtype→ dhcp → fcc → dfcc → monoclinic has been observed in our studies on gadolinium. The measured equation of state of gadolinium is presented to 169 GPa at ambient temperature. Magnetic ordering temperature of gadolinium has been studied using designer diamond anvils to a pressure of 25 GP and a temperature of 10 K. The magnetic ordering temperature has been determined from the four-point electrical resistivity measurements carried out on gadolinium. Furthermore, our experiments show that the magnetic transition temperature decreases with increasing pressure to 19 GPa and then increases when gadolinium is subjected to higher pressures.

  13. Quantitative analysis of vitamin D3 in a feed using normal phase high pressure liquid chromatography.

    PubMed

    Cohen, H; Lapointe, M

    1979-09-01

    A procedure is described for the separation and quantification of Vitamin D3 from different feeds and premixes. The study was conducted, first using a liquid partition step as a preliminary clean-up after extraction, then chromatography on activated Silica gel 60 before final analysis on a high pressure liquid chromatograph (HPLC) using a LiChrosorb NH2 (10 mu) column and a variable wavelength UV detector set at 264 nm. Total analysis on the HPLC was achieved in fifteen minutes. The detector response curve for an authentic D3 standard was linear using peak areas with a minimum detectable amount being 5 ng. The overall percent recovery of D3 in feeds was 94.4 +/- 2.4%. The minimum detectable amount of D3 in animal feeds was found to be in the region of 2,000 I.U./kg.

  14. Structural and magnetic phase transitions in gadolinium under high pressures and low temperatures

    DOE PAGES

    Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; ...

    2014-11-07

    High pressure structural transition studies have been carried out on rare earth metal gadolinium in a diamond anvil cell at room temperature to 169 GPa. Gadolinium has been compressed to 38% of its initial volume at this pressure. With increasing pressure, a crystal structure sequence of hcp → Smtype→ dhcp → fcc → dfcc → monoclinic has been observed in our studies on gadolinium. The measured equation of state of gadolinium is presented to 169 GPa at ambient temperature. Magnetic ordering temperature of gadolinium has been studied using designer diamond anvils to a pressure of 25 GP and a temperaturemore » of 10 K. The magnetic ordering temperature has been determined from the four-point electrical resistivity measurements carried out on gadolinium. Furthermore, our experiments show that the magnetic transition temperature decreases with increasing pressure to 19 GPa and then increases when gadolinium is subjected to higher pressures.« less

  15. Theoretical calculations of phase transitions and optical properties of solid iodine under high pressures

    NASA Astrophysics Data System (ADS)

    San, Xiaojiao; Wang, Liancheng; Ma, Yanming; Liu, Zhiming; Cui, Tian; Liu, Bingbing; Zou, Guangtian

    2008-04-01

    The structural stability and optical properties of solid iodine under pressure have been studied using the ab initio pseudopotential plane-wave method. The dependence of lattice parameters on pressure indicates that the first structural phase transition from phase I to phase V occurs at about 20 GPa. From the pressure dependence of our elastic constants for solid iodine in phase I, it is found that the first structural transformation from molecular phase I to the intermediate phase V occurs at about 20 GPa due to the softening of the elastic constant C44, which is very close to the transition pressure of 20 GPa obtained by geometry optimizations and 23.2 GPa obtained by experimental measurements. The optimized structure for phase V is a face-centered orthorhombic (fco) phase with equal interatomic distances d1 = d2 = d3, but this fco structure is mechanically unstable, with shear elastic stiffness coefficient C44<0. To understand the modulated phase V, we use a periodic crystal structure to mimic the incommensurate phase V and obtain some quantitative information. In our calculation, the modulated phase is thermodynamically and mechanically stable. It is believed that phase V is not a monatomic phase but an intermediate state between a molecular and a monatomic state.

  16. Ambient-condition growth of high-pressure phase centrosymmetric crystalline KDP microstructures for optical second harmonic generation

    PubMed Central

    Ren, Yan; Zhao, Xian; Hagley, Edward W.; Deng, Lu

    2016-01-01

    Noncentrosymmetric potassium dihydrogen phosphate (KH2PO4 or KDP) in the tetragonal crystal phase is arguably the most extensively studied nonlinear optical crystal in history. It has prolific applications ranging from simple laser pointers to laser inertial confinement fusion systems. Recently, type IV high-pressure KDP crystal sheets with a monoclinic crystal phase having centrosymmetric properties have been observed. However, it was found that this new crystal phase is highly unstable under ambient conditions. We report ambient-condition growth of one-dimensional, self-assembled, single-crystalline KDP hexagonal hollow/solid-core microstructures that have a molecular structure and symmetry identical to the type IV KDP monoclinic crystal that was previously found to exist only at extremely high pressures (>1.6 GPa). Furthermore, we report highly efficient bulk optical second harmonic generation (SHG) from these ambient condition–grown single-crystalline microstructures, even though they have a highly centrosymmetric crystal phase. However, fundamental physics dictates that a bulk optical medium with a significant second-order nonlinear susceptibility supporting SHG must have noncentrosymmetric properties. Laue diffraction analysis reveals a weak symmetry-breaking twin-crystal lattice that, in conjunction with tight confinement of the light field by the tubular structure, is attributed to the significant SHG even with sample volumes <0.001 mm3. A robust polarization-preserving effect is also observed, raising the possibility of advanced optical technological applications. PMID:27574703

  17. Optical properties of the high-pressure phases of SnO(2): first-principles calculation.

    PubMed

    Li, Yanlu; Fan, Weiliu; Sun, Honggang; Cheng, Xiufeng; Li, Pan; Zhao, Xian; Hao, Jingcheng; Jiang, Minhua

    2010-01-21

    We present a detailed investigation on the optical properties, including dielectric function, reflectivity, absorption, refractive index, and electron energy-loss spectrum, of the high-pressure phase SnO(2) in the rutile, pyrite, fluorite, and cotunnite structures by using the density functional theory (DFT) plane-wave pseudopotential method. The results indicate that with the increasing of pressure the band gaps become larger, the density of states are broader, so the curves of optical properties have a little blue shift. Except that the fluorite phase has some metallic properties, the other three phases exhibit excellent dielectric behavior. Interestingly, the fluorite and cotunnite SnO(2) phases always have some special characteristics, such as higher plasma frequency, which need further fundamental and application research.

  18. Liquid water-ice I phase diagrams under high pressure: sodium chloride and sucrose models for food systems.

    PubMed

    Guignon, Bérengère; Otero, Laura; Molina-García, Antonio D; Sanz, Pedro D

    2005-01-01

    The knowledge of high pressure and low temperature phase diagrams of aqueous systems is required in fields such as food sciences, biology, cryo-microscopy and geology, to reduce processing costs, improve treatments results or advance in physical phenomena understanding. The phase transition curve between liquid water and ice I for sucrose and sodium chloride solutions has been obtained for concentrations ranging from 16% to 36% and from 1.63% to 16.09% (w/w), respectively. An accurate experimental method, based on the pressurization of an ice-solution mixture, adequate to build the entire phase transition curve at constant concentration, has been developed. Simon-like equations have been used to empirically describe the phase transition curves, so that they allow easy data interpolation.

  19. Phase equilibria in fluid mixtures at high pressures - The He-CH4 system.

    NASA Technical Reports Server (NTRS)

    Streett, W. B.; Erickson, A. L.; Hill, J. L. E.

    1972-01-01

    An experimental study of phase equilibria in the He-CH4 system has been carried out over the temperature range 95 to 290 K and at pressures to 10,000 atm. The experimental results consist of equilibrium phase composition for twenty-eight isotherms in the region of coexistence of two fluid phases, together with the pressure-temperature trace of the three-phase boundary at which a CH4-rich solid phase is in equilibrium with the two fluid phases. The system exhibits a fluid-fluid phase separation which persists to temperatures and pressures beyond the range of this experiment. These findings are relevant to problems of deep atmosphere and interior structures in the outer planets.-

  20. High-temperature and high-pressure phase transitions in uranium

    NASA Astrophysics Data System (ADS)

    Bouchet, J.; Bottin, F.

    2017-02-01

    The phase diagram of uranium has been explored up to 100 GPa and 2000 K by means of ab initio molecular dynamics (AIMD) simulations. The lattice dynamics and energetics of the stable phases observed experimentally in this range of pressure and temperature are studied in this work. The phonon spectra of the α and γ phases are shown to evolve strongly as a function of temperature, unveiling the huge anharmonic effects present in this material. If the elastics constants and the bulk and shear moduli of the γ phase do not disclose any temperature effects, the shear modulus of the α phase decreases strongly as a function of temperature. Using the pressure- and temperature-dependent vibrational density of states and the Gibbs free energy of these two structures, we found a line transition between the α and γ phases which slightly underestimates the experimental one. Coherently with experiments, the bct structure is never found stable between 0 and 100 GPa.

  1. The Phase Transition of Zn0.854Cu0.146O Under High Pressure

    SciTech Connect

    Y Jin; J Zhang; P Zhu; W Gao; Q Cui

    2011-12-31

    Pressure induced phase transition of hexagonal Zn{sub 0.854}Cu{sub 0.146}O is studied by using synchrotron angle dispersive X-ray diffraction (ADXRD) up to 43.1 GPa at room temperature. A structural transformation from a hexagonal phase to a cubic phase is observed, which starts at 10.2 GPa and finishes at about 16.5 GPa. The phase transition leads to a volume collapse of 17% at 10.2 GPa. The cubic phase of Zn{sub 0.854}Cu{sub 0.146}O remains stable up to the highest experiment pressure. The pressure-volume data are fitted with the Birch-Murnaghan equation of state. The bulk modulus obtained upon compression from the fitting are 175(2) and 259(6) GPa for the hexagonal and cubic phases, respectively.

  2. Magnetoresistance of the high-pressure ferromagnetic phases (GaSb)2M (M=Cr,Mn)

    NASA Astrophysics Data System (ADS)

    Pronin, A. A.; Kondrin, M. V.; Gizatullin, V. R.; Sazanova, O. A.; Lyapin, A. G.; Popova, S. V.; Ivanov, V. Y.

    2014-08-01

    For the first time magnetoresistance of the ferromagnetic high-pressure phases (GaSb)2M (M=Cr,Mn) has been measured in a wide range of temperature and magnetic field. It was found that the magnetic field dependencies of resistivity of both systems contain several contributions, including relatively smaller s-d exchange (Yosida-type) components in low fields and a quadratic positive term (PMR) in the low temperature region. The magnitude of the predominated negative term (NMR), which can be attributed to the quantum corrections effects, demonstrates a peak in the vicinity of Curie temperature.

  3. Structural phase transitions in Bi2Se3 under high pressure

    SciTech Connect

    Yu, Zhenhai; Gu, Genda; Wang, Lin; Hu, Qingyang; Zhao, Jinggeng; Yan, Shuai; Yang, Ke; Sinogeikin, Stanislav; Mao, Ho -kwang

    2015-11-02

    Raman spectroscopy and angle dispersive X-ray diffraction (XRD) experiments of bismuth selenide (Bi2Se3) have been carried out to pressures of 35.6 and 81.2 GPa, respectively, to explore its pressure-induced phase transformation. The experiments indicate that a progressive structural evolution occurs from an ambient rhombohedra phase (Space group (SG): R-3m) to monoclinic phase (SG: C2/m) and eventually to a high pressure body-centered tetragonal phase (SG: I4/mmm). Evidenced by our XRD data up to 81.2 GPa, the Bi2Se3 crystallizes into body-centered tetragonal structures rather than the recently reported disordered body-centered cubic (BCC) phase. Furthermore, first principles theoretical calculations favor the viewpoint that the I4/mmm phase Bi2Se3 can be stabilized under high pressure (>30 GPa). Remarkably, the Raman spectra of Bi2Se3 from this work (two independent runs) are still Raman active up to ~35 GPa. Furthermore, it is worthy to note that the disordered BCC phase at 27.8 GPa is not observed here. The remarkable difference in atomic radii of Bi and Se in Bi2Se3 may explain why Bi2Se3 shows different structural behavior than isocompounds Bi2Te3 and Sb2Te3.

  4. Real-Time Optical Monitoring of Flow Kinetics and Gas Phase Reactions Under High-Pressure OMCVD Conditions

    NASA Technical Reports Server (NTRS)

    Dietz, N.; McCall, S.; Bachmann, K. J.

    2001-01-01

    This contribution addresses the real-time optical characterization of gas flow and gas phase reactions as they play a crucial role for chemical vapor phase depositions utilizing elevated and high pressure chemical vapor deposition (HPCVD) conditions. The objectives of these experiments are to validate on the basis of results on real-time optical diagnostics process models simulation codes, and provide input parameter sets needed for analysis and control of chemical vapor deposition at elevated pressures. Access to microgravity is required to retain high pressure conditions of laminar flow, which is essential for successful acquisition and interpretation of the optical data. In this contribution, we describe the design and construction of the HPCVD system, which include access ports for various optical methods of real-time process monitoring and to analyze the initial stages of heteroepitaxy and steady-state growth in the different pressure ranges. To analyze the onset of turbulence, provisions are made for implementation of experimental methods for in-situ characterization of the nature of flow. This knowledge will be the basis for the design definition of experiments under microgravity, where gas flow conditions, gas phase and surface chemistry, might be analyzed by remote controlled real-time diagnostics tools, developed in this research project.

  5. Phase relationships in Fe-Ni alloys at high pressures and temperatures

    NASA Technical Reports Server (NTRS)

    Huang, Eugene; Bassett, William A.; Weathers, Maura S.

    1988-01-01

    Diffusionless phase transformations in Fe-Ni alloys with up to 35 wt pct Ni were studied using resistance-heated diamond anvil cells and synchrotron radiation. At temperatures up to 600 C and pressures up to 25 GPa, Fe-35 percent Ni showed only the face-centered cubic (fcc) phase while Fe-25 percent Ni and Fe-10 percent Ni showed the body-centered cubic (bcc) and hexagonal close-packed (hcp) phases in addition to the fcc phase. The phase relationships of these solid phases are topologically similar to those of pure iron. The triple point becomes lower in temperature, and the slope (dT/dP) of the fcc/hcp boundary decreased as Ni-content increases in the alloys. From these results it is inferred that Fe-Ni alloys in the earth's inner core might exist as two phases, fcc and hcp. The existence of these two phases could have played an important role in the separation of the inner and outer core.

  6. Phase diagram of ammonium perchlorate: Raman spectroscopic constrains at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Dunuwille, Mihindra; Yoo, Choong-Shik

    2016-06-01

    We present the pressure-temperature (PT) induced physical and chemical transformations in ammonium perchlorates (APs) up to 50 GPa and 450 °C, using diamond anvil cells and confocal micro-Raman spectroscopy, which provide new constraints for the phase diagram of AP. The results show spectral evidences for three new polymorphs (III, IV, and VI) of AP, in addition to two previously known phases (I and II), at various PT conditions with varying degrees of hydrogen bonding and lack of strong spectral evidence for previously known high-temperature cubic phase (phase V). Upon further heating, AP chemically decomposes to N2, N2O, and H2O. The present phase diagram is, therefore, in sharp contrast to the previous one, underscoring a rich polymorphism, a large stability field for solids, and a replacement of the melt with a decomposition line.

  7. A two-dimensional modeling of the warm-up phase of a high-pressure mercury discharge lamp

    SciTech Connect

    Araoud, Z.; Ben Ahmed, R.; Ben Hamida, M. B.; Charrada, K.; Franke, St.; Stambouli, M.; Zissis, G.

    2010-06-15

    The main objective of this work is to provide a better understanding of the warm-up phase of high-intensity discharge lamps. As an example of application, we chose the high-pressure mercury lamp. Based on two-dimensional fluid model parameters, such as the electric current, the length and the diameter of the burner are modified and the effect of the convective transport is studied. This allows us to obtain a thorough understanding of the physics of these lamps in their transitory phase. The simulation of the warm-up phase is a must for the proper predictions of the lamp behavior and can be conducted by solving the energy balance, momentum, and Laplace's equations for the plasma, using the frame of the local thermodynamic equilibrium coupled with the energy balance of the wall.

  8. High pressure Laue diffraction and its application to study microstructural changes during the α → β phase transition in Si

    SciTech Connect

    Popov, D. Park, C.; Kenney-Benson, C.; Shen, G.

    2015-07-15

    An approach using polychromatic x-ray Laue diffraction is described for studying pressure induced microstructural changes of materials under pressure. The advantages of this approach with respect to application of monochromatic x-ray diffraction and other techniques are discussed. Experiments to demonstrate the applications of the method have been performed on the α → β phase transition in Si at high pressures using a diamond anvil cell. We present the characterization of microstructures across the α–β phase transition, such as morphology of both the parent and product phases, relative orientation of single-crystals, and deviatoric strains. Subtle inhomogeneous strain of the single-crystal sample caused by lattice rotations becomes detectable with the approach.

  9. Synthesis of new Diamond-like B-C Phases under High Pressure and Temperatures

    SciTech Connect

    Ming, L. C.; Zinin, P. V.; Sharma, S. K.

    2014-04-22

    A cubic BC3 (c-BC3) phase was synthesized by direct transformation from graphitic phases at a pressure of 39 GPa and temperature of 2200 K in a laser-heated diamond anvil cell (DAC). A combination of x-ray diffraction (XRD), electron diffraction (ED), transmission electron microscopy (TEM) imaging, and electron energy loss spectroscopy (EELS) measurements lead us to conclude that the obtained phase is hetero-nano-diamond, c-BC3. The EELS measurements show that the atoms inside the cubic structure are bonded by sp3 bonds.

  10. In situ observations of a high-pressure phase of H2O ice

    USGS Publications Warehouse

    Chou, I.-Ming; Blank, J.G.; Goncharov, A.F.; Mao, Ho-kwang; Hemley, R.J.

    1998-01-01

    A previously unknown solid phase of H2O has been identified by its peculiar growth patterns, distinct pressure-temperature melting relations, and vibrational Raman spectra. Morphologies of ice crystals and their pressure-temperature melting relations were directly observed in a hydrothermal diamond-anvil cell for H2O bulk densities between 1203 and 1257 kilograms per cubic meter at temperatures between -10??and 50??C. Under these conditions, four different ice forms were observed to melt: two stable phases, ice V and ice VI, and two metastable phases, ice IV and the new ice phase. The Raman spectra and crystal morphology are consistent with a disordered anisotropic structure with some similarities to ice VI.

  11. Structural phase stability in group IV metals under static high pressure

    SciTech Connect

    Velisavljevic, Nenad; Chesnut, Garry N; Dattelbaum, Dana M; Vohra, Yogesh K; Stemshorn, Andrew

    2009-01-01

    In group IV metals (Ti, Zr, and Hf) room temperature compression leads to a martensitic transformation from a ductile {alpha} to a brittle {omega} phase. {alpha} {yields} {omega} phase boundary decreases to lower pressure at high temperature and can limit the use of group IV metals in industrial applications. There is a large discrepancy in the transition pressure reported in literature, with some of the variation attributed to experimental conditions (i.e. hydrostatic vs. non-hydrostatic). Shear deformation in non-hydrostatic experiments drives {alpha} {yields} {omega} transition and decreases transition pressure. Impurities can also aid or suppress {alpha} {yields} {omega} transition. By performing x-ray diffraction experiments on samples in a diamond anvil cell we show that interstitial impurities, such as C, N, and O can obstruct {alpha} {yields} {omega} transition and stabilize {alpha} phase to higher pressure. We also show that reduction in grain size can also influence {alpha} {yields} {omega} phase boundary and help stabilize {alpha} phase to higher pressure under non-hydrostatic conditions.

  12. An extended high pressure-temperature phase diagram of NaBH4.

    PubMed

    George, Lyci; Drozd, Vadym; Couvy, Helene; Chen, Jiuhua; Saxena, Surendra K

    2009-08-21

    We have studied the structural stability of NaBH(4) under pressures up to 17 GPa and temperatures up to 673 K in a diamond anvil cell and formed an extended high P-T phase diagram using combined synchrotron x-ray diffraction and Raman spectroscopy. Even though few reports on phase diagram of NaBH(4) are found in current literature, up to our knowledge this is the first experimental work using diamond anvil cell in a wide pressure/temperature range. Bulk modulus, its temperature dependence, and thermal expansion coefficient for the ambient cubic phase of NaBH(4) are found to be 18.76(1) GPa, -0.0131 GPa K(-1), and 12.5x10(-5)+23.2x10(-8) T/K, respectively. We have also carried out Raman spectroscopic studies at room temperature up to 30 GPa to reinvestigate the phase transitions observed for NaBH(4). A comparative symmetry analysis also has been carried out for different phases of NaBH(4).

  13. Hyperbaric reservoir fluids: High-pressure phase behavior of asymmetric methane + n-alkane systems

    NASA Astrophysics Data System (ADS)

    Flöten, E.; de Loos, Th. W.; de Swaan Arons, J.

    1995-01-01

    In this paper, experimental three-phase equilibrium (solid n-alkane + liquid + vapor) data for binary methane + n-alkane systems are presented. For the binary system methane + tetracosane, the three-phase curve was determined based on two phase equilibrium measurements in a composition range from x c24 = 0.0027 to x c24 = 1.0. The second critical endpoint of this system was found at p = (1114.7 ± 0.5) M Pa. T = (322.6 ± 0.25) K, and a mole fraction of tetracosane in the critical fluidphase of x c24 = 0.0415 ± 0.0015. The second critical endpoint occurs where solid tetracosane is in equilibrium with a critical fluid phase ( S c24 + L = V). For the binary systems of methane with the n-alkanes tetradecane, triacontane, tetracontane, and pentacontane, only the coordinates of the second critical endpoints were measured. The second critical endpoint temperature is found close to the atmospheric melting point temperature of the n-alkane. The pressures at the second critical endpoints do not exceed 200 MPa. Based on these experimental data and data from the literature, correlations for the pressure. temperature, and fluid phase composition at the second critical endpoint of binary methane + n-alkane systems with n-alkanes between octane and pentacontane were developed.

  14. Phase Diagram and Physical Properties of H[subscript 2]O at High Pressures and temperatures: Applications to Planetary Interiors

    SciTech Connect

    Lin, Jung-Fu; Schwegler, Eric; Yoo, Choong-Shik

    2007-02-22

    Here we discuss the phase diagram and physical properties of H{sub 2}O under pressure-temperature conditions relevant to planetary interiors. Recent studies show that the melting curve of H{sub 2}O increases rapidly above a recently discovered triple point at approximately 35 to 47 GPa and 1000 K, indicating a large increase in {Delta}V/{Delta}S (volume versus entropy change) and associated changes in the physical properties of H{sub 2}O at high pressures and temperatures. Existence of the triple point is thought to be associated with the formation of a superionic phase, dynamically-disordered ice VII, or extension of the ice VII-ice X phase boundary; although the precise pressure and temperature of the triple point, curvature of the melting line, and nature of the solid-solid transition below the triple point all remain to be further explored. The steep increase in the melting curve of H{sub 2}O at high pressures and temperatures has important implications on our understanding of planetary interiors. Depending on its curvature, the melting line of H{sub 2}O may intersect the isentropes of Neptune and Uranus as well as the geotherm of Earth's lower mantle. Furthermore, if the triple point is due to the occurrence of the theoretically predicted superionic phase, besides leading to significant ionic conductivity, fast proton diffusion would cause enhanced chemical reactivity and formation of complex compounds in these planets. For example, reaction of H{sub 2}O with iron and other metals to form metal hydrides such as FeH{sub x} could provide a mechanism for incorporation of hydrogen as a light element into Earth's core. The equation of state of water is also presented as it pertains to the properties of hydrous fluid and melt phases in the mantle.

  15. Stability of rhombohedral phases in vanadium at high-pressure and high-temperature: first-principles investigations

    NASA Astrophysics Data System (ADS)

    Wang, Yi X.; Wu, Q.; Chen, Xiang R.; Geng, Hua Y.

    2016-09-01

    The pressure-induced transition of vanadium from BCC to rhombohedral structures is unique and intriguing among transition metals. In this work, the stability of these phases is revisited by using density functional theory. At finite temperatures, a novel transition of rhombohedral phases back to BCC phase induced by thermal electrons is discovered. This reentrant transition is found not driven by phonons, instead it is the electronic entropy that stabilizes the latter phase, which is totally out of expectation. Parallel to this transition, we find a peculiar and strong increase of the shear modulus C44 with increasing temperature. It is counter-intuitive in the sense that it suggests an unusual harding mechanism of vanadium by temperature. With these stability analyses, the high-pressure and finite-temperature phase diagram of vanadium is proposed. Furthermore, the dependence of the stability of RH phases on the Fermi energy and chemical environment is investigated. The results demonstrate that the position of the Fermi level has a significant impact on the phase stability, and follows the band-filling argument. Besides the Fermi surface nesting, we find that the localization/delocalization of the d orbitals also contributes to the instability of rhombohedral distortions in vanadium.

  16. Phase relation of CaSO4 at high pressure and temperature up to 90 GPa and 2300 K

    NASA Astrophysics Data System (ADS)

    Fujii, Taku; Ohfuji, Hiroaki; Inoue, Toru

    2016-05-01

    Calcium sulfate (CaSO4), one of the major sulfate minerals in the Earth's crust, is expected to play a major role in sulfur recycling into the deep mantle. Here, we investigated the crystal structure and phase relation of CaSO4 up to ~90 GPa and 2300 K through a series of high-pressure experiments combined with in situ X-ray diffraction. CaSO4 forms three thermodynamically stable polymorphs: anhydrite (stable below 3 GPa), monazite-type phase (stable between 3 and ~13 GPa) and barite-type phase (stable up to at least 93 GPa). Anhydrite to monazite-type phase transition is induced by pressure even at room temperature, while monazite- to barite-type transition requires heating at least to 1500 K at ~20 GPa. The barite-type phase cannot always be quenched from high temperature and is distorted to metastable AgMnO4-type structure or another modified barite structure depending on pressure. We obtained the pressure-volume data and density of anhydrite, monazite- and barite-type phases and found that their densities are lower than those calculated from the PREM model in the studied P-T conditions. This suggests that CaSO4 is gravitationally unstable in the mantle and fluid/melt phase into which sulfur dissolves and/or sulfate-sulfide speciation may play a major role in the sulfur recycling into the deep Earth.

  17. Stability of rhombohedral phases in vanadium at high-pressure and high-temperature: first-principles investigations

    PubMed Central

    Wang, Yi X.; Wu, Q.; Chen, Xiang R.; Geng, Hua Y.

    2016-01-01

    The pressure-induced transition of vanadium from BCC to rhombohedral structures is unique and intriguing among transition metals. In this work, the stability of these phases is revisited by using density functional theory. At finite temperatures, a novel transition of rhombohedral phases back to BCC phase induced by thermal electrons is discovered. This reentrant transition is found not driven by phonons, instead it is the electronic entropy that stabilizes the latter phase, which is totally out of expectation. Parallel to this transition, we find a peculiar and strong increase of the shear modulus C44 with increasing temperature. It is counter-intuitive in the sense that it suggests an unusual harding mechanism of vanadium by temperature. With these stability analyses, the high-pressure and finite-temperature phase diagram of vanadium is proposed. Furthermore, the dependence of the stability of RH phases on the Fermi energy and chemical environment is investigated. The results demonstrate that the position of the Fermi level has a significant impact on the phase stability, and follows the band-filling argument. Besides the Fermi surface nesting, we find that the localization/delocalization of the d orbitals also contributes to the instability of rhombohedral distortions in vanadium. PMID:27581551

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

    DOE PAGES

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

    2016-05-10

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

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

    SciTech Connect

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

    2016-05-10

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

  20. Beryl-II, a high-pressure phase of beryl: Raman and luminescence spectroscopy to 16.4 GPa

    NASA Astrophysics Data System (ADS)

    O'Bannon, Earl; Williams, Quentin

    2016-10-01

    The Raman and Cr3+ and V2+ luminescence spectra of beryl and emerald have been characterized up to 15.0 and 16.4 GPa, respectively. The Raman spectra show that an E 1g symmetry mode at 138 cm-1 shifts negatively by -4.57 (±0.55) cm-1/GPa, and an extrapolation of the pressure dependence of this mode indicates that a soft-mode transition should occur near 12 GPa. Such a transition is in accord with prior theoretical results. Dramatic changes in Raman mode intensities and positions occur between 11.2 and 15.0 GPa. These changes are indicative of a phase transition that primarily involves tilting and mild distortion of the Si6O18 rings. New Raman modes are not observed in the high-pressure phase, which indicates that the local bonding environment is not altered dramatically across the transition (e.g., changes in coordination do not occur). Both sharp line and broadband luminescence are observed for both Cr3+ and V2+ in emerald under compression to 16.4 GPa. The R-lines of both Cr3+ and V2+ shift to lower energy (longer wavelength) under compression. Both R-lines of Cr3+ split at ~13.7 GPa, and the V2+ R1 slope changes at this pressure and shifts more rapidly up to ~16.4 GPa. The Cr3+ R-line splitting and FWHM show more complex behavior, but also shift in behavior at ~13.7 GPa. These changes in the pressure dependency of the Cr3+ and V2+ R-lines and the changes in R-line splitting and FWHM at ~13.7 GPa further demonstrate that a phase transition occurs at this pressure, in good agreement with our Raman results. The high-pressure phase of beryl appears to have two Al sites that become more regular under compression. Hysteresis is not observed in our Raman or luminescence spectra on decompression, suggesting that this transition is second order in nature: The occurrence of a second-order transition near this pressure is also in accord with prior theoretical results. We speculate that the high-pressure phase (beryl-II) might be a mildly modulated structure, and/or that

  1. Structural and Phase State of Fractured Rotor of High-Pressure Steam Turbine

    NASA Astrophysics Data System (ADS)

    Smirnov, A. N.; Ababkov, N. V.; Kozlov, E. V.; Koneva, N. A.; Popova, N. A.

    2016-03-01

    The structural and phase state of the metal of a fractured rotor of a steam turbine is studied with the use of modern methods of physical research. The metal is shown to contain gradient structures. The cause of the failure of the rotor is established. The gradient structures are determined by the developed method of acoustic scanning.

  2. Molecular dynamics for Raman modes of high pressure phases of hydrogen

    NASA Astrophysics Data System (ADS)

    Magdau, Ioan-Bogdan; Ackland, Graeme

    2013-06-01

    We present ab initio molecular dynamics (MD) calculations of hydrogen at high temperature. We calculated the Raman spectra for phases III and IV and make direct comparison of Raman vibrons with experiment. The MD structures are sensitive to initial conditions and system size, but experimental comparison provides excellent discrimination between structures found, and enables us to explain some of the existing anomalies in the literature. Structures observed for pressure-temperature conditions of phase IV are based on layers of ordered molecules and layers of either static or freely rotating hexagonal trimers, however only two are consistent with experiment. The high temperature phase IV is a hexagonal structure with alternate layers of freely rotating hydrogen molecules, and hexagonal trimers. The low temperature phase III is similar to the C2/c structure previously proposed. These structures are qualitatively different from previous work which introduced spurious features through finite size effects. The MD properly accounts for anharmonic effects and gives much better agreement with Raman data than lattice dynamics calculation.

  3. Monte Carlo simulations of high-pressure phase equilibria of CO2-H2O mixtures.

    PubMed

    Liu, Yang; Panagiotopoulos, Athanassios Z; Debenedetti, Pablo G

    2011-05-26

    Histogram-reweighting grand canonical Monte Carlo simulations were used to obtain the phase behavior of CO(2)-H(2)O mixtures over a broad temperature and pressure range (50 °C ≤ T ≤ 350 °C, 0 ≤ P ≤ 1000 bar). We performed a comprehensive test of several existing water (SPC, TIP4P, TIP4P2005, and exponential-6) and carbon dioxide (EPM2, TraPPE, and exponential-6) models using conventional Lorentz-Berthelot combining rules for the unlike-pair parameters. None of the models we studied reproduce adequately experimental data over the entire temperature and pressure range, but critical assessments were made on the range of T and P where particular model pairs perform better. Away from the critical region (T ≤ 250 °C), the exponential-6 model combination yields the best predictions for the CO(2)-rich phase, whereas the TraPPE/TIP4P2005 model combination provides the most accurate coexistence composition and pressure for the H(2)O-rich phase. Near the critical region (250 °C < T ≤ 350 °C), the critical points are not accurately estimated by any of the models studied, but the exponential-6 models are able to qualitatively capture the critical loci and the shape of the phase envelopes. Local improvements can be achieved at specific temperatures by introducing modification factors to the Lorentz-Berthelot combining rules, but the modified combining rule is still not able to achieve global improvements over the entire temperature and pressure range. Our work points to the challenge and importance of improving current atomistic models so as to accurately predict the phase behavior of this important binary mixture.

  4. The origin of low velocity layers in subduction zones: elasticity of hydrous phases at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Mookherjee, M.; Chantel, J.; Frost, D. J.

    2012-12-01

    A 5-10 km thick low velocity layer (LVL) at the top of the subducting slab has been seismically detected in many subduction zone settings. The LVL may persist up to a depth of 250 km. The shear wave velocity of the LVL could be 10 % slower than the surrounding mantle. Based on thermal profile of the subducting slabs it is hard to relate the LVL with partial melting or pore fluids. We have undertaken experimental and theoretical studies to constrain the pressure and temperature dependence of elasticity of eclogitic rocks formed from hydrated oceanic crust. In particular, we focus on hydrous phases such as lawsonite [CaAl2Si2O7(OH)2.H2O]. Our study shows that lawsonite has unusual shear modulus at high pressure and temperatures relevant at 250 km depths. Formation of hydrous phases such as lawsonite at the expense of garnet additionally lowers the seismic velocities.

  5. Neutron diffraction and electrical transport studies on the incommensurate magnetic phase transition in holmium at high pressures.

    PubMed

    Thomas, Sarah A; Uhoya, Walter O; Tsoi, Georgiy M; Wenger, Lowell E; Vohra, Yogesh K; Chesnut, Gary N; Weir, Samuel T; Tulk, Christopher A; dos Santos, Antonio M

    2012-05-30

    Neutron diffraction and electrical transport measurements have been made on the heavy rare earth metal holmium at high pressures and low temperatures in order to elucidate its transition from a paramagnetic (PM) to a helical antiferromagnetic (AFM) ordered phase as a function of pressure. The electrical resistance measurements show a change in the resistance slope as the temperature is lowered through the antiferromagnetic Néel temperature. The temperature of this antiferromagnetic transition decreases from approximately 122 K at ambient pressure at a rate of -4.9 K GPa(-1) up to a pressure of 9 GPa, whereupon the PM-to-AFM transition vanishes for higher pressures. Neutron diffraction measurements as a function of pressure at 89 and 110 K confirm the incommensurate nature of the phase transition associated with the antiferromagnetic ordering of the magnetic moments in a helical arrangement and that the ordering occurs at similar pressures as determined from the resistance results for these temperatures.

  6. Neutron diffraction and electrical transport studies on the incommensurate magnetic phase transition in holmium at high pressures

    SciTech Connect

    Thomas, Sarah; Uhoya, Walter; Tsoi, Georgiy; Wenger, Lowell E; Vohra, Yogesh; Chesnut, Gary Neal; Weir, S. T.; Tulk, Christopher A; Moreira Dos Santos, Antonio F

    2012-01-01

    Neutron diffraction and electrical transport measurements have been made on the heavy rare earth metal holmium at high pressures and low temperatures in order to elucidate its transition from a paramagnetic (PM) to a helical antiferromagnetic (AFM) ordered phase as a function of pressure. The electrical resistance measurements show a change in the resistance slope as the temperature is lowered through the antiferromagnetic Neel temperature. The temperature of this antiferromagnetic transition decreases from approximately 122 K at ambient pressure at a rate of -4.9 K GPa(-1) up to a pressure of 9 GPa, whereupon the PM-to-AFM transition vanishes for higher pressures. Neutron diffraction measurements as a function of pressure at 89 and 110 K confirm the incommensurate nature of the phase transition associated with the antiferromagnetic ordering of the magnetic moments in a helical arrangement and that the ordering occurs at similar pressures as determined from the resistance results for these temperatures.

  7. Effects of 3 GPa High Pressure Treatment on the β1 → α + β2 Phase Transition Dynamics of TC4 Titanium Alloy

    NASA Astrophysics Data System (ADS)

    Wang, Hai-Yan; Chen, Yan; Liu, Jian-Hua; Wang, Wen-Kui

    2013-03-01

    The temperature, duration, activation energy, and Avrami exponent of the solid phase transformation β1 → α + β2 of TC4 titanium alloy treated at 3 GPa in a cooling process are calculated by means of differential scanning calorimetric curves. Then the effects of high pressure on the β1 → α + β2 phase transformation dynamics of TC4 alloy in a cooling process are investigated. The results show that 3 GPa high pressure treatment can increase the activation energy of the TC4 alloy. The beginning time, end time, and duration of the β1 → α + β2 phase transition of the 3 GPa high pressure treated TC4 alloy at the cooling rate of 10°C/min are increased by 2.90°C, 7.78°C and -29.28 s respectively. It is known that 3 GPa high pressure treatment has little effect on the phase transition mechanism.

  8. High-pressure superconducting phase diagram of 6Li: Isotope effects in dense lithium

    PubMed Central

    Schaeffer, Anne Marie; Temple, Scott R.; Bishop, Jasmine K.; Deemyad, Shanti

    2015-01-01

    We measured the superconducting transition temperature of 6Li between 16 and 26 GPa, and report the lightest system to exhibit superconductivity to date. The superconducting phase diagram of 6Li is compared with that of 7Li through simultaneous measurement in a diamond anvil cell (DAC). Below 21 GPa, Li exhibits a direct (the superconducting coefficient, α, Tc∝M−α, is positive), but unusually large isotope effect, whereas between 21 and 26 GPa, lithium shows an inverse superconducting isotope effect. The unusual dependence of the superconducting phase diagram of lithium on its atomic mass opens up the question of whether the lattice quantum dynamic effects dominate the low-temperature properties of dense lithium. PMID:25538300

  9. First principles simulation of a superionic phase of hydrogen fluoride (HF) at high pressures and temperatures

    SciTech Connect

    Goldman, N; Fried, L E

    2006-04-10

    The authors have conducted Ab initio molecular dynamics simulations of hydrogen fluoride (HF) at pressures of 5-66 GPa along the 900 K isotherm. They predict a superionic phase at 33 GPa, where the fluorine atoms are fixed in a bcc lattice while the hydrogen atoms diffuse rapidly with a diffusion constant of between 2 x 10{sup -5} and 5 x 10{sup -5} cm{sup 2}/s. They find that a transformation from asymmetric to symmetric hydrogen bonding occurs in HF at 66 GPa and 900 K. With superionic HF they have discovered a model system where symmetric hydrogen bonding occurs at experimentally achievable conditions. Given previous results on superionic H{sub 2}O[1,2,3] and NH{sub 3}[1], they conclude that high P,T superionic phases of electronegative element hydrides could be common.

