Stability limit of liquid water in metastable equilibrium with subsaturated vapors.

PubMed

Wheeler, Tobias D; Stroock, Abraham D

2009-07-07

A pure liquid can reach metastable equilibrium with its subsaturated vapor across an appropriate membrane. This situation is analogous to osmotic equilibrium: the reduced chemical potential of the dilute phase (the subsaturated vapor) is compensated by a difference in pressure between the phases. To equilibrate with subsaturated vapor, the liquid phase assumes a pressure that is lower than its standard vapor pressure, such that the liquid phase is metastable with respect to the vapor phase. For sufficiently subsaturated vapors, the liquid phase can even assume negative pressures. The appropriate membrane for this metastable equilibrium must provide the necessary mechanical support to sustain the difference in pressure between the two phases, limit nonhomogeneous mechanisms of cavitation, and resist the entry of the dilutant (gases) into the pure phase (liquid). In this article, we present a study of the limit of stability of liquid water--the degree of subsaturation at which the liquid cavitates--in this metastable state within microscale voids embedded in hydrogel membranes. We refer to these structures as vapor-coupled voids (VCVs). In these VCVs, we observed that liquid water cavitated when placed in equilibrium with vapors of activity aw,vapair

Experimental pressure-temperature phase diagram of boron: resolving the long-standing enigma

PubMed Central

Parakhonskiy, Gleb; Dubrovinskaia, Natalia; Bykova, Elena; Wirth, Richard; Dubrovinsky, Leonid

2011-01-01

Boron, discovered as an element in 1808 and produced in pure form in 1909, has still remained the last elemental material, having stable natural isotopes, with the ground state crystal phase to be unknown. It has been a subject of long-standing controversy, if α-B or β-B is the thermodynamically stable phase at ambient pressure and temperature. In the present work this enigma has been resolved based on the α-B-to- β-B phase boundary line which we experimentally established in the pressure interval of ∼4 GPa to 8 GPa and linearly extrapolated down to ambient pressure. In a series of high pressure high temperature experiments we synthesised single crystals of the three boron phases (α-B, β-B, and γ-B) and provided evidence of higher thermodynamic stability of α-B. Our work opens a way for reproducible synthesis of α-boron, an optically transparent direct band gap semiconductor with very high hardness, thermal and chemical stability. PMID:22355614

Stability limits and transformation pathways of α-quartz under high pressure

NASA Astrophysics Data System (ADS)

Hu, Q. Y.; Shu, J.-F.; Yang, W. G.; Park, C.; Chen, M. W.; Fujita, T.; Mao, H.-K.; Sheng, H. W.

2017-03-01

Ubiquitous on Earth, α-quartz plays an important role in modern science and technology. However, despite extensive research in the past, the mechanism of the polymorphic transitions of α-quartz at high pressures remains poorly understood. Here, combining in situ single-crystal x-ray diffraction experiment and advanced ab initio modeling, we report two stability limits and competing transition pathways of α-quartz under high pressure. Under near-equilibrium compression conditions at room temperature, α-quartz transits to a new P 2 /c silica phase via a structural intermediate. If the thermally activated transition is kinetically suppressed, the ultimate stability of α-quartz is controlled by its phonon instability and α-quartz collapses into a different crystalline phase. Our studies reveal that pressure-induced solid-state transformation of α-quartz undergoes a succession of structural stability limits, due to thermodynamic and mechanical catastrophes, and exhibits a hierarchy of transition pathways contingent upon kinetic conditions.

Influence of hydrogen on the stability of iron phases under pressure

NASA Astrophysics Data System (ADS)

Skorodumova, N. V.; Ahuja, R.; Johansson, B.

2004-04-01

The influence of hydrogen presence on the stability of iron phases (bcc, hcp, dhcp, fcc, simple cubic) in a wide pressure interval at 0 K has been studied by the first-principles projector augmented-wave (PAW) method. Hydrogen is shown to occupy different interstitial lattice positions depending on the type of structure and pressure. An introduction of hydrogen impurities (˜6 at. %) leads to a stabilization of the close-packed iron structures, shifting the calculated pressure of the bcc-hcp transition from ˜9 GPa for pure iron to 7 GPa for Fe (6 at. % H). This tendency is further enhanced in the iron hydride structures. The iron hydrides in the close-packed structures (hcp, dhcp, fcc) are essentially degenerate in energy and found to be most stable in the whole pressure range.

Prediction of B1 to B10 phase transition in LuN under pressure: An ab-initio investigation

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

Sahoo, B. D., E-mail: bdsahoo@barc.gov.in; Mukherjee, D.; Joshi, K. D.

2016-05-23

Ab-initio total energy calculations have been performed in lutetium nitride (LuN) as a function of hydrostatic compression to understand the high pressure behavior of this compound. Our calculations predict a phase transition from ambient rocksalt type structure (B1 phase) to a tetragonal structure (B10 phase) at ~ 240 GPa. The phase transition has been identified as first order in nature with volume discontinuity of ~ 6%. The predicted high pressure phase has been found to be stable up to at least 400 GPa, the maximum pressure up to which calculations have been performed.Further, to substantiate the results of static lattice calculations analysismore » of lattice dynamic stability of B1 and B10 phase has been carried out at different pressures. Apart from this, we have analyzed the lattice dynamic stability CsCl type (B2) phase around the 240 GPa, the pressure reported for B1 to B2 transition in previous all-electron calculations by Gupta et al. 2013. We find that the B2 structure is lattice dynamically unstable at this pressure and remains unstable up to ~ 400 GPa, ruling out the possibility of B1 to B2 phase transition at least up to ~ 400 GPa. Further, the theoretically determined equation of state has been utilized to derive various physical quantities such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus of B1 phase at ambient conditions.« less

The Stability of Hydrous Silicates in Earth's Lower Mantle: Experimental constraints from the System MgO-Al2O3-SiO2-H2O

NASA Astrophysics Data System (ADS)

Walter, M. J.; Thomson, A. R.; Wang, W.; Lord, O. T.; Kleppe, A. K.; Ross, J.; Kohn, S. C.

2014-12-01

Laser-heated diamond anvil cell experiments were performed at pressures from ~ 30 to 125 GPa on bulk compositions in the system MgO-Al2O3-SiO2-