  10. Observation of an Ultrahard Phase of Graphite Quenched from High-pressure

    DTIC Science & Technology

    2011-02-01

    that of cubic boron nitride (401 GPa) and rivals that of diamond (468 GPa). Above 5.9 GPa, the smoothly varying curve shows no evidence of...and exploited to design new, novel, and improved materials that cannot be obtained through conventional synthesis approaches. Such materials...work examines the synthesis , physical and chemical properties, metastability, and recovery mechanism of an ultrahard phase of carbon, formed from

  11. Superconductivity and crystal structure of high-pressure phases in V-Ru-H system

    NASA Astrophysics Data System (ADS)

    Animonov, V. Ye.; Belash, I. T.; Ponyatovskiy, Ye. G.; Rashchupkin, V. I.; Romanenko, I. M.

    1987-10-01

    In the search for materials which, upon hydrogenation, form phase with higher superconductor transition temperature, V-Ru alloys were selected for study. Specimens were produced by mixing electrolytic powder of each metal into three batches with 10, 18, 33 atom percent. respectively, compacting the mixtures under a pressure of 20 kbar at room temperature, and then sintering them in an induction furnace in an argon atmosphere. The compacts were annealed at 1200 C in vacuum (10 to the -6 torr) for 24 h then cooled in the furnace. The specimens of three alloys, now containing 10, 18.5., 34+0.4 atom percent Ru, respectively, were hydrogenated in an H2 atmosphere at 300 C under pressures up to 70 kbar for 24 h and then quenched under pressure to about -180 C. The hydrogen content was then determined accurately within 5 percent, from the amount of H2 evolving during thermal decomposition at 500 C. The superconducting transition temperature was measured by the inductive method. The results reveal formation of a phase with the atomic hydrogen-to-metal ratio H:Me approx = 1 and an f.c.c. metal sublattice in the V sub 90 Ru sub 10-H alloy, only this phase being superconductive at temperatures T greater than or = 2K with a 0.3 K wide transition range.

  12. Low-temperature and high-pressure phase transitions in ferroelectric dabcoHBF4

    NASA Astrophysics Data System (ADS)

    Szafranski, Marek

    2004-09-01

    NH--N hydrogen bonded ferroelectric dabcoHBF4, [C6H13N2]+·BF4-, has been studied by dielectric spectroscopy, differential thermal analysis and pyroelectric charge measurement investigations in the low-temperature range between 12 and 300 K, and at elevated hydrostatic pressures up to 1 GPa. The p-T phase diagram has been determined and described. In addition to the known first-order phase transitions at 378 and 153 K, two new structural transitions of continuous type have been revealed, i.e., the transition at 37 K and the pressure-induced one occurring above the triple point situated at 80 MPa and 165 K. Both of these transitions have essentially displacive character and a mechanism related to distortions of the hydrogen bonded polycationic chains, preserving polar properties of the crystal. The possible order-disorder contribution to the transition at 153 K between the ferroelectric phases II and III is discussed in relation to the conformational properties of the dabco cation.

  13. Enhanced superconductivity in the high pressure phase of SnAs studied from first principles

    NASA Astrophysics Data System (ADS)

    Sreenivasa Reddy, P. V.; Kanchana, V.; Millichamp, T. E.; Vaitheeswaran, G.; Dugdale, S. B.

    2017-01-01

    First principles calculations are performed using density functional theory and density functional perturbation theory for SnAs. Total energy calculations show the first order phase transition from an NaCl structure to a CsCl one at around 37 GPa, which is also confirmed from enthalpy calculations and agrees well with experimental work. Calculations of the phonon structure and hence the electron-phonon coupling, λep, and superconducting transition temperature, Tc, across the phase diagram are performed. These calculations give an ambient pressure Tc, in the NaCl structure, of 3.08 K, in good agreement with experiment whilst at the transition pressure, in the CsCl structure, a drastically increased value of Tc = 12.2 K is found. Calculations also show a dramatic increase in the electronic density of states at this pressure. The lowest energy acoustic phonon branch in each structure also demonstrates some softening effects. Electronic structure calculations of the Fermi surface in both phases are presented for the first time as well as further calculations of the generalised susceptibility with the inclusion of matrix elements. These calculations indicate that the softening is not derived from Fermi surface nesting and it is concluded to be due to a wavevector-dependent enhancement of the electron-phonon coupling.

  14. Phase Equilibria of the Carbon Dioxide + 1-Decanol System at High Pressures.

    PubMed

    Ioniţă, Simona; Feroiu, Viorel; Geană, Dan

    2013-11-14

    In this work experimental vapor-liquid equilibrium (VLE) data and three-phase vapor-liquid-liquid equilibrium (VLLE) data are presented for the carbon dioxide + 1-decanol system. The VLE data were measured at five temperatures, (303.2, 308.2, 323.2, 333.2, and 343.2) K, and pressures up to 16 MPa. The VLLE data cover pressure-temperature (P-T) values from 289 K and 5 MPa to the upper critical end point (UCEP). We have used two models to represent the complex fluid phase behavior (P-T critical curve, VLLE line, and VLE isotherms) of the carbon dioxide + 1-decanol system: the cubic general equation of state (GEOS) and Peng-Robinson (PR) equation in conjunction with van der Waals two parameters conventional mixing rules (2PCMR). A correlation method involving temperature-dependent interaction parameters and a semipredictive approach with independent temperature interaction parameters have been used. Comparisons with experimental data reported in this work and available in the literature indicate that the topology of fluid phase behavior is satisfactorily given by the semipredictive procedure both for the critical line and in subcritical region, considering the relative simple used cubic equations of state.

  15. New investigations on shock-wave synthesized high-pressure phases in the system Si-Al-O-N

    NASA Astrophysics Data System (ADS)

    Schlothauer, T.; Greif, A.; Keller, K.; Schwarz, M. R.; Kroke, E.; Heide, G.

    2012-12-01

    The shock-wave synthesis of nanostructured high-pressure phases at a gram-scale permits the analysis of spinel type nitrides with different chemical composition using methods not suitable for microgram amounts of material. Methods with a significant mass loss through the analytical process like TG-MS or FT-IR or bulk methods at the g-scale like 29Si-MAS-NMR or neutron diffraction were used. The synthesis of pure high-pressure modifications (gamma-phases) of different SiAlON-compounds using amorphous H-bearing precursors at pressures of 30-40 GPa is a necessary prerequisite for precise determinations of crystal chemical features. Etching with HF is a well-known method to purify the high-pressure nitrides (Sekine 2002). The etched parts were analyzed by neutron diffraction, TG-MS, and carrier gas hot extraction (CGHE). Volatile elements like H2 and Cl2, as well as non-stoichiometric oxygen and nitrogen, and NOx, H2O are enriched in the disordered rims. This degassing process ends at temperatures of approximately 600°C, while the spinel structure remains well preserved up to 1300°C. Under these conditions the gamma-phases stay unchanged under air, argon and vacuum. Furthermore chlorine, an important impurity of the H-bearing precursors neither influences the synthesized products nor the synthesis process itself. IR-spectroscopy of gamma-Si3(O,N)4 shows that peak shifts of octahedral lattice vibrations (≈ 680 cm-1) and both tetrahedral vibrations (ny3 and ny4) (Jeanloz 1980, Preudhomme & Tarte 1971) to higher frequencies with decreasing oxygen content occur. This effect is also visible in samples contaminated with impurities of low pressure modifications. The more complex structure of gamma-SiAlON and the simultaneously exchange of the cation- and the anion-positions prevents the appearance of this important feature. Yet to be synthesized pure gamma-SiAlON using similar H-bearing precursors is necessary to resolve its structure. Sekine, T., H. He, T. Kobayashi, K

  16. A molecular dynamics study of ambient and high pressure phases of silica: Structure and enthalpy variation with molar volume

    NASA Astrophysics Data System (ADS)

    Rajappa, Chitra; Sringeri, S. Bhuvaneshwari; Subramanian, Yashonath; Gopalakrishnan, J.

    2014-06-01

    Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, α-PbO2-type, and pyrite-type - for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume—for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase.

  17. A molecular dynamics study of ambient and high pressure phases of silica: structure and enthalpy variation with molar volume.

    PubMed

    Rajappa, Chitra; Sringeri, S Bhuvaneshwari; Subramanian, Yashonath; Gopalakrishnan, J

    2014-06-28

    Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, α-PbO2-type, and pyrite-type - for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase.

  18. High pressure structural phase transition of osmium nitride (OsN)

    NASA Astrophysics Data System (ADS)

    Sarwan, Madhu; Abdul Shukoor, V.; Dubey, Ritu; Singh, Sadhna

    2015-05-01

    The structural phase transition and relative volume change of OsN compound has been investigated by means of interaction potential model (IPM) which consists of Coulomb interaction, three-body interaction (TBI), van der Waal interaction (vdW) and short range overlap repulsive interactions up to second neighbor ions. It is found that the OsN transforms from zinc-blende structure (B3) to rock-salt structure (B1) at 87.0 GPa. The second order elastic constants are also investigated. These results are compared with available results.

  19. A route to possible civil engineering materials: the case of high-pressure phases of lime.

    PubMed

    Bouibes, A; Zaoui, A

    2015-07-23

    Lime system has a chemical composition CaO, which is known as thermodynamically stable. The purpose here is to explore further possible phases under pressure, by means of variable-composition ab initio evolutionary algorithm. The present investigation shows surprisingly new stable compounds of lime. At ambient pressure we predict, in addition to CaO, CaO2 as new thermodynamically stable compound. The latter goes through two phases transition from C2/c space group structure to Pna21 at 1.5 GPa, and Pna21 space group structure to I4/mcm at 23.4 GPa. Under increasing pressure, further compounds such as CaO3 become the most stable and stabilize in P-421m space group structure above 65 GPa. For the necessary knowledge of the new predicted compounds, we have computed their mechanical and electronic properties in order to show and to explain the main reasons leading to the structural changes.

  20. Phase relations in the system diopside-jadeite at high pressures and high temperatures

    NASA Astrophysics Data System (ADS)

    Liu, Lin-Gun

    1980-05-01

    Phase behaviour in the system diopside-jadeite (CaMgSi 2O 6sbnd NaAlSi 2O 6) have been investigated in the pressure region 100-300 kbar at about 1000°C in a diamond-anvil press coupled with laser heating. The omphacite solid solution extends from 30 to at least 200 kbar for the entire system. Omphacites, ranging in composition from pure diopside to more than 40 mole % jadeite, transform to diopside (II) at pressures greater than 230 kbar. Diopside (II), which probably possesses a perovskite-type structure, cannot be preserved when experiments are quenched to ambient conditions. Jadeite-rich omphacites were found to decompose into an assemblage of NaAlSiO 4(CaFe 2O 4-type structure) + stishovite + diopside (II) (?) at pressures greater than about 260 kbar. These results suggest that an eclogitic model mantle would not display the 400-km seismic discontinuity. Moreover, sodium in the transition zone and lower mantle would most likely be accommodated in phases of omphacite and diopside (II).

  1. A route to possible civil engineering materials: the case of high-pressure phases of lime

    PubMed Central

    Bouibes, A.; Zaoui, A.

    2015-01-01

    Lime system has a chemical composition CaO, which is known as thermodynamically stable. The purpose here is to explore further possible phases under pressure, by means of variable-composition ab initio evolutionary algorithm. The present investigation shows surprisingly new stable compounds of lime. At ambient pressure we predict, in addition to CaO, CaO2 as new thermodynamically stable compound. The latter goes through two phases transition from C2/c space group structure to Pna21 at 1.5 GPa, and Pna21 space group structure to I4/mcm at 23.4 GPa. Under increasing pressure, further compounds such as CaO3 become the most stable and stabilize in P-421m space group structure above 65 GPa. For the necessary knowledge of the new predicted compounds, we have computed their mechanical and electronic properties in order to show and to explain the main reasons leading to the structural changes. PMID:26202342

  2. In-situ Phase Transformation and Deformation of Iron at High Pressure andTemperature

    SciTech Connect

    Miyagi, Lowell; Kunz, Martin; Knight, Jason; Nasiatka, James; Voltolini, Marco; Wenk, Hans-Rudolf

    2008-07-01

    With a membrane based mechanism to allow for pressure change of a sample in aradial diffraction diamond anvil cell (rDAC) and simultaneous infra-red laser heating, itis now possible to investigate texture changes during deformation and phasetransformations over a wide range of temperature-pressure conditions. The device isused to study bcc (alpha), fcc (gamma) and hcp (epislon) iron. In bcc iron, room temperature compression generates a texture characterized by (100) and (111) poles parallel to the compression direction. During the deformation induced phase transformation to hcp iron, a subset of orientations are favored to transform to the hcp structure first and generate a texture of (01-10) at high angles to the compression direction. Upon further deformation, the remaining grains transform, resulting in a texture that obeys the Burgers relationship of (110)bcc // (0001)hcp. This is in contrast to high temperature results that indicate that texture is developed through dominant pyramidal {2-1-12}<2-1-13> and basal (0001)-{2-1-10} slip based on polycrystal plasticity modeling. We also observe that the high temperature fcc phase develops a 110 texture typical for fcc metals deformed in compression.

  3. A route to possible civil engineering materials: the case of high-pressure phases of lime

    NASA Astrophysics Data System (ADS)

    Bouibes, A.; Zaoui, A.

    2015-07-01

    Lime system has a chemical composition CaO, which is known as thermodynamically stable. The purpose here is to explore further possible phases under pressure, by means of variable-composition ab initio evolutionary algorithm. The present investigation shows surprisingly new stable compounds of lime. At ambient pressure we predict, in addition to CaO, CaO2 as new thermodynamically stable compound. The latter goes through two phases transition from C2/c space group structure to Pna21 at 1.5 GPa, and Pna21 space group structure to I4/mcm at 23.4 GPa. Under increasing pressure, further compounds such as CaO3 become the most stable and stabilize in P-421m space group structure above 65 GPa. For the necessary knowledge of the new predicted compounds, we have computed their mechanical and electronic properties in order to show and to explain the main reasons leading to the structural changes.

  4. Polyamorphic phase transition of Yb-based metallic glass at high pressure

    NASA Astrophysics Data System (ADS)

    li, L.; Li, R.; Liu, H.; Chupas, P.

    2013-12-01

    A family of Yb-based bulk metallic glasses (BMG) has been fabricated based on strong liquid characteristic and excellent glass-forming ability. Using a diamond anvil cell with high-energy synchrotron X-ray, the total scattering of metallic glass Yb-Mg-Zn was studied at pressure up to 30GPa in a hydrostatic isopropanol pressure-medium. The local structure was investigated through direct Fourier transformation of the structure factor [S(Q)], pair distribution function (PDF) [G(r)] with background correction. Polyamorphic phase transition is achieved because smaller atoms are extruded into the clearance of the larger rare earth atoms and 4f electrons delocalized. Phase transition from a low-density state to a high-density state occurs, smaller atoms can be extruded is one of two reasons for the high compressibility of rare earth BMG. The second reason is the delocalization of 4f electrons, which can induce the volume collapse of rare earth atoms.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  6. Study of Raman Spectroscopy on Phase Relations of CaCO3 at High Temperature and High Pressure

    NASA Astrophysics Data System (ADS)

    Li, M.; Zheng, H.; Duan, T.

    2006-05-01

    Laser Raman Spectroscopy was used to study phase relations between calcite I, calcite II and aragonite at high pressure and high temperature. The experiment was performed in an externally heated Basselt type diamond anvil cell (DAC). Natural calcite (calcite I) was used as starting mineral. The sample and a small chip of quartz were loaded in a cavity (300 μm in diameter and 250 μm in depth) in a rhenium gasket. The Na2CO3 aqueous solution of 1mol/L was also loaded as a pressure medium to yield hydrostatic pressure. The whole assembly was pressurized first and then heated stepwise to 400°C. Pressure and temperature in the chamber were determined by the shift of Raman band at 464 cm-1 of quartz and by NiCr-NiSi thermocouple, respectively. The Raman spectra were measured by a Renishaw 1000 spetrometer with 50 mW of 514.5nm argon-ion laser as the excitation light source. The slit width was 50 μm and the corresponding resolution was ±1 cm-1. From the experiments, we observed the phase transitions between calcite I and calcite II, calcite I and aragonite, calcite II and aragonite, respectively. Our data showed a negative slope for the boundary between calcite I and calcite II, which was similar to Bridgman's result, although Hess et al. gave a positive slope. The boundary with a negative slope for calcite II and aragonite was also defined, which had never been done before. And all these data can yield a more complete phase diagram of CaCO3 than the studies of Hess et al. and Suito et al.Reference:Bridgeman P. W.(1939) Journal: American Journal of Science, Vol. 237, p. 7-18Bassett W. A. et al. (1993) Journal: Review of Scientific Instruments, Vol. 64, p. 2340-2345Suito K. et al. (2001) Journal: American Mineralogist, Vol. 86, p. 997- 1002Hess N. J. et al. (1991) In A. K. Singh, Ed., Recent Trends in High Pressure Research; Proc. X IIIth AIRAPT International Conference on High Pressure Science and Technology, p. 236-241. Oxford & IBH Publishing Co. Pvt, Ltd., New

  7. New high-pressure phase of Fe3S predicted from first-principles calculation

    NASA Astrophysics Data System (ADS)

    Ishikawa, T.; Tsuchiya, T.

    2010-12-01

    It has long been recognized that the Earth's outer core must contain a significant amount of light elements, candidates for which have included hydrogen, carbon, silicon, sulfur and oxygen. High-P,T experiments (Jephcoat and Olson, 1987; Mao et al., 1998; Fiquet et al., 2001;Uchida et al., 2001) extended this argument to the inner core on the basis of the equation of state analysis of the hexagonal-closed-pack (hcp) form of pure iron, which concluded that it still has 4-5% excess density compared to the inner core values, although significant extrapolations were usually applied. At present, one of the most popular light-element candidates is sulfur. Therefore, it is crucial to determine the melting behavior of the Fe-FeS binary under core conditions, before models of core formation can be developed. The Fe-FeS binary was known to form a eutectic at low pressures (Usselman, 1975). Sherman (1995), however, suggested the stabilization of an intermediate iron sulfide compound Fe3S with AuCu3 form theoretically, and then Fei et al. (1997) found in the high-P,T experiments that Fe3S2 forms over 14 GPa, and Fe3S and Fe2S further form over 21 GPa (Fei et al., 2000). Fe3S, which is the most iron-rich sulfide compound known to exist, has a tetragonal cell isostructural with the Fe3P structure (space group No.82, Z = 8) and no phase transition has so far been identified up to 80 GPa (Seagle et al., 2006) and even at over 200 GPa (Kuwayama private comm.). These are supportive of an ab initio investigation (Martin et al., 2004), which found that the Fe3P structure is the most stable among fcc, LaF3, YF3 and Fe3P postulations. In this study, we explored higher-pressure phases of Fe3S using first-principles calculations. Comparing enthalpies among candidate structures, we found a new structure which is more stable than the Fe3P structure at the inner core pressures. In our presentation, we will make a detailed report with respect to the new stable structure and discuss phase

  8. Characterization of the high-pressure structures and phase transformations in SnO2. A density functional theory study.

    PubMed

    Gracia, L; Beltrán, A; Andrés, J

    2007-06-14

    Theoretical investigations concerning the high-pressure polymorphs, the equations of state, and the phase transitions of SnO2 have been performed using density functional theory at the B3LYP level. Total energy calculations and geometry optimizations have been carried out for all phases involved, and the following sequence of structural transitions from the rutile-type (P42/mnm) driven by pressure has been obtained (the transition pressure is in parentheses): --> CaCl2-type, Pnnm (12 GPa) --> alpha-PbO2-type, Pbcn (17 GPa) --> pyrite-type, Pa (17 GPa) --> ZrO2-type orthorhombic phase I, Pbca (18 GPa) --> fluorite-type, Fmm (24 GPa) --> cotunnite-type orthorhombic phase II, Pnam (33 GPa). The highest bulk modulus values, calculated by fitting pressure-volume data to the second-order Birch-Murnaghan equation of state, correspond to the cubic pyrite and the fluorite-type phases with values of 293 and 322 GPa, respectively.

  9. High-pressure high-temperature phase diagram of gadolinium studied using a boron-doped heater anvil

    SciTech Connect

    Montgomery, J. M.; Samudrala, G. K.; Velisavljevic, N.; Vohra, Y. K.

    2016-04-07

    A boron-doped designer heater anvil is used in conjunction with powder x-ray diffraction to collect structural information on a sample of quasi-hydrostatically loaded gadolinium metal up to pressures above 8GPa and 600K. The heater anvil consists of a natural diamond anvil that has been surface modified with a homoepitaxially grown chemical-vapor-deposited layer of conducting boron-doped diamond, and is used as a DC heating element. Internally insulating both diamond anvils with sapphire support seats allows for heating and cooling of the high-pressure area on the order of a few tens of seconds. This device is then used to scan the phase diagram of the sample by oscillating the temperature while continuously increasing the externally applied pressure and collecting in situ time-resolved powder diffraction images. In the pressure-temperature range covered in this experiment, the gadolinium sample is observed in its hcp, αSm, and dhcp phases. Under this temperature cycling, the hcp → αSm transition proceeds in discontinuous steps at points along the expected phase boundary. From these measurements (representing only one hour of synchrotron x-ray collection time), a single-experiment equation of state and phase diagram of each phase of gadolinium is presented for the range of 0–10GPa and 300–650K

  10. Seismic signature of ultra-high pressure hydrous phases in subduction zones and constrains on water recycling

    NASA Astrophysics Data System (ADS)

    Rosa, A. D.; Sanchez-Valle, C.

    2012-12-01

    Seismic anomalies in deep slabs including low velocity zones and seismic anisotropies have often been attributed to the presence of hydrated regions. Superhydrous phase B and phase D which can respectively contain up to 5.8 wt.% and 10 wt.% of water are considered as important water carriers in cold slabs. Phase equilibrium studies have also shown that these phases can represent up to 50 vol.% in water saturated peridotites [1]. Recent Brillouin scattering experiments performed at ambient conditions have revealed the potential for both phases to be responsible for the observed negative velocity anomalies [2]. In addition, due to their layered structure both phases may easily align in a stress field and therefore significantly contribute to observed seismic anisotropies. The detailed knowledge of their seismic properties at high pressure is therefore essential to infer the hydration state of deep subducted slabs. Here, we report the single-crystal elastic properties of superhydrous phase B (chemical composition Mg10.4Si3.1H2.7O18) using Brillouin scattering in the diamond anvil cell. The results on the elasticity studies are combined with previous plasticity studies on phase D [3] and most plausible slip systems of superhydrous B to evaluate the velocity contrast between hydrous and anhydrous peridotites and the contribution of these phases to seismic anisotropy in deep subducted slabs. The results will be discussed in the light of seismic observations to draw a better picture of water recycling via subduction beyond 410 km depth. [1] Iwamori, H. (2004), Earth Planet. Sc. Lett. 227, 57-71. [2] Rosa, A.D., C. Sanchez-Valle and S. Ghosh (2012) Geophys. Res. Lett., 39, L06304. [3] Rosa A.D., et al. (2011) Abstract DI44A-03 Fall AGU Meeting 2011.

  11. 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.

  12. Isolation and determination of deoxynivalenol by reversed-phase high-pressure liquid chromatography

    PubMed Central

    Gupta, Vikas Kumar; Chattopadhyay, Pronobesh; Kalita, Mohan Ch; Chaurasia, Asshwani Kumar; Gogoi, Hemanta Kumar; Singh, Lokendra

    2011-01-01

    Deoxynivalenol (DON) is a mycotoxin produced by food contamination. It is a pharmacologically active compound that acts on the serotonin receptor, leading to several neuroendocrine and hematological disorders. In this article we describe a simple, accurate, and sensitive method for the quantification of DON. DON was quantified using a Phenomenex® ODS analytical C18 column (150 mm × 46 mm, 5 μm) with a mobile phase composed of mixture of water-acetonitrile-methanol (5:4:1, v/v/v) at a flow rate of 1.5 ml/min and at 254 nm in an ultraviolet (UV) detector The method has been validated with isolated samples of DON and provides a tool for the control of substandard and counterfeit commercial food products. PMID:23781426

  13. Phase diagram for ammonia-water mixtures at high pressures - Implications for icy satellites

    NASA Technical Reports Server (NTRS)

    Cynn, H. C.; Boone, S.; Koumvakalis, A.; Nicol, M.; Stevenson, D. J.

    1989-01-01

    The (NH3)x(H2O)1-x phase diagram for X from 0 to 0.50 has been reexamined at temperatures from 125 K to 400 K and at pressures from 6.0 GPa using diamond anvil cells, and the implications of the findings for icy satellites are addressed. Titan is likely to have a thicker NH3-H2O ocean than previously suspected, because the stability field of NH3-H2O is found to be smaller than previously supposed. The implications for methane and ammonia volcanism on Titan are briefly discussed. The experimentally observed reactivity between the liquid and iron may also have implications for planetary and satellite evolution.

  14. Phase Transformations and Metallization of Magnesium Oxide at High Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    McWilliams, R. Stewart; Spaulding, Dylan K.; Eggert, Jon H.; Celliers, Peter M.; Hicks, Damien G.; Smith, Raymond F.; Collins, Gilbert W.; Jeanloz, Raymond

    2012-12-01

    Magnesium oxide (MgO) is representative of the rocky materials comprising the mantles of terrestrial planets, such that its properties at high temperatures and pressures reflect the nature of planetary interiors. Shock-compression experiments on MgO to pressures of 1.4 terapascals (TPa) reveal a sequence of two phase transformations: from B1 (sodium chloride) to B2 (cesium chloride) crystal structures above 0.36 TPa, and from electrically insulating solid to metallic liquid above 0.60 TPa. The transitions exhibit large latent heats that are likely to affect the structure and evolution of super-Earths. Together with data on other oxide liquids, we conclude that magmas deep inside terrestrial planets can be electrically conductive, enabling magnetic field-producing dynamo action within oxide-rich regions and blurring the distinction between planetary mantles and cores.

  15. Experimental study on pressure drop of bends in dense phase pneumatic conveying under high pressure

    NASA Astrophysics Data System (ADS)

    Yuan, Gaoyang; Liang, Cai; Chen, Xiaoping; Xu, Pan; Xu, Guiling; Shen, Liu

    2014-04-01

    The transport test using nitrogen as conveying gas are carried out at high operating pressure up to 4MPa in the experimental equipment for dense phase pneumatic conveying. The transport powders in the experiment are anthracite coal and petroleum coke. The pressure drop characteristics in bends are acquired with the different transport powder. The experimental results show that under the similar mass flow, the pressure drop of vertical upward bend is greater than the horizontal bend and the horizontal bend is greater than the vertical downward bend at the same superficial gas velocity, while there is a best superficial gas velocity minimizes the pressure drop of the bend. Under the similar mass flow rate and the similar particle size, the pressure drop of the bend with the petroleum coke is greater than the pressure drop with the anthracite coal as the same superficial gas velocity. According to Barth's additional pressure drop method, the pressure drop fitting formulas of the vertical upward bend, the horizontal bend and the vertical downward bend are obtained, and the predicted results are in accordance with that of the experiments.

  16. Collapsed tetragonal phase in SrCo2As2 under high pressure

    NASA Astrophysics Data System (ADS)

    Jayasekara, W. T.; Ueland, B. G.; Kreyssig, A.; Pandey, Abhishek; Sangeetha, N. S.; Fabbris, G.; Feng, Yejun; Haskel, D.; Johnston, D. C.; Goldman, A. I.

    2015-03-01

    SrCo2As2 possesses the same tetragonal ThCr2Si2 structure as the AFe2As2 (A = Ca, Sr, Ba) family of high-temperature superconductors but does not manifest magnetic order or superconductivity down to a temperature of 1.8 K. Nevertheless, inelastic neutron scattering data show the presence of magnetic fluctuations peaked at a wavevector of (1/2 1/2 1), which corresponds to the stripe antiferromagnetic propagation vector found for AFe2As2. Here, we present evidence from high-energy x-ray diffraction experiments which show that SrCo2As2 undergoes a transition to a collapsed-tetragonal phase characterized by a 10% reduction of the c-lattice parameter for an applied pressure of 5 GPa at 7 K. This fascinating result opens another path for studying the role of magnetic ordering, spin fluctuations, and magnetoelastic coupling in the development of superconductivity in the Fe-pnictides and related materials. - Work at Ames Laboratory was supported by US DOE, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Contract No. DE-AC02-07CH11358. This research used resources of the Advanced Photon Source, a US DOE, Office of Science User Facility.

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

    NASA Astrophysics Data System (ADS)

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

    1982-10-01

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

  18. Evidence for plasma phase transition in high pressure hydrogen from ab-initio simulations

    SciTech Connect

    Morales, M; Pierleoni, C; Schwegler, E; Ceperley, D

    2010-02-08

    We have performed a detailed study of molecular dissociation in liquid hydrogen using both Born-Oppenheimer molecular dynamics with Density Functional Theory and Coupled Electron-Ion Monte Carlo simulations. We observe a range of densities where (dP/d{rho}){sub T} = 0 that coincides with sharp discontinuities in the electronic conductivity, which is clear evidence of the plasma phase transition for temperatures 600K {le} T {le} 1500K. Both levels of theory exhibit the transition, although Quantum Monte Carlo predicts higher transition pressures. Based on the temperature dependence of the discontinuity in the electronic conductivity, we estimate the critical point of the transition at temperatures slightly below 2000 K. We examine the influence of proton zero point motion by using Path Integral Molecular Dynamics with Density Functional Theory; the main effect is to shift the transition to lower pressures. Furthermore, we calculate the melting curve of molecular hydrogen up to pressures of 200 GPa, finding a reentrant melting line in good agreement with previous calculations. The melting line crosses the metalization line at 700 K and 220 GPa using density functional energetics and at 550 K and 290 GPa using Quantum Monte Carlo energetics.

  19. Zinc-blende to rock-salt structural phase transition of BP and BAs under high pressure

    NASA Astrophysics Data System (ADS)

    Sarwan, Madhu; Bhardwaj, Purvee; Singh, Sadhna

    2013-11-01

    In the present paper, we have investigated the pressure induced phase transition and thermophysical properties of BP and BAs by means of modified interaction potential model (MIPM). The MIPM consists of Coulomb interaction, three-body interaction (TBI) modified by taking covalency effect, van-der Waal interaction (vdW), short range overlap repulsive interaction and zero point energy effect. These compounds crystallize in zinc-blende (ZB) structure at ambient condition and transform to rock-salt (RS) structure at pressures 111 and 93 GPa and their equation of state show volume collapse of 14% and 4% respectively for BP and BAs. The second order elastic constants have also been computed at zero and high pressures. Our results are in good agreement with the experimental results. The mechanical and thermophysical properties in ZB structure are also predicted.

  20. High pressure synthesis of a new phase of YbAg2: Structure, valence of Yb and properties

    DOE PAGES

    Tsvyashchenko, A. V.; Menushenkov, A. P.; Sidorov, V. A.; ...

    2015-08-05

    The new phase of YbAg2 was obtained using high-pressure and high-temperature reaction. YbAg2 crystallizes in the MgZn2 structure (the space group P63/mmc space group, No 194) with a = 5.68153(3) Å and c = 9.31995(7) Å and the unit cell volume V = 260.54(3) Å3. The XANES analysis showed that the valence state of Yb is +2.8. The low-temperature dependences of the electrical resistivity and magnetic susceptibility can be adequately described by a T2 term that supports the Fermi-liquid picture. Furthermore, the Kadowaki–Woods relation gives a low value of the degeneracy (N = 2).

  1. High pressure synthesis of a new phase of YbAg2: Structure, valence of Yb and properties

    SciTech Connect

    Tsvyashchenko, A. V.; Menushenkov, A. P.; Sidorov, V. A.; Petrova, A. E.; Fomicheva, L. N.; Chernysheva, O. V.; Lebed, Yu. B.; Axenov, S. N.; Bud’ko, S. L.; Sun, Liling; Zhao, Zhongxian

    2015-08-05

    The new phase of YbAg2 was obtained using high-pressure and high-temperature reaction. YbAg2 crystallizes in the MgZn2 structure (the space group P63/mmc space group, No 194) with a = 5.68153(3) Å and c = 9.31995(7) Å and the unit cell volume V = 260.54(3) Å3. The XANES analysis showed that the valence state of Yb is +2.8. The low-temperature dependences of the electrical resistivity and magnetic susceptibility can be adequately described by a T2 term that supports the Fermi-liquid picture. Furthermore, the Kadowaki–Woods relation gives a low value of the degeneracy (N = 2).

  2. Connecting the Water Phase Diagram to the Metastable Domain: High-Pressure Studies in the Supercooled Regime.

    PubMed

    Fanetti, Samuele; Pagliai, Marco; Citroni, Margherita; Lapini, Andrea; Scandolo, Sandro; Righini, Roberto; Bini, Roberto

    2014-11-06

    Pressure is extremely efficient to tune intermolecular interactions, allowing the study of the mechanisms regulating, at the molecular level, the structure and dynamics of condensed phases. Among the simplest molecules, water represents in many respects a mystery despite its primary role in ruling most of the biological, physical, and chemical processes occurring in nature. Here we report a careful characterization of the dynamic regime change associated with low-density and high-density forms of liquid water by measuring the line shape of the OD stretching mode of HOD in liquid water along different isotherms as a function of pressure. Remarkably, the high-pressure studies have been here extended down to 240 K, well inside the supercooled regime. Supported by molecular dynamics simulations, a correlation among amorphous and crystalline solids and the two different liquid water forms is attempted to provide a unified picture of the metastable and thermodynamic regimes of water.

  3. Hydrogen bond symmetrization and superconducting phase of HBr and HCl under high pressure: An ab initio study.

    PubMed

    Duan, Defang; Tian, Fubo; He, Zhi; Meng, Xing; Wang, Liancheng; Chen, Changbo; Zhao, Xiusong; Liu, Bingbing; Cui, Tian

    2010-08-21

    Ab initio calculations are performed to probe the hydrogen bonding, structural, and superconducting behaviors of HBr and HCl under high pressure. The calculated results show that the hydrogen bond symmetrization (Cmc2(1)-->Cmcm transition) of HBr and HCl occurs at 25 and 40 GPa, respectively, which can be attributed to the symmetry stretching A(1) mode softening. After hydrogen bond symmetrization, a pressure-induced soft transverse acoustic phonon mode of Cmcm phase is identified and a unique metallic phase with monoclinic structure of P2(1)/m (4 molecules/cell) for both compounds is revealed by ab initio phonon calculations. This phase preserves the symmetric hydrogen bond and is stable in the pressure range from 134 to 196 GPa for HBr and above 233 GPa for HCl, while HBr is predicted to decompose into Br(2)+H(2) above 196 GPa. Perturbative linear-response calculations predict that the phase P2(1)/m is a superconductor with T(c) of 27-34 K for HBr at 160 GPa and 9-14 K for HCl at 280 GPa.

  4. High-pressure high-temperature phase diagram of gadolinium studied using a boron-doped heater anvil

    DOE PAGES

    Montgomery, J. M.; Samudrala, G. K.; Velisavljevic, N.; ...

    2016-04-07

    A boron-doped designer heater anvil is used in conjunction with powder x-ray diffraction to collect structural information on a sample of quasi-hydrostatically loaded gadolinium metal up to pressures above 8GPa and 600K. The heater anvil consists of a natural diamond anvil that has been surface modified with a homoepitaxially grown chemical-vapor-deposited layer of conducting boron-doped diamond, and is used as a DC heating element. Internally insulating both diamond anvils with sapphire support seats allows for heating and cooling of the high-pressure area on the order of a few tens of seconds. This device is then used to scan the phasemore » diagram of the sample by oscillating the temperature while continuously increasing the externally applied pressure and collecting in situ time-resolved powder diffraction images. In the pressure-temperature range covered in this experiment, the gadolinium sample is observed in its hcp, αSm, and dhcp phases. Under this temperature cycling, the hcp → αSm transition proceeds in discontinuous steps at points along the expected phase boundary. From these measurements (representing only one hour of synchrotron x-ray collection time), a single-experiment equation of state and phase diagram of each phase of gadolinium is presented for the range of 0–10GPa and 300–650K« less

  5. First principles prediction of a new high-pressure phase and transport properties of Mg2Si

    NASA Astrophysics Data System (ADS)

    Kessair, S.; Arbouche, O.; Amara, K.; Benallou, Y.; Azzaz, Y.; Zemouli, M.; Bekki, M.; Ameri, M.; Bouazza, B. S.

    2016-12-01

    We have investigated the structural properties of seven different structure types of Mg2Si which include the cubic CaF2, orthorhombic PbCl2, hexagonal Ni2In, tetragonal Al2Cu, Laves phase (cubic MgCu2), hexagonal MgZn2 and dihexagonal MgNi2 type of structures, using a full potential linearized augmented plane wave method as implemented in WIEN2k within the framework of density functional theory. The exchange-correlation potential is treated by the new form of generalized gradient approximation (GGA-PBEsol). In total energy calculations it is clearly seen that cubic CaF2-type structure is stable at ambient conditions, and it undergoes a first-order phase transition to orthorhombic PbCl2-type, then to the hexagonal Ni2In-type structure and finally to the cubic Laves phase MgCu2-type. A new structure type is predicted to be stable at high pressure. Moreover, we intend to combine the electronic structure calculations performed by mean of generalized gradient approximation and modified Becke-Johnson potential with Boltzmann transport theory as incorporated in BoltzTraP code to interpret and predict the thermoelectric performance of each stable phase as a function of the chemical potential at various temperatures. We find a high thermoelectric thermopower values in cubic CaF2-type structure that could promise an excellent candidate for potential thermoelectric applications.

  6. [In situ experimental study of phase transition of calcite by Raman spectroscopy at high temperature and high pressure].

    PubMed

    Liu, Chuan-jiang; Zheng, Hai-fei

    2012-02-01

    The phase transitions of calcite at high temperature and high pressure were investigated by using hydrothermal diamond anvil cell combined with Raman spectroscopy. The result showed that the Raman peak of 155 cm(-1) disappeared, the peak of 1 087 cm(-1) splited into 1083 and 1 090 cm(-1) peaks and the peak of 282 cm(-1) abruptly reduced to 231 cm(-1) at ambient temperature when the system pressure increased to 1 666 and 2 127 MPa respectively, which proved that calcite transformed to calcite-II and calcite-III. In the heating process at the initial pressure of 2 761 MPa and below 171 degrees C, there was no change in Raman characteristic peaks of calcite-III. As the temperature increased to 171 degrees C, the color of calcite crystal became opaque completely and the symmetric stretching vibration peak of 1 087 cm(-1), in-plane bending vibration peak of 713 cm(-1) and lattice vibration peaks of 155 and 282 cm(-1) began to mutate, showing that the calcite-III transformed to a new phase of calcium carbonate at the moment. When the temperature dropped to room temperature, this new phase remained stable all along. It also indicated that the process of phase transformation from calcite to the new phase of calcium carbonate was irreversible. The equation of phase transition between calcite-III and new phase of calcium carbonate can be determined by P(MPa) = 9.09T x (degrees C) +1 880. The slopes of the Raman peak (v1 087) of symmetrical stretching vibration depending on pressure and temperature are dv/dP = 5.1 (cm(-1) x GPa(-1)) and dv/dT = -0.055 3(cm(-1) x degrees C(-1)), respectively.

  7. Combined high-pressure and high-temperature vibrational studies of dolomite: phase diagram and evidence of a new distorted modification

    NASA Astrophysics Data System (ADS)

    Efthimiopoulos, I.; Jahn, S.; Kuras, A.; Schade, U.; Koch-Müller, M.

    2017-02-01

    A combined high-pressure mid-infrared absorption and Raman spectroscopy study on a natural CaMg0.98Fe0.02(CO3)2 dolomite sample was performed both at ambient and high temperatures. A pressure-temperature phase diagram was constructed for all the reported dolomite ambient- and high-pressure polymorphs. In addition, a local distortion of the ambient-pressure dolomite structure was identified close to 11 GPa, just before the transition toward the first known high-pressure phase. All the Clausius-Clapeyron slopes are found to be positive with similar magnitudes. Complementary first-principles calculations suggest a metastable nature of the high-pressure dolomite polymorphs. Finally, theoretical spectroscopy is used to interpret and discuss the observed changes in the measured vibrational spectra.

  8. Theoretical investigation of the high pressure structure, lattice dynamics, phase transition, and thermal equation of state of titanium metal

    NASA Astrophysics Data System (ADS)

    Hu, Cui-E.; Zeng, Zhao-Yi; Zhang, Lin; Chen, Xiang-Rong; Cai, Ling-Cang; Alfè, Dario

    2010-05-01

    We report a detailed first-principles calculation to investigate the structures, elastic constants, and phase transition of Ti. The axial ratios of both α-Ti and ω-Ti are nearly constant under hydrostatic compression, which confirms the latest experimental results. From the high pressure elastic constants, we find that the α-Ti is unstable when the applied pressures are larger than 24.2 GPa, but the ω-Ti is mechanically stable at all range of calculated pressure. The calculated phonon dispersion curves agree well with experiments. Under compression, we captured a large softening around Γ point of α-Ti. When the pressure is raised to 35.9 GPa, the frequencies around the Γ point along Γ-M-K and Γ-A in transverse acoustical branches become imaginary, indicating a structural instability. Within quasiharmonic approximation, we obtained the full phase diagram and accurate thermal equations of state of Ti. The phase transition ω-Ti→α-Ti→β-Ti at zero pressure occurs at 146 K and 1143 K, respectively. The predicted triple point is at 9.78 GPa, 931 K, which is close to the experimental data. Our thermal equations of state confirm the available experimental results and are extended to a wider pressure and temperature range.

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

    SciTech Connect

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

    2015-08-14

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

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

    DOE PAGES

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

    2015-08-14

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

  11. Theoretical studies of phase transformations of mantle minerals: Implications for high-pressure research and Earth processes

    NASA Astrophysics Data System (ADS)

    Marton, Frederic C.

    Theoretical computational methods of mineral physics are powerful tools with which to investigate the materials of the Earth's deep interior. Here I use both quantum mechanical and themodynamical models to study the phase transformations of mantle minerals, discussing the implications of my results for high-pressure, high-temperature experimental research, modeling of thermodynamic processes under geological conditions, and plate tectonics. First, using the first-principles LAPW method, a phase transition is predicted for Al2O3 from the corundum to the Rh 2O3(II) structure at high pressure. These results show that free Al2O3 in the deep lower mantle is unlikely to have the corundum structure, although it is probably not sufficiently abundant to give an observable seismological signal. This transition should also affect fluorescence of Cr3+-doped corundum (ruby), used as a pressure calibrant in diamond anvil experiments. Next, I investigate the latent heat of reactions of metastable (Mg, Fe) 2SiO4 phase transitions. Under geological conditions, the heat released should be governed by the change in enthalpy, with a strong pressure dependence. The effects of solid solution on heat release are also quite strong, with increases ranging from 10% to 100% for a composition of Fo90 relative to Fo100. Due to these effects, calculations of temperature increases made using simplifying assumptions should be viewed with caution. Finally, I explore the effects of mineralogy on the descent velocities of subducting slabs. Thermo-kinetic modeling of olivine polymorphs is used to predict mineralogy and I compare the resultant buoyant force to the opposing viscous drag. As slabs first enter the transition zone, negative buoyancy anomalies should accelerate them, whereas positive anomalies that form when the slabs' ends exit the transition zone should decelerate them. These effects may induce geologically abrupt changes in plate motions. Also, metastable olivine in slabs should create

  12. Structures of two intermediate phases between the B1 and B2 phases of PbS under high pressure

    SciTech Connect

    Li, Yanchun E-mail: liuj@ihep.ac.cn; Lin, Chuanlong; Li, Xiaodong; Liu, Jing E-mail: liuj@ihep.ac.cn; Xu, Jian; Li, Gong

    2014-12-15

    The structural transitions of PbS were investigated at pressures up to 50 GPa using synchrotron powder and single crystal X-ray diffraction (XRD) methods in diamond anvil cells. We found two intermediate phases between the B1 phase under atmospheric pressure and the B2 phase at 21.1 GPa, which is different to previous reports. The structures of these two intermediate phases were indexed as B27 and B33, respectively. Their structural parameters were investigated using density functional theory (DFT) calculations. Our results provide a new insight into understanding the transition pathway between the B1 and B2 phases in PbS.

  13. High-Efficiency, Ultra-High Pressure Electrolysis With Direct Linkage to PV Arrays - Phase II SBIR Final Report

    SciTech Connect

    Martin A Shimko

    2009-08-08

    In this Phase II SBIR, Avalence LLC met all proposed objectives. Because the original Phase III partner pulled out of the project, several alternative sites/partners were used to achieve the goals. The on-site operation and PV measurements were performed on a smaller unit at General Motors proving grounds in Milford, MI. The actual equipment targeted for AC Transit will be delivered to Robins Air Force Base in September of 2009 to support the fueling of a fuel cell powered fork lift and 'Bobcat'. In addition the Transit Agency Site Requirements and Constraints were performed for the Greater New Haven Transit District (GNHTD) for the Hamden, CT Public Works building that will be the site for a similar fueling station to be delivered in the Spring of 2010. The Detailed Design Package was also based on the Design for the GNHTD unit. The work on this project successfuly demonstrated the potential of Avalence's high pressure technology to address the need for renewably produced hydrogen fuel for transportation applications. Several follow-on projects in a numerber of related applications are now underway as a result of this SBIR project.

  14. Separation and quantitation of free fatty acids and fatty acid methyl esters by reverse phase high pressure liquid chromatography.

    PubMed

    Aveldano, M I; VanRollins, M; Horrocks, L A

    1983-01-01

    Reverse phase high pressure liquid chromatography (HPLC) on octadecylsilyl columns separates mixtures of either free fatty acids or fatty acid methyl esters prepared from mammalian tissue phospholipids. Acetonitrile-water mixtures are used for the elution of esters. Aqueous phosphoric acid is substituted for water for the separation of the free acids. Unsaturated compounds are detected and quantitated by their absorption at 192 nm. Saturates are detected better at 205 nm. The order of elution of fatty acids in complex mixtures varies as a function of acetonitrile concentration. At any given concentration, some compounds overlap. However, by varying the solvent strength, any fatty acid of interest can be resolved including many geometrical and positional isomers. Methyl esters prefractionated according to unsaturation by argentation thin-layer chromatography (TLC) are rapidly and completely separated by elution with CH3CN alone. Argentation TLC-reverse phase HPLC can be used as an analytical as well as a preparative procedure. Octylsilyl columns are used for rapid resolution and improved detection of minor or low ultraviolet-absorbing components in the fractions. For example, monoenoic fatty acids with up to 32 carbons have been detected in bovine brain glycerophospholipids. Specific radioactivities of 3H- and 14C-labeled fatty acids and the distribution of radioactivity among acyl groups from complex lipids are measured. The method is not recommended for complete compositional analysis, but is useful for determinations of specific radioactivities during studies on turnover and metabolic conversions of labeled fatty acids.

  15. Radiation-induced solid-state polymerization in an acrylamide-water system: The effect of phase transformations of metastable high-pressure ice VIII

    SciTech Connect

    Kiryukhin, D.P.; Barkalov, I.M.; Barkalov, O.I.

    1995-07-01

    A drastic suppression of the chain post polymerization process in the quenched high-pressure phase of an acrylamide-water eutectic mixture was observed upon warming of the samples irradiated with {gamma}-rays at 77 K. This effect is explained by dispersion of the samples in the temperature region of the transition of the quenched high-pressure phase into the equilibrium phase ({approximately}150K). The size of the resulting microcrystals of monomer was estimated to be approximately 0.1 {mu}m.

  16. Equations of State and Phase Transformation of Depleted Uranium DU-238 by High Pressure-Temperature Diffraction Studies

    SciTech Connect

    Zhao,Y.; Zhang, J.; Brown, D.; Korzekwa, D.; Hixson, R.

    2007-01-01

    We have conducted in situ high-pressure diffraction experiments on depleted uranium (DU-238) at pressures up to 8.5 GPa and temperatures up to 1123 K. From the pressure (P)-volume (V)-temperature (T) measurements, thermoelastic parameters were derived for a-uranium based on a modified high-T Birch-Murnaghan equation of state and a thermal-pressure approach. With the pressure derivative of the bulk modulus K0' fixed at 4.0, we obtained ambient bulk modulus K0=117(2) GPa, temperature derivative of bulk modulus at constant pressure ({partial_derivative}K/{partial_derivative}T)P=-3.4(4)x10-2 GPa/K and at constant volume ({partial_derivative}K/{partial_derivative}T)v=-1.1(6)x10-2 GPa/K, volumetric thermal expansivity aT=a+bT, with a=1.2({+-}0.4)x10-5 K-1 and b=8.0({+-}0.7)x10-8 K-2, and the pressure derivative of thermal expansion ({partial_derivative}a/{partial_derivative}P)T=-2.5(5)x10-6 GPa-1 K-1. Within the experimental errors, the ambient bulk modulus and volumetric thermal expansion derived from this work are in good agreement with previous experimental results, whereas all other thermoelastic parameters represent the first determinations for the a phase of uranium. We also studied the a- phase transformation and obtained a phase boundary described by T (in K)=1032+7.4P (in GPa). Although the -phase uranium cannot be pressure quenched to ambient conditions, it was observed to be stable upon cooling from 1123 to 300 K at pressures of 7-8 GPa. These observations indicate that pressure, in addition to the commonly utilized alloying techniques, provides an alternative route for stabilizing the {gamma}-uranium at room temperature.

  17. Investigation of Fe-FeS phase diagram and liquid structure at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Morard, G.; Sanloup, C.; Fiquet, G.; Mezouar, M.; Andrault, D.; Guignot, N.

    2007-12-01

    Sulfur is believed to be an alloying light element in iron-rich planetary cores such as those of the Earth and Mars 1, 2. Recent studies have suggested that Mars, like the Earth, could have a liquid metallic outer core together with a solid inner core 3. Hence, it is important to investigate the evolution of the Fe-FeS phase diagram and of the structural properties of the liquid Fe-FeS alloys in respect to pressure, temperature and sulphur content. A new cell assembly has been developed to heat samples to more than 1300 K at 17 GPa using the Paris Edinburgh Press4. This allows us to conduct detailed structural investigations of the Fe-FeS eutectic liquid by in situ X-ray diffraction5 . Analysis of these data highlights an increase of the liquid compacity with increasing pressure. We also show that the eutectic liquid structure is closer to that of FeSi, explaining the closure of the miscibility gap in the Fe-S-Si system 6. The evolution of the Fe-FeS eutectic liquid structure at high pressure could have significant effect on extrapolated wave speed of metallic Fe-FeS alloy at core pressures. We have used a double-sided laser-heated diamond-anvil cell 7 to study the Fe-FeS phase diagram up to 65 GPa and 2500 K8. We used laser heated diamond anvil cell coupled with synchrotron radiation and confirm a S- solubility below 4 at% (2.3 %wt) up to 65 GPa. The eutectic temperatures present a uniform increase, with a rate of ~15K/GPa, up to 65 GPa and 2200 K. Finally, we present new constraints on the phase diagram evolution to very high pressures which provide unambiguous evidence for an upper limit of 4-8 %wt for the inner core S- content. Therefore, sulphur is not favoured to be the major light element in the Earth's core. 1. Allegre, C. J., Poirier, J. P., Humler, E. & Hofmann, A. W. The chemical composition of the Earth. Earth Planet. Sc. Lett. 134, 515-526 (1995). 2. Sohl, F. & Spohn, T. The interior structure of Mars : Implications from SNC meteorites. J. Geophys. Res

  18. The 10Å phase: a high-pressure expandable sheet silicate stable during subduction of hydrated lithosphere

    NASA Astrophysics Data System (ADS)

    Fumagalli, Patrizia; Stixrude, Lars; Poli, Stefano; Snyder, Don

    2001-03-01

    H 2O storage and release in deep subducting lithosphere is controlled by complex reaction suites involving a variety of hydrous phases. As a result of its relatively large thermal stability and intermediate composition, the 10Å phase (Mg 3Si 4O 10(OH) 2· nH 2O) has been regarded as a relevant H 2O reservoir in a wide range of rock compositions and mineral assemblages. High-pressure syntheses of the 10Å phase were carried out at 6.7 GPa and 650°C under fluid-saturated conditions in a Walker-type multi-anvil apparatus, from 5 min to 430 h. X-ray powder diffraction of large platy hexagonal crystals of the 10Å phase (up to 100 μm) were indexed on the basis of a trioctahedral-type structure. Long-term run products (>110 h) reveal sensitivity of the 10Å phase to treatment with acetone leading to the appearance of diffractions at greater d-spacings (10.2-11.6 Å) with respect to the basal peak of the 10Å phase (9.64-10.07 Å). This swelling behavior is strongly related to synthesis run duration. The Raman spectrum of the 10Å phase at frequencies less than 800 cm -1 shows a strong similarity to talc. In the Si-O stretching region (800-1100 cm -1), the 10Å phase exhibits three modes (909, 992 and 1058 cm -1), as compared to two in talc. The bending mode of water (ν 2) is found at 1593 cm -1. In the OH stretching region, peaks at 3593, 3622 and 3668 cm -1 were observed. The acetone treated sample shows a C-H stretching mode at 2923 cm -1 while the double bond CO signal is absent. The swelling behavior of the 10Å phase is interpreted as due to intercalation of acetone with pre-existing interlayer water. The efficiency of this process is dependent on the amount of the interlayer water which in turn depends on run duration. The relation between the response to acetone treatment and run duration is therefore interpreted as a time-dependent hydration of the 10Å phase. The fractions transformed from non-expandable to expandable fractions was fitted to the Avrami

  19. Timing and conditions of high-pressure metamorphism in the western Grenville Province: Constraints from accessory mineral composition and phase equilibrium modeling

    NASA Astrophysics Data System (ADS)

    Marsh, Jeffrey H.; Culshaw, Nicholas G.

    2014-07-01

    Previous geochronological analyses of high pressure (HP) metamorphic rocks in the western Grenville Province, Ontario, Canada have yielded precise U-Pb zircon ages; however, uncertainty has remained as to whether these ages represent the timing of HP metamorphism or the granulite/amphibolite facies overprint accompanying exhumation to a hot middle orogenic crust. Detailed study of these HP rocks, involving garnet, rutile, and zircon trace element analysis, phase equilibrium modeling, and zircon U-Pb geochronology, has yielded much improved constraints on the timing and conditions of HP metamorphism. Zircon from five of the six HP samples yield anchored discordia upper intercept and 207Pb/206Pb weighted average ages between 1097 and 1085 Ma, and typically have trace element compositions consistent with growth in a garnet-rich, plagioclase-poor eclogite-type assemblage (i.e. no negative Eu anomaly and flat HREE trends). Titanium-in-zircon and Zr-in-rutile thermometry indicates that the range of zircon crystallization temperatures for most samples (643-767 °C) is close to that of rutile inclusions in garnet (668-753 °C) and matrix rutile (690-772 °C). Phase relations in a pseudosection calculated for the sample that best preserves the HP assemblage indicate that: (1) the stability field for the inclusions observed in garnet and kyanite is between 11.5 < P < 14 kbar and 600 < T < 700 °C, and (2) zircon and rutile crystallization temperatures intersect the inferred HP assemblage field (Grt + Cpx + Ky + Rt + Hbl + Qtz) and garnet and kyanite modal isopleths at P > ~ 15 kbar, indicating that the ca. 1090 Ma zircon ages date metamorphism at eclogite facies conditions. Thus, the deep burial of mafic lower crust that resulted in HP metamorphism in the western CGB occurred just prior to the main "Ottawan" phase of continental collision in the western Grenville Province (ca. 1080-1040 Ma).

  20. Phase relations and sound velocity measurements of iron-sulfur systems at high pressure: implications for the Earth's inner core

    NASA Astrophysics Data System (ADS)

    Ohtani, E.; Kamada, S.; Sakai, T.; Terasaki, H.; Shibazaki, Y.; Sakamaki, T.; Takahashi, S.; Sakairi, T.; Fukui, H.; Baron, A. Q.

    2012-12-01

    The sound velocity is one of the most important physical properties which can be assessed by seismology. In spite of its importance, the technical difficulty provides limitation of the measurements under the core conditions. Here we show the results of measurements of the sound velocity of hcp-iron, Fe3S, and FeH by the inelastic X-ray scattering (IXS) method using DAC at high pressure and temperature. Inelastic X-ray scattering spectra were taken at BL35XU, Spring-8. We made the measurements of hcp-iron at pressures up to 180 GPa at room temperature, which is the highest pressure for the IXS measurement. Sound velocity measurements at high pressure and temperature were made up to 91 GPa at 700 K, and to 62 GPa and 1000 K using the external heating diamond anvil cell. The present results revealed that there is almost no temperature effect on the sound velocity of hcp-Fe at least up to 1000 K. We also measured the sound velocity and density of Fe3S up to 85 GPa at room temperature, and clarified the effect of sulfur and hydrogen on the sound velocity of iron at high pressure. Phase relations of the Fe-S (Kamada et al., 2010; 2012) and Fe-S-O systems (Terasaki et al., 2011) were studied up to the core pressures based on the laser heated diamond anvil cell combined with the in situ synchrotron X-ray diffraction at SPring-8. Fe3S dissolves first at the solidus before melting of FeO and metallic iron alloy at the liquidus of the systems up to 180 GPa. The maximum solubility of sulfur in hcp-iron approaches to about 7.5 at % at 86 GPa and 8 at % at 123 GPa, and it does not increase so much at higher pressures. The temperature at ICB based on the extrapolation of the liquidus and solidus temperatures of the outer core composition in the Fe-S-O is about 4360-5630 K assuming that the outer core composition is Fe75O5S20 in the atomic ratio. The temperature at the core-mantle boundary will be 3340-4300 K by the adiabatic decompression from the temperature at the inner core

  1. A theoretical study of high-pressure-induced phases of LiAlH4 using calculated NQCC parameters

    NASA Astrophysics Data System (ADS)

    Rafiee, Marjan A.

    2016-12-01

    Quadrupolar parameters of nuclei can be used as a tool to understand the electronic structure of compounds. Lithium alanate (LiAlH4) is a potential hydrogen storage material because of its high capacity of 10.5 wt % H2. However, the drawbacks of its dehydrogenation process are the relatively high temperatures and the slow dehydrogenation kinetics; furthermore, its reversibility is rather poor. Understanding the bonding nature of Al and H is essential for improving its dehydrogenation performance. In this work the charge density distribution in LiAlH4 is studied. Thus using calculated nuclear quadrupole coupling constants of hydrogens (2H-NQCCs), the electronic structure of α-LiAlH4 with high pressure forms of LiAlH4, (β- and γ-LiAlH4) were compared. The results show that easier condition for dehydrogenation is expected in β-LiAlH4. Comparison of calculated dehydrogenation enthalpies of LiAlH4 phases verifies this prediction. The electric field gradient (EFG) of quadrupolar nuclei were calculated to obtain NQCC parameters. All calculations performed using Gaussian 03 at B3LYP/6-31G* level of theory.

  2. Pressure-induced structural phase transition, elastic and thermodynamic properties of ReC under high pressure

    NASA Astrophysics Data System (ADS)

    Lei, Hui-Ru; Zhu, Jun; Hao, Yan-Jun; Zhang, Lin; Zhao, Yu-Xin; Zhan, Guo-Fu

    2015-10-01

    The pressure-induced structural phase transition of rhenium monocarbon (ReC) is investigated via the projector augmented wave (PAW) method with the generalized gradient approximation (GGA). Using the first-principles calculations, the equilibrium structural parameters of ReC in rocksalt (NaCl), cesium chloride (CsCl), zinc blende (ZB), wurtzite (WZ), nickel arsenide (NiAs) and tungsten carbide (WC) types are successfully obtained, and the results are well consistent with other theoretical data. It is firstly noted that WC-ReC translates into CsCl-ReC at 510.50 GPa by analyzing the enthalpy difference versus pressure. From the calculated elastic constants, the aggregate elastic modulus (B, G, E), the Poisson's ratio (σ) and the Debye temperature ΘD of WC-type are also derived. It is observed that all the data of WC-ReC obtained increase monotonically with increasing pressure. Meanwhile, the thermodynamic properties of WC-ReC under high temperature and high pressure are investigated applying nonempirical Debye model in the quasi-harmonic approximation.

  3. Electronic, mechanical, phase transition, and thermo-physical properties of TMC (TM = V, Nb, and Ta): high pressure ab initio study

    NASA Astrophysics Data System (ADS)

    Chauhan, Mamta; Gupta, Dinesh C.

    2015-12-01

    The structural, electronic, mechanical, phase transition, and thermo-physical properties of refractory carbides, viz. VC, NbC, and TaC have been computed in stable B1 and high pressure B2 phases by means of two different ab initio calculations using pseudo- and full-potential schemes. These materials have mixed covalent-, metallic-, and ionic-type bonding. The calculations of elastic constants show the mechanical stability of these materials in B1 phase only. The brittle nature and anisotropy is observed in these materials in B1 phase. Non-central forces are present in both the phases. Elastic wave velocities and Debye temperature have also been calculated. The present results on structural, phase transition, elastic, and other properties are in reasonably good agreement with the available experimental and theoretical data. The calculations in high pressure phase need experimental verification.

  4. Magnetic phase transition of high-pressure phase (VO)2P2O7 studied by high-field ESR measurements

    NASA Astrophysics Data System (ADS)

    Hiraka, K.; Nagasaka, Y.; Kunimoto, T.; Inagaki, Y.; Okubo, S.; Ohta, H.; Saito, T.; Azuma, M.; Takano, M.

    2004-05-01

    The high-pressure phase of (VO)2P2O7 (HP-VOPO) is a S=1/2 Heisenberg antiferromagnetic alternating chain compound with one spin gap. The high-field ESR measurements of the HP-VOPO single crystal have been performed using the pulsed magnetic field up to 30T. Small anomaly is observed in ESR mode for both a- and b-axis. The linewidth became broad around Bc=20T when the field is applied along the a- and b-axis. The magnetic state of HP-VOPO above Bc will be discussed.

  5. High-pressure structural configuration and phase transition in celsian, BaAl2Si2O8

    NASA Astrophysics Data System (ADS)

    Curetti, Nadia; Benna, Piera; Bruno, Emiliano

    2016-10-01

    In situ high-pressure X-ray diffraction study was performed on celsian (Cls97Or3) from Jakobsberg, Sweden. A single crystal of celsian was loaded in an ETH-type diamond anvil cell, and unit-cell parameters were measured at 20 different pressures up to 6.0 GPa at room T. The evolution of the unit-cell parameters and volume as a function of pressure shows a discontinuity at P ~ 5.7 GPa indicating a displacive first-order phase transition. The P-V data were fitted by a second-order Birch-Murnaghan EoS only up to 2.55 GPa, because at higher pressures a slight change in the compressional behavior of the unit-cell volume is observed, indicating a pre-transition volume softening. The resulting EoS coefficients are V 0 = 1461.4(1) Å3 and K T0 = 88.1(6) GPa. A second crystal of celsian was loaded in the DAC cell, and single-crystal in situ HP X-ray diffraction was performed at P = 0.0001, 2.1, 4.2, 5.5, 5.9, 6.5 and 7.8 GPa. The data collections between 0 and 5.5 GPa show only a- and b-type reflections confirming the I2/c space group. The appearance of c and d-type reflections at 5.9, 6.5 and 7.8 GPa, the analysis of the systematic absence and the structural refinements define the HP phase transition as an I2/c-P21/c transition. The most significant changes with compression in celsian are the deformation in the Ba polyhedra and the variation in the T-O-T angles.

  6. High-pressure structural configuration and phase transition in celsian, BaAl2Si2O8

    NASA Astrophysics Data System (ADS)

    Curetti, Nadia; Benna, Piera; Bruno, Emiliano

    2017-03-01

    In situ high-pressure X-ray diffraction study was performed on celsian (Cls97Or3) from Jakobsberg, Sweden. A single crystal of celsian was loaded in an ETH-type diamond anvil cell, and unit-cell parameters were measured at 20 different pressures up to 6.0 GPa at room T. The evolution of the unit-cell parameters and volume as a function of pressure shows a discontinuity at P 5.7 GPa indicating a displacive first-order phase transition. The P- V data were fitted by a second-order Birch-Murnaghan EoS only up to 2.55 GPa, because at higher pressures a slight change in the compressional behavior of the unit-cell volume is observed, indicating a pre-transition volume softening. The resulting EoS coefficients are V 0 = 1461.4(1) Å3 and K T0 = 88.1(6) GPa. A second crystal of celsian was loaded in the DAC cell, and single-crystal in situ H P X-ray diffraction was performed at P = 0.0001, 2.1, 4.2, 5.5, 5.9, 6.5 and 7.8 GPa. The data collections between 0 and 5.5 GPa show only a- and b-type reflections confirming the I2/ c space group. The appearance of c and d-type reflections at 5.9, 6.5 and 7.8 GPa, the analysis of the systematic absence and the structural refinements define the H P phase transition as an I2/ c- P21/ c transition. The most significant changes with compression in celsian are the deformation in the Ba polyhedra and the variation in the T-O-T angles.

  7. Effects of gasket on coupled plastic flow and strain-induced phase transformations under high pressure and large torsion in a rotational diamond anvil cell

    NASA Astrophysics Data System (ADS)

    Feng, Biao; Levitas, Valery I.

    2016-01-01

    Combined plastic flow and strain-induced phase transformations (PTs) under high pressure in a sample within a gasket subjected to three dimensional compression and torsion in a rotational diamond anvil cell (RDAC) are studied using a finite element approach. The results are obtained for the weaker, equal-strength, and stronger high-pressure phases in comparison with low-pressure phases. It is found that, due to the strong gasket, the pressure in the sample is relatively homogenous and the geometry of the transformed zones is mostly determined by heterogeneity in plastic flow. For the equal-strength phases, the PT rate is higher than for the weaker and stronger high-pressure phases. For the weaker high-pressure phase, transformation softening induces material instability and leads to strain and PT localization. For the stronger high-pressure phase, the PT is suppressed by strain hardening during PT. The effect of the kinetic parameter k that scales the PT rate in the strain-controlled kinetic equation is also examined. In comparison with a traditional diamond anvil cell without torsion, the PT progress is much faster in RDAC under the same maximum pressure in the sample. Finally, the gasket size and strength effects are discussed. For a shorter and weaker gasket, faster plastic flow in radial and thickness directions leads to faster PT kinetics in comparison with a longer and stronger gasket. The rates of PT and plastic flows are not very sensitive to the modest change in a gasket thickness. Multiple experimental results are reproduced and interpreted. Obtained results allow one to design the desired pressure-plastic strain loading program in the experiments for searching new phases, reducing PT pressure by plastic shear, extracting kinetic properties from experiments with heterogeneous fields, and controlling homogeneity of all fields and kinetics of PTs.

  8. Calculation of stability of sodic phases in high-pressure metapelites and observation of Sambagawa metamorphic rocks

    NASA Astrophysics Data System (ADS)

    Kouketsu, Y.; Enami, M.

    2010-12-01

    P-T pseudosection analyses of high-pressure metapelites from several subduction related regions were carried out by using the computer program Perple_X 07 in order to determine the mineral equilibrium, particularly the stability of sodic phases, in the model system MnO-Na2O-K2O-CaO-FeO-MgO-Al2O3-SiO2-H2O. Metapelites from Sambagawa, Western Alps, New Caledonia, Greece, and South Tianshan were selected for these analyses. Although the occurrence of sodic pyroxene in these metapelite samples is free or very rare, all the samples are considered to have undergone high-pressure metamorphism under blueschist-eclogite facies conditions. The bulk rock compositions of these metapelites have relatively low XNa [=Na/(Al + Na)] values. Therefore, the rare occurrences of sodic pyroxene in these samples are possibly due to their characteristic bulk rock compositions, although this has not been proved yet. The calculation results for the stability of sodic phases under the blueschist and eclogite facies conditions indicate the following. (1) Sodic pyroxene in the studied metapelites is stable only under higher-pressure conditions of P > 2.5 GPa, although its stable P-T range increases toward the lower-pressure side with increasing XNa value of the bulk-rock composition. (2) Paragonite and glaucophane are stable throughout the wide XNa range of bulk-rock compositions of host rocks under the blueschist and quartz-eclogite facies conditions. (3) The stability field of paragonite enlarges with the presence of CO2 in the metamorphic fluid. Thus, the high stability of paragonite and glaucophane in metapelites and the close relationship between the stability of sodic pyroxene and the bulk-rock composition explain why omphacite-bearing metapelites are rarely found. Observations of Sambagawa metapelites were carried out on the basis of these results. In the Besshi region of the Sambagawa belt, quartz grains with a high residual pressure of up to 0.8 GPa extensively occur as inclusions in

  9. High Pressure Biomass Gasification

    SciTech Connect

    Agrawal, Pradeep K

    2016-07-29

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

  10. High-Pressure Vibrational Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Pogson, Mark

    1987-09-01

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

  11. Ammonia-water mixtures at high pressures - Melting curves of ammonia dihydrate and ammonia monohydrate and a revised high-pressure phase diagram for the water-rich region. [in primordial solar system ices

    NASA Technical Reports Server (NTRS)

    Boone, S.; Nicol, M. F.

    1991-01-01

    The phase relations of some mixtures of ammonia and water are investigated to create a phase diagram in pressure-temperature-composition space relevant to the geophysical study of bodies in the outer solar system. The mixtures of NH3(x)H2O(1-x), where x is greater than 0.30 but less than 0.51, are examined at pressures and temperatures ranging from 0-6.5 GPa and 125-400 K, respectively. The ruby luminescence technique monitors the pressure and a diamond-anvil cell compresses the samples, and the phases are identified by means of normal- and polarized-light optical microscopy. The melting curve for NH3H2O(2) is described by the equation T = 176 + 60P - 8.5P squared for the ranges of 0.06-1.4 GPa and 179-243 K. The equation for NH3H2O is T = 194 + 37P - P squared, which represents a minor correction of a previous description by Johnson et al. (1985). Observed phase transitions are consistent with the high-pressure stability limit of NH3H2O(2), and the transition boundary is found to be linear.

  12. High-Temperature Phase Transitions in CsH2PO4 Under Ambient and High-Pressure Conditions: A Synchrotron X-ray Diffraction Study

    SciTech Connect

    Botez,C.; Hermosillo, J.; Zhang, J.; Qian, J.; Zhao, Y.; Majzlan, J.; Chianelli, R.; Pantea, C.

    2007-01-01

    To clarify the microscopic origin of the temperature-induced three-order-of-magnitude jump in the proton conductivity of CsH2PO4 (superprotonic behavior), we have investigated its crystal structure modifications within the 25-300 C temperature range under both ambient- and high-pressure conditions using synchrotron x-ray diffraction. Our high-pressure data show no indication of the thermal decomposition/polymerization at the crystal surface recently proposed as the origin of the enhanced proton conductivity. Instead, we found direct evidence that the superprotonic behavior of the title material is associated with a polymorphic structural transition to a high-temperature cubic phase. Our results are in excellent agreement with previous high-pressure ac impedance measurements.

  13. High pressure synthesis gas fermentation

    SciTech Connect

    Not Available

    1992-01-01

    The construction of the high pressure gas phase fermentation system has been completed. Photographs of the various components of the system are presented, along with an operating procedure for the equipment.

  14. High pressure homogenization and two-phased anaerobic digestion for enhanced biogas conversion from municipal waste sludge.

    PubMed

    Wahidunnabi, Abdullahil K; Eskicioglu, Cigdem

    2014-12-01

    This study compared advanced anaerobic digestion combining two-phased anaerobic digestion (2PAD) with high pressure homogenization (HPH) pretreatment to conventional anaerobic digestion of municipal sludge at laboratory scale. The study began with examination of thickened waste activated sludge (TWAS) solubilization due to HPH pretreatment at different pressure (0-12,000 psi) and chemical dose (0.009-0.036 g NaOH/g total solids). Homogenizing pressure was found as the most significant factor (p-value < 0.05) for increasing solubilization of particulate chemical oxygen demand (COD) and biopolymers in TWAS. Based on the preliminary results, a pretreatment with chemical dose of 0.009 g NaOH/g total solids and pressure of 12,000 psi was selected for digester studies. Upon acclimation of anaerobic inocula to pretreatments, a total number of twelve lab-scale digesters were operated under scenarios including single-stage (control), 2PAD, and HPH coupled with 2PAD (HPH + 2PAD) at sludge retention times (SRTs) of 20, 14 and 7 days. Between mesophilic and thermophilic temperatures, mesophilic digestion was found to benefit more from pretreatments. Relative (to control) improvements in methane yield and volatile solids (VS) removals increased noticeably as SRT was shortened from 20 to 14 and 7 days. HPH + 2PAD system was found to achieve the maximum methane production (0.61-1.32 L CH4/Ldigester-d) and VS removals (43-64%). Thermophilic control, 2PAD and HPH + 2PAD systems resulted in significant pathogen removals meeting Class A biosolids requirements according to Organic Matter Recycling Regulations (OMRR) of British Columbia (BC) at 20 d SRT. Energy analysis indicated that all the digestion scenarios attained positive energy balance with 2PAD system operated at 20 d SRT producing the maximum net energy of 4.76 GJ/tonne CODadded.

  15. Synchrotron X-ray diffraction studies of phase transitions and mechanical properties of nanocrystalline materials at high pressure

    SciTech Connect

    Prilliman, Stephen Gerald

    2003-01-01

    The behavior of nanocrystals under extreme pressure was investigated using synchrotron x-ray diffraction. A major part of this investigation was the testing of a prototype synchrotron endstation on a bend magnet beamline at the Advanced Light Source for high pressure work using a diamond anvil cell. The experiments conducted and documented here helped to determine issues of efficiency and accuracy that had to be resolved before the construction of a dedicated ''super-bend'' beamline and endstation. The major conclusions were the need for a cryo-cooled monochromator and a fully remote-controllable pressurization system which would decrease the time to change pressure and greatly reduce the error created by the re-placement of the diamond anvil cell after each pressure change. Two very different types of nanocrystal systems were studied, colloidal iron oxide (Fe2O3) and thin film TiN/BN. Iron oxide nanocrystals were found to have a transition from the γ to the α structure at a pressure strongly dependent on the size of the nanocrystals, ranging from 26 GPa for 7.2 nm nanocrystals to 37 GPa for 3.6 nm nanocrystals. All nanocrystals were found to remain in the α structure even after release of pressure. The transition pressure was also found, for a constant size (5.7 nm) to be strongly dependent on the degree of aggregation of the nanocrystals, increasing from 30 GPa for completely dissolved nanocrystals to 45 GPa for strongly aggregated nanocrystals. Furthermore, the x-ray diffraction pattern of the pressure induced α phase demonstrated a decrease in intensity for certain select peaks. Together, these observations were used to make a complete picture of the phase transition in nanocrystalline systems. The size dependence of the transition was interpreted as resulting from the extremely high surface energy of the α phase which would increase the thermodynamic offset and thereby increase the kinetic barrier to transition that must be

  16. The local phase transitions of the solvent in the neighborhood of a solvophobic polymer at high pressures

    SciTech Connect

    Budkov, Yu. A.; Vyalov, I. I.; Kolesnikov, A. L.; Georgi, N.; Chuev, G. N.; Kiselev, M. G.

    2014-11-28

    We investigate local phase transitions of the solvent in the neighborhood of a solvophobic polymer chain which is induced by a change of the polymer-solvent repulsion and the solvent pressure in the bulk solution. We describe the polymer in solution by the Edwards model, where the conditional partition function of the polymer chain at a fixed radius of gyration is described by a mean-field theory. The contributions of the polymer-solvent and the solvent-solvent interactions to the total free energy are described within the mean-field approximation. We obtain the total free energy of the solution as a function of the radius of gyration and the average solvent number density within the gyration volume. The resulting system of coupled equations is solved varying the polymer-solvent repulsion strength at high solvent pressure in the bulk. We show that the coil-globule (globule-coil) transition occurs accompanied by a local solvent evaporation (condensation) within the gyration volume.

  17. Determination of the phase boundary of the omega to beta transition in Zr using in situ high-pressure and high-temperature X-ray diffraction

    SciTech Connect

    Ono, Shigeaki; Kikegawa, Takumi

    2015-05-15

    The high-pressure behavior of zirconium has been examined using the synchrotron X-ray diffraction technique to a pressure of 38 GPa and a temperature of 800 K employing a hydrothermal diamond anvil cell technique. The structural transition from the ω to the β phase was observed. This transition has a negative dP/dT gradient, which is in general agreement with those reported in previous studies. The transition boundary was determined to be, P (GPa)=41.2–0.025×T (K). The negative slope of the transition, dP/dT, determined in our study using the diamond anvil cell technique was less than half that estimated by the previous study using a large press apparatus. - Graphical abstract: Experimental results and phase boundary of the ω–β transition in Zr. - Highlights: • X-ray diffraction patterns of zirconium were measured by the synchrotron experiments. • High-pressure experiments were performed by an external-heated diamond anvil cell. • Phase diagram of zirconium was determined at high pressures and high temperatures. • Phase boundary between omega and beta transition has a negative dP/dT slope.

  18. 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

  19. Metallization in the molten and solid state and phase diagrams of the GeSe2 and GeS2 under high pressure

    NASA Astrophysics Data System (ADS)

    Brazhkin, V. V.; Bychkov, E.; Kondrin, M. V.

    2014-12-01

    We found that under high pressure, the GeSe2 and GeS2 melts pass into the metallic state. In the vicinity of the melting curves, their metallization begins at 3.5 and 7 GPa, respectively. The position of the semiconductor-metal transition line on the phase diagram for GeSe2 liquid is established. The GeS2-II and GeSe2-III high-pressure crystalline modifications are semiconductors, whereas the GeSe2-III modification at pressures exceeding 3.5-4 GPa is a metal (σ ≈ 103 Ω-1 cm-1). The ( P, T) phase diagrams for these compounds are constructed in the pressure range up to 10 GPa. Metallization during the GeSe2-II-GeSe2-III transition is evidently responsible for the small jump of entropy and the corresponding almost vertical slope of the transition line.

  20. New design of fiber-optic reflectometer for determining the phase boundary of multicomponent fluid mixtures at high pressures and high temperatures

    NASA Astrophysics Data System (ADS)

    Wu, Weize; Ke, Jie; Poliakoff, Martyn

    2006-02-01

    A dynamic synthetic method based on an optic fiber sensor has been developed to measure phase boundaries of multicomponent fluid at high temperatures >300°C and pressures >30MPa. The breakthrough has been the design of the equilibrium cell containing the optic fiber, which gives highly reproducible signals for the phase transition. We demonstrate that this method can clearly distinguish between dew points and bubble points in the phase transitions of mixtures. Overall, the method is characterized by speed, simplicity, high pressures, and high temperatures.

  1. Development of a laser-induced plasma probe to measure gas phase plasma signals at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Gounder, J. D.; Kutne, P.; Meier, W.

    2012-08-01

    The ability of laser induced breakdown spectroscopy (LIBS) technique for on line simultaneous measurement of elemental concentrations has led to its application in a wide number of processes. The simplicity of the technique allows its application to harsh environments such as present in boilers, furnaces and gasifiers. This paper presents the design of a probe using a custom optic which transforms a round beam into a ring (Donut) beam, which is used for forming a plasma in an atmosphere of nitrogen at high pressure (20 bar) and temperature (200 °C). The LIBS experiments were performed using a high pressure cell to characterize and test the effectiveness of the donut beam transmitted through the LIBS probe and collect plasma signal in back scatter mode. The first tests used the second harmonic of a Nd:YAG laser, pulse width 7 ns, to form a plasma in nitrogen gas at five different pressures (1, 5, 10, 15 and 20 bar) and three different gas temperatures (25, 100 and 200 °C). The uniqueness of this probe is the custom made optic used for reshaping the round laser beam into a ring (Donut) shaped laser beam, which is fed into the probe and focused to form a plasma at the measurement point. The plasma signal is collected and collimated using the laser focusing lens and is reflected from the laser beam axis onto an achromatic lens by a high reflection mirror mounted in the center section of the donut laser beam. The effect of gas pressure and temperature on N(I) lines in the high pressure cell experiment shows that the line intensity decreases with pressure and increases with temperature. Mean plasma temperature was calculated using the ratios of N(I) line intensities ranging from 7400 K to 8900 K at 1 bar and 2400 K to 3200 K at 20 bar for the three different gas temperatures. The results show that as a proof of principle the donut beam optics in combination with the LIBS probe can be used for performing extensive LIBS measurements in well controlled laboratory

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  3. Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures

    NASA Astrophysics Data System (ADS)

    Kanno, H.; Kajiwara, K.; Miyata, K.

    2010-05-01

    Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for TH (homogeneous ice nucleation temperature) and Tm (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the TH curve for a DMSO solution of R =20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at Pc2=˜200 MPa and at Tc2<-100 °C (Pc2: pressure of SCP, Tc2: temperature of SCP). The presence of two TH peaks for DMSO solutions (R =15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R ≤15) at high pressures and low temperatures (<-90 °C). The pressure dependence of the two TH curves for DMSO solutions of R =10 and 12 indicates that the two phase-separated components in the DMSO solution of R =10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

  4. Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures.

    PubMed

    Kanno, H; Kajiwara, K; Miyata, K

    2010-05-21

    Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for T(H) (homogeneous ice nucleation temperature) and T(m) (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the T(H) curve for a DMSO solution of R=20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at P(c2)= approximately 200 MPa and at T(c2)<-100 degrees C (P(c2): pressure of SCP, T(c2): temperature of SCP). The presence of two T(H) peaks for DMSO solutions (R=15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (Rhigh pressures and low temperatures (<-90 degrees C). The pressure dependence of the two T(H) curves for DMSO solutions of R=10 and 12 indicates that the two phase-separated components in the DMSO solution of R=10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

  5. High-Pressure Phase Transition and Stability of CeSb, LaSb, and LuSb with NaCl-TYPE Structure

    NASA Astrophysics Data System (ADS)

    Singh, Sadhna; Singh, R. K.; Gour, Atul

    We have predicted the phase transition pressures and corresponding relative volume changes of CeSb, LaSb, and LuSb having NaCl-type structure under high pressure using three-body interaction potential approach (TBIPA) incorporated with short-range van der Walls (vdW) interaction and zero point energy effects. We have obtained phase transition pressures and relative volume changes which are in close agreement with measured values. Thus TBIPA with vdW interaction and zero point energy effects are found to be promising potential models for the prediction of transition pressure and stability of rare-earth compounds.

  6. High-pressure phases in shock-induced melt of the unique highly shocked LL6 chondrite Northwest Africa 757

    NASA Astrophysics Data System (ADS)

    Hu, Jinping; Sharp, Thomas G.

    2016-07-01

    Northwest Africa 757 is unique in the LL chondrite group because of its abundant shock-induced melt and high-pressure minerals. Olivine fragments entrained in the melt transform partially and completely into ringwoodite. Plagioclase and Ca-phosphate transform to maskelynite, lingunite, and tuite. Two distinct shock-melt crystallization assemblages were studied by FIB-TEM analysis. The first melt assemblage, which includes majoritic garnet, ringwoodite plus magnetite-magnesiowüstite, crystallized at pressures of 20-25 GPa. The other melt assemblage, which consists of clinopyroxene and wadsleyite, solidified at ~15 GPa, suggesting a second veining event under lower pressure conditions. These shock features are similar to those in S6 L chondrites and indicate that NWA 757 experienced an intense impact event, comparable to the impact event that disrupted the L chondrite parent body at 470 Ma.

  7. Predicted Suppression of the Superconducting Transition of New High-Pressure Yttrium Phases with Increasing Pressure from First-Principles Calculations

    NASA Astrophysics Data System (ADS)

    Chen, Yue; Hu, Qing-Miao; Yang, Rui

    2012-10-01

    Structure searches for new high-pressure phases of Y metal have been performed by using evolutionary algorithms in conjunction with a first-principles, pseudopotential plane-wave method based on density functional theory. The oF16-Fddd and hP3-P3121 phases are predicted to be energetically favorable at pressures over 97 GPa. These two phases are shown to be dynamically stable by computing their phonon dispersions. We thus propose that oF16-Fddd and hP3-P3121 are the most probable crystal structures Y may take in the 97-206 GPa range. The superconducting critical temperatures (Tc) of the new phases are estimated using the Allen-Dynes formula. The Tc is predicted to decrease with increasing pressure over about 100 GPa, in sharp contrast to its observed monotonic increase under lower pressure. The electronic origins of the stabilities of the proposed high-pressure phases have also been investigated.

  8. Phase formation in the (1-y)BiFeO3-yBiScO3 system under ambient and high pressure

    NASA Astrophysics Data System (ADS)

    Salak, A. N.; Khalyavin, D. D.; Pushkarev, A. V.; Radyush, Yu. V.; Olekhnovich, N. M.; Shilin, A. D.; Rubanik, V. V.

    2017-03-01

    Formation and thermal stability of perovskite phases in the BiFe1-yScyO3 system (0≤y≤0.70) were studied. When the iron-to-scandium substitution rate does not exceed about 15 at%, the single-phase perovskite ceramics with the rhombohedral R3c symmetry (as that of the parent compound, BiFeO3) can be prepared from the stoichiometric mixture of the respective oxides at ambient pressure. Thermal treatment of the oxide mixtures with a higher content of scandium results in formation of two main phases, namely a BiFeO3-like R3c phase and a cubic (I23) sillenite-type phase based on γ-Bi2O3. Single-phase perovskite ceramics of the BiFe1-yScyO3 composition were synthesized under high pressure from the thermally treated oxide mixtures. When y is between 0 and 0.25 the high-pressure prepared phase is the rhombohedral R3c with the √2ap×√2ap×2√3ap superstructure (ap 4 Å is the pseudocubic perovskite unit-cell parameter). The orthorhombic Pnma phase (√2ap×4ap×2√2ap) was obtained in the range of 0.30≤y≤0.60, while the monoclinic C2/c phase (√6ap×√2ap×√6ap) is formed when y=0.70. The normalized unit-cell volume drops at the crossover from the rhombohedral to the orthorhombic composition range. The perovskite BiFe1-yScyO3 phases prepared under high pressure are metastable regardless of their symmetry. At ambient pressure, the phases with the compositions in the ranges of 0.20≤y≤0.25, 0.30≤y<0.50 and 0.50≤y≤0.70 start to decompose above 970, 920 and 870 K, respectively.

  9. 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.

  10. The effects of Na on high pressure phases of CuIn(0.5)Ga(0.5)Se(2) from ab initio calculation.

    PubMed

    Pluengphon, P; Bovornratanaraks, T; Vannarat, S; Pinsook, U

    2012-03-07

    The effects of Na atoms on high pressure structural phase transitions of CuIn(0.5)Ga(0.5)Se(2) (CIGS) were studied by an ab initio method using density functional theory. At ambient pressure, CIGS is known to have chalcopyrite (I42d) structure. The high pressure phase transitions of CIGS were proposed to be the same as the order in the CuInSe(2) phase transitions which are I42d → Fm3m → Cmcm structures. By using the mixture atoms method, the Na concentration in CIGS was studied at 0.1, 1.0 and 6.25%. The positive mixing enthalpy of Na at In/Ga sites (Na(InGa)) is higher than that of Na at Cu sites (Na(Cu)). It confirmed previous studies that Na preferably substitutes on the Cu sites more than the (In, Ga) sites. From the energy-volume curves, we found that the effect of the Na substitutes is to reduce the hardness of CIGS under high pressure. The most significant effects occur at 6.25% Na. We also found that the electronic density of states of CIGS near the valence band maximum is increased noticeably in the chalcopyrite phase. The band gap is close in the cubic and orthorhombic phases. Also, the Na(Cu)-Se bond length in the chalcopyrite phase is significantly reduced at 6.25% Na, compared with the pure Cu-Se bond length. Consequently, the energy band gap in this phase is wider than in pure CIGS, and the gap increased at the rate of 31 meV GPa(-1) under pressure. The Na has a small effect on the transition pressure. The path of transformation from the cubic to orthorhombic phase was derived. The Cu-Se plane in the cubic phase displaced relatively parallel to the (In, Ga)-Se plane by 18% in order to transform to the Cmcm phase. The enthalpy barrier is 0.020 eV/atom, which is equivalent to a thermal energy of 248 K. We predicted that Fm3m and Cmcm can coexist in some pressure range.

  11. High Pressure and high temperature phase transition in FeTiO3: implications for the deep interior of giant planet

    NASA Astrophysics Data System (ADS)

    Hamane, D.; Zhang, M.; Yagi, T.; Yanming, M.

    2011-12-01

    The discovery of the structural phase transition of perovskite into a CaIrO3-type phase at high pressures invites the investigation of further phase transitions in order to understand the deep interior of giant planet. Recent experimental studies for FeTiO3 have detected a new dissociation to a dense compound assemblage rather than the CaIrO3-type phase at high pressures. Since the phase relation of FeTiO3 is expected to be significant for estimating the ultrahigh-pressure behavior of ABX3 compounds such as MgSiO3, we investigated the phase transition in FeTiO3 up to 80 GPa and 2600K by synchrotron X-ray diffraction using a laser-heated diamond anvil cell and analytical transmission electron microscopy observations. We conclude that FeTiO3 ilmenite transforms into the following phase(s) with increasing pressure: FeTiO3 (perovskite) at 18-30 GPa, 1/2 Fe2TiO4 (Ca2TiO4-type) + TiO2 (OI-type) at 30-45 GPa and high temperature, FeO (wüstite) + TiO2 (OI) at 30-45 GPa and low temperature, and 2/3 FeO (wüstite) + 1/3 FeTi3O7 (orthorhombic phase) above 45 GPa. We also estimates the structural model of FeTi3O7 phase by using the particle swarm optimization simulation, and Rietveld refinement based on this model structure gave an excellent fit with the experimentally obtained X-ray diffraction pattern. This new high-density FeTi3O7 structure consists of the polyhedra for monocapped prisms FeO7, bicapped prisms TiO8, and tricapped prisms TiO9 with Imm2 symmetry. The dense compound assemblage found in FeTiO3 is promising for investigating the behavior of ABX3 compounds under ultrahigh pressures, and our experimental results suggest that the AB3X7 type oxide instead of cotunnite SiO2 may produce the denser assemblage even in the silicate system at ultra high pressure. This new model has not yet been proposed as a candidate, but our suggestion will be important for predicting the mineral assemblage in the deep interiors of giant planets.

  12. Theoretical study of high-pressure phase stability of NaZr2(PO4)3 via elastic constants and equation of state

    NASA Astrophysics Data System (ADS)

    Chinnappan, Ravi; Panigrahi, B. K.

    2017-03-01

    Phase stability of NaZr_2(PO_4)_3 has been studied through density functional theory calculations of elastic constants, equation of state and enthalpies. The changes in elastic constants as a function of pressure show that the ambient rhombohedral (Rbar{3}c) NaZr_2(PO_4)_3 becomes unstable above 8 GPa and this instability is driven by a softening of C_{44} elastic constant through one of the Born stability criteria. High-pressure equation-of-state and enthalpy calculations further show that the ambient rhombohedral (Rbar{3}c) structure transforms first into another rhombohedral ( R3) phase and subsequently to LiZr_2(PO_4)_3-type orthorhombic phase at pressures above 6 and 8 GPa respectively which are in agreement with a recent x-ray diffraction study. Analysis of interatomic distances show that LiZr_2(PO_4)_3-type orthorhombic structure allows for shorter Na-O and Zr-P bonds at high pressures which appears to enable strong bonding and stability. Calculated formation enthalpy and bulk modulus of the ambient phase of NaZr_2(PO_4)_3 are found to be in reasonable agreement with the respective experimental values.

  13. 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).

  14. Structural phase transitions of ionic layered PbFX (X = Cl{sup −}or Br{sup –}) compounds under high pressure

    SciTech Connect

    Sorb, Y.A. Sornadurai, D.

    2015-05-15

    The PbFX (X = Cl{sup –}or Br{sup –}) compounds crystallize in tetragonal structure with space group P4/nmm. High pressure X-ray diffraction studies carried out on PbFCl compound reveals that it undergoes pressure induced structural transitions at ∼18 GPa and ∼38 GPa to orthorhombic and monoclinic (P2{sub 1}/m) phases respectively. Like PbFCl, a similar phase transition from tetragonal to orthorhombic phase is observed in PbFBr at intermediate pressure. These phase transitions seem to be similar to the transitions involving other matlockite structure compounds such as BaFX (X = Cl{sup –}, Br{sup –}or I{sup –}). PbFCl has a larger structural stability range compared to BaFCl and is attributed to the large anisotropic coordination of the Pb{sup 2+} and Cl{sup –}ions.

  15. The particle image velocimetry method in the study of the dynamics of phase transitions induced by high pressures in triolein and oleic acid

    NASA Astrophysics Data System (ADS)

    Tefelski, D. B.; Kulisiewicz, L.; Wierschem, A.; Delgado, A.; Rostocki, A. J.; Siegoczyński, R. M.

    2011-03-01

    Particle image velocimetry (PIV) is an optical measurement method capable of providing visualisation of velocity field of particle flow in fluids. After analysis of data acquired in the form of an image sequence, it is possible to retrieve information about flow parameters as mean values of velocity, vorticity, shear and normal strain. This paper presents the results of high pressure experiments using this method applied to triolein and oleic acid samples in their phase transition region. A high pressure optical chamber, He-Ne laser and light-sheet optics together with a digital camera and image acquisition computer allow us to study the motion of particles in high pressure conditions. The set-up was similar to that presented in Özmutlu et al. [Momentum and energy transfer during phase change of water under high hydrostatic pressure, Innov. Food Sci. Emerg. Technol. 7(3) (2006), pp. 161-168] and Kulisiewicz et al. [Visualization of pressure-shift freezing and thawing of concentrated aqueous sucrose solutions, High Press. Res. 27(2) (2007), pp. 291-297]. The analysis of phase transition dynamics in triolein and oleic acid is an extension to the work presented in Tefelski et al. [The investigation of the dynamics of the phase transformation in triolein and oleic acid under pressure, J. Phys.: Conf. Ser. 121(142004) (2008), pp. 1-6]. Oleic acid is a monounsaturated fatty acid and has a bent rod shape. Triolein is a triglyceride and has a "chair"-like shape. It is the base particle of many vegetable oils, especially olive oil. Triolein consists of three chains of oleic acid bound by a glycerol part. Information obtained by the study of phase transitions dynamics is important for food science and food technology processes which involve high pressure treatment. The PIV method shows differences in the solidification process of both substances in time, the existence of inhomogeneities (layers of different densities in the observed flow) and allows us to calculate the

  16. Large-aperture variable-volume view cell for the determination of phase-equilibria in high pressure systems and supercritical fluids

    NASA Astrophysics Data System (ADS)

    Licence, Peter; Dellar, Martin P.; Wilson, Richard G. M.; Fields, Peter A.; Litchfield, David; Woods, Helen M.; Poliakoff, Martyn; Howdle, Steven M.

    2004-10-01

    A high-pressure, variable-volume view cell incorporating a custom engineered, optically transparent sapphire piston is described. The view cell has an unbroken field of vision that enables the entire sample volume to be observed at all times. When lit from the rear of the cell, a near perfect view of any physical transition or change in state is available to the experimenter. The system has been shown to be particularly suitable for the determination of phase equilibria and cloud point measurements in supercritical fluid systems and has been rated for experiments up to 400 bar, 200 °C.

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

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

  18. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice.

    PubMed

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-11-20

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures.

  19. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice

    PubMed Central

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-01-01

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures. PMID:24253589

  20. Effects of grinding-induced grain boundary and interfaces on electrical transportation and structure phase transition in ZnSe under high pressure

    NASA Astrophysics Data System (ADS)

    Jie, Yang; Pei, Wang; Guo-Zhao, Zhang; Xiao-Xue, Zhou; Jing, Li; Cai-Long, Liu

    2016-06-01

    Interface and scale effects are the two most important factors which strongly affect the structure and the properties of nano-/micro-crystals under pressure. We conduct an experiment under high pressure in situ alternating current impedance to elucidate the effects of interface on the structure and electrical transport behavior of two ZnSe samples with different sizes obtained by physical grinding. The results show that (i) two different-sized ZnSe samples undergo the same phase transitions from zinc blend to cinnabar-type phase and then to rock salt phase; (ii) the structural transition pressure of the 859-nm ZnSe sample is higher than that of the sample of 478 nm, which indicates the strong scale effect. The pressure induced boundary resistance change is obtained by fitting the impedance spectrum, which shows that the boundary conduction dominates the electrical transport behavior of ZnSe in the whole experimental pressure range. By comparing the impedance spectra of two different-sized ZnSe samples at high pressure, we find that the resistance of the 478-nm ZnSe sample is lower than that of the 859-nm sample, which illustrates that the sample with smaller particle size has more defects which are due to physical grinding. Project supported by the National Natural Science Foundation of China (Grant Nos. 11404133 and 11374121) and the Program of Science and Technology Development Plan of Jilin Province, China (Grant No. 20140520105JH).

  1. Theoretical calculations of high-pressure phases of NiF2: An ab initio constant-pressure study

    NASA Astrophysics Data System (ADS)

    Kürkçü, Cihan; Merdan, Ziya; Öztürk, Hülya

    2016-12-01

    We have studied the structural properties of the antiferromagnetic NiF2 tetragonal structure with P42/ mnm symmetry using density functional theory (DFT) under rapid hydrostatic pressure up to 400 GPa. For the exchange correlation energy we used the local density approximation (LDA) of Ceperley and Alder (CA). Two phase transformations are successfully observed through the simulations. The structures of XF2-type compounds crystallize in rutile-type structure. NiF2 undergoes phase transformations from the tetragonal rutile-type structure with space group P42/ mnm to orthorhombic CaCl2-type structure with space group Pnnm and from this orthorhombic phase to monoclinic structure with space group C2/ m at 152 GPa and 360 GPa, respectively. These phase changes are also studied by total energy and enthalpy calculations. According to these calculations, we perdict these phase transformations at about 1.85 and 30 GPa.

  2. Order-disorder phase transition and dissociation of hydrogen sulfide under high pressure: Ab initio molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Wang, Liancheng; Tian, Fubo; Feng, Wanxiang; Chen, Changbo; He, Zhi; Ma, Yanming; Cui, Tian; Liu, Bingbing; Zou, Guangtian

    2010-04-01

    The structural and dynamical properties of phase IV and V of hydrogen sulfide were investigated by means of extensive ab initio molecular dynamics simulations. Starting from an experimental proposal for the structure of phase IV, an Ibca symmetry with a stable hydrogen bonding network is found at 15 GPa and 100 K. Molecular dynamics simulations at increasing temperature and at the pressure of 15 GPa suggest that phase IV will transform to a proton disordered structure at 15 GPa and 350 K. The newfound structure has a hexagonal lattice of P63/mmc symmetry, which is believed to be the remaining crystalline structure of phase V. The high mobility of protons in phase V is believed to be the key point to the dissociation and decomposition of hydrogen sulfide.

  3. High-pressure differential thermal analysis (DTA) of the phase behaviors of didodecyl-dimethylammoniumbromide (DDAB) and ditetradecyl-dimethylammoniumbromide (DTAB)

    NASA Astrophysics Data System (ADS)

    Hamann, F.; Reuter, John; Wuerflinger, A.; Godlewska, Malgorzata; Dynarowicz, Patrycja

    1998-01-01

    Dialkyldimethylammonium halides are known for their applications as commercial detergents and for their membrane-mimetic properties. They display both thermotropic and lyotropic liquid crystalline properties. In this work we establish the T(p)-phase diagrams of two representatives, namely didodecyl- and ditetradecyl-ammonium bromides. The transitions between crystal, smectic Ii and smectic I phases were recorded using a high-pressure differential thermal analysis device. For both compounds the stable range of smectic II phase is pressure-limited, resulting in a triple point crystal/smectic II/smectic I. Enthalpy changes at ambient pressure have been determined with the aid of a commercial heat flux differential scanning calorimeter. Volume changes were calculated from the slopes of the transitions lines, employing the Clausius Clapeyron equation.

  4. Initial phases of explosion earthquakes accompanying Vulcanian eruptions at Lokon-Empung volcano, Indonesia

    NASA Astrophysics Data System (ADS)

    Yamada, Taishi; Aoyama, Hiroshi; Nishimura, Takeshi; Yakiwara, Hiroshi; Nakamichi, Haruhisa; Oikawa, Jun; Iguchi, Masato; Hendrasto, Muhamad; Suparman, Yasa

    2016-11-01

    We examine the initial phases of explosion earthquakes accompanying Vulcanian eruptions at Lokon-Empung volcano in Indonesia to reveal the triggering process of explosive eruptions. In 2012-2013, 56 Vulcanian eruptions at Lokon-Empung were observed by our temporary observation network being comprised of four broadband seismometers and two infrasound microphones at 1.6-6.8 km from the active vent. The seismic records of each explosion earthquake share almost the same waveform characteristics of initial phases, consisting of a small compressional onset (P phase) and a subsequent large dilatational phase (D phase). Particle orbits of both phases show straight motion from beneath the active vent, which suggests that these phases are composed of a longitudinal body wave. For each explosion, the origin times of the P phase precedes 0.8-2.5 s before the occurrence of an explosion at the vent that are detected by infrasound data. Since the signal-to-noise ratio of the P phase is insufficient for a quantitative analysis, we analyze the D phase dominating the initial phases. Our analysis for the signals of 0.2-1.0 Hz shows the D phase are well explained by a cylindrical contraction source with a half-cosine shaped time function located at 1.0-1.3 km depth beneath the active vent. We also recognize that some explosions are followed by a prominent tremor that coincides with continuous ash emission (ET). The seismic amplitudes and intensity of the D phase of events in ET are larger than the explosions without accompanying tremor (EX). The frequency distribution of the time interval from the previous eruption is also different in the events in ET and EX. The implosion source in the initial phases of explosion earthquakes at several km beneath the active vent has been reported at Sakurajima volcano. Since our result shows considerable agreement with the previous works at Sakurajima, both Lokon-Empung and Sakurajima may share similar initial processes of Vulcanian eruptions.

  5. Steam-water two-phase flow in large diameter vertical piping at high pressures and temperatures

    SciTech Connect

    Hasanein, H.A.; Kawaji, Masahiro; Chan, A.M.C.; Yoshioka, Yuzuru

    1996-08-01

    No information on steam/water two-phase flow behavior in large diameter pipes (10 inch or larger) at elevated pressures is available in the open literature. However, there are many applications, in the nuclear, chemical and petroleum industries among others where two-phase flows in large diameter pipes at elevated pressures and temperatures are encountered routinely or under accident scenarios. Experimental data on steam-water two-phase flow in a large diameter (20 inch, 50.08 cm I.D.) vertical pipe at elevated pressures and temperatures (2.8 MPa/230 C--6.4 MPa/280 C) have been obtained. Void fraction, two-phase mass flux, phase and velocity distributions as well as pressure drop along the test pipe have been measured using the Ontario Hydro Technologies (OHT) Pump Test Loop. The void fraction distributions were found to be axially symmetric and nearly flat over a wide range of two-phase flow conditions. The two-phase flow regime could be inferred from the dynamic void fluctuations data. For the 280 C tests, the flow was found to be relatively stable with bubbly flow at low average void fractions and churn turbulent or wispy-annular flow at higher void fractions. At 230 C, the flow became rather oscillatory and slugging was suspected at relatively low voids. It has also been found that the average void fractions in the test section can be determined reasonably accurately using the axial pressure drop data.

  6. Publisher's Note: High-temperature superconductivity stabilized by electron-hole interband coupling in collapsed tetragonal phase of KFe2As2 under high pressure [Phys. Rev. B 91 , 060508(R) (2015)

    DOE PAGES

    Nakajima, Yasuyuki; Wang, Renxiong; Metz, Tristin; ...

    2015-03-09

    Here, we report a high-pressure study of simultaneous low-temperature electrical resistivity and Hall effect measurements on high quality single-crystalline KFe2As2 using designer diamond anvil cell techniques with applied pressures up to 33 GPa. In the low pressure regime, we show that the superconducting transition temperature Tc finds a maximum onset value of 7 K near 2 GPa, in contrast to previous reports that find a minimum Tc and reversal of pressure dependence at this pressure. Upon applying higher pressures, this Tc is diminished until a sudden drastic enhancement occurs coincident with a first-order structural phase transition into a collapsed tetragonalmore » phase. The appearance of a distinct superconducting phase above 13 GPa is also accompanied by a sudden reversal of dominant charge carrier sign, from hole- to electron-like, which agrees with our band calculations predicting the emergence of an electron pocket and diminishment of hole pockets upon Fermi surface reconstruction. Our results suggest the high-temperature superconducting phase in KFe2As2 is substantially enhanced by the presence of nested electron and hole pockets, providing the key ingredient of high-Tc superconductivity in iron pnictide superconductors.« less

  7. Phase transitions and equation of state of CsI under high pressure and the development of a focusing system for x-rays

    SciTech Connect

    Wu, Yan.

    1990-11-01

    The phase transitions and equation of state of ionic solid cesium iodide were studied under high pressure and room temperature in a diamond anvil cell. The studies were carried out using both energy dispersive and angular dispersive diffraction methods on synchrotron radiation sources over the pressure range from atmospheric pressure to over 300 gigapascals (3 million atmospheres). CsI undergoes a distinct phase transition at about 40 GPa, a pressure that is much lower than the reported insulator-metal transition at 110 GPa, from the atmospheric pressure B2(CsCl) structure to an orthorhombic structure. At higher pressures, a continuous distortion in the structure was observed with a final structure similar to a hcp lattice under ultra high pressure. No volume discontinuity was observed at the insulator-metal transition. The newly found transition sequence is different from the result of previous static compression studies. The current structure has a smaller unit cell volume than the previous assignment. This has resolved a long existing controversy among the previous static compression studies, the dynamic compression studies, and the theoretical studies. The current results also explain the apparent discrepancy between the present study and the previous static studies. We also present the development of a focusing system for high energy x-rays (> 12 keV) that is particularly suited for high pressure diffraction studies. This system uses a pair of multilayer coated spherical mirrors in a Kirkpatrick-Baez geometry. A focused beam size less than 10 micron in diameter can be readily achieved with sufficient intensity to perform diffraction studies. 93 refs., 46 figs., 15 tabs.

  8. The effect of morphology and confinement on the high-pressure phase transition in ZnO nanostructure

    SciTech Connect

    Kotmool, Komsilp; Bovornratanaraks, Thiti; Chakraborty, Sudip; Ahuja, Rajeev

    2015-03-21

    The transition pressure (P{sub t}) of the B4-to-B1 phase transformation of zinc oxide nanoparticle (n-ZnO) structures was investigated in terms of their size and morphology. Nanorods, nanopencils, nanopyramids, nanowires, and nanotubes of the B4 phase in various sizes were directly built up by accounting for the atomic basis of the core and surface regions. The previously proposed transformation path was performed for constructing shapes and sizes compatible with B1 phases. Using systematic density functional theory, the surfaces were cleaved from the optimized crystal structures at different pressures in both the B4 and B1 phases. A method for calculating the surface energy at different pressures is proposed using an asymmetric slab model. Using the proposed model, the transition pressure of n-ZnO structures was found to significantly depend on their morphology and size, which is in good agreement with the available experimental reports.

  9. High-temperature high-pressure phases of lithium from electron force field (eFF) quantum electron dynamics simulations

    PubMed Central

    Kim, Hyungjun; Su, Julius T.; Goddard, William A.

    2011-01-01

    We recently developed the electron force field (eFF) method for practical nonadiabatic electron dynamics simulations of materials under extreme conditions and showed that it gave an excellent description of the shock thermodynamics of hydrogen from molecules to atoms to plasma, as well as the electron dynamics of the Auger decay in diamondoids following core electron ionization. Here we apply eFF to the shock thermodynamics of lithium metal, where we find two distinct consecutive phase changes that manifest themselves as a kink in the shock Hugoniot, previously observed experimentally, but not explained. Analyzing the atomic distribution functions, we establish that the first phase transition corresponds to (i) an fcc-to-cI16 phase transition that was observed previously in diamond anvil cell experiments at low temperature and (ii) a second phase transition that corresponds to the formation of a new amorphous phase (amor) of lithium that is distinct from normal molten lithium. The amorphous phase has enhanced valence electron-nucleus interactions due to localization of electrons into interstitial locations, along with a random connectivity distribution function. This indicates that eFF can characterize and compute the relative stability of states of matter under extreme conditions (e.g., warm dense matter). PMID:21873210

  10. Polymorphism of iron at high pressure: A 3D phase-field model for displacive transitions with finite elastoplastic deformations

    NASA Astrophysics Data System (ADS)

    Vattré, A.; Denoual, C.

    2016-07-01

    A thermodynamically consistent framework for combining nonlinear elastoplasticity and multivariant phase-field theory is formulated at large strains. In accordance with the Clausius-Duhem inequality, the Helmholtz free energy and time-dependent constitutive relations give rise to displacive driving forces for pressure-induced martensitic phase transitions in materials. Inelastic forces are obtained by using a representation of the energy landscape that involves the concept of reaction pathways with respect to the point group symmetry operations of crystal lattices. On the other hand, additional elastic forces are derived for the most general case of large strains and rotations, as well as nonlinear, anisotropic, and different elastic pressure-dependent properties of phases. The phase-field formalism coupled with finite elastoplastic deformations is implemented into a three-dimensional Lagrangian finite element approach and is applied to analyze the iron body-centered cubic (α-Fe) into hexagonal close-packed (ɛ-Fe) phase transitions under high hydrostatic compression. The simulations exhibit the major role played by the plastic deformation in the morphological and microstructure evolution processes. Due to the strong long-range elastic interactions between variants without plasticity, a forward α → ɛ transition is energetically unfavorable and remains incomplete. However, plastic dissipation releases considerably the stored strain energy, leading to the α ↔ ɛ ↔α‧ (forward and reverse) polymorphic phase transformations with an unexpected selection of variants.

  11. ``Cs-tetra-ferri-annite:`` High-pressure and high-temperature behavior of a potential nuclear waste disposal phase

    SciTech Connect

    Comodi, P.; Zanazzi, P.F.; Weiss, Z.; Rieder, M.; Drabek, M.

    1999-03-01

    Structure deformations induced by pressure and temperature in synthetic Cs-tetra-ferri-annite 1M [Cs{sub 1.78}(Fe{sup 2+}{sub 5.93}Fe{sup 3+}{sub 0.07})(Si{sub 6.15}Fe{sup 3+}{sub 1.80}Al{sub 0.05})O{sub 20}(OH){sub 4}], space group C2/m, were analyzed to investigate the capability of the mica structure to store the radiogenic isotopes {sup 135}Cs and {sup 137}Cs. Cs-tetra-ferri-annite is not a mineral name, but for the sake of brevity is used here to designate a synthetic analog of the mineral tetra-ferri-annite. The bulk modulus and its pressure derivative determined by fitting the unit-cell volumes between 0 a/nd 47 kbar to a third-order Birch-Murnaghan equation of state are K{sub 0} = 257(8) kbar and K{prime}{sub 0} = 21(1), respectively. Between 23 C and 582 C, the a and b lattice parameters remain essentially unchanged, but the thermal expansion coefficient of the c axis is {alpha}{sub c} = 3.12(9) {times} 10{sup {minus}5} {degree}C{sup {minus}1}. High pressure (P) and high temperature (T) produce limited internal strain in the structure. The tetrahedral rotation angle, {alpha}, is very small and does not change significantly throughout the P and T range investigated. Above 450 C in air, Cs-tetra-ferri-annite underwent an oxidation of octahedral iron in the M2cis site, balanced by the loss of H and shown by a decrease of the unit-cell volume. Independent isobaric data on thermal expansion and isothermal compressibility data define the geometric equation of state for Cs-tetra-ferri-annite. On the whole, the data confirm that the structure of Cs-tetra-ferri-annite may be a suitable candidate for the storage of large ions, such as Cs in the interlayer and should be considered as a potential Synroc component.

  12. The effects of growth temperature and growth phase on the inactivation of Listeria monocytogenes in whole milk subject to high pressure processing.

    PubMed

    Hayman, Melinda M; Anantheswaran, Ramaswamy C; Knabel, Stephen J

    2007-04-10

    The aim of this study was to explore the effect of a wide range of growth temperatures, growth phases and plating media on the inactivation of Listeria monocytogenes by high pressure processing (HPP). In part one, L. monocytogenes was grown to mid-stationary phase at 4, 15, 25, 35 or 43 degrees C, inoculated into whole UHT milk at approximately 10(7) CFU/ml and high pressure processed at 400 MPa at room temperature (20-25 degrees C). Afterward, the HPP milk was plated on Tryptic Soy Yeast Extract Agar (TSYEA) and Modified Oxford Agar (MOX) to determine the degree of injury. For part two, cells were grown to mid-exponential, late-exponential or mid-stationary phase at 15 or 43 degrees C and processed in the same way. Time to reach a 5-log reduction was determined and data were analysed by ANOVA. The results from part one showed that both growth temperature and plating medium had a significant effect (P < 0.001) on the inactivation of stationary phase L. monocytogenes by HPP. Tukey's pairwise comparisons revealed that the effects of all temperatures, except 35 and 43 degrees C, were significantly different (P < 0.05). Cells grown at 15 degrees C were most sensitive to HPP, followed by cells grown at 4, 25 or 35 degrees C, with cells grown at 43 degrees C appearing to be the most resistant. Inactivation of cells grown at 4, 15 or 25 degrees C followed first order kinetics, whereas cells grown at 35 or 43 degrees C displayed non-linear inactivation kinetics due to tailing. In part two, both growth phase and plating medium had significant effects on the inactivation (P < or = 0.001) of L. monocytogenes by HPP. Cells grown at 15 degrees C to mid-stationary phase were the most pressure-resistant when tested on both media, and were significantly more resistant (P < 0.05) than cells grown at the same temperature to the other two phases of growth. There was no significant difference between mid- and late-exponential phase cells grown at 15 degrees C. When cells were grown at

  13. A new high-pressure phase of Fe2SiO4 and the relationship between spin and structural transitions

    NASA Astrophysics Data System (ADS)

    Yamanaka, T.; Kyono, A.; Nakamoto, Y.; Kharlamova, S. A.; Struzhkin, V. V.; Gramsch, S.; Mao, H.; Hemley, R. J.

    2013-12-01

    Structure transformation of Fe2SiO4 Angle-dispersive powder x-ray diffraction was carried out at beam line 16-BMD APS. Structure of a new high-pressure phase of I-Fe2SiO4 spinel was determined by Rietveld profile fitting of x-ray diffraction data up to 64GPa at ambient temperature. A structural transition from the cubic spinel to the new structure was observed at 34GPa. Diffraction patterns taken at 44.6GPa and 54.6GPa indicate a two-phase mixture of spinel and new high-pressure phase. Reversible transition from I-Fe2SiO4 to spinel was confirmed. Laser heating experiment at 1500K proved the decomposition of Fe2SiO4 spinel to two oxides of FeO and SiO2. Spin transition X-ray emission measurements of Fe2SiO4 were carried out up to 65GPa at ambient temperature at beam line 16-IDD APS. The spin transition exerts an influence to Fe2SiO4 spinel structure and triggers two distinct curves of the lattice constant in the spinel phase. Although the compression curve of the spinel is discontinuous at approximately 20 GPa, Fe Kβ emission measurements show that the transition from a high spin (HS) to an intermediate spin (IS) state begins at 17GPa in the spinel phase. The IS electronic state is gradually enhanced with pressure, which results in an isostructural phase transition. HS-to-LS transition of iron bearing spinels starts from 15.6GPa in Fe3O4 and 19.6GPa in Fe2TiO4. The transition is more capable due to Fe2+ in the octahedral site. The extremely shortened octahedral bonds result in a distortion of 6-fold cation site. New structure of Fe2SiO4 Monte Carlo method was applied to find candidates for the high-pressure phase using the diffraction intensities with fixed lattice constants determined by DICVOL. Rietveld profile fitting was then performed using the initial model. The new structure is a body centered orthorhombic phase (I-Fe2SiO4) with space group Imma and Z=4, with two crystallographically distinct FeO6 octahedra. Silicon exists in six-fold coordination in I-Fe2Si

  14. Molecular interactions in crystalline dibromomethane and diiodomethane, and the stabilities of their high-pressure and low-temperature phases.

    PubMed

    Podsiadło, Marcin; Dziubek, Kamil; Szafrański, Marek; Katrusiak, Andrzej

    2006-12-01

    Dibromomethane, CH2Br2, and diiodomethane, CH2I2, have been in situ pressure-crystallized in a diamond-anvil cell and their structures determined by single-crystal X-ray diffraction at 0.61 and 0.16 GPa, respectively. The pressure-frozen CH2Br2 crystal is isostructural with its C2/c phase obtained by cooling. CH2I2 is known to form several phases at low temperature, one of which is isostructural with CH2Br2. However, pressure freezing leads to the polar Fmm2 phase. The formation of the polar CH2I2 structure at 0.16 GPa has been rationalized by the electrostatic and anisotropic van der Waals interactions of the I atoms. No ferroelectric behaviour of the Fmm2 polar phase II of CH2I2 has been determined. The diffraction, calorimetric and dielectric constant studies reveal considerable temperature hysteresis of transformations between the CH2I2 phases, as well as metastable regions strongly dependent on the sample shape and history.

  15. Identification of high-pressure phases III and IV in hydrogen: Simulating Raman spectra using molecular dynamics

    NASA Astrophysics Data System (ADS)

    Magdău, Ioan B.; Ackland, Graeme J.

    2013-05-01

    We present a technique for extracting Raman intensities from ab initio molecular dynamics (MD) simulations at high temperature. The method is applied to the highly anharmonic case of dense hydrogen up to 500 K for pressures ranging from 180 to 300 GPa. On heating or pressurizing we find first-order phase transitions under the experimental conditions of the phase III-IV boundary. At even higher pressures, close to 350 GPa, we find a second phase transformation to the previously proposed Cmca-4. Our method enables, for the first time, a direct comparison of Raman vibrons between theory and experiment at finite temperature. This turns out to provide excellent discrimination between subtly different structures found in MD. We find candidate structures whose Raman spectra are in good agreement with experiment. The new phase obtained in high-temperature simulations adopts a dynamic, simple hexagonal structure with three layer types: freely rotating hydrogen molecules, static hexagonal trimers, and rotating hexagonal trimers. We show that previously calculated structures for phase IV are inconsistent with experiment, and their appearance in simulation is due to finite-size effects.

  16. X-ray diffraction and Raman study of DL-alanine at high pressure: revision of phase transitions.

    PubMed

    Tumanov, Nikolay A; Boldyreva, Elena V

    2012-08-01

    The effect of pressure on DL-alanine has been studied by X-ray powder diffraction (up to 8.3 GPa), single-crystal X-ray diffraction and Raman spectroscopy (up to ~6 GPa). No structural phase transitions have been observed. At ~1.5-2 GPa, cell parameters b and c become accidentally equal to each other, but the space-group symmetry does not change. There is no phase transition between 1.7 and 2.3 GPa, contrary to what has been reported earlier [Belo et al. (2010). Vibr. Spectrosc. 54, 107-111]. The presence of the second phase transition, which was claimed to appear within the pressure range from 6.0 to 7.3 GPa (Belo et al., 2010), is also argued. The changes in the Raman spectra have been shown to be continuous in all the pressure ranges studied.

  17. High Pressure-Temperature Phase Diagram of 1,1-Diamino-2,2-dinitroethylene (FOX-7).

    PubMed

    Bishop, Matthew M; Velisavljevic, Nenad; Chellappa, Raja; Vohra, Yogesh K

    2015-09-17

    The pressure-temperature (P-T) phase diagram of 1,1-diamino-2,2-dinitroethylene (FOX-7) was determined by in situ synchrotron infrared radiation spectroscopy with the resistively heated diamond anvil cell (DAC) technique. The stability of high-P-T FOX-7 polymorphs is established from ambient pressure up to 10 GPa and temperatures until decomposition. The phase diagram indicates two near isobaric phase boundaries at ∼2 GPa (α → I) and ∼5 GPa (I → II) that persists from 25 °C until the onset of decomposition at ∼300 °C. In addition, the ambient pressure, high-temperature α → β phase transition (∼111 °C) lies along a steep boundary (∼100 °C/GPa) with a α-β-δ triple point at ∼1 GPa and 300 °C. A 0.9 GPa isobaric temperature ramping measurement indicates a limited stability range for the γ-phase between 0.5 and 0.9 GPa and 180 and 260 °C, terminating in a β-γ-δ triple point. With increasing pressure, the δ-phase exhibited a small negative dT/dP slope (up to ∼0.2 GPa) before turning over to a positive 70 °C/GPa slope, at higher pressures. The decomposition boundary (∼55 °C/GPa) was identified through the emergence of spectroscopic signatures of the characteristic decomposition products as well as trapped inclusions within the solid KBr pressure media.

  18. Nanomaterials under high-pressure.

    PubMed

    San-Miguel, Alfonso

    2006-10-01

    The use of high-pressure for the study and elaboration of homogeneous nanostructures is critically reviewed. Size effects, the interaction between nanostructures and guest species or the interaction of the nanosystem with the pressure transmitting medium are emphasized. Phase diagrams and the possibilities opened by the combination of pressure and temperature for the elaboration of new nanomaterials is underlined through the examination of three different systems: nanocrystals, nano-cage materials which include fullerites and group-14 clathrates, and single wall nanotubes. This tutorial review is addressed to scientist seeking an introduction or a panoramic view of the study of nanomaterials under high-pressure.

  19. High pressure synthesis gas fermentation

    SciTech Connect

    Not Available

    1991-01-01

    Construction of the high pressure gas phase fermentation system is nearing completion. All non-explosion proof components will be housed separately in a gas-monitored plexiglas cabinet. A gas-monitoring system has been designed to ensure the safety of the operations in case of small or large accidental gas releases. Preliminary experiments investigating the effects of high pressure on Clostridium 1jungdahlii have shown that growth and CO uptake are not negatively affected and CO uptake by an increased total pressure of 100 psig at a syngas partial pressure of 10 psig.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  1. Lattice-dynamical studies of Ti in the hcp- and ω -phase by Raman scattering at high-pressure

    NASA Astrophysics Data System (ADS)

    Olijnyk, H.; Nakano, S.; Jephcoat, A. P.; Takemura, K.

    2006-09-01

    Ti metal was investigated by Raman spectroscopy for pressures up to 46GPa . The E2g mode of the hcp phase shows no softening on approaching the transition to the ω phase, which contrasts the behavior of its heavier homologue Zr, however, it exhibits an anomalously low mode Grüneisen parameter. It is shown that this unusual behavior is also reflected in the pressure response of elastic modulus C44 . At ambient conditions the contributions to the temperature shift of this mode due to thermal expansion are one order of magnitude smaller than the explicit contribution. The E2g mode of the ω phase exhibits a positive frequency shift with an ambient pressure mode Grüneisen parameter γ≈2 , slightly higher than that of Zr, becoming smaller under compression. Predictions of a recent first principles calculation [Rudin , Phys. Rev. B 69, 094117 (2004)], limited to normal pressure and in quite good agreement with experimental data for hcp Ti, underestimate the frequency of the E2g mode of the ω phase by 17%.

  2. Can high pressure I-II transitions in semiconductors be affected by plastic flow and nanocrystal precipitation in phase I?

    NASA Astrophysics Data System (ADS)

    Weinstein, B. A.; Lindberg, G. P.

    Pressure-Raman spectroscopy in ZnSe and ZnTe single crystals reveals that Se and Te nano-crystals (NCs) precipitate in these II-VI hosts for pressures far below their I-II phase transitions. The inclusions are evident from the appearance and negative pressure-shift of the A1 Raman peaks of Se and Te (trigonal phase). The Se and Te NCs nucleate at dislocations and grain boundaries that arise from pressure-induced plastic flow. This produces chemical and structural inhomogeneities in the zincblende phase of the host. At substantially higher pressures, the I-II transition proceeds in the presence of these inhomogenities. This can affect the transition's onset pressure Pt and width ΔPt, and the occurrence of metastable phases along the transition path. Precipitation models in metals show that nucleation of inclusions depends on the Peierls stress τp and a parameter α related to the net free energy gained on nucleation. For favorable values of τp and α, NC precipitation at pressures below the I-II transition could occur in other compounds. We propose criteria to judge whether this is likely based on the observed ranges of τp in the hosts, and estimates of α derived from the cohesive energy densities of the NC materials. One finds trends that can serve as a useful guide, both to test the proposed criteria, and to decide when closer scrutiny of phase transition experiments is warranted, e.g., in powders where high dislocation densities are initially created

  3. Evidence for a High-Pressure Phase Transition of ε-2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20) Using Vibrational Spectroscopy

    SciTech Connect

    Ciezak, J.; Jenkins, T; Liu, Z

    2007-01-01

    The high-pressure response of {epsilon}-2,4,6,8,10,12-hexanitrohexaazaisowurtizane (CL-20) has been examined to 27 GPa in diamond anvil cells using vibrational spectroscopy. The results reveal evidence of an {epsilon}{yields}{Upsilon} pressure-induced phase transition between 4.1 and 6.4 GPa and suggest the existence of a {Upsilon}{yields}{zeta} transition near 18.7 GPa. Several Raman and infrared frequencies were found to decrease in intensity as the phase boundaries are approached. An anomalous intensity increase was noted in the C-N-C infrared mode that is believed to result from an increase in the Raman cross-section due to a stronger interlayer coupling under pressure.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  5. Equation of state modeling of the phase equilibria of ionic liquid mixtures at low and high pressure.

    PubMed

    Karakatsani, Eirini K; Economou, Ioannis G; Kroon, Maaike C; Bermejo, Maria D; Peters, Cor J; Witkamp, Geert-Jan

    2008-10-28

    Accurate design of processes based on ionic liquids (ILs) requires knowledge of the phase behavior of the systems involved. In this work, the truncated perturbed chain polar statistical associating fluid theory (tPC-PSAFT) is used to correlate the phase behavior of binary and ternary IL mixtures. Both non-polar and polar solvents are examined, while methyl imidazolium ILs are used in all cases. tPC-PSAFT accounts explicitly for weak dispersion interactions, highly directive polar interactions between permanent dipolar and quadrupolar molecules and association between hydrogen bonding molecules. For mixtures of non-polar solvents, tPC-PSAFT predicts accurately the binary mixture data. For the case of polar solvents, a binary interaction parameter is fitted to the experimental data and the agreement between experiment and correlation is very good in all cases.

  6. Reverse-phase high pressure liquid chromatographic analysis of harpagoside, scorodioside and verbascoside from Scrophularia scorodonia: quantitative determination of harpagoside.

    PubMed

    Díaz, A; Fernández, L; Ollivier, E; Martín, T; Villaescusa, L; Balansard, G

    1998-02-01

    A reversed-phase high performance liquid chromatographic method has been developed for the determination of the main compounds (harpagoside, scorodioside, and verbascoside) from different samples of Scrophularia scorodonia. The chromatographic method has been validated and applied for quantitative determination of harpagoside. The results show the highest levels of harpagoside in the leaf extract. The purity and identity of peaks were controlled by diode-array detection and comparison with standards.

  7. Kinetics of the wurtzite-to-rock-salt phase transformation in ZnO at high pressure.

    PubMed

    Solozhenko, Vladimir L; Kurakevych, Oleksandr O; Sokolov, Petr S; Baranov, Andrey N

    2011-05-05

    Kinetics of the wurtzite-to-rock-salt transformation in ZnO has been studied in the 5-7 GPa pressure range at temperatures below the activation of diffusion processes. The detailed analysis of non-isothermal experimental data using the general evolution equation describing the kinetics of direct phase transformations in solids allowed us to study the kinetic particularities of both nucleation and growth of the rock-salt phase in parent wurtzite ZnO. The main rate-limiting processes are thermally activated nucleation (E(N) = 383 kJ mol(-1) at 6.9 GPa) and thermally nonactivated (most probably quasi-martensitic) growth (k(G) = 0.833 min(-1) at 6.9 GPa). The high impact of thermal deactivation of nucleation places has been evidenced in the case of slow heating, which indirectly indicates that the rs-ZnO nucleation places are mainly produced by pressure-induced stresses in the parent phase.

  8. Low temperature and high pressure thermoelastic and crystallographic properties of SrZrO3 perovskite in the Pbnm phase

    NASA Astrophysics Data System (ADS)

    Knight, Kevin S.; Bull, Craig L.

    2016-12-01

    The thermoelastic and structural properties of SrZrO3 perovskite in the Pnma (Pbnm) phase have been studied using neutron powder diffraction at 82 temperatures between 11 K and 406 K at ambient pressure, and at sixteen pressures between 0.07 and 6.7 GPa at ambient temperature. The bulk modulus, derived by fitting the equation of state to a second order Birch-Murnaghan equation-of-state, 157(5) GPa, is in excellent agreement with that deduced in a recent resonant ultrasound investigation. Experimental axial compressional moduli are in agreement with those calculated from the elastic stiffness coefficients derived by ab-initio calculation, although the experimental bulk modulus is significantly softer than that calculated. Following low temperature saturation for temperatures less than 40 K, the unit cell monotonically increases with a predicted high temperature limit in the volume expansivity of ∼2.65 × 10-5 K-1. Axial linear thermal expansion coefficients are found to be in the order αb < αc < αa for all temperatures greater than 20 K with the b axis indicating a weak, low temperature negative expansion coefficient at low temperatures. The thermoelastic properties of SrZrO3 can be approximated by a two-term Debye model for the phonon density of states with Debye temperatures of 238(4) K and 713(6) K derived in a self-consistent manner by simultaneously fitting the isochoric heat capacity and the unit cell volume. Atomic displacement parameters have been fitted to a modified Debye model in which the zero-point term is an additional refinable variable and shows the cations and anions have well separated Debye temperatures, mirroring the need for two Debye-like distributions in the vibrational density of states. The temperature dependence of the crystal structure is presented in terms of the amplitudes of the seven symmetry-adapted basis vectors of the aristotype phase that are consistent with space group Pbnm, thus permitting a direct measure of the order

  9. Paramagnetic defects as probes for the study of ferroelastic phase transition in lithium niobate and lithium tantalate under high pressure

    NASA Astrophysics Data System (ADS)

    Malovichko, G.; Grachev, V.; Andreev, V.; Nachal'Naya, T.

    It was found by optical polarization microscopy and the EPR study that lithium niobate and tantalate crystals undergo irreversible lattice changes under anisotropic hydrostatic compression. Regions having different cell orientations were registered. The observed changes were explained in terms of "strain switching" of ferroelastic domains. Possible sequence of phase transitions in these crystals (Pm3m<->R (3) over bar3 c<->R 3 c) and the symmetry of the condensed soft modes ( R-25 and Gamma(15) , correspondingly) were obtained by the analysis of the Gibbs free energy under external pressure.

  10. High-pressure systems for gas-phase free continuous incubation of enriched marine microbial communities performing anaerobic oxidation of methane.

    PubMed

    Deusner, Christian; Meyer, Volker; Ferdelman, Timothy G

    2010-02-15

    Novel high-pressure biotechnical systems that were developed and applied for the study of anaerobic oxidation of methane (AOM) are described. The systems, referred to as high-pressure continuous incubation system (HP-CI system) and high-pressure manifold-incubation system (HP-MI system), allow for batch, fed-batch, and continuous gas-phase free incubation at high concentrations of dissolved methane and were designed to meet specific demands for studying environmental regulation and kinetics as well as for enriching microbial biomass in long-term incubation. Anoxic medium is saturated with methane in the first technical stage, and the saturated medium is supplied for biomass incubation in the second stage. Methane can be provided in continuous operation up to 20 MPa and the incubation systems can be operated during constant supply of gas-enriched medium at a hydrostatic pressure up to 45 MPa. To validate the suitability of the high-pressure systems, we present data from continuous and fed-batch incubation of highly active samples prepared from microbial mats from the Black Sea collected at a water depth of 213 m. In continuous operation in the HP-CI system initial methane-dependent sulfide production was enhanced 10- to 15-fold after increasing the methane partial pressure from near ambient pressure of 0.2 to 10.0 MPa at a hydrostatic pressure of 16.0 MPa in the incubation stage. With a hydraulic retention time of 14 h a stable effluent sulfide concentration was reached within less than 3 days and a continuing increase of the volumetric AOM rate from 1.2 to 1.7 mmol L(-1) day(-1) was observed over 14 days. In fed-batch incubation the AOM rate increased from 1.5 to 2.7 and 3.6 mmol L(-1) day(-1) when the concentration of aqueous methane was stepwise increased from 5 to 15 mmol L(-1) and 45 mmol L(-1). A methane partial pressure of 6 MPa and a hydrostatic pressure of 12 MPa in manifold fed-batch incubation in the HP-MI system yielded a sixfold increase in the

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

    NASA Astrophysics Data System (ADS)

    Kim, Moojin; Jin, GuangHai

    2009-04-01

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

  12. Quantum Monte Carlo computations of phase stability, equations of state, and elasticity of high-pressure silica.

    PubMed

    Driver, K P; Cohen, R E; Wu, Zhigang; Militzer, B; Ríos, P López; Towler, M D; Needs, R J; Wilkins, J W

    2010-05-25

    Silica (SiO(2)) is an abundant component of the Earth whose crystalline polymorphs play key roles in its structure and dynamics. First principle density functional theory (DFT) methods have often been used to accurately predict properties of silicates, but fundamental failures occur. Such failures occur even in silica, the simplest silicate, and understanding pure silica is a prerequisite to understanding the rocky part of the Earth. Here, we study silica with quantum Monte Carlo (QMC), which until now was not computationally possible for such complex materials, and find that QMC overcomes the failures of DFT. QMC is a benchmark method that does not rely on density functionals but rather explicitly treats the electrons and their interactions via a stochastic solution of Schrödinger's equation. Using ground-state QMC plus phonons within the quasiharmonic approximation of density functional perturbation theory, we obtain the thermal pressure and equations of state of silica phases up to Earth's core-mantle boundary. Our results provide the best constrained equations of state and phase boundaries available for silica. QMC indicates a transition to the dense alpha-PbO(2) structure above the core-insulating D" layer, but the absence of a seismic signature suggests the transition does not contribute significantly to global seismic discontinuities in the lower mantle. However, the transition could still provide seismic signals from deeply subducted oceanic crust. We also find an accurate shear elastic constant for stishovite and its geophysically important softening with pressure.

  13. High-pressure Powder X-ray Diffraction Study of Cu5Si and Pressure-driven Isostructural Phase Transition

    SciTech Connect

    Li, C.; Yu, Z.; Liu, H.; Lu, T.

    2012-12-03

    The structural behaviour of Cu5Si under high-pressure (HP) has been studied by angular dispersive X-ray diffraction up to 49.9 GPa. The experimental results suggest that a pressure-induced isostructural phase transition occurs around 13.5 GPa as revealed by a discontinuity in volume as a function of pressure. The lattice parameter decreases with the pressure increasing for both low-pressure (LP) and HP phases of Cu5Si. However, a plot of the lattice parameter vs. pressure shows the existence of a plateau between 11.7 and 15.3 GPa. The bulk moduli, derived from the fitting of Birch–Murnaghan equation of state, are 150(2) GPa and 210(3) GPa for the LP phase and the HP phase of Cu5Si, respectively. A change in the electronic state of the copper is assumed to govern the observed structural phase transition.

  14. Construction of a Direct Water-Injected Two-Stroke Engine for Phased Direct Fuel Injection-High Pressure Charging Investigations

    NASA Technical Reports Server (NTRS)

    Somsel, James P.

    1998-01-01

    The development of a water injected Orbital Combustion Process (OCP) engine was conducted to assess the viability of using the powerplant for high altitude NASA aircraft and General Aviation (GA) applications. An OCP direct fuel injected, 1.2 liter, three cylinder, two-stroke engine has been enhanced to independently inject water directly into the combustion chamber. The engine currently demonstrates low brake specific fuel consumption capability and an excellent power to weight ratio. With direct water injection, significant improvements can be made to engine power, to knock limits/ignition advance timing, and to engine NO(x) emissions. The principal aim of the testing was to validate a cyclic model developed by the Systems Analysis Branch at NASA Ames Research Center. The work is a continuation of Ames' investigations into a Phased Direct Fuel Injection Engine with High Pressure Charging (PDFI-ITPC).

  15. Evidence of iso-structural phase transition in high pressure Raman spectroscopic studies of CaCu3Ti4O12

    NASA Astrophysics Data System (ADS)

    Tyagi, Shekhar; Sharma, Gaurav; Sathe, V. G.

    2017-02-01

    High pressure Raman spectroscopic studies on Polycrystalline CaCu3Ti4O12 and SrCu3Ti4O12 compounds are carried out in order to validate the theoretical predictions of a structural transformation near 3-4 GPa and an insulator to metal transition above 7 GPa [S. B. Fagan et al., Phys. Rev. B 72, 014106 (2005)]. Our studies showed normal hardening and broadening of peaks with increasing pressure up to 20 GPa besides a discontinuity between 8 and 9 GPa which is attributed to an isostructural phase transition. The Ag(1) peak occurring at 442 cm-1 showed asymmetric Fano lineshape and the lineshape parameter 'q' shows an increase with increasing pressure. This is completely against the theoretical predictions of an insulator to metal transition above 7 GPa.

  16. 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.

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

    PubMed

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

    2006-04-01

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

  18. Phase relation of C-Mg-Fe-Si-O system under various oxygen fugacity conditions at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Takahashi, S.; Ohtani, E.; Terasaki, H.; Ito, Y.; Shibazaki, Y.; Ishii, M.; Funakoshi, K.; Higo, Y.

    2010-12-01

    Many exoplanets have been found recently based on the spectroscopic observation. A carbon-rich circumstellar gas was reported to exist around “beta-Pictoris”, which has an exoplanet (Roberge et al., 2006). In such gas, carbon-enriched planet, “carbon-planet” may be formed. Carbon-bearing phase, such as carbide, carbonate, graphite and diamond are likely to compose the carbon-planet interior. Therefore, it is important to investigate phase relations of carbon-rich systems under high pressure conditions. In this study, C-enriched Mg-Si-Fe-O-C system was investigated at high pressure and temperature in order to understand the internal structure of the carbon-planet. Phase relations were studied based on 2 series of experiments; (I)textural observation and chemical analysis of the recovered sample from 4 GPa and 1873K and (II)in situ X-ray diffraction experiments under high pressure and temperature. For the starting materials, we used several different mineral assemblages, as shown below: (i) MgCO3 + Fe + Si + C, (ii) (Mg1.8,Fe0.2)SiO4 + Fe + SiO2 + C, (iii) (Mg1.8,Fe0.2)SiO4 + Fe + Si + C, (iv) MgO + Fe + SiO2 + C, (v) MgO + Fe + Si + C. Oxygen fugacity (fO2) of the sample vaies dependign on these assembleges due to different O amount in the starting materials. The sample was enclosed in graphite or MgO capsule. MgO capsule enables us to estimate fO2 in the sample based on the FeO content of the capsule contacting with the samples. Chemical analyses of the recovered samples were performed using electron microprobe. In situ X-ray diffraction experiments were conducted at 4 GPa and up to 1873 K at BL04B1 beamline, SPring-8 synchrotron facility. Different mineral assemblages and their compositions were observed in the recovered samples depending on the redox condition of the sample. The compositions of metallic melt phases changes from Fe-C composition (C = 6.9~8.2 wt.%) in oxidizing conditions (ΔIW = -2.4 ~ -1.7) to Fe-Si composition (Si = 18 wt.%) in the more

  19. Elastic behaviour and high-pressure phase transition of the P21/n LiAlGe2O6pyroxene

    NASA Astrophysics Data System (ADS)

    Artac, Andreas; Miletich-Pawliczek, Ronald; Nestola, Fabrizio; Redhammer, Günther J.; Secco, Luciano

    2014-05-01

    In a recent work by Redhammer et al. (2012), investigating a synthetic pyroxene sample with composition LiAlGe2O6, a new space group for the big family of pyroxenes has been surprisingly discovered renewing the interest for Li-bearing pyroxene compounds. Actually, the authors of that work intended to investigate the effect of the Si-Ge substitution on the high-pressure behaviour and possibly on the phase transition with respect to spodumene, LiAlSi2O6, investigated by Arlt and Angel in 2000. Spodumene in fact, not only shows a strong first order phase transition at 3.19 GPa from C2/c to P21/c but the low symmetry C2/c shows the greatest bulk modulus never found in pyroxenes (i.e. 144.2 GPa with the first pressure derivative fixed to 4). Redhammer et al. (2012) discovered that substituting Si for Ge in the spodumene structure the effect is dramatic in terms of symmetry change at room conditions with the Ge-spodumene showing a P21/n space group, first discovery of such symmetry in the big family of pyroxene. In this work we loaded one crystal of LiAlGe2O6 in a diamond-anvil cell and investigated the elastic behaviour and its possible high-pressure phase transition by single-crystal X-ray diffraction. In detail, we measured the unit-cell parameters using a Huber four-circle diffractometer equipped with a point detector up to about 9 GPa. The crystal structure was measured at different pressures loading simultaneously two fragments of the same crystal with a different orientation in the same diamond-anvil cell in order to cover a wider portion of the reciprocal space. The intensity data were measured on a STADI IV four-circle diffractometer equipped with a CCD using a diamond-backing plate cell, which gives better structural results with respect to a beryllium backing plate one (i.e. Periotto et al. 2011). The first important result of our work is that we found at about 5.2 GPa a very strong first-order phase transformation from P21/n to P21/c and this is the first

  20. Dynamic mechanical behavior and high pressure phase stability of a zirconium-based bulk metallic glass and its composite with tungsten

    NASA Astrophysics Data System (ADS)

    Martin, Morgana

    2008-10-01

    The research involved performing controlled impact experiments on BMG composites consisting of amorphous Zr57Nb5Cu 15:4Ni12:6Al10 (LM106 or Vitreloy106) with crystalline tungsten reinforcement particles. Monolithic LM106 was also examined to aid in the understanding of the composite. The mechanical behavior of the composite was investigated over a range of strain rates (10-3 s -1 to 106 s-1), stress states (compression, compression-shear, tension), and temperatures (RT to 600°C) to determine the dependence of mechanical properties and deformation and failure modes (i.e., homogeneous deformation vs. inhomogeneous shear banding) on these parameters. Mechanical testing in the quasi-static to intermediate strain-rate regimes was performed using an Instron, Drop Weight Tower, and Split Hopkinson Pressure Bar, respectively. High-strain-rate mechanical properties of the BMG-matrix composite and monolithic BMG were investigated using dynamic compression (reverse Taylor) and dynamic tension (spall) impact experiments performed using a gas gun instrumented with velocity interferometry and high-speed digital photography. These experiments provided information about dynamic strength and deformation modes, and allowed for validation of constitutive models via comparison of experimental and simulated transient deformation profiles and free surface velocity traces. Hugoniot equation of state measurements were performed on the monolithic BMG to investigate the high pressure phase stability of the glass and the possible implications of a high pressure phase transformation on mechanical properties. Specimens were recovered for post-impact microstructural and thermal analysis to gain information about the mechanisms of dynamic deformation and fracture, and to examine for possible shock-induced phase transformations of the amorphous phase. For the composite, mechanical testing revealed positive strain-rate sensitivity of its yield stress and negative strain-rate sensitivity of its

  1. Anomaly in neural phase coherence accompanies reduced sensorimotor integration in adults who stutter.

    PubMed

    Sengupta, Ranit; Shah, Shalin; Gore, Katie; Loucks, Torrey; Nasir, Sazzad M

    2016-12-01

    Despite advances in our understanding of the human speech system, the neurophysiological basis of stuttering remains largely unknown. Here, it is hypothesized that the speech of adults who stutter (AWS) is susceptible to disruptions in sensorimotor integration caused by neural miscommunication within the speech motor system. Human speech unfolds over rapid timescales and relies on a distributed system of brain regions working in a parallel and synchronized manner, and a breakdown in neural communication between the putative brain regions could increase susceptibility to dysfluency. Using a speech motor adaptation paradigm under altered auditory feedback with simultaneous recording of EEG, the oscillatory cortical dynamics was investigated in stuttering and fluent adults (FA). Auditory feedback perturbation involved the shifting of the formant frequencies of the target vowel sound. Reduced adaptation in response to the feedback error was observed in AWS and was accompanied by differences in EEG spectral powers and anomalies in phase coherence evolving over the course of speech motor training. It is understood that phase coherence possibly captures neural communication within speech motor networks. Thus, the phase coherence network of the two groups exhibited differences involving the EEG frequency bands. These findings in anomalous neural synchrony provide novel evidence for compromised neuronal communication at short time scales within the speech motor network of AWS.

  2. High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

    SciTech Connect

    Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

    2016-12-01

    High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

  3. High pressure annular two-phase flow in a narrow duct. Part 1: Local measurements in the droplet field, and Part 2: Three-field modeling

    SciTech Connect

    Trabold, T.A.; Kumar, R.

    1999-07-01

    In Part 1, detailed measurements were made in a high pressure, adiabatic (boiled at the inlet) annular flow in a narrow, high aspect ratio duct using a gamma densitometer, hot-film anemometer and high-speed video photography. Measurements of void fraction, droplet frequency, velocity, drop size, and interfacial area concentration have been made to support the three field computational capability. An important aspect of this testing is the use of a modeling fluid (R-134a) in a vertical duct which permits visual access in annular flow. This modeling fluid accurately simulates the low liquid-to-vapor density ratio of steam-water flows at high pressures. These measurements have been taken in a narrow duct of hydraulic diameter 4.85 mm, and a cross-section aspect ratio of 22.5. However, the flow displays profiles of various shapes not only in the narrow dimension, but also in the width dimension. In particular, the shape of the droplet profiles depends on the entrained droplet flux from the edges in the vapor core. The average diameter from these profiles compare well with the models developed in the literature. Interfacial area concentration for these low density ratio flows is higher than the highest concentration reported for air-water flows. Video records show that along with the bow-shaped waves, three-dimensional {lambda}-shaped waves appear in annular flows for high flow rates. Part 2 outlines the development of a three-field modeling approach in annular flow and the predictive capability of an analysis code. Models have been developed here or adapted from the literature for the thin film near the wall as well as the droplets in the vapor core, and have been locally applied in a fully developed, two-phase adiabatic boiling annular flow in a duct heated at the inlet at high pressure. Numerical results have been obtained using these models that are required for the closure of the continuity and momentum equations. The two-dimensional predictions are compared with

  4. 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.

  5. In vivo biosynthesis of L-(/sup 35/S)Cys-arginine vasopressin, -oxytocin, and -somatostatin: rapid estimation using reversed phase high pressure liquid chromatography. [Rats

    SciTech Connect

    Franco-Bourland, R.E.; Fernstrom, J.D.

    1981-01-01

    L(/sup 35/S)Cys-arginine vasopressin, -oxytocin, and -somatostatin were purified from hypothalami and neurohypophyses 4 h after rats received L(/sup 35/S)Cys via the third ventricle. After acetic acid extraction, Sephadex G-25 filtration, and chemoadsorption to C18-silica (Sep-Pak cartridges), the labeled peptides were rapidly separated by gradient elution, reversed phase, high pressure liquid chromatography (HPLC). The identity and isotopic purity of the labeled peptides were determined by several reversed phase HPLC procedures in conjunction with chemical modification. The labeled peptide fractions were at least 50% radiochemically pure. Using this HPLC isolation procedure, incorporation of L-(/sup 35/S)Cys into each peptide was determined in hydrated and dehydrated rats. Label incorporation into arginine vasopressin and oxytocin in the hypothalamus and the neurohypophysis of dehydrated rats was 2-3 times greater than that in hydrated rats. Incorporation of label into hypothalamic and neurohypophyseal somatostatin was unaffected by the hydration state of the animal. This procedure thus provides a very rapid, but sensitive, set of techniques for studying the control of small peptide biosynthesis in the brain.

  6. Relationship Between the 3D Porosity and β-Phase Distributions and the Mechanical Properties of a High Pressure Die Cast AZ91 Mg Alloy

    NASA Astrophysics Data System (ADS)

    Biswas, Somjeet; Sket, Federico; Chiumenti, Michele; Gutiérrez-Urrutia, Iván; Molina-Aldareguía, Jon M.; Pérez-Prado, Maria Teresa

    2013-09-01

    Currently, most magnesium lightweight components are fabricated by casting as this process is cost effective and allows forming parts with complex geometries and weak textures. However, cast microstructures are known to be heterogeneous and contain unpredictable porosity distributions, which give rise to a large variability in the mechanical properties. This work constitutes an attempt to correlate the microstructure and the mechanical behavior of a high pressure die cast (HPDC) Mg AZ91 alloy, aimed at facilitating process optimization. We have built a stairway-shaped die to fabricate alloy sections with different thicknesses and, thus, with a range of microstructures. The grain size distributions and the content of β-phase (Mg17Al12) were characterized by optical and electron microscopy techniques as well as by electron backscatter diffraction (EBSD). The bulk porosity distribution was measured by 3D computed X-ray microtomography. It was found that the through-thickness microhardness distribution is mostly related to the local area fraction of the β-phase and to the local area fraction of the pores. We correlate the tensile yield strength to the average pore size and the fracture strength and elongation to the bulk porosity volume fraction. We propose that this empirical approach might be extended to the estimation of mechanical properties in other HPDC Mg alloys.

  7. Physicochemical and thermodynamic characterization of the encapsulation of methyl jasmonate by natural and modified cyclodextrins using reversed-phase high-pressure liquid chromatography.

    PubMed

    López-Nicolás, José Manuel; Escorial Camps, Marta; Pérez-Sánchez, Horacio; García-Carmona, Francisco

    2013-11-27

    Although the combinations of methyl jasmonate (MeJA) and cyclodextrins (CDs) have been used by different authors to stimulate the production of several metabolites, no study has been published about the possible formation of MeJA-CD complexes when these two molecules are added together to the reaction medium as elicitors. For this reason and because knowledge of the possible complexation process of MeJA with CD under different physicochemical conditions is essential if these two molecules are to be used in cell cultures, this paper looks at the complexation of MeJA with natural and modified CDs using a reversed-phase high-pressure liquid chromatography (RP-HPLC) system. The interaction of MeJA with β-CD was more efficient than with α- and γ-CDs. However, a modified CD, HP-β-CD, was the most effective of all of the CDs tested. Moreover, MeJA formed complexes with CD with a 1:1 stoichiometry, and the formation constants of these complexes were strongly dependent upon the temperature of the mobile phase used but not the pH. To obtain information about the mechanism of the affinity of MeJA for CD, the thermodynamic parameters ΔG°, ΔH°, and ΔS° were calculated. Finally, molecular modeling studies were carried out to propose which molecular interactions are established in the complexation process.

  8. Investigation of Fe-X (X=S, Si, C) Alloys Phase Diagrams at High Pressure and High Temperature using Ultrasonic Interferometry

    NASA Astrophysics Data System (ADS)

    Chantel, J.; Jing, Z.; Yu, T.; Wang, Y.

    2015-12-01

    Light elements have been suggested to be present in the liquid iron cores of the terrestrial planets and moons based on seismological and geochemical observations. It is therefore critical to determine precisely the phase diagrams for Fe-X (X=S, Si, C, O, H, etc.) alloying liquids in order to constrain the light element abundances in planetary cores, and to understand the dynamics and chemical evolution of the planets. Our goal is to refine the phase diagrams of Fe-S, Fe-Si and Fe-C at high pressures. We have successfully determined, at pressures up to 7 GPa, the temperatures of both solidus and liquidus of Fe alloys, with various S, Si and C contents, using ultrasonic wave velocity measurements in multi-anvil apparatus. During the heating of the experiment, we observe the solidus through the disappearance of the P-waves signal when the sample is partially molten, and the liquidus through the appearance of the signal from the liquid when the sample is entirely molten. Those observations have been confirmed during in-situ synchrotron experiments on Fe-5wt%C, Fe-10wt%C, Fe-5wt%Si and Fe-25wt%Si, using the ultrasonic measurements in conjunction with x-ray diffraction at the GSECARS Beamline 13-ID-D. In fact the ultrasonic interferometry allow to determine the solidus and liquidus temperatures more precisely than the x-ray diffraction. Traditional quench experiments used to determine phase relations require a large number of experiments. It is particularly challenging when the phase loop is narrow such as the case of the Fe-Si system. This new off-line in situ technique is a powerful tool to study partially or entirely molten samples without access to a synchrotron radiation source.

  9. The effect of pressure and mobile phase velocity on the retention properties of small analytes and large biomolecules in ultra-high pressure liquid chromatography.

    PubMed

    Fekete, Szabolcs; Veuthey, Jean-Luc; McCalley, David V; Guillarme, Davy

    2012-12-28

    A possible complication of ultra-high pressure liquid chromatography (UHPLC) is related to the effect of pressure and mobile phase velocity on the retention properties of the analytes. In the present work, numerous model compounds have been selected including small molecules, peptides, and proteins (such as monoclonal antibodies). Two instrumental setups were considered to attain elevated pressure drops, firstly the use of a post-column restrictor capillary at low mobile phase flow rate (pure effect of pressure) and secondly the increase of mobile phase flow rate without restrictor (i.e. a combined effect of pressure and frictional heating). In both conditions, the goal was to assess differences in retention behaviour, depending on the type or character of the analyte. An important conclusion is that the effect of pressure and mobile phase velocity on retention varied in proportion with the size of the molecule and in some cases showed very different behaviour. In isocratic mode, the pure effect of pressure (experiments with a post-column restrictor capillary) induces an increase in retention by 25-100% on small molecules (MW<300 g/mol), 150% for peptides (~1.3 kDa), 800% for insulin (~6 kDa) and up to >3000% for myoglobin (~17 kDa) for an increase in pressure from 100 bar up to 1100 bar. The important effect observed for the isocratic elution of proteins is probably related to conformational changes of the protein in addition to the effect of molecular size. Working in gradient elution mode, the pressure related effects on retention were found to be less pronounced but still present (an increase of apparent retention factor between 0.2 and 2.5 was observed).

  10. High pressure sequence of Ba3NiSb2O9 structural phases: new S = 1 quantum spin-liquids based on Ni^2+

    NASA Astrophysics Data System (ADS)

    Balicas, Luis

    2012-02-01

    A quantum spin-liquid (QSL) is a ground-state where strong quantum- mechanical ?uctuations prevents a phase-transition towards conventional magnetic order and makes the spin ensemble to remain in a liquid-like state. Most QSL candidates studied to date are two-dimensional frustrated magnets with either a triangular or a kagome lattice composed of S = 1/2 spins. Here, we report the use of a high pressure, high temperature technique to transform the antiferromagnetically ordered (TN = 13.5 K) 6H-A phase of Ba3NiSb2O9 into two new QSL candidates with larger S = 1 (Ni^2+) moments: the 6H-B phase of Ba3NiSb2O9 which crystallizes in a triangular lattice and the 3C-phase of Ba3NiSb2O9 which forms a three-dimensional edge-shared tetrahedral lattice. Both compounds show no evidence for magnetic order down to T = 0.35 K despite Curie-Weiss temperatures θCW of -75.5 K (6H-B) and -182.5 K (3C), respectively. Below ˜25 K the magnetic susceptibility of the 6H-B phase is found to saturate at a constant value χ = 0.013 emu/mol which is followed below 7 K, by a linear in temperature dependence for the magnetic contribution to the specificheat (CM) which displays a giant coefficient γ = 168 mJ/mol-K^2 comparable to values observed in heavy-fermion metallic systems. Taken together, both observations indicate the development of a Fermi-liquid like ground-state characterized by a Wilson ratio of 5.6 in this otherwise insulating material It also points to the formation at finite temperatures of a well defined Fermi surface of S = 1 spin-excitations which behave as charged quasiparticles. For the 3C phase one observes CM T ^2 indicating a unique S = 1 three-dimensional QSL ground-state as previously reported for Na3Ir4O8 although this later compound is composed of Ir^4+ ions having S = 1/2. [4pt] Work done in collaboration with J. G. Cheng, G. Li, J. S. Zhou, J. B. Goodenough, C Xu and H. D. Zhou.

  11. High-pressure high-temperature phase relations in FeTiO3 up to 35 GPa and 1600 °C

    NASA Astrophysics Data System (ADS)

    Akaogi, M.; Abe, K.; Yusa, H.; Ishii, T.; Tajima, T.; Kojitani, H.; Mori, D.; Inaguma, Y.

    2017-01-01

    Phase relations in FeTiO3 were precisely determined at 25-35 GPa and 600-1600 °C using multianvil high-pressure experiments with tungsten carbide anvils. Pressure generation up to about 36 GPa at 1600 °C was evaluated using Al2O3 solubility in MgSiO3 perovskite (Pv) in the system MgSiO3-Al2O3. At about 28 GPa, FeTiO3 Pv dissociates into an assemblage of calcium titanate (CT)-type Fe2TiO4 + orthorhombic-I (OI)-type TiO2 below 1200 °C. However, above 1200 °C at 28 GPa, FeTiO3 Pv decomposes into a new, denser phase assemblage of CT-type Fe2TiO4 + a new compound of FeTi2O5. The new phase FeTi2O5 was recovered as an amorphous phase at 1 atm. In situ X-ray diffraction experiments at 35.1 GPa indicated that the new phase (N-p) FeTi2O5 has orthorhombic symmetry with cell parameters a = 8.567(2) Å, b = 5.753(1) Å and c = 5.257(1) Å. In addition, the assemblage of CT-type Fe2TiO4 + OI-type TiO2 changes to FeO wüstite (Wu) + OI-type TiO2 at about 33 GPa below 1000 °C. The phase assemblages in FeTiO3 are denser in the order: FeTiO3 (Pv) → 1/2Fe2TiO4 (CT) + 1/2TiO2 (OI) → 1/3Fe2TiO4 (CT) + 1/3FeTi2O5 (N-p) → FeO (Wu) + TiO2 (OI). Our results indicate that the upper stability limit of FeTiO3 Pv is about 28 GPa at 600-1600 °C. This puts a constraint on peak shock pressure for formation of naturally discovered lithium niobate-type FeTiO3 which was interpreted to be retrograde transition product of FeTiO3 Pv on release of shock pressure.

  12. Role of phonons in negative thermal expansion and high pressure phase transitions in β-eucryptite: An ab-initio lattice dynamics and inelastic neutron scattering study

    NASA Astrophysics Data System (ADS)

    Singh, Baltej; Gupta, Mayanak Kumar; Mittal, Ranjan; Zbiri, Mohamed; Rols, Stephane; Patwe, Sadequa Jahedkhan; Achary, Srungarpu Nagabhusan; Schober, Helmut; Tyagi, Avesh Kumar; Chaplot, Samrath Lal

    2017-02-01

    β-Eucryptite (LiAlSiO4) shows anisotropic thermal expansion as well as one-dimensional super-ionic conductivity. We have performed the lattice dynamical calculations using ab-initio density functional theory along with inelastic neutron scattering measurements. The anisotropic stress dependence of the phonon spectrum is calculated to obtain the thermal expansion behavior along various axes. The calculations show that the Grüneisen parameters of the low-energy phonon modes around 10 meV have large negative values and govern the negative thermal expansion behavior at low temperatures along both the "a"- and "c"-axes. On the other hand, anisotropic elasticity along with anisotropic positive values of the Grüneisen parameters of the high-energy modes in the range 30-70 meV are responsible for the thermal expansion at high temperatures, which is positive in the a-b plane and negative along the c-axis. The analysis of the polarization vectors of the phonon modes sheds light on the mechanism of the anomalous thermal expansion behavior. The softening of a Γ-point mode at about 2 GPa may be related to the high-pressure phase transition.

  13. Magnetic phase separation and strong enhancement of the neel temperature at high pressures in a new multiferroic Ba3TaFe3Si2O14

    NASA Astrophysics Data System (ADS)

    Lyubutin, I. S.; Starchikov, S. S.; Gavriliuk, A. G.; Troyan, I. A.; Nikiforova, Yu. A.; Ivanova, A. G.; Chumakov, A. I.; Rüffer, R.

    2017-01-01

    The high pressure properties of a new multiferroic of the langasite family Ba3TaFe3Si2O14 were investigated in diamond-anvil cells (DAC) in the temperature range of 4.2-295 K by a new method of synchrotron Mossbauer spectroscopy. Strong enhancement of the Neel temperature T N was observed at pressures above 20 GPa associated with the structural transformation. The highest value of T N is about 130K which is almost five times larger than the value at ambient pressure (about 27K). It was suggested that the high value of T N appears due to redistribution of Fe ions over 3f and 2d tetrahedral sites of the langasite structure. In this case, the short Fe-O distances and favorable Fe-O-Fe bond angles create conditions for strong superexchange interactions between iron ions, and effective two-dimensional (2D) magnetic ordering appears in the (ab) plane. The separation of the sample into two magnetic phases with different T N values of about 50 and 130K was revealed, which can be explained by the strong two dimensional 2D magnetic ordering in the (ab) plane and 3D ordering involving inter-plane interaction.

  14. High pressure in situ x-ray absorption spectroscopy cell for studying simultaneously the liquid phase and the solid-liquid interface

    SciTech Connect

    Grunwaldt, Jan-Dierk; Ramin, Michael; Rohr, Markus; Michailovski, Alexej; Patzke, Greta R.; Baiker, Alfons

    2005-05-15

    A high pressure in situ x-ray absorption spectroscopy cell with two different path lengths and path positions is presented for studying element-specifically both the liquid phase and the solid-liquid interface at pressures up to 250 bar and temperatures up to 220 deg. C. For this purpose, one x-ray path probes the bottom, while the other x-ray path penetrates through the middle of the in situ cell. The basic design of the cell resembles a 10 ml volume batch reactor, which is equipped with in- and outlet lines to dose compressed gases and liquids as well as a stirrer for good mixing. Due to the use of a polyetheretherketone inset it is also suitable for measurements under corrosive conditions. The characteristic features of the cell are illustrated using case studies from catalysis and solid state chemistry: (a) the ruthenium-catalyzed formylation of an amine in 'supercritical' carbon dioxide in the presence of hydrogen; (b) the cycloaddition of carbon dioxide to propylene oxide in the presence of a solid Zn-based catalyst, and (c) the solvothermal synthesis of MoO{sub 3} nanorods from MoO{sub 3}-2H{sub 2}O.

  15. High pressure in situ x-ray absorption spectroscopy cell for studying simultaneously the liquid phase and the solid/liquid interface

    NASA Astrophysics Data System (ADS)

    Grunwaldt, Jan-Dierk; Ramin, Michael; Rohr, Markus; Michailovski, Alexej; Patzke, Greta R.; Baiker, Alfons

    2005-05-01

    A high pressure in situ x-ray absorption spectroscopy cell with two different path lengths and path positions is presented for studying element-specifically both the liquid phase and the solid/liquid interface at pressures up to 250 bar and temperatures up to 220 °C. For this purpose, one x-ray path probes the bottom, while the other x-ray path penetrates through the middle of the in situ cell. The basic design of the cell resembles a 10 ml volume batch reactor, which is equipped with in- and outlet lines to dose compressed gases and liquids as well as a stirrer for good mixing. Due to the use of a polyetheretherketone inset it is also suitable for measurements under corrosive conditions. The characteristic features of the cell are illustrated using case studies from catalysis and solid state chemistry: (a) the ruthenium-catalyzed formylation of an amine in "supercritical" carbon dioxide in the presence of hydrogen; (b) the cycloaddition of carbon dioxide to propylene oxide in the presence of a solid Zn-based catalyst, and (c) the solvothermal synthesis of MoO3 nanorods from MoO3•2H2O.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Detection of seven pesticides in cucumbers using hollow fibre-based liquid-phase microextraction and ultra-high pressure liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Wang, Jianfeng; Du, Zhenxia; Yu, Wenlian; Qu, Shuping

    2012-07-20

    A liquid-phase microextraction (LPME) methodology based on the use of porous polyvinylidene fluoride (PVDF) hollow fibres was developed for extracting seven pesticides from cucumbers. The seven pesticides include propoxur, carbofuran, atrazine, cyanatryn, metolachlor, prometryn and tebuconazole. The PVDF hollow fibre provides higher extraction efficiency due to its higher porosity and better solvent compatibility. A new desorption methodology was developed since some pesticides were absorbed by the wall pore of the PVDF. Ultra-high pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was used for pesticide analysis. In order to obtain high recoveries and enrichment factors of the analytes, several parameters such as method of sealing, acceptor phase (organic solvents), stirring speed, extraction time, salting out effect, desorption mode and time were optimized. A fast, simple method for closing fibre ends was practiced by using mechanical crimping. Pesticides were extracted from the sample to the organic solvent and then desorbed in a mixture of methanol:water (1:1 v/v) prior to chromatographic analysis. Limits of detection (LOD) for the multi-reaction-monitoring (MRM) mode of the method varies from 0.01 to 0.31 μg/kg with optimized sample preparation. Calibration curves are linear with R² ≥ 0.991. Enrichment factor of the hollow fibre LPME ranges from 100 to 147. Matrix effect has been considered and is in the range of 76-122%. The relative recoveries from cucumber samples are between 63% and 119% with the relative standard deviation (RSD, n=6) lower than 20%.

  1. Distinction of synthetic dl-α-tocopherol from natural vitamin E (d-α-tocopherol) by reversed-phase liquid chromatography. Enhanced selectivity of a polymeric C18 stationary phase at low temperature and/or at high pressure.

    PubMed

    Yui, Yuko; Miyazaki, Shota; Ma, Yan; Ohira, Masayoshi; Fiehn, Oliver; Ikegami, Tohru; McCalley, David V; Tanaka, Nobuo

    2016-06-10

    Separation of diastereomers of dl-α-tocopherol was studied by reversed-phase liquid chromatography using three types of stationary phases, polymeric ODS, polymeric C30, and monomeric ODS. Polymeric ODS stationary phase (Inertsil ODS-P, 3mmID, 20cm) was effective for the separation of the isomers created by the presence of three chiral centers on the alkyl chain of synthetic dl-α-tocopherol. Considerable improvement of the separation of isomers was observed on ODS-P phase at high pressure and at low temperature. Complete separation of four pairs of diastereomers was achieved at 12.0°C, 536bar, while three peaks were observed when the separation was carried out either at 12.0°C at low pressure or at 20°C at 488bar. Higher temperature (30.0°C) with the ODS-P phase resulted in only partial separation of the diastereomers even at high pressure. Only slight resolution was observed for the mixture of diastereomers with the C30 stationary phase (Inertsil C30) at 12.0°C and 441bar, although the stationary phase afforded greater resolution for β- and γ-tocopherol than ODS-P. A monomeric C18 stationary phase did not show any separation at 12.0°C and 463bar. The results suggest that the binding site of the polymeric ODS-P phase is selective for flexible alkyl chains that provided the longest retention for the natural form, (R,R,R) form, and the enantiomer, (S,S,S) form, of dl-α-tocopherol.

  2. A first-principle study on the phase transition, electronic structure, and mechanical properties of three-phase ZrTi2 alloy under high pressure*

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    We employed density-functional theory (DFT) within the generalized gradient approximation (GGA) to investigate the ZrTi2 alloy, and obtained its structural phase transition, mechanical behavior, Gibbs free energy as a function of pressure, P-V equation of state, electronic and Mulliken population analysis results. The lattice parameters and P-V EOS for α, β and ω phases revealed by our calculations are consistent with other experimental and computational values. The elastic constants obtained suggest that ω-ZrTi2 and α-ZrTi2 are mechanically stable, and that β-ZrTi2 is mechanically unstable at 0 GPa, but becomes more stable with increasing pressure. Our calculated results indicate a phase transition sequence of α → ω → β for ZrTi2. Both the bulk modulus B and shear modulus G increase linearly with increasing pressure for three phases. The G/B values illustrated good ductility of ZrTi2 alloy for three phases, with ω<α<β at 0 GPa. The Mulliken population analysis showed that the increment of d electron occupancy stabilized the β phase. A low value for B '0 is the feature of EOS for ZrTi2 and this softness in the EOS is representative of pressure induced s-d electron transfer. Supplementary material in the form of one pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjb/e2016-70218-0

  3. 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.

  4. Deposition profile of Ti film inside a trench and its correlation with gas-phase ionization in high-pressure magnetron sputtering

    SciTech Connect

    Nafarizal, N.; Takada, N.; Nakamura, K.; Sago, Y.; Sasaki, K.

    2006-11-15

    This article reports the relationship between the degree of ionization of Ti in the gas phase and the thickness profile of Ti film inside a trench in magnetron sputtering deposition. A conventional magnetron sputtering plasma source was used for depositing Ti films inside trenches formed on rf-biased SiO{sub 2} substrates. It was found that a high bottom coverage was obtained when a high gas pressure and a long distance between the target and the substrate were employed for the deposition. On the other hand, at a short distance between the target and the substrate, the bottom coverage was small and was almost independent of the gas pressure. The deposition profile was compared with the spatial distributions of Ti and Ti{sup +} densities measured by laser-induced fluorescence (LIF) imaging spectroscopy. The LIF results revealed that the density ratio of Ti{sup +} to Ti in the downstream region increased with the gas pressure up to 0.3, while in the upstream region, it was small (<0.05) and was roughly constant with the gas pressure. In the case with the enhanced density ratio of 0.3, the flux ratio of Ti{sup +} to Ti was estimated to be 4.4. Hence, it was concluded that, with a high gas pressure and a long distance between the target and substrate, the deposition profile with a high bottom coverage was obtained by accelerating Ti{sup +} toward the bottom of the trench. The high-pressure magnetron sputtering discharge is useful for enhancing the degree of ionization and the bottom coverage.

  5. Determination of six microcystins and nodularin in surface and drinking waters by on-line solid phase extraction-ultra high pressure liquid chromatography tandem mass spectrometry.

    PubMed

    Beltrán, Eduardo; Ibáñez, María; Sancho, Juan Vicente; Hernández, Félix

    2012-11-30

    Microcystins and nodularin are cyclic peptides hepatotoxins produced by cyanobacterial genera (blue-green algae). Toxic cyanobacterial blooms are a worldwide problem, as reported in several countries, like China, Australia, or the United States. Therefore, it is necessary to develop sensitive and reliable analytical methodology to determine this type of toxins in water at parts per billion levels, or even lower. In this work, the potential of solid-phase extraction coupled on-line to ultra-high-pressure liquid chromatography/electrospray tandem mass spectrometry (SPE-UHPLC-MS/MS) has been investigated for the efficient quantification and confirmation of microcystins LR, RR, YR, LY, LW, LF and nodularin in surface and drinking water samples, at sub-ppb levels. The method developed involves the injection of only 1 mL of water sample into the on-line SPE-UHPLC-MS/MS system and allows the rapid determination of the compounds selected (8 min of chromatographic run), avoiding laborious sample treatment. The method was validated in surface and drinking water by means of recovery experiments at 0.25 and 1 μg L(-1). Average recoveries (n=5) ranged from 71 to 116%, with relative standard deviations (RSDs) lower than 15%. For microcystins LR, RR, YR and nodularin, a third level was also assayed (0.1 μg L(-1)) obtaining satisfactory data too. Limits of detection between 0.002 and 0.0405 μg L(-1) were estimated (0.0005 μg L(-1) for nodularin). The developed method was applied to the analysis of water samples collected in the province of Castellón (Spain). The acquisition of three MS/MS transitions for each compound allowed the unequivocal confirmation of positive samples, which was supported by the accomplishment of ion intensity ratios and retention time when compared with reference standards.

  6. 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.

  7. Structural phase transitions of (Bi1−xSbx )2(Te1−y Se y)3 compounds under high pressure and the influence of the atomic radius on the compression processes of tetradymites

    DOE PAGES

    Zhao, Jinggeng; Yu, Zhenhai; Hu, Qingyang; ...

    2016-12-14

    Recently, A2B3-type tetradymites have developed into a hot topic in physical and material research fields, where the A and B atoms represent V and VI group elements, respectively. In this study, in situ angle-dispersive X-ray diffraction measurements were performed on Bi2Te2Se, BiSbTeSe2, and Sb2Te2Se tetradymites under high pressure. Bi2Te2Se transforms from a layered rhombohedral structure (phase I) into 7-fold monoclinic (phase II) and body-centered tetragonal (phase IV) structures at about 8.0 and 14.3 GPa, respectively, without an 8-fold monoclinic structure (phase III) similar to that in Bi2Te3. Thus, the compression behavior of Bi2Te2Se is the same as that of Bi2Se3,more » which could also be obtained from first-principles calculations and in situ high-pressure electrical resistance measurements. Under high pressure, BiSbTeSe2 and Sb2Te2Se undergo similar structural phase transitions to Bi2Te2Se, which indicates that the compression process of tellurides can be modulated by doping Se in Te sites. According to these high-pressure investigations of A2B3-type tetradymites, the decrease of the B-site atomic radius shrinks the stable pressure range of phase III and expands that of phase II, whereas the decrease of the A-site atomic radius induces a different effect, i.e. expanding the stable pressure range of phase III and shrinking that of phase II. Lastly, the influence of the atomic radius on the compression process of tetradymites is closely related to the chemical composition and the atom arrangement in the quintuple layer.« less

  8. Structural phase transitions of (Bi1$-$xSbx )2(Te1$-$y Se y)3 compounds under high pressure and the influence of the atomic radius on the compression processes of tetradymites

    DOE PAGES

    Zhao, Jinggeng; Yu, Zhenhai; Hu, Qingyang; ...

    2016-12-14

    Recently, A2B3-type tetradymites have developed into a hot topic in physical and material research fields, where the A and B atoms represent V and VI group elements, respectively. In this study, in situ angle-dispersive X-ray diffraction measurements were performed on Bi2Te2Se, BiSbTeSe2, and Sb2Te2Se tetradymites under high pressure. Bi2Te2Se transforms from a layered rhombohedral structure (phase I) into 7-fold monoclinic (phase II) and body-centered tetragonal (phase IV) structures at about 8.0 and 14.3 GPa, respectively, without an 8-fold monoclinic structure (phase III) similar to that in Bi2Te3. Thus, the compression behavior of Bi2Te2Se is the same as that of Bi2Se3,more » which could also be obtained from first-principles calculations and in situ high-pressure electrical resistance measurements. Under high pressure, BiSbTeSe2 and Sb2Te2Se undergo similar structural phase transitions to Bi2Te2Se, which indicates that the compression process of tellurides can be modulated by doping Se in Te sites. According to these high-pressure investigations of A2B3-type tetradymites, the decrease of the B-site atomic radius shrinks the stable pressure range of phase III and expands that of phase II, whereas the decrease of the A-site atomic radius induces a different effect, i.e. expanding the stable pressure range of phase III and shrinking that of phase II. Lastly, the influence of the atomic radius on the compression process of tetradymites is closely related to the chemical composition and the atom arrangement in the quintuple layer.« less

  9. New type of phase transformation in gas hydrate forming system at high pressures. Some experimental and computational investigations of clathrate hydrates formed in the SF6-H2O system.

    PubMed

    Aladko, E Ya; Ancharov, A I; Goryainov, S V; Kurnosov, A V; Larionov, E G; Likhacheva, A Yu; Manakov, A Yu; Potemkin, V A; Sheromov, M A; Teplykh, A E; Voronin, V I; Zhurko, F V

    2006-10-26

    In this work, we present a new, previously unknown type of structure transformation in the high-pressure gas hydrates, which is related to the existence of two different isostructural phases of the sulfur hexafluoride clathrate hydrates. Each of these phases has its own stability field on the phase diagram. The difference between these hydrates consists of partial filling of small D cages by SF(6) molecules in the high-pressure phase; at 900 MPa, about half of small cages are occupied. Our calculations indicate that the increase of population of small cavities is improbable, therefore, at any pressure value, a part of the cavities remains vacant and the packing density is relatively low. This fact allowed us to suppose the existence of the upper pressure limit of hydrate formation in this system; the experimental results obtained confirm this assumption.

  10. 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.

  11. 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.

  12. 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)

  13. High-pressure--high-temperature polymorphism in ta: resolving an ongoing experimental controversy.

    PubMed

    Burakovsky, L; Chen, S P; Preston, D L; Belonoshko, A B; Rosengren, A; Mikhaylushkin, A S; Simak, S I; Moriarty, J A

    2010-06-25

    Phase diagrams of refractory metals remain essentially unknown. Moreover, there is an ongoing controversy over the high-pressure melting temperatures of these metals: results of diamond anvil cell (DAC) and shock wave experiments differ by at least a factor of 2. From an extensive ab initio study on tantalum we discovered that the body-centered cubic phase, its physical phase at ambient conditions, transforms to another solid phase, possibly hexagonal omega phase, at high temperature. Hence the sample motion observed in DAC experiments is very likely not due to melting but internal stresses accompanying a solid-solid transformation, and thermal stresses associated with laser heating.

  14. [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

  15. Real-Time Optical Monitoring and Simulations of Gas Phase Kinetics in InN Vapor Phase Epitaxy at High Pressure

    NASA Technical Reports Server (NTRS)

    Dietz, Nikolaus; Woods, Vincent; McCall, Sonya D.; Bachmann, Klaus J.

    2003-01-01

    Understanding the kinetics of nucleation and coalescence of heteroepitaxial thin films is a crucial step in controlling a chemical vapor deposition process, since it defines the perfection of the heteroepitaxial film both in terms of extended defect formation and chemical integrity of the interface. The initial nucleation process also defines the film quality during the later stages of film growth. The growth of emerging new materials heterostructures such as InN or In-rich Ga(x)In(1-x)N require deposition methods operating at higher vapor densities due to the high thermal decomposition pressure in these materials. High nitrogen pressure has been demonstrated to suppress thermal decomposition of InN, but has not been applied yet in chemical vapor deposition or etching experiments. Because of the difficulty with maintaining stochiometry at elevated temperature, current knowledge regarding thermodynamic data for InN, e.g., its melting point, temperature-dependent heat capacity, heat and entropy of formation are known with far less accuracy than for InP, InAs and InSb. Also, no information exists regarding the partial pressures of nitrogen and phosphorus along the liquidus surfaces of mixed-anion alloys of InN, of which the InN(x)P(1-x) system is the most interesting option. A miscibility gap is expected for InN(x)P(1-x) pseudobinary solidus compositions, but its extent is not established at this point by experimental studies under near equilibrium conditions. The extension of chemical vapor deposition to elevated pressure is also necessary for retaining stoichiometric single phase surface composition for materials that are characterized by large thermal decomposition pressures at optimum processing temperatures.

  16. Phase transitions and photoinduced transformations at high pressure in the molecular donor-acceptor fullerene complex (Cd(dedtc){sub 2}){sub 2} · C{sub 60}

    SciTech Connect

    Meletov, K. P.; Konarev, D. V.; Tolstikova, A. O.

    2015-06-15

    The Raman spectra of crystals of C{sub 60} fullerene-cadmium diethyldithiocarbamate molecular donor-acceptor complexes (Cd(dedtc){sub 2}){sub 2} · C{sub 60} were measured at pressures of up to 17 GPa, and the crystal lattice parameters of these complexes were determined at pressures of up to 6 GPa. An increase in pressure up to ∼2 GPa leads to changes in the Raman spectra, which are manifested by splitting of the intramolecular H{sub g}(1)-H{sub g}(8) phonon modes and by softening of the A{sub g}(2) mode of the C{sub 60} molecule. A further increase in pressure up to 17 GPa does not induce significant new changes to the Raman spectra, while a decrease is accompanied by the reverse transformation at a pressure of about 2 GPa. The pressure dependence of the lattice parameters also exhibits a reversible feature at 2 GPa related to a jumplike decrease in compressibility. All these data are indicative of a phase transition in the vicinity of 2 GPa related to the formation of covalent bonds between C{sub 60} molecules and, probably, the appearance of C{sub 120} dimers in fullerene layers. It was also found that, in the pressure interval from 2 to 6.3 GPa, the Raman spectra of complexes exhibit photoinduced transformations under prolonged exposure to laser radiation with a wavelength of λ = 532 nm and power density up to 5000 W/cm{sup 2}. These changes are manifested by splitting and softening of the A{sub g}(2) mode and resemble analogous changes accompanying the photopolymerization of C{sub 60} fullerene. The intensity of new bands exhibits exponential growth with increasing exposure time. The photopolymer yield depends on both the laser radiation power and external pressure. The A{sub g}(2) mode splitting under irradiation can be related to the formation of photo-oligomers with various numbers of intermolecular covalent bonds per C{sub 60} molecule.

  17. 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

  18. 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.

  19. Elastic Anomalies Accompanying Phase Transitions in (CaSr)TiO3 Perovskite III: Experimental Investigation of Polycrystalline Samples

    SciTech Connect

    Carpenter,M.; Li, B.; Liebermann, R.

    2007-01-01

    Bulk and shear moduli of polycrystalline samples of perovskites with different compositions across the CaTiO3-SrTiO3 solid solution have been measured at ambient conditions and in-situ at high pressures by pulse-echo ultrasonic methods. The samples were prepared as dense pellets by hot pressing synthetic powders at {approx}7.5 GPa and {approx}1000 C. Any variations of bulk modulus due to phase transitions are small, but significant anomalies have been observed in the shear modulus at ambient conditions. These are associated with a sequence of symmetry changes PmFormulam -> I4/mcm -> Pbcm -> Pnma with increasing CaTiO3 content. Comparison with variations in elastic properties predicted using Landau theory suggests that a substantial part of the elastic softening observed in tetragonal samples could be due to anelastic contributions from transformation twin walls. This additional softening does not occur in orthorhombic samples, and the transition from tetragonal to orthorhombic symmetry results in a stiffening of the shear modulus. No overt evidence was found for a phase transition I4/mcm {leftrightarrow} Pnma at high pressures in Ca0.35Sr0.65TiO3 but small changes in the trends of both bulk and shear moduli in the range 2.5-3 GPa could be due either to a different transition or a change in compression mechanism. A PmFormulam {leftrightarrow} I4/mcm transition at {approx}2 GPa in Ca0.05Sr0.95TiO3 shows the same form of softening as observed for the transition as a function of composition. A simple model of twin wall contributions to the compliance of tetragonal samples failed to match the observed variations that, alternatively, seem to follow {Delta}G {proportional_to} q4 where {Delta}G is the change in shear modulus and q4 the driving order parameter for the PmFormulam {leftrightarrow} I4/mcm transition. Analogous elastic behavior is expected to occur in (Mg,Fe)SiO3 and CaSiO3 perovskites at high pressures and temperatures.

  20. Combined Theoretical and in Situ Scattering Strategies for Optimized Discovery and Recovery of High-Pressure Phases: A Case Study of the GaN-Nb2O5 System.

    PubMed

    Woerner, William R; Qian, Guang-Rui; Oganov, Artem R; Stephens, Peter W; Dharmagunawardhane, H A Naveen; Sinclair, Alexandra; Parise, John B

    2016-04-04

    The application of pressure in solid-state synthesis provides a route for the creation of new and exciting materials. However, the onerous nature of high-pressure techniques limits their utility in materials discovery. The systematic search for novel oxynitrides-semiconductors for photocatalytic overall water splitting-is a representative case where quench high-pressure synthesis is useful and necessary in order to obtain target compounds. We utilize state of the art crystal structure prediction theory (USPEX) and in situ synchrotron-based X-ray scattering to speed up the discovery and optimization of novel compounds using high-pressure synthesis. Using this approach, two novel oxynitride phases were discovered in the GaN-Nb2O5 system. The (Nb2O5)0.84:(NbO2)0.32:(GaN)0.82 rutile structured phase was formed at 1 GPa and 900 °C and gradually transformed to a α-PbO2-related structure above 2.8 GPa and 1000 °C. The low-pressure rutile type phase was found to have a direct optical band gap of 0.84 eV and an indirect gap of 0.51 eV.

  1. Combined Theoretical and in Situ Scattering Strategies for Optimized Discovery and Recovery of High-Pressure Phases: A Case Study of the GaN–Nb 2 O 5 System

    SciTech Connect

    Woerner, William R.; Qian, Guang-Rui; Oganov, Artem R.; Stephens, Peter W.; Dharmagunawardhane, H. A. Naveen; Sinclair, Alexandra; Parise, John B.

    2016-04-04

    The application of pressure in solid-state synthesis provides a route for the creation of new and exciting materials. However, the onerous nature of high-pressure techniques limits their utility in materials discovery. The systematic search for novel oxynitrides—semiconductors for photocatalytic overall water splitting—is a representative case where quench high-pressure synthesis is useful and necessary in order to obtain target compounds. We utilize state of the art crystal structure prediction theory (USPEX) and in situ synchrotron-based X-ray scattering to speed up the discovery and optimization of novel compounds using high-pressure synthesis. Using this approach, two novel oxynitride phases were discovered in the GaN–Nb2O5 system. The (Nb2O5)0.84:(NbO2)0.32:(GaN)0.82 rutile structured phase was formed at 1 GPa and 900 °C and gradually transformed to a α-PbO2-related structure above 2.8 GPa and 1000 °C. The low-pressure rutile type phase was found to have a direct optical band gap of 0.84 eV and an indirect gap of 0.51 eV.

  2. Combined Theoretical and in Situ Scattering Strategies for Optimized Discovery and Recovery of High-Pressure Phases: A Case Study of the GaN–Nb2O5 System

    DOE PAGES

    Woerner, William R.; Qian, Guang-Rui; Oganov, Artem R.; ...

    2016-03-22

    The application of pressure in solid-state synthesis provides a route for the creation of new and exciting materials. However, the onerous nature of high-pressure techniques limits their utility in materials discovery. The systematic search for novel oxynitrides—semiconductors for photocatalytic overall water splitting—is a representative case where quench high-pressure synthesis is useful and necessary in order to obtain target compounds. In this paper, we utilize state of the art crystal structure prediction theory (USPEX) and in situ synchrotron-based X-ray scattering to speed up the discovery and optimization of novel compounds using high-pressure synthesis. Using this approach, two novel oxynitride phases weremore » discovered in the GaN–Nb2O5 system. The (Nb2O5)0.84:(NbO2)0.32:(GaN)0.82 rutile structured phase was formed at 1 GPa and 900°C and gradually transformed to a α-PbO2-related structure above 2.8 GPa and 1000°C. The low-pressure rutile type phase was found to have a direct optical band gap of 0.84 eV and an indirect gap of 0.51 eV.« less

  3. Combined Theoretical and in Situ Scattering Strategies for Optimized Discovery and Recovery of High-Pressure Phases: A Case Study of the GaN–Nb2O5 System

    SciTech Connect

    Woerner, William R.; Qian, Guang-Rui; Oganov, Artem R.; Stephens, Peter W.; Dharmagunawardhane, H. A. Naveen; Sinclair, Alexandra; Parise, John B.

    2016-03-22

    The application of pressure in solid-state synthesis provides a route for the creation of new and exciting materials. However, the onerous nature of high-pressure techniques limits their utility in materials discovery. The systematic search for novel oxynitrides—semiconductors for photocatalytic overall water splitting—is a representative case where quench high-pressure synthesis is useful and necessary in order to obtain target compounds. In this paper, we utilize state of the art crystal structure prediction theory (USPEX) and in situ synchrotron-based X-ray scattering to speed up the discovery and optimization of novel compounds using high-pressure synthesis. Using this approach, two novel oxynitride phases were discovered in the GaN–Nb2O5 system. The (Nb2O5)0.84:(NbO2)0.32:(GaN)0.82 rutile structured phase was formed at 1 GPa and 900°C and gradually transformed to a α-PbO2-related structure above 2.8 GPa and 1000°C. The low-pressure rutile type phase was found to have a direct optical band gap of 0.84 eV and an indirect gap of 0.51 eV.

  4. Quantitation of the main constituents of vanilla by reverse phase HPLC and ultra-high-pressure-liquid-chromatography with UV detection: method validation and performance comparison.

    PubMed

    Cicchetti, Esmeralda; Chaintreau, Alain

    2009-09-01

    Vanilla's main constituents, i. e., vanillin, para-hydroxybenzaldehyde, and their corresponding acids, can be easily quantified by RP LC with UV detection and external calibration. This paper describes two methods that were developed using HPLC and ultra-high-pressure LC (UHPLC), respectively, and validated according to the International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH). Both methods were highly specific, exhibited good linearities with high precision, and achieved good accuracies of quantitative results. The UHPLC method was more sensitive, five times shorter, and gave better peak resolutions than the HPLC alternative.

  5. High-pressure neutron diffraction

    SciTech Connect

    Xu, Hongwu

    2011-01-10

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

  6. High-pressure phase relations in the composition of albite NaAlSi3O8 constrained by an ab initio and quasi-harmonic Debye model, and their implications

    NASA Astrophysics Data System (ADS)

    Deng, L.; Liu, X.; Liu, H.; Dong, J.

    2010-12-01

    The high pressure physical-chemical behaviors of feldspar in subducted slab are very important to the geodynamic process in the deep interior of the Earth. Albite (NaAlSi3O8;Ab) is one of the few end members in the feldspar family, and its high-P behavior is obviously a prerequisite to the full understanding of the physical-chemical properties of feldspar at high pressures. So far it has been well accepted that Ab breaks down to the phase assemblage of Jadeite+Stishovite(NaAlSi2O6; Jd, SiO2; St,JS hereafter) at ~9-10 GPa. The JS phase assemblage might be stable up to ~23 GPa, and eventually directly change into the phase assemblage of calcium-ferrite type NaAlSiO4 (Cf) +2St (CS hereafter). However, some independent researches suggest there is an intermediate phase Na-hollandite (Na-Hall; a phase with the composition of NaAlSi3O8 and the structure of hollandite) between JS phase assemblage transition into CS phase assemblage (Liu 1978; Tutti 2007; Sekine and Ahrens, 1992; Beck et al., 2004). Whether Na-Hall is a thermodynamic stable phase under high P-T conditions remains unknown. In this work, phase relations in the composition of albite NaAlSi3O8 at pressures up to 40 GPa were constrained by a theoretical method that combines the ab initio calculation and quasi-harmonic Debyemodel. First, the P-T dependence of the thermodynamic potentials of the individual phase, St, Cf, Jd and the hypothetical Na-Holl were derived. Our results are generally in consistent agreement with available experimental data and previous theoretical predictions. Second, the Gibbs free energy of the hypothetical Na-Holl phase was compared with that of the phase assemblages JS and CS. Our results show that the Na-Holl phase is not a thermodynamically stable phase over the studied P-T conditions of 0-40 GPa and 100-600 K, which rules it out as a possible intermediate phase along the transition path from the JS phase assemblage to CS phase assemblage. Our calculations have predicted that the JS

  7. Phase volume changes accompanying water extraction from aqueous electrolyte solutions by 1-octanol

    SciTech Connect

    Sun, Y.; Moyer, B.A.

    1995-03-01

    The extraction of water by 1-octanol was calculated as a function of aqueous electrolyte concentration and initial O/A volume ratio for a series of representative salts, including LiCl, NaCl, KCl, NaNO{sub 3}, NaClO{sub 4}, MgCl{sub 2}, and CaCl{sub 2}. These results were then used to calculate the resultant phase-volume changes and aqueous-electrolyte-concentration changes. Such corrections are necessitated for precise extraction measurements employing 1-octanol as a diluent, especially as the O/A phase ratio exceeds unity. 20 refs., 2 figs., 1 tab.

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  10. 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.

  11. Electrokinetically pumped high pressure sprays

    DOEpatents

    Schoeniger, Joseph S.; Paul, Phillip H.; Schoeniger, Luke

    2002-01-01

    An electrokinetic pump capable of producing high pressure is combined with a nozzle having a submicron orifice to provide a high pressure spray device. Because of its small size, the device can be contained within medical devices such as an endoscope for delivering biological materials such as DNA, chemo therapeutic agents, or vaccines to tissues and cells.

  12. Infrared spectroscopic and modeling studies of H{sub 2}/CH{sub 4} microwave plasma gas phase from low to high pressure and power

    SciTech Connect

    Rond, C. Lombardi, G.; Gicquel, A.; Hamann, S.; Röpcke, J.; Wartel, M.

    2014-09-07

    InfraRed Tunable Diode Laser Absorption Spectroscopy technique has been implemented in a H{sub 2}/CH{sub 4} Micro-Wave (MW frequency f = 2.45 GHz) plasma reactor dedicated to diamond deposition under high pressure and high power conditions. Parametric studies such as a function of MW power, pressure, and admixtures of methane have been carried out on a wide range of experimental conditions: the pressure up to 270 mbar and the MW power up to 4 kW. These conditions allow high purity Chemical Vapor Deposition diamond deposition at high growth rates. Line integrated absorption measurements have been performed in order to monitor hydrocarbon species, i.e., CH{sub 3}, CH{sub 4}, C{sub 2}H{sub 2}, C{sub 2}H{sub 4}, and C{sub 2}H{sub 6}. The densities of the stable detected species were found to vary in the range of 10{sup 12}–10{sup 17} molecules cm{sup −3}, while the methyl radical CH{sub 3} (precursor of diamond growth under these conditions) measured into the plasma bulk was found up to 10{sup 14} molecules cm{sup −3}. The experimental densities have been compared to those provided by 1D-radial thermochemical model for low power and low pressure conditions (up to 100 mbar/2 kW). These densities have been axially integrated. Experimental measurements under high pressure and power conditions confirm a strong increase of the degree of dissociation of the precursor, CH{sub 4}, associated to an increase of the C{sub 2}H{sub 2} density, the most abundant reaction product in the plasma.

  13. 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.

  14. High-pressure orthorhombic ferromagnesite as a potential deep-mantle carbon carrier

    DOE PAGES

    Liu, Jin; Lin, Jung -Fu; Prakapenka, Vitali B.

    2015-01-06

    In this study, knowledge of the physical and chemical properties of candidate deep-carbon carriers such as ferromagnesite [(Mg,Fe)CO3] at high pressure and temperature of the deep mantle is necessary for our understanding of deep-carbon storage as well as the global carbon cycle of the planet. Previous studies have reported very different scenarios for the (Mg,Fe)CO3 system at deep-mantle conditions including the chemical dissociation to (Mg,Fe)O+CO2, the occurrence of the tetrahedrally-coordinated carbonates based on CO4 structural units, and various high-pressure phase transitions. Here we have studied the phase stability and compressional behavior of (Mg,Fe)CO3 carbonates up to relevant lower-mantle conditions ofmore » approximately 120 GPa and 2400 K. Our experimental results show that the rhombohedral siderite (Phase I) transforms to an orthorhombic phase (Phase II with Pmm2 space group) at approximately 50 GPa and 1400 K. The structural transition is likely driven by the spin transition of iron accompanied by a volume collapse in the Fe-rich (Mg,Fe)CO3 phases; the spin transition stabilizes the high-pressure phase II at much lower pressure conditions than its Mg-rich counterpart. It is conceivable that the low-spin ferromagnesite phase II becomes a major deep-carbon carrier at the deeper parts of the lower mantle below 1900 km in depth.« less

  15. Volume and pressure dependences of the electronic, vibrational, and crystal structures of C s2CoC l4 : Identification of a pressure-induced piezochromic phase at high pressure

    NASA Astrophysics Data System (ADS)

    Nataf, L.; Aguado, F.; Hernández, I.; Valiente, R.; González, J.; Sanz-Ortiz, M. N.; Wilhelm, H.; Jephcoat, A. P.; Baudelet, F.; Rodríguez, F.

    2017-01-01

    This work investigates the high-pressure structure of C s2CoC l4 and how it affects the electronic and vibrational properties using optical absorption, Raman spectroscopy, x-ray diffraction, and x-ray absorption in the 0-15 GPa range. In particular, we focus on the electronic and local structures of C o2 + , since compression of C s2CoC l4 yields structural transformations associated with change of coordination around C o2 + , which are eventually responsible for the intense piezochromism at 7 GPa. This study provides a complete characterization of the electronic and vibrational structures of C s2CoC l4 in the Pnma phase as a function of the cell volume and the local CoC l4 bond length, RCo-Cl, as well as its corresponding equation of state. In addition, our interest is to elucidate whether the phase transition undergone by C s2CoC l4 at 7 GPa leads to a perovskite-layer-type structure where C o2 + is sixfold coordinated, decomposes into CsCl +CsCoC l3 , or it involves an unknown phase with different coordination sites for C o2 + . We show that C o2 + is sixfold coordinated in the high-pressure phase. The analysis of optical spectra and x-ray diffraction data suggests the formation of an interconnected structure of exchange-coupled C o2 + through edge-sharing octahedra at high pressure.

  16. Activation of alpha chymotrypsin by three phase partitioning is accompanied by aggregation.

    PubMed

    Rather, Gulam Mohmad; Mukherjee, Joyeeta; Halling, Peter James; Gupta, Munishwar Nath

    2012-01-01

    Precipitation of alpha chymotrypsin in the simultaneous presence of ammonium sulphate and t-butanol (three phase partitioning) resulted in preparations which showed self aggregation of the enzyme molecules. Precipitation with increasing amounts of ammonium sulphate led to increasing size of aggregates. While light scattering estimated the hydrodynamic diameter of these aggregates in the range of 242-1124 nm; Nanoparticle tracking analysis (NTA) gave the value as 130-462 nm. Scanning electron microscopy and gel filtration on Sephadex G-200 showed extensive aggregation in these preparations. Transmission electron microscopy showed that the aggregates had irregular shapes. All the aggregates had about 3× higher catalytic activity than the native enzyme. These aggregates did not differ in λ(max) of fluorescence emission which was around 340 nm. However, all the aggregates showed higher fluorescence emission intensity. Far-UV and near-UV circular dichroism also showed no significant structural changes as compared to the native molecule. Interestingly, HPLC gel filtration (on a hydroxylated silica column) gave 14 nm as the diameter for all preparations. Light scattering of preparations in the presence of 10% ethylene glycol also dissociated the aggregates to monomers of 14 nm. Both these results indicated that hydrophobic interactions were the driving force behind this aggregation. These results indicate: (1) Even without any major structural change, three phase partitioning led to protein molecules becoming highly prone to aggregation. (2) Different methods gave widely different estimates of sizes of aggregates. It was however possible to reconcile the data obtained with various approaches. (3) The nature of the gel filtration column is crucial and use of this technique for refolding and studying aggregation needs a rethink.

  17. Characteristics of the electric field accompanying a longitudinal acoustic wave in a metal. Anomaly in the superconducting phase

    NASA Astrophysics Data System (ADS)

    Avramenko, Yu. A.; Bezuglyi, E. V.; Burma, N. G.; Kolobov, I. G.; Fil', V. D.; Shevchenko, O. A.; Gokhfeld, V. M.

    2002-05-01

    The temperature dependence of the amplitude and phase of the electric potential arising at a plane boundary of a conductor when a longitudinal acoustic wave is incident normally on it is investigated theoretically and experimentally. The surface potential is formed by two contributions, one of which is spatially periodic inside the sample, with the period of the acoustic field; the second is aperiodic and arises as a result of an additional nonuniformity of the electron distribution in a surface layer of the metal. In the nonlocal of parameters region the second contribution is dominant. The phases of these contributions are shifted by approximately π/2. For metals found in the normal state the experiment is in qualitative agreement with the theory. The superconducting transition is accompanied by catastrophically rapid vanishing of the electric potential, in sharp contrast to the theoretical estimates, which predict behavior similar to the BCS dependence of the attenuation coefficient for longitudinal sound.

  18. CONDENSED MATTER: ELECTRONIC STRUCTURE, ELECTRICAL, MAGNETIC, AND OPTICAL PROPERTIES: Phase Transition and Optical Properties of Solid Oxygen under High Pressure: A Density Functional Theory Study

    NASA Astrophysics Data System (ADS)

    Liu, Yan-Hui; Tian, Fu-Bo; Ma, Yan-Ming; He, Zhi; Cui, Tian; Liu, Bing-Bing; Zou, Guang-Tian

    2008-07-01

    Crystal structures and optical properties of the δ-O2 phase and the ∈-O8 phase have been investigated by using the ab initio pseudopotential plane-wave method. It is found that the phase transition is of the first order with a discontinuous volumetric change from the antiferromagnetic δ-O2 phase to the nonmagnetic ∈-O8 phase, consistent with the experimental findings. The energy band calculations show that the direct band gap changes into an indirect band gap after the phase transition. The apparent change in the optical properties can be used for identifying the phase transition from δ-O2 to ∈-O8.

  19. The high-pressure phase diagram of synthetic epsomite (MgSO4·7H2O and MgSO4·7D2O) from ultrasonic and neutron powder diffraction measurements

    NASA Astrophysics Data System (ADS)

    Gromnitskaya, E. L.; Yagafarov, O. F.; Lyapin, A. G.; Brazhkin, V. V.; Wood, I. G.; Tucker, M. G.; Fortes, A. D.

    2013-03-01

    We present an ultrasonic and neutron powder diffraction study of crystalline MgSO4·7H2O (synthetic epsomite) and MgSO4·7D2O under pressure up to ~3 GPa near room temperature and up to ~2 GPa at lower temperatures. Both methods provide complementary data on the phase transitions and elasticity of magnesium sulphate heptahydrate, where protonated and deuterated counterparts exhibit very similar behaviour and properties. Under compression in the declared pressure intervals, we observed three different sequences of phase transitions: between 280 and 295 K, phase transitions occurred at approximately 1.4, 1.6, and 2.5 GPa; between 240 and 280 K, only a single phase transition occurred; below 240 K, there were no phase transformations. Overall, we have identified four new phase fields at high pressure, in addition to that of the room-pressure orthorhombic structure. Of these, we present neutron powder diffraction data obtained in situ in the three phase fields observed near room temperature. We present evidence that these high-pressure phase fields correspond to regions where MgSO4·7H2O decomposes to a lower hydrate by exsolving water. Upon cooling to liquid nitrogen temperatures, the ratio of shear modulus G to bulk modulus B increases and we observe elastic softening of both moduli with pressure, which may be a precursor to pressure-induced amorphization. These observations may have important consequences for modelling the interiors of icy planetary bodies in which hydrated sulphates are important rock-forming minerals, such as the large icy moons of Jupiter, influencing their internal structure, dynamics, and potential for supporting life.

  20. Grain size dependence of elastic anomalies accompanying the α β phase transition in polycrystalline quartz

    NASA Astrophysics Data System (ADS)

    McKnight, Ruth E. A.; Moxon, T.; Buckley, A.; Taylor, P. A.; Darling, T. W.; Carpenter, M. A.

    2008-02-01

    The effects of grain size on the elastic properties of quartz through the α-β phase transition have been investigated by resonant ultrasound spectroscopy. It is found that there are three regimes, dependent on grain size, within which elastic properties show different evolutions with temperature. In the large grain size regime, as represented by a quartzite sample with ~100-300 µm grains, microcracking is believed to occur in the vicinity of the transition point, allowing grains to pull apart. In the intermediate grain size regime, as represented by novaculite (1-5 µm grain size) and Ethiebeaton agate (~120 nm grain size), bulk and shear moduli through the transition follow closely the values expected from averages of single crystal data. The novaculite sample, however, has a transition temperature ~7 °C higher than that of single crystal quartz. This is assumed to be due to the development of internal pressure arising from anisotropic thermal expansion. In the small grain size region, agates from Mexico (~65 nm) and Brazil (~50 nm) show significant reductions in the amount of softening of the bulk modulus as the transition point is approached from below. This is consistent with a tendency for the transition to become more second order in character. The apparent changes towards second order character do not match quantitative predictions for samples with homogeneous strain across elastically clamped nanocrystals, however. Some of the elastic variations are also due to the presence of moganite in these samples. True 'nanobehaviour' for quartz in ceramic samples thus appears to be restricted to grain sizes of less than ~50 nm.

  1. High Pressure Industrial Water Facility

    NASA Technical Reports Server (NTRS)

    1992-01-01

    In conjunction with Space Shuttle Main Engine testing at Stennis, the Nordberg Water Pumps at the High Pressure Industrial Water Facility provide water for cooling the flame deflectors at the test stands during test firings.

  2. Experimental Investigation of Magnetic Superconducting, and other Phase Transitions in Novel f-Electron Materials at Ultra-high Pressures Using Designer Diamond Anvils

    SciTech Connect

    Maple, M. Brian

    2005-09-13

    Pressure is a powerful control parameter, owing to its ability to affect crystal and electronic structure without introducing defects, for the investigation of condensed matter systems. Some f-electron, heavy-fermion materials display interesting and novel behavior when exposed to pressures achievable with conventional experimental techniques; however, a growing number of condensed matter systems require extreme conditions such as ultrahigh pressures, high magnetic fields, and ultralow temperatures to sufficiently explore the important properties. To that end, we have been funded to develop an ultrahigh pressure facility at the University of California, San Diego (UCSD) in order to investigate superconductivity, magnetism, non-Fermi liquid behavior, and other phenomena under extreme conditions. Our goals for the second year of this grant were as follows: (a) perform electrical resistivity measurements on novel samples at a myriad of pressures using conventional piston-cylinder techniques, Bridgman anvil techniques, and diamond anvil cell technology; (b) install, commission, and operate an Oxford Kelvinox MX-100 dilution refrigerator for access to ultralow temperatures and high magnetic fields. (c) continue the development of diamond anvil cell (DAC) technology. During the past year, we have successfully installed the Oxford Kelvinox MX-100 dilution refrigerator and verified its operability down to 12 mK. We have begun an experimental program to systematically investigate the f-electron compound URu2Si2 under pressure and in the presence of magnetic fields. We have also continued our collaborative work with Sam Weir at Lawrence Livermore National Laboratory (LLNL) on Au4V and implemented a new corollary study on Au1-xVx using ultrahigh pressures. We have continued developing our DAC facility by designing and constructing an apparatus for in situ pressure measurement as well as designing high pressure cells. This report serves to highlight the progress we have made

  3. 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).

  4. The mechanism and effect of defects in the B1 B2 phase transition of KCl under high pressure: molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Kinoshita, Takahiro; Mashimo, Tsutomu; Kawamura, Katsuyuki

    2005-02-01

    Molecular dynamics (MD) simulations of the pressure-induced phase transition of potassium chloride (KCl) were performed with 2744 and 9000 atoms to study crystalline states, the process and the effects of defects under high hydrostatic pressure. In this study, we adopted the Born-Mayer-Huggins-type potential function to describe the interatomic interaction. The potential parameters used in this study were empirically optimized on the basis of Hugoniot equation of state data. The simulation results for perfect crystals (1372 K+ and 1372 Cl-) showed that the B1-B2 phase transition occurred with large hysteresis, and the thermodynamic transition pressure was calculated to be 3.5 GPa. The simulation results indicated that the phase transition proceeded through displacements of atomic lines parallel to the \\langle 100\\rangle axis direction of the B1-type structure, and that these lines corresponded to the atomic lines parallel to the \\langle 111\\rangle axis direction of the B2-type structure after the phase transition. In the case of the larger cells containing 9000 atoms with weak or strong van der Waals interactions, some clusters or dislocations, respectively, were generated in the resultant B2 phase. As regards dislocations, the phase transitions started around dislocations and the phase transition pressure decreased.

  5. On the room-temperature phase diagram of high pressure hydrogen: An ab initio molecular dynamics perspective and a diffusion Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Chen, Ji; Ren, Xinguo; Li, Xin-Zheng; Alfè, Dario; Wang, Enge

    2014-07-01

    The finite-temperature phase diagram of hydrogen in the region of phase IV and its neighborhood was studied using the ab initio molecular dynamics (MD) and the ab initio path-integral molecular dynamics (PIMD). The electronic structures were analyzed using the density-functional theory (DFT), the random-phase approximation, and the diffusion Monte Carlo (DMC) methods. Taking the state-of-the-art DMC results as benchmark, comparisons of the energy differences between structures generated from the MD and PIMD simulations, with molecular and dissociated hydrogens, respectively, in the weak molecular layers of phase IV, indicate that standard functionals in DFT tend to underestimate the dissociation barrier of the weak molecular layers in this mixed phase. Because of this underestimation, inclusion of the quantum nuclear effects (QNEs) in PIMD using electronic structures generated with these functionals leads to artificially dissociated hydrogen layers in phase IV and an error compensation between the neglect of QNEs and the deficiencies of these functionals in standard ab initio MD simulations exists. This analysis partly rationalizes why earlier ab initio MD simulations complement so well the experimental observations. The temperature and pressure dependencies for the stability of phase IV were also studied in the end and compared with earlier results.

  6. Publisher's Note: High-temperature superconductivity stabilized by electron-hole interband coupling in collapsed tetragonal phase of KFe2As2 under high pressure [Phys. Rev. B 91 , 060508(R) (2015)

    SciTech Connect

    Nakajima, Yasuyuki; Wang, Renxiong; Metz, Tristin; Wang, Xiangfeng; Wang, Limin; Cynn, Hyunchae; Weir, Samuel T.; Jeffries, Jason R.; Paglione, Johnpierre

    2015-03-09

    Here, we report a high-pressure study of simultaneous low-temperature electrical resistivity and Hall effect measurements on high quality single-crystalline KFe2As2 using designer diamond anvil cell techniques with applied pressures up to 33 GPa. In the low pressure regime, we show that the superconducting transition temperature Tc finds a maximum onset value of 7 K near 2 GPa, in contrast to previous reports that find a minimum Tc and reversal of pressure dependence at this pressure. Upon applying higher pressures, this Tc is diminished until a sudden drastic enhancement occurs coincident with a first-order structural phase transition into a collapsed tetragonal phase. The appearance of a distinct superconducting phase above 13 GPa is also accompanied by a sudden reversal of dominant charge carrier sign, from hole- to electron-like, which agrees with our band calculations predicting the emergence of an electron pocket and diminishment of hole pockets upon Fermi surface reconstruction. Our results suggest the high-temperature superconducting phase in KFe2As2 is substantially enhanced by the presence of nested electron and hole pockets, providing the key ingredient of high-Tc superconductivity in iron pnictide superconductors.

  7. 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.

  8. Emotional fluctuations in Bob Dylan's lyrics measured by the dictionary of affect accompany events and phases in his life.

    PubMed

    Whissell, Cynthia

    2008-04-01

    Lyrics for Bob Dylan's songs between 1962 and 2001 (close to 100,000 words) were scored with the help of the Dictionary of Affect in Language (Whissell, 2006). Means for Pleasantness, Activation, and Imagery are reported for 22 Blocks characterizing this time span. Significant but weak differences across Blocks were found for all three measures at the level of individual words. Emotional fluctuations in words included in Bob Dylan's lyrics accompanied events and phases in his life, although they were not entirely dictated by these events. Dylan used more highly Imaged and more Active words at times when his work was critically acclaimed. More Passive word choices characterized times of prolonged stress, and more Pleasant choices times of experimentation. Dylan's three popularity peaks were used to divide the singer's career into three stages (rhetor, poet, sage) which differed in terms of pronouns used.

  9. 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.

  10. 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.

  11. 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.

  12. Pretreatment in a high-pressure microwave processor for MIB-1 immunostaining of cytological smears and paraffin tissue sections to visualize the various phases of the mitotic cycle.

    PubMed

    Suurmeijer, A J; Boon, M E

    1999-08-01

    In many pathology laboratories, both microwave ovens and pressure cookers are used for pretreatment of cytologic smears and paraffin sections to allow MIB-1 staining. For both methods there are two problems. First, the results cannot be used for quantitation because standardization is impossible. Second, the staining results are often suboptimal, resulting in negative staining of cells in the G(1)- and S-phases. When pretreatment is performed in a microwave processor, allowing microwave heating under pressure, precise temperature monitoring becomes possible. In addition, the importance of the pH of the buffer was studied using a test battery series. Optimal staining is achieved at a temperature of 115C, 10 min, pH 6. This method proved to be highly reproducible. Because the immunostaining results are optimal, the various phases of the cell cycle can be defined in the sections and smears. In addition, the perinucleolar staining of the late G(1)-phase is optimally visualized and nuclei of the stable pKi-67 pathway can be identified. Under suboptimal conditions, in particular, the number of cells in the late G(1)-phase are underestimated in the MIB-1 counts.

  13. Understanding the ε and ζ High-Pressure Solid Phases of Oxygen. Systematic Periodic Density Functional Theory Studies Using Localized Atomic Basis.

    PubMed

    Ochoa-Calle, A J; Zicovich-Wilson, C M; Hernández-Lamoneda, R; Ramírez-Solís, A

    2015-03-10

    The experimentally characterized ε and ζ phases of solid oxygen are studied by periodic Hartree-Fock (HF) and Density Functional Theory calculations at pressures from 10 to 160 GPa using different types of exchange-correlation functionals with Gaussian atomic basis sets. Full geometry optimizations of the monoclinic C2/m (O2)4 unit cell were done to study the evolution of the structural and electronic properties with pressure. Vibrational calculations were performed at each pressure. While periodic HF does not predict the ε-ζ phase transition in the considered range, Local Density approximation and Generalized Gradient approximation methods predict too low transition pressures. The performance of hybrid functional methods is dependent on the amount of non-local HF exchange. PBE0, M06, B3PW91, and B3LYP approaches correctly predict the structural and electronic changes associated with the phase transition. GGA and hybrid functionals predict a pressure range where both phases coexist, but only the latter type of methods yield results in agreement with experiment. Using the optimized (O2)4 unit cell at each pressure we show, through CASSCF(8,8) calculations, that the greater accuracy of the optimized geometrical parameters with increasing pressure is due to a decreasing multireference character of the unit cell wave function. The mechanism of the transition from the non-conducting to the conducting ζ phase is explained through the Electron Pair Localization Function, which clearly reveals chemical bonding between O2 molecules in the ab crystal planes belonging to different unit cells due to much shorter intercell O2-O2 distances.

  14. Determination and temperature effects of lidocaine (lignocaine) hydrochloride, epinephrine, methylparaben, 2,6-dimethylaniline, and p-hydroxybenzoic acid in USP lidocaine injection by ion-pair reversed-phase high pressure liquid chromatography

    SciTech Connect

    Smith, D.J.

    1981-05-01

    USP Lidocaine injection was assayed using ion-pair high pressure liquid chromatography with an octylsilane (RP-8) reversed-phase column packing and a mobile phase consisting of D-10-camphorsulfonic acid/methanol/acetic acid/water. The effect of temperature was investigated to determine the optimum temperature for separating the drug components and their degradation products. Lidocaine (lignocaine) hydrochloride, epinephrine, methylparaben, and p-hydroxybenzoic acid were separated at 50 degrees C. 2,6-Dimethylaniline was separated from lidocaine at 15 degrees C. An aliquot of the sample was injected directly into the liquid chromatograph, and after separation the compounds were quantitated by their spectrophotometric response at 254 nm (lidocaine) or 280 nm (lidocaine plus epinephrine).

  15. Determination and temperature effects of lidocaine (lignocaine) hydrochloride, epinephrine, methylparaben, 2,6-dimethylaniline, and p-hydroxybenzoic acid in USP lidocaine injection by ion-pair reversed-phase high pressure liquid chromatography.

    PubMed

    Smith, D J

    1981-05-01

    USP Lidocaine injection was assayed using ion-pair high pressure liquid chromatography with an octylsilane (RP-8) reversed-phase column packing and a mobile phase consisting of D-10-camphorsulfonic acid/methanol/acetic acid/water. The effect of temperature was investigated to determine the optimum temperature for separating the drug components and their degradation products. Lidocaine (lignocaine) hydrochloride, epinephrine, methylparaben, and p-hydroxybenzoic acid were separated at 50 degrees C. 2,6-Dimethylaniline was separated from lidocaine at 15 degrees C. An aliquot of the sample was injected directly into the liquid chromatograph, and after separation the compounds were quantitated by their spectrophotometric response at 254 nm (lidocaine) or 280 nm (lidocaine plus epinephrine).

  16. 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.

  17. Elasticity of orthoenstatite at high-pressure

    NASA Astrophysics Data System (ADS)

    Zhang, D.; Jackson, J. M.; Chen, B.; Zhao, J.; Yan, J.

    2011-12-01

    Orthoenstatite is an abundant yet complex mineral in Earth's upper mantle. Despite its abundance, the properties of orthopyroxene at high pressure remain ambiguous (e.g., Zhang et al. 2011; Jahn 2008; Kung et al. 2004). We explored select properties of a synthetic powdered orthoenstatite (Mg0.8757Fe0.13)2Si2O6 sample by X-ray diffraction (XRD) and nuclear resonance inelastic X-ray scattering (NRIXS) as a function of pressure in a neon pressure medium at 300 K. The XRD measurements were carried out at beamline 12.2.2 of the Advanced Light Source (Berkeley, CA), and the sample was studied up to 34 GPa. NRIXS measurements were carried out at sector 3ID-B of the Advanced Photon Source (Chicago, IL) in the pressure range of 3 to 17 GPa. From the raw NRIXS data, the partial phonon density of states (DOS) was derived (e.g., Sturhahn 2004). The volume (or pressure) dependence of several properties, such as the Lamb-Mössbauer factor, mean force constant, specific heat, vibrational entropy, and vibrational kinetic energy were determined from the DOS. We will discuss our results from these combined studies and the implications for Earth's upper mantle. References Zhang, D., J.M. Jackson, W. Sturhahn, and Y. Xiao (2011): Local structure variations observed in orthoenstatite at high-pressures. American Mineralogist, in press. Jahn, S. (2008) High-pressure phase transitions in MgSiO3 orthoenstatite studied by atomistic computer simulation. American Mineralogist, 93(4), 528-532. Kung, J., Li, B., Uchida, T., Wang, Y., Neuville, D., and Liebermann, R. (2004) In situ measurements of sound velocities and densities across the orthopyroxene high-pressure clinopyroxene transition in MgSiO3 at high pressure. Physics of the Earth and Planetary Interiors, 147(1), 27-44. Sturhahn, W. (2004): Nuclear Resonant Spectroscopy. J. Phys. Condens. Matter, 16, S497-S530.

  18. Characterization of free thiol variants of an IgG1 by reversed phase ultra high pressure liquid chromatography coupled with mass spectrometry.

    PubMed

    Liu, Hongbin; Jeong, Justin; Kao, Yung-Hsiang; Zhang, Yonghua Taylor

    2015-05-10

    RP-HPLC has been demonstrated as a powerful tool to study antibody free thiol and disulfide variants. Recently, the introduction of UHPLC columns with wide pore size (300Å) and small particle size (1.7μm) offered the opportunity to further improve the separation of such variants. This paper describes a systematic evaluation of stationary phases, operating parameters, and mobile phases for a UHPLC based method to separate free thiol variants of a recombinant monoclonal antibody (referred as mAb A), targeting high resolution, high throughput and improved recovery. Among the four different stationary phases evaluated, UHPLC diphenyl columns were found to provide the best separation. Using an optimized UHPLC method, free thiol variants of mAb A were separated in 5min. Importantly, the UHPLC method revealed minor variants that had coeluted in an HPLC based method, and the UHPLC method is also applicable as a platform method for characterization of other mAbs as well. Furthermore, an on-line UHPLC-MS method was developed to characterize the separated variants, and this method can streamline the characterization of fully assembled monoclonal and bispecific therapeutic antibodies.

  19. High pressure paint gun injuries.

    PubMed

    Booth, C M

    1977-11-19

    Despite their use for the past 20 years the dangers of injuries from high pressure paint guns are not widely known. Two cases treated incorrectly through ignorance in our casualty department resulted in amputation of digits. Paint solvents are far moe damaging than paint of grease injection. All cases should be treated urgently by an experienced surgeon as fairly extensive surgery may be needed.

  20. 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.

  1. 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.

  2. 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

  3. Experimental Investigation of Magnetic, Superconducting, and other Phase Transitions in novel F-Electron Materials at Ultra-high Pressures - Final Progress Report

    SciTech Connect

    Maple, Brian; Jeffires, Jason

    2006-07-28

    This grant, entitled “Experimental investigation of magnetic, superconducting and other phase transitions in novel f-electron materials at ultrahigh pressures,” spanned the funding period from May 1st, 2003 until April 30th, 2006. The major goal of this grant was to develop and utilize an ultrahigh pressure facility—capable of achieving very low temperatures, high magnetic fields, and extreme pressures as well as providing electrical resistivity, ac susceptibility, and magnetization measurement capabilities under pressure—for the exploration of magnetic, electronic, and structural phases and any corresponding interactions between these states in novel f-electron materials. Realizing this goal required the acquisition, development, fabrication, and implementation of essential equipment, apparatuses, and techniques. The following sections of this report detail the establishment of an ultrahigh pressure facility (Section 1) and measurements performed during the funding period (Section 2), as well as summarize the research project (Section 3), project participants and their levels of support (Section 4), and publications and presentations (Section 5).

  4. Liquid-vapor equilibrium of the systems butylmethylimidazolium nitrate-CO2 and hydroxypropylmethylimidazolium nitrate-CO2 at high pressure: influence of water on the phase behavior.

    PubMed

    Bermejo, M Dolores; Montero, Marta; Saez, Elisa; Florusse, Louw J; Kotlewska, Aleksandra J; Cocero, M José; van Rantwijk, Fred; Peters, Cor J

    2008-10-30

    Ionic liquids (IL) are receiving increasing attention due to their potential as "green" solvents, especially when used in combination with SC-CO2. In this work liquid-vapor equilibria of binary mixtures of CO2 with two imidazolium-based ionic liquids (IL) with a nitrate anion have been experimentally determined: butylmethylimidazolium nitrate (BMImNO3) and hydroxypropylmethylimidazolium nitrate (HOPMImNO3), using a Cailletet apparatus that operates according to the synthetic method. CO2 concentrations from 5 up to 30 mol % were investigated. It was found that CO2 is substantially less soluble in HOPMImNO3 than in BMImNO3. Since these ILs are very hygroscopic, water easily can be a major contaminant, causing changes in the phase behavior. In case these Ils are to be used in practical applications, for instance, together with CO2 as a medium in supercritical enzymatic reactions, it is very important to have quantitative information on how the water content will affect the phase behavior. This work presents the first systematic study on the influence of water on the solubility of carbon dioxide in hygroscopic ILs. It was observed that the presence of water reduces the absolute solubility of CO2. However, at fixed ratios of CO2/IL, the bubble point pressure remains almost unchanged with increasing water content. In order to explain the experimental results, the densities of aqueous mixtures of both ILs were determined experimentally and the excess molar volumes calculated.

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

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

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

  6. Preparation and kinetic performance assessment of thick film 10-20 μm open tubular silica capillaries in normal phase high pressure liquid chromatography.

    PubMed

    Forster, Simon; Kolmar, Harald; Altmaier, Stephan

    2013-11-08

    It is well-known that the open tubular column design basically can offer very high plate numbers. Experimental realization has however not kept pace with theoretical considerations, lacking efficient methods for the deposition of a thick film porous layer within a microbore capillary. A previously published sol-gel synthesis method was extended from 20 μm to 10 μm inner diameter fused silica capillaries and the resulting columns were compared to a monolithic reference capillary in terms of kinetic performance at pressure maximum. Column permeability was investigated and pressure/flow-diagrams were obtained with a 400-fold permeability gain for the open tubes. Structural characterizations regarding layer thickness and surface porosity were carried out and displayed via scanning electron microscopy and nitrogen sorption analysis. Chromatographic results in normal phase mode at elevated mobile phase flow rate reveal the intrinsic performance potential of this column format when it comes to kinetic performance limitation plots, which were constructed for all columns prepared and compared to the monolithic silica reference capillary.

  7. High pressure studies of potassium perchlorate

    SciTech Connect

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

    2016-07-29

    Two experiments are reported on KClO4 at extreme conditions. A static high pressure Raman study was first conducted to 18.9 GPa. Evidence for at least two new phases was observed: one between 2.4 and 7.7 GPa (possibly sluggish), and the second near 11.7 GPa. Then, the X-ray induced decomposition rate of potassium perchlorate (KClO4 hv→ KCl + 2O2) was studied up to 15.2 GPa. The time-dependent growth of KCl and O2 was monitored. The decomposition rate slowed at higher pressures. As a result, we present the first direct evidence for O2 crystallization at higher pressures, demonstrating that O2 molecules aggregate at high pressure.

  8. High pressure studies of potassium perchlorate

    DOE PAGES

    Pravica, Michael; Wang, Yonggang; Sneed, Daniel; ...

    2016-07-29

    Two experiments are reported on KClO4 at extreme conditions. A static high pressure Raman study was first conducted to 18.9 GPa. Evidence for at least two new phases was observed: one between 2.4 and 7.7 GPa (possibly sluggish), and the second near 11.7 GPa. Then, the X-ray induced decomposition rate of potassium perchlorate (KClO4 hv→ KCl + 2O2) was studied up to 15.2 GPa. The time-dependent growth of KCl and O2 was monitored. The decomposition rate slowed at higher pressures. As a result, we present the first direct evidence for O2 crystallization at higher pressures, demonstrating that O2 molecules aggregatemore » at high pressure.« less

  9. High-pressure optical studies

    SciTech Connect

    Drickamer, H.G.

    1981-01-01

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

  10. Isothermal equation of state and high-pressure phase transitions of synthetic meridianiite (MgSO4·11D2O) determined by neutron powder diffraction and quasielastic neutron spectroscopy

    PubMed Central

    Fortes, A. Dominic; Fernandez-Alonso, Felix; Tucker, Matthew; Wood, Ian G.

    2017-01-01

    We have collected neutron powder diffraction data from MgSO4·11D2O (the deuterated analogue of meridianiite), a highly hydrated sulfate salt that is thought to be a candidate rock-forming mineral in some icy satellites of the outer solar system. Our measurements, made using the PEARL/HiPr and OSIRIS instruments at the ISIS neutron spallation source, covered the range 0.1 < P < 800 MPa and 150 < T < 280 K. The refined unit-cell volumes as a function of P and T are parameterized in the form of a Murnaghan integrated linear equation of state having a zero-pressure volume V 0 = 706.23 (8) Å3, zero-pressure bulk modulus K 0 = 19.9 (4) GPa and its first pressure derivative, K′ = 9 (1). The structure’s compressibility is highly anisotropic, as expected, with the three principal directions of the unit-strain tensor having compressibilities of 9.6 × 10−3, 3.4 × 10−2 and 3.4 × 10−3 GPa−1, the most compressible direction being perpendicular to the long axis of a discrete hexadecameric water cluster, (D2O)16. At high pressure we observed two different phase transitions. First, warming of MgSO4·11D2O at 545 MPa resulted in a change in the diffraction pattern at 275 K consistent with partial (peritectic) melting; quasielastic neutron spectra collected simultaneously evince the onset of the reorientational motion of D2O molecules with characteristic time-scales of 20–30 ps, longer than those found in bulk liquid water at the same temperature and commensurate with the lifetime of solvent-separated ion pairs in aqueous MgSO4. Second, at ∼ 0.9 GPa, 240 K, MgSO4·11D2O decomposed into high-pressure water ice phase VI and MgSO4·9D2O, a recently discovered phase that has hitherto only been formed at ambient pressure by quenching small droplets of MgSO4(aq) in liquid nitrogen. The fate of the high-pressure enneahydrate on further compression and warming is not clear from the neutron diffraction data, but its occurrence

  11. 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.

  12. 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.

  13. Accelerated materials design approaches based on structural classification: application to low enthalpy high pressure phases of SH3 and SeH3

    NASA Astrophysics Data System (ADS)

    Flores-Livas, José A.; Sanna, Antonio; Goedecker, Stefan

    2017-01-01

    We propose a methodology that efficiently asseses major characteristics in the energy landscape for a given space of configurations (crystal structures) under pressure. In this work we study SH3 and SeH3 , both of fundamental interest due to their superconducting properties. Starting from the crystal fingerprint, which defines configurational distances between crystalline structures, we introduce an optimal one dimensional metric space that is used to both classify and characterize the structures. Furthermore, this is correlated to the electronic structure. Our analysis highlights the uniqueness of the Im - 3m phase of H3S and H33Se for superconductivity. This approach is an useful tool for future material design applications.

  14. Structure and properties of superelastic hard carbon phase created in fullerene-metal composites by high temperature-high pressure treatment

    NASA Astrophysics Data System (ADS)

    Chernogorova, O.; Drozdova, E.; Ovchinnikova, I.; Soldatov, A. V.; Ekimov, E.

    2012-06-01

    Treatment of a fullerene soot extract and metal (Co) powder mixture under pressure of 5 and 8 GPa at 1000 °C leads to the transformation of fullerites into superelastic hard phase (SHP) and to simultaneous sintering of the powder mixture to nonporous composite material reinforced by the SHP particles. The structure of the SHP particles reveals a topological relation to the initial fullerite crystal morphology. Upon indentation, the SHP particles demonstrate an elastic recovery of up to 96%. The universal microhardness of the SHP particles HU = 26 GPa, and their microhardness HV = 35 GPa. A high ratio between the microhardness and elastic modulus (HV/E = 0.19-0.21) of the SHP particles makes them perspective candidates for design of materials with superior wear resistance and tribological properties.

  15. High-pressure anatectic paragneisses from the Namche Barwa, Eastern Himalayan Syntaxis: Textural evidence for partial melting, phase equilibria modeling and tectonic implications

    NASA Astrophysics Data System (ADS)

    Guilmette, C.; Indares, A.; Hébert, R.

    2011-05-01

    Rare kyanite-bearing anatectic paragneisses are found as boudins within sillimanite-bearing paragneisses of the core of the Namche Barwa Antiform, Tibet. In the present study, we document an occurrence from the NW side of the Yarlung Zangbo River. These rocks mainly consist of the assemblage garnet + K-feldspar + kyanite ± biotite + quartz + rutile ± plagioclase with kyanite locally pseudomorphed by sillimanite. The documented textures are consistent with the rocks having undergone biotite-dehydration melting in the kyanite stability field, under high-P granulite facies conditions, and having experienced melt extraction. However textures related to melt crystallization are ubiquitous both in polymineralic inclusions in garnet and in the matrix, suggesting that a melt fraction had remained in these rocks. Phase equilibria modelling was undertaken in the NCKFMASTHO system with THERMOCALC. P-T pseudosections built with the bulk compositions of one aluminous and one sub-aluminous paragneiss samples predict a biotite-kyanite-garnet-quartz-plagioclase-K-feldspar-liquid-rutile ± ilmenite field, in which biotite-dehydration melting occurs, located in the P-T range of ~ 800-875 °C and ~ 10-17 kbar. In addition, the topologies of these pseudosections are consistent with substantial melt loss during prograde metamorphism. A second set of P-T pseudosections with melt-reintegrated model bulk compositions were thus constructed to evaluate the effect of melt loss. The integration of textural information, precise mineral modes, mineral chemistry, and phase equilibria modelling allowed to constrain a P-T path where the rocks are buried to lower crustal depths at peak P-T conditions higher than 14 kbar and 825 °C, possibly in the order of 15-16 kbar and 850 °C, followed by decompression and cooling to P-T conditions of around 9 kbar and 810 °C, under which the remaining melt was solidified. The implications for granite production at the NBA and for Himalayan tectonic models

  16. Three-Dimensional Unsteady Simulation of a Modern High Pressure Turbine Stage Using Phase Lag Periodicity: Analysis of Flow and Heat Transfer

    NASA Technical Reports Server (NTRS)

    Shyam, Vikram; Ameri, Ali; Luk, Daniel F.; Chen, Jen-Ping

    2010-01-01

    Unsteady three-dimensional RANS simulations have been performed on a highly loaded transonic turbine stage and results are compared to steady calculations as well as experiment. A low Reynolds number k- turbulence model is employed to provide closure for the RANS system. A phase-lag boundary condition is used in the periodic direction. This allows the unsteady simulation to be performed by using only one blade from each of the two rows. The objective of this paper is to study the effect of unsteadiness on rotor heat transfer and to glean any insight into unsteady flow physics. The role of the stator wake passing on the pressure distribution at the leading edge is also studied. The simulated heat transfer and pressure results agreed favorably with experiment. The time-averaged heat transfer predicted by the unsteady simulation is higher than the heat transfer predicted by the steady simulation everywhere except at the leading edge. The shock structure formed due to stator-rotor interaction was analyzed. Heat transfer and pressure at the hub and casing were also studied. Thermal segregation was observed that leads to the heat transfer patterns predicted by steady and unsteady simulations to be different.

  17. Drug-to-antibody determination for an antibody-drug-conjugate utilizing cathepsin B digestion coupled with reversed-phase high-pressure liquid chromatography analysis.

    PubMed

    Adamo, Michael; Sun, Guoyong; Qiu, Difei; Valente, Joseph; Lan, Wenkui; Song, Hangtian; Bolgar, Mark; Katiyar, Amit; Krishnamurthy, Girija

    2017-01-20

    Antibody drug conjugates or ADCs are currently being evaluated for their effectiveness as targeted chemotherapeutic agents across the pharmaceutical industry. Due to the complexity arising from the choice of antibody, drug and linker; analytical methods for release and stability testing are required to provide a detailed understanding of both the antibody and the drug during manufacturing and storage. The ADC analyzed in this work consists of a tubulysin drug analogue that is randomly conjugated to lysine residues in a human IgG1 antibody. The drug is attached to the lysine residue through a peptidic, hydrolytically stable, cathepsin B cleavable linker. The random lysine conjugation produces a heterogeneous mixture of conjugated species with a variable drug-to-antibody ratio (DAR), therefore, the average amount of drug attached to the antibody is a critical parameter that needs to be monitored. In this work we have developed a universal method for determining DAR in ADCs that employ a cathepsin B cleavable linker. The ADC is first cleaved at the hinge region and then mildly reduced prior to treatment with the cathepsin B enzyme to release the drug from the antibody fragments. This pre-treatment allows the cathepsin B enzyme unrestricted access to the cleavage sites and ensures optimal conditions for the cathepsin B to cleave all the drug from the ADC molecule. The cleaved drug is then separated from the protein components by reversed phase high performance liquid chromatography (RP-HPLC) and quantitated using UV absorbance. This method affords superior cleavage efficiency to other methods that only employ a cathepsin digestion step as confirmed by mass spectrometry analysis. This method was shown to be accurate and precise for the quantitation of the DAR for two different random lysine conjugated ADC molecules.

  18. Structural behaviour of niobium oxynitride under high pressure

    SciTech Connect

    Sharma, Bharat Bhooshan Poswal, H. K. Pandey, K. K. Sharma, Surinder M.; Yakhmi, J. V.; Ohashi, Y.; Kikkawa, S.

    2014-04-24

    High pressure investigation of niobium oxynitrides (NbN{sub 0.98}O{sub 0.02}) employing synchrotron based angle dispersive x-ray diffraction experiments was carried out in very fine pressure steps using membrane driven diamond anvil cell. Ambient cubic phase was found to be stable up to ∼18 GPa. At further high pressure cubic phase showed rhombohedral distortion.

  19. High-pressure injection injuries.

    PubMed

    Neal, N C; Burke, F D

    1991-11-01

    A retrospective review of the 11 patients attending the Hand Unit at the Derbyshire Royal Infirmary over the last 5 years with high-pressure injection injuries is presented. The machines and materials that cause these injuries are outlined and the methods of treatment and rehabilitation are described in detail. The study demonstrates the morbidity of high-pressure injection injuries, particularly those inflicted by paint spray guns, and highlights a frequent delay between injury and decompression of the injured part. We wish to emphasize the importance of early diagnosis, referral, exploration and rehabilitation to ensure an optimal outcome, and to point out that failure to refer early is becoming an increasing focus of negligence claims.

  20. 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.

  1. Cryogenic, Absolute, High Pressure Sensor

    NASA Technical Reports Server (NTRS)

    Chapman, John J. (Inventor); Shams. Qamar A. (Inventor); Powers, William T. (Inventor)

    2001-01-01

    A pressure sensor is provided for cryogenic, high pressure applications. A highly doped silicon piezoresistive pressure sensor is bonded to a silicon substrate in an absolute pressure sensing configuration. The absolute pressure sensor is bonded to an aluminum nitride substrate. Aluminum nitride has appropriate coefficient of thermal expansion for use with highly doped silicon at cryogenic temperatures. A group of sensors, either two sensors on two substrates or four sensors on a single substrate are packaged in a pressure vessel.

  2. 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

  3. 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

  4. Exotic stable cesium polynitrides at high pressure

    DOE PAGES

    Peng, Feng; Han, Yunxia; Liu, Hanyu; ...

    2015-11-19

    New polynitrides containing metastable forms of nitrogen are actively investigated as potential high energy-density materials. Using a structure search method based on the CALYPSO methodology, we investigated the stable stoichiometries and structures of cesium polynitrides at high pressures. Along with the CsN3, we identified five new stoichiometric compounds (Cs3N, Cs2N, CsN, CsN2, and CsN5) with interesting structures that may be experimentally synthesizable at modest pressures (i.e., less than 50 GPa). Nitrogen species in the predicted structures have various structural forms ranging from single atom (N) to highly endothermic molecules (N2, N3 , N4, N5, N6) and chains (N∞). Polymeric chainsmore » of nitrogen were found in the high-pressure C2/c phase of CsN2. This structure contains a substantially high content of single N-N bonds that exceeds the previously known nitrogen chains in pure forms, and also exhibit metastability at ambient conditions. We also identified a very interesting CsN crystal that contains novel N44- anion. In conclusion, to our best knowledge, this is the first time a charged N4 species being reported. Results of the present study suggest that it is possible to obtain energetic polynitrogens in main-group nitrides under high pressure.« less

  5. 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.

  6. High-pressure, high-temperature deformation of CaGeO3 (perovskite)±MgO aggregates: Elasto-ViscoPlastic Self-Consistent modeling and implications for multi-phase rheology of the lower mantle

    NASA Astrophysics Data System (ADS)

    Hilairet, N.; Tomé, C.; Wang, H.; Merkel, S.; Wang, Y.; Nishiyama, N.

    2014-12-01

    As the largest rocky layer in the Earth, the lower mantle plays a critical role in controlling convective patterns in our planet. Current mineralogical mantle models suggest that the lower mantle is dominated by (Mg,Fe)SiO3 perovskite (SiPv; about 70 - 90% in volume fraction) and (Mg,Fe)O ferropericlase (Fp). Knowledge of rheological properties of the major constituent minerals and stress/strain partitioning among these phases during deformation is critical in understanding dynamic processes of the deep Earth. For the lower mantle, the strength contrast between SiPv and Fp has been estimated [1], the former being much stronger than the latter. However fundamental issues of stress-strain interactions among the major phases still remain to be properly addressed. Here we examine rheological properties of a two-phase polycrystal consisting of CaGeO3 perovskite (GePv) and MgO, deformed in the D-DIA at controlled speed ~1 - 3×10-5 s-1 at high pressures and temperatures (between 3 to 10 GPa and 300 to 1200 K), with bulk axial strains up to ~20% [2]. We use Elasto-ViscoPlastic Self-Consistent modeling (EVPSC) [3] to reproduce lattice strains and textures measured in-situ with synchrotron X-ray diffraction. We compare the results to those on an identical deformation experiment with a single phase (GePv) polycrystal. We will discuss stress distributions between the two phases in the composite, textural developments, relationships with active slip systems, and finally the potential implications for rheological properties of the lower mantle. [1] Yamazaki, D., and S. Karato (2002), Fabric development in (Mg,Fe)O during large strain, shear deformation: implications for seismic anisotropy in Earth's lower mantle, Physics of the Earth and Planetary Interiors, 131(3-4), 251-267. [2] Wang, Y., N. Hilairet, N. Nishiyama, N. Yahata, T. Tsuchiya, G. Morard, and G. Fiquet (2013), High-pressure, high-temperature deformation of CaGeO3 (perovskite)+/- MgO aggregates: Implications for

  7. High-pressure modifications of CaZn{sub 2}, SrZn{sub 2}, SrAl{sub 2}, and BaAl{sub 2}: Implications for Laves phase structural trends

    SciTech Connect

    Kal, Subhadeep; Stoyanov, Emil; Belieres, Jean-Philippe; Groy, Thomas L.; Norrestam, Rolf; Haeussermann, Ulrich

    2008-11-15

    High-pressure forms of intermetallic compounds with the composition CaZn{sub 2}, SrZn{sub 2}, SrAl{sub 2}, and BaAl{sub 2} were synthesized from CeCu{sub 2}-type precursors (CaZn{sub 2}, SrZn{sub 2}, SrAl{sub 2}) and Ba{sub 21}Al{sub 40} by multi-anvil techniques and investigated by X-ray powder diffraction (SrAl{sub 2} and BaAl{sub 2}), X-ray single-crystal diffraction (CaZn{sub 2}), and electron microscopy (SrZn{sub 2}). Their structures correspond to that of Laves phases. Whereas the dialuminides crystallize in the cubic MgCu{sub 2} (C15) structure, the dizincides adopt the hexagonal MgZn{sub 2} (C14) structure. This trend is in agreement with the structural relationship displayed by sp bonded Laves phase systems at ambient conditions. - Graphical abstract: CeCu{sub 2}-type polar intermetallics can be transformed to Laves phases upon simultaneous application of pressure and temperature. The observed structures are controlled by the valence electron concentration.

  8. Quantum-mechanical simulation of MgAl2O4 under high pressure

    NASA Astrophysics Data System (ADS)

    Gracia, L.; Beltrán, A.; Andrés, J.; Franco, R.; Recio, J. M.

    2002-12-01

    The equations of state and phase diagrams of the cubic spinel and two high-pressure polymorphs of MgAl2O4 have been investigated up to 65 GPa using density functional theory, the space-filling polyhedral partition of the unit cell, and the static approximation. Energy-volume curves have been obtained for the spinel phase, the recently observed calcium ferrite-type and calcium titanite-type phases, and the MgO+α-Al2O3 mixture. Zero-pressure unit lengths and compressibilities are well described by the theoretical model, that predicts static bulk moduli about 215 GPa for all the high-pressure forms. Computed equations of state are also in good agreement with the most recent experimental data for all compounds and polymorphs considered. We do not find a continuous pressure-induced phase sequence but the static simulations predict that the oxide mixture, the ferrite phase, and the titanite phase become more stable than the spinel form at 15, 35, and 62 GPa, respectively. A microscopic analysis in terms of polyhedral and bond compressibilities leads to identify the ionic displacements accompanying the phase transformations and to an appealing interpretation of the spinel response to compression.

  9. 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

  10. High pressure studies of the erbium hydrogen system

    NASA Astrophysics Data System (ADS)

    Palasyuk, T.; Tkacz, M.; Vajda, P.

    2005-07-01

    High-pressure X-ray diffraction investigations up to 25 GPa using diamond anvil cell techniques (DAC) have been carried out on erbium and a series of erbium hydrides. The equations of state have been evaluated for ErH 1.95, ErH 2.091 (in the β-phase) and for γ-ErH 3. For comparison, the compressibility of pure erbium metal has also been determined in the same pressure range. A rapid drop of lattice volume at a pressure of about 14.5 GPa has been observed for ErH 2.091 accompanied by a color change of reflected light. This phenomenon was not observed in ErH 1.95 where the molar volume varied smoothly up to the highest pressure. A pressure-induced transformation from hexagonal to cubic phase has been detected for erbium trihydride. For pure erbium metal, a transition from hexagonal to samarium structure has been revealed, confirming previously reported behavior.

  11. High Pressure Hydrogen from First Principles

    NASA Astrophysics Data System (ADS)

    Morales, M. A.

    2014-12-01

    Typical approximations employed in first-principles simulations of high-pressure hydrogen involve the neglect of nuclear quantum effects (NQE) and the approximate treatment of electronic exchange and correlation, typically through a density functional theory (DFT) formulation. In this talk I'll present a detailed analysis of the influence of these approximations on the phase diagram of high-pressure hydrogen, with the goal of identifying the predictive capabilities of current methods and, at the same time, making accurate predictions in this important regime. We use a path integral formulation combined with density functional theory, which allows us to incorporate NQEs in a direct and controllable way. In addition, we use state-of-the-art quantum Monte Carlo calculations to benchmark the accuracy of more approximate mean-field electronic structure calculations based on DFT, and we use GW and hybrid DFT to calculate the optical properties of the solid and liquid phases near metallization. We present accurate predictions of the metal-insulator transition on the solid, including structural and optical properties of the molecular phase. This work was supported by the U.S. Department of Energy at the Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and by LDRD Grant No. 13-LW-004.

  12. Electrochemical studies at high pressure

    SciTech Connect

    Cruanes, M.T.

    1993-01-01

    This research has dealt with the development and application of a methodology that permits electrochemical measurements at high pressure. The initial efforts focused on the design and construction of an electrochemical cell functional at hydrostatic pressures as high as 10 kbar. This cell was equipped with an Ag/AgCl/KCl (0.1M) reference electrode which provides reliable control of the potential at all pressures. The potential of this reference electrode can be considered to be constant with pressure. Measurements of formal potentials (E[degrees][prime]) of several transition-metal complexes vs the Ag/AgCl electrode rendered volumes of reactions whose magnitudes support the prediction of the negligible pressure dependence of the reference electrode. The main systems that have been investigated at high pressure are surface-modified electrodes. The author studied the effect of compression on the dynamics of charge transport in quaternized poly(4-vinylpyridine) (QPVP) films placed on gold electrodes, loaded with potassium ferricyanide, and equilibrated in potassium nitrate. Pressure accomplished the continuous change in the structure of the polymer network. This change causes a pronounced restriction in the propagation of charge and in the motion of mass. This high-pressure methodology has also allowed the spatial characterization of electron transfer events taking place between a gold electrode and ferrocene molecules covalently attached to the end of 1-undodecanethiol chains self-assembled on the electrode surface. The volumes of reaction and activation for the oxidation process are both positive, indicating that a volume expansion is associated with the formation of ferricinium. A model is proposed in which the creation of a vacancy in the self-assembled monolayer, for the accommodation of the ferricinium ion or a charge-compensating anion, is coupled with the electron transfer step.

  13. High-pressure orthorhombic ferromagnesite as a potential deep-mantle carbon carrier

    SciTech Connect

    Liu, Jin; Lin, Jung -Fu; Prakapenka, Vitali B.

    2015-01-06

    In this study, knowledge of the physical and chemical properties of candidate deep-carbon carriers such as ferromagnesite [(Mg,Fe)CO3] at high pressure and temperature of the deep mantle is necessary for our understanding of deep-carbon storage as well as the global carbon cycle of the planet. Previous studies have reported very different scenarios for the (Mg,Fe)CO3 system at deep-mantle conditions including the chemical dissociation to (Mg,Fe)O+CO2, the occurrence of the tetrahedrally-coordinated carbonates based on CO4 structural units, and various high-pressure phase transitions. Here we have studied the phase stability and compressional behavior of (Mg,Fe)CO3 carbonates up to relevant lower-mantle conditions of approximately 120 GPa and 2400 K. Our experimental results show that the rhombohedral siderite (Phase I) transforms to an orthorhombic phase (Phase II with Pmm2 space group) at approximately 50 GPa and 1400 K. The structural transition is likely driven by the spin transition of iron accompanied by a volume collapse in the Fe-rich (Mg,Fe)CO3 phases; the spin transition stabilizes the high-pressure phase II at much lower pressure conditions than its Mg-rich counterpart. It is conceivable that the low-spin ferromagnesite phase II becomes a major deep-carbon carrier at the deeper parts of the lower mantle below 1900 km in depth.

  14. Spin-phonon coupling and high-pressure phase transitions of RMnO3 (R=Ca and Pr): An inelastic neutron scattering and first-principles study

    DOE PAGES

    Mishra, S. K.; Gupta, M. K.; Mittal, R.; ...

    2016-06-22

    Here, we report inelastic neutron scattering measurements over 7–1251 K in CaMnO3 covering various phase transitions, and over 6–150 K in PrMnO3 covering the magnetic transition. The excitations around 20 meV in CaMnO3 and at 17 meV in PrMnO3 at low temperatures are found to be associated with magnetic origin. We observe coherent magnetic neutron scattering in localized regions in reciprocal space and show it to arise from long-range correlated magnetic spin-waves below the magnetic transition temperature (TN) and short-range stochastic spin-spin fluctuations above TN. In spite of the similarity of the structure of the two compounds, the neutron inelasticmore » spectrum of PrMnO3 exhibits broad features at 150 K unlike well-defined peaks in the spectrum of CaMnO3. This might result from the difference in the nature of interactions in the two compounds (magnetic and Jahn-Teller distortion). Ab initio phonon calculations have been used to interpret the observed phonon spectra. The ab initio calculations at high pressures show that the variations of Mn-O distances are isotropic for CaMnO3 and highly anisotropic for PrMnO3. The calculation in PrMnO3 shows the suppression of Jahn-Teller distortion and simultaneous insulator-to-metal transition. It appears that this transition may not be associated with the occurrence of the tetragonal phase above 20 GPa as reported in the literature, since the tetragonal phase is found to be dynamically unstable, although it is found to be energetically favored over the orthorhombic phase above 20 GPa. CaMnO3 does not show any phase transition up to 60 GPa.« less

  15. 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.

  16. 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.

  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. Trace level analysis of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and its biodegradation intermediates in liquid media by solid-phase extraction and high-pressure liquid chromatography analysis.

    PubMed

    Chow, Teresa M; Wilcoxon, Monte R; Piwoni, Marvin D; Adrian, Neal R

    2004-10-01

    The use of solid-phase extraction for the analysis of liquid media containing low microg/L levels of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), mononitroso-RDX (MNX), dinitroso-RDX (DNX), and trinitroso-RDX (TNX) is examined. Aqueous samples (100 mL) consisting of water and a microbiological basal medium are spiked with known concentrations of RDX, MNX, DNX, and TNX. The compounds are extracted from the liquid media using a Porapak RDX cartridge and then eluted from the cartridge with 5 mL of acetonitrile. The eluent is concentrated to 1 mL before analysis by high-pressure liquid chromatography (HPLC). The method detection limits for RDX are 0.1 microg/L in water and 0.5 microg/L in the basal medium after a 100-fold concentration. For MNX, DNX, and TNX, the method detection limits are approximately 0.5 microg/L in water and approximately 1 microg/L in the basal medium after a 100-fold concentration. Interferences in the basal medium and a contaminant in the standard made quantitation for MNX and TNX, respectively, is less accurate below the 1 microg/L level. Solid-phase extraction of the liquid media gave good recoveries of nitramines and nitroso intermediates from a microbiological basal medium, allowing HPLC detection of RDX and the nitroso intermediates in the low microg/L (ppb) range.

  20. 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.

  1. 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.

  2. 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.

  3. Is sodium a superconductor under high pressure?

    PubMed

    Tutchton, Roxanne; Chen, Xiaojia; Wu, Zhigang

    2017-01-07

    Superconductivity has been predicted or measured for most alkali metals under high pressure, but the computed critical temperature (Tc) of sodium (Na) at the face-centered cubic (fcc) phase is vanishingly low. Here we report a thorough, first-principles investigation of superconductivity in Na under pressures up to 260 GPa, where the metal-to-insulator transition occurs. Linear-response calculations and density functional perturbation theory were employed to evaluate phonon distributions and the electron-phonon coupling for bcc, fcc, cI16, and tI19 Na. Our results indicate that the maximum electron-phonon coupling parameter, λ, is 0.5 for the cI16 phase, corresponding to a theoretical peak in the critical temperature at Tc≈1.2 K. When pressure decreases or increases from 130 GPa, Tc drops quickly. This is mainly due to the lack of p-d hybridization in Na even at 260 GPa. Since current methods based on the Eliashberg and McMillian formalisms tend to overestimate the Tc (especially the peak values) of alkali metals, we conclude that under high pressure-before the metal-to-insulator transition at 260 GPa-superconductivity in Na is very weak, if it is measurable at all.

  4. 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

  5. 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.

  6. High pressure chemistry of substituted acetylenes

    SciTech Connect

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

    2011-01-25

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

  7. 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.

  8. High pressure synthesis gas fermentation

    SciTech Connect

    Not Available

    1991-01-01

    The purpose of this research project is to build and test a pressure fermentation system for the production of ethanol from synthesis gas. The fermenters, pumps, controls, and analytical system will be procured or fabricated and assembled in our laboratory. This system will then be used to determine the effects of high pressure on growth and ethanol production by clostridium ljungdahlii. The limits of cell concentration and mass transport relationships will be found in continuous stirred tank reactor and immobilized cell reactors. The minimum retention times and reactor volumes will be found for ethanol production in these reactors. Retention times of a few seconds are expected to result from these experiments. 2 figs., 2 tabs.

  9. Phase transitions of the system Ag sub 2 HgI sub 4 -Cu sub 2 HgI sub 4 at normal and high pressure studied by differential scanning calorimetry

    SciTech Connect

    Friesel, M.; Baranowski, B.; Lunden, A. )

    1990-02-08

    Differential scanning calorimetry has been applied for studying the system Ag{sub 2}HgI{sub 4}-Cu{sub 2}HgI{sub 4} at both normal and high pressure. It is confirmed that there is a miscibility gap in the ordered phase and that the order-disorder phase transition has a eutectoid point at 307 K and 42.7 mol % Cu{sub 2}HgI{sub 4} at normal pressure, which is about 30 K higher than expected from a calculation for ideal eutectic behavior. The order-disorder transition is of first-order character over the whole composition range, confirming the interpretation by Suchow and ruling out the suggestion by Jaffray that it should be of second-order character in the middle part of the range. The transition enthalpy is equal to 7.3 {plus minus} 0.2 kJ/mol for the eutectoid composition. The phase diagram of the eutectoid composition was determined for pressures up to 0.72 GPa, and the temperature of the order-disorder transition increased from 307 to about 325 K, The correlation was not linear over the whole pressure range, but an average dT/dP slope of 25 K/GPa is in good agreement with the 24 K/GPa calculated by means of van Laar,s formula. The transition enthalpy (kJ/mol) decreased linearly with increasing pressure with d{Delta}H/dp = -4.0 kJ/(mol GPa). A calculation from simple additive rule gives instead d{Delta}H/dp = -1.5 kJ/(mol GPa).

  10. 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.

  11. Volatile compounds in low-acid fermented sausage "espetec" and sliced cooked pork shoulder subjected to high pressure processing. A comparison of dynamic headspace and solid-phase microextraction.

    PubMed

    Rivas-Cañedo, Ana; Juez-Ojeda, Cristina; Nuñez, Manuel; Fernández-García, Estrella

    2012-05-01

    Two extraction techniques, dynamic headspace extraction (DHE) and solid-phase microextraction (SPME), were compared to assess the effect of high-pressure treatment (400MPa, 10min, 12°C) on the volatile compounds of low-acid fermented sausage "espetec" and sliced cooked pork shoulder stored at 4°C. DHE was more efficient at extracting low-boiling compounds such as ethanal, 2,3-butanedione and alcohols, while SPME extracted more efficiently a higher number of chemical families, especially fatty acids. The effect of pressurisation on the volatile fraction of "espetec" was better categorized by DHE, whereas SPME was more appropriate for cooked pork shoulder. The volatile fraction of "espetec" changed slightly after pressurisation, mainly showing a decrease in the levels of lipid-derived compounds, like linear alkanes, aldehydes, or 1-alcohols in pressurised samples. The volatile profile of cooked pork shoulder underwent substantial changes during refrigerated storage, mainly due to microbial metabolism, most of these changes being limited by HPP.

  12. A fully automated method for simultaneous determination of aflatoxins and ochratoxin A in dried fruits by pressurized liquid extraction and online solid-phase extraction cleanup coupled to ultra-high-pressure liquid chromatography-tandem mass spectrometry.

    PubMed

    Campone, Luca; Piccinelli, Anna Lisa; Celano, Rita; Russo, Mariateresa; Valdés, Alberto; Ibáñez, Clara; Rastrelli, Luca

    2015-04-01

    According to current demands and future perspectives in food safety, this study reports a fast and fully automated analytical method for the simultaneous analysis of the mycotoxins with high toxicity and wide spread, aflatoxins (AFs) and ochratoxin A (OTA) in dried fruits, a high-risk foodstuff. The method is based on pressurized liquid extraction (PLE), with aqueous methanol (30%) at 110 °C, of the slurried dried fruit and online solid-phase extraction (online SPE) cleanup of the PLE extracts with a C18 cartridge. The purified sample was directly analysed by ultra-high-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) for sensitive and selective determination of AFs and OTA. The proposed analytical procedure was validated for different dried fruits (vine fruit, fig and apricot), providing method detection and quantification limits much lower than the AFs and OTA maximum levels imposed by EU regulation in dried fruit for direct human consumption. Also, recoveries (83-103%) and repeatability (RSD < 8, n = 3) meet the performance criteria required by EU regulation for the determination of the levels of mycotoxins in foodstuffs. The main advantage of the proposed method is full automation of the whole analytical procedure that reduces the time and cost of the analysis, sample manipulation and solvent consumption, enabling high-throughput analysis and highly accurate and precise results.

  13. 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.

  14. Spin-phonon coupling and high-pressure phase transitions of RMnO3 (R=Ca and Pr): An inelastic neutron scattering and first-principles study

    SciTech Connect

    Mishra, S. K.; Gupta, M. K.; Mittal, R.; Kolesnikov, Alexander I.; Chaplot, S. L.

    2016-06-22

    Here, we report inelastic neutron scattering measurements over 7–1251 K in CaMnO3 covering various phase transitions, and over 6–150 K in PrMnO3 covering the magnetic transition. The excitations around 20 meV in CaMnO3 and at 17 meV in PrMnO3 at low temperatures are found to be associated with magnetic origin. We observe coherent magnetic neutron scattering in localized regions in reciprocal space and show it to arise from long-range correlated magnetic spin-waves below the magnetic transition temperature (TN) and short-range stochastic spin-spin fluctuations above TN. In spite of the similarity of the structure of the two compounds, the neutron inelastic spectrum of PrMnO3 exhibits broad features at 150 K unlike well-defined peaks in the spectrum of CaMnO3. This might result from the difference in the nature of interactions in the two compounds (magnetic and Jahn-Teller distortion). Ab initio phonon calculations have been used to interpret the observed phonon spectra. The ab initio calculations at high pressures show that the variations of Mn-O distances are isotropic for CaMnO3 and highly anisotropic for PrMnO3. The calculation in PrMnO3 shows the suppression of Jahn-Teller distortion and simultaneous insulator-to-metal transition. It appears that this transition may not be associated with the occurrence of the tetragonal phase above 20 GPa as reported in the literature, since the tetragonal phase is found to be dynamically unstable, although it is found to be energetically favored over the orthorhombic phase above 20 GPa. CaMnO3 does not show any phase transition up to 60 GPa.

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

    NASA Astrophysics Data System (ADS)

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

    2001-12-01

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

  16. 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.

  17. Elasticity of Mantle Minerals and their High-Pressure Polymorphs at High Pressures and Temperatures

    NASA Astrophysics Data System (ADS)

    Liebermann, R. C.; Li, B.; Kung, J.; Weidner, D. J.

    2002-12-01

    In his 1952 paper, Francis Birch concluded "New phases are required to account for the high elasticity of the deeper part of the mantle (below 900 km), and it is suggested that, beginning at about 200 to 300 km, there is a gradual shift toward high-pressure modifications of the ferro-magnesian silicates, probably close-packed oxides, with the transition complete at about 800 to 900 km." In the subsequent quarter century, experimental evidence for such transitions to high-pressure polymorphs emerged in laboratories around the world, most notably in those of Akimoto in Japan and Ringwood in Australia; these studies confirmed the existence of stable silicate phases with the wadsleyite, ringwoodite, majorite, ilmenite [now akimotoite], and perovskite structures. In the 1970s and 1980s, single crystal and polycrystalline specimens of these high-pressure phases were synthesized, thereby enabling studies of their elastic properties in the laboratory at ambient conditions [see Brillouin studies of the Weidner and Basssett laboratories, and ultrasonic studies by Mizutani and Fujisawa in Japan and Liebermann and colleagues in Australia]. This work often started with experiments on crystal chemical analogues of mantle silicates, following the original suggestions of Goldschmidt and Bernal in the 1930s (repeated by Birch in 1952), and then moved on to the real mantle compositions. Prior to 1988, most of these acoustic experiments were conducted versus presssure at room temperature or versus temperature at room presssure; these conditions fell far short of those achieved in the Earth's mantle. Substantial progress has been made in the past decade, making it feasible to perform acoustic experiments at conditions approaching those for the transition zone (at depths greater than 400 km); this progress has been achieved in many laboratories, including those at the University of Washington, Geophysical Laboratory, Bayreuth Geoinstitut, Nagoya University, Australian National

  18. The high-pressure C2/ c P21/ c phase transition along the LiAlSi2O6 LiGaSi2O6 solid solution

    NASA Astrophysics Data System (ADS)

    Nestola, Fabrizio; Ballaran, Tiziana Boffa; Ohashi, Haruo

    2008-09-01

    Two synthetic single-crystals with composition Li(Al0.53Ga0.47)Si2O6 and LiGaSi2O6 and space group C2/ c at room conditions have been studied under pressure by means of X-ray diffraction using a diamond anvil cell. The unit-cell parameters were determined at 12 and 10 different pressures up to P = 8.849 and P = 7.320 GPa for Li(Al0.53Ga0.47)Si2O6 and LiGaSi2O6, respectively. The sample with mixed composition shows a C2/c to P21/ c phase transformation between 1.814 and 2.156 GPa, first-order in character. The transition is characterised by a large and discontinuous decrease in the unit-cell volume and by the appearance of the b-type reflections ( h + k = odd) typical of the primitive symmetry. The Ga end-member shows the same C2/c to P21/ c transformation at a pressure between 0.0001 and 0.39 GPa. The low-pressure value at which the transition occurred did not allow collecting any data in the C2/ c pressure stability field except that on room pressure. Our results compared with those relative to spodumene (LiAlSi2O6, Arlt and Angel 2000a) indicate that the substitution of Al for Ga at the M1 site of Li-clinopyroxenes strongly affects the transition pressure causing a decrease from 3.17 GPa (spodumene) to less than 0.39 GPa (LiGaSi2O6) and decreases the volume discontinuity at the transition. As already found for other compounds, the C2 /c low-pressure phases are more rigid than the P21 /c high-pressure ones. Moreover, the increase of the M1 cation radius causes a decrease in the bulk modulus K T0. The axial compressibility among the Li-bearing clinopyroxenes indicates that the c axis is the most rigid for the C2 /c phases while it becomes the most compressible for the P21 /c phases.

  19. Paramagnetic-diamagnetic phase transition accompanied by coordination bond formation-dissociation in the dithiolate complex Na[Ni(pdt)2]·2H2O.

    PubMed

    Takaishi, Shinya; Ishihara, Nozomi; Kubo, Kazuya; Katoh, Keiichi; Breedlove, Brian K; Miyasaka, Hitoshi; Yamashita, Masahiro

    2011-07-18

    Bis(2,3-pyrazinedithiolate)nickel complex Na[Ni(pdt)(2)]·2H(2)O formed one-dimensional stacks of the Ni(pdt)(2) units and showed strong antiferromagnetic interactions along the stacking direction. A first-order phase transition between the paramagnetic and diamagnetic states, which was driven by dimerization of the Ni(pdt)(2) units, accompanied by coordination bond formation, was observed.

  20. Single solid phase extraction method for the simultaneous analysis of polar and non-polar pesticides in urine samples by gas chromatography and ultra high pressure liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Cazorla-Reyes, Rocío; Fernández-Moreno, José Luis; Romero-González, Roberto; Frenich, Antonia Garrido; Vidal, José Luis Martínez

    2011-07-15

    A new multiresidue method has been developed and validated for the simultaneous extraction of more than two hundred pesticides, including non-polar and polar pesticides (carbamates, organochlorine, organophosphorous, pyrethroids, herbicides and insecticides) in urine at trace levels by gas and ultra high pressure liquid chromatography coupled to ion trap and triple quadrupole mass spectrometry, respectively (GC-IT-MS/MS, UHPLC-QqQ-MS/MS). Non-polar and polar pesticides were simultaneously extracted from urine samples by a simple and fast solid phase extraction (SPE) procedure using C(18) cartridges as sorbent, and dichloromethane as elution solvent. Recovery was in the range of 60-120%. Precision values expressed as relative standard deviation (RSD) were lower than 25%. Identification and confirmation of the compounds were performed by the use of retention time windows, comparison of spectra (GC-amenable compounds) or the estimation of the ion ratio (LC-amenable compounds). For GC-amenable pesticides, limits of detection (LODs) ranged from 0.001 to 0.436 μg L(-1) and limits of quantification (LOQs) from 0.003 to 1.452 μg L(-1). For LC-amenable pesticides, LODs ranged from 0.003 to 1.048 μg L(-1) and LOQs ranged from 0.011 to 3.494 μg L(-1). Finally, the optimized method was applied to the analysis of fourteen real samples of infants from agricultural population. Some pesticides such as methoxyfenozide, tebufenozide, piperonyl butoxide and propoxur were found at concentrations ranged from 1.61 to 24.4 μg L(-1), whereas methiocarb sulfoxide was detected at trace levels in two samples.

  1. Proteomic analysis of oil body membrane proteins accompanying the onset of desiccation phase during sunflower seed development

    PubMed Central

    Thakur, Anita; Bhatla, Satish C

    2015-01-01

    A noteworthy metabolic signature accompanying oil body (OB) biogenesis during oilseed development is associated with the modulation of the oil body membranes proteins. Present work focuses on 2-dimensional polyacrylamide gel electrophoresis (2-D PAGE)-based analysis of the temporal changes in the OB membrane proteins analyzed by LC-MS/MS accompanying the onset of desiccation (20–30 d after anthesis; DAA) in the developing seeds of sunflower (Helianthus annuus L.). Protein spots unique to 20–30 DAA stages were picked up from 2-D gels for identification and the identified proteins were categorized into 7 functional classes. These include proteins involved in energy metabolism, reactive oxygen scavenging, proteolysis and protein turnover, signaling, oleosin and oil body biogenesis-associated proteins, desiccation and cytoskeleton. At 30 DAA stage, exclusive expressions of enzymes belonging to energy metabolism, desiccation and cytoskeleton were evident which indicated an increase in the metabolic and enzymatic activity in the cells at this stage of seed development (seed filling). Increased expression of cruciferina-like protein and dehydrin at 30 DAA stage marks the onset of desiccation. The data has been analyzed and discussed to highlight desiccation stage-associated metabolic events during oilseed development. PMID:26786011

  2. Behavior of silver molybdate at high-pressure

    SciTech Connect

    Arora, A.K.; Nithya, R.; Misra, Sunasira; Yagi, Takehiko

    2012-12-15

    Behavior of cubic spinel phase of Ag{sub 2}MoO{sub 4} is investigated at high pressure using X-ray diffraction and Raman spectroscopy. The P-V data are fitted to a third order Birch-Murnaghan equation of state using a value of B{sub 0}=113 GPa and B Prime {sub 0}=4. The compound is also found to exhibit a phase transition around 5 GPa to a tetragonal structure and the two phases are found to coexist over a range of pressures. Raman spectra exhibit dramatic changes across the phase transition. Increase of X-ray background scattering and broadening of the Raman peaks associated with MoO{sub 4} tetrahedral ions in the high pressure phase suggest evolution of positional disorder. However, no evidence of pressure-induced amorphization was found up to 47 GPa. - Graphical abstract: Evolution of the integrated intensity of all the diffraction peaks between 12 and 18 degree 2{theta} as a function of pressure. The rapid decrease of the intensity suggests evolution of positional disorder in the high-pressure tetragonal phase. Highlights: Black-Right-Pointing-Pointer First in-situ X-ray diffraction and Raman study of cubic silver molybdate at high pressure. Black-Right-Pointing-Pointer Commencement of a structural transition to a tetragonal phase is found at 2.3 GPa. Black-Right-Pointing-Pointer The high-pressure phase is found to have positional disorder. Black-Right-Pointing-Pointer A bulk modulus of 113 GPa is obtained from the equation of state.

  3. Rapid and automated analysis of aflatoxin M1 in milk and dairy products by online solid phase extraction coupled to ultra-high-pressure-liquid-chromatography tandem mass spectrometry.

    PubMed

    Campone, Luca; Piccinelli, Anna Lisa; Celano, Rita; Pagano, Imma; Russo, Mariateresa; Rastrelli, Luca

    2016-01-08

    This study reports a fast and automated analytical procedure for the analysis of aflatoxin M1 (AFM1) in milk and dairy products. The method is based on the simultaneous protein precipitation and AFM1 extraction, by salt-induced liquid-liquid extraction (SI-LLE), followed by an online solid-phase extraction (online SPE) coupled to ultra-high-pressure-liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis to the automatic pre-concentration, clean up and sensitive and selective determination of AFM1. The main parameters affecting the extraction efficiency and accuracy of the analytical method were studied in detail. In the optimal conditions, acetonitrile and NaCl were used as extraction/denaturant solvent and salting-out agent in SI-LLE, respectively. After centrifugation, the organic phase (acetonitrile) was diluted with water (1:9 v/v) and purified (1mL) by online C18 cartridge coupled with an UHPLC column. Finally, selected reaction monitoring (SRM) acquisition mode was applied to the detection of AFM1. Validation studies were carried out on different dairy products (whole and skimmed cow milk, yogurt, goat milk, and powder infant formula), providing method quantification limits about 25 times lower than AFM1 maximum levels permitted by EU regulation 1881/2006 in milk and dairy products for direct human consumption. Recoveries (86-102%) and repeatability (RSD<3, n=6) meet the performance criteria required by EU regulation N. 401/2006 for the determination of the levels of mycotoxins in foodstuffs. Moreover, no matrix effects were observed in the different milk and dairy products studied. The proposed method improves the performance of AFM1 analysis in milk samples as AFM1 determination is performed with a degree of accuracy higher than the conventional methods. Other advantages are the reduction of sample preparation procedure, time and cost of the analysis, enabling high sample throughput that meet the current concerns of food safety and the public

  4. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  6. Preparation of a hierarchically porous AlPO4 monolith via an epoxide-mediated sol-gel process accompanied by phase separation

    NASA Astrophysics Data System (ADS)

    Li, Wenyan; Zhu, Yang; Guo, Xingzhong; Nakanishi, Kazuki; Kanamori, Kazuyoshi; Yang, Hui

    2013-08-01

    Monolithic aluminum phosphate (AlPO4) with a macro-mesoporous structure has been successfully prepared via the sol-gel process accompanied by phase separation in the presence of poly(ethylene oxide) (PEO). Gelation of the system has been mediated by propylene oxide (PO), while PEO induces a phase separation. The dried gel is amorphous, whereas the crystalline tridymite phase precipitates upon heating above 1000 °C. Heat treatment does not spoil the macroporous morphology of the AlPO4 monoliths. Nitrogen adsorption-desorption measurements revealed that the skeletons of the dried gels possess a mesostructure with a median pore size of about 30 nm and a surface area as high as 120 m2 g-1. Hydrothermal treatment before heat treatment can increase the surface area to 282 m2 g-1.

  7. 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

  8. High pressure and Multiferroics materials. A happy marriage

    SciTech Connect

    Gilioli, Edmondo; Ehm, Lars

    2014-10-31

    We found that the community of material scientists is strongly committed to the research area of multiferroic materials, both for the understanding of the complex mechanisms supporting the multiferroism and for the fabrication of new compounds, potentially suitable for technological applications. The use of high pressure is a powerful tool in synthesizing new multiferroic, in particular magneto-electric phases, where the pressure stabilization of otherwise unstable perovskite-based structural distortions may lead to promising novel metastable compounds. Moreover, the in situ investigation of the high-pressure behavior of multiferroic materials has provided insight into the complex interplay between magnetic and electronic properties and the coupling to structural instabilities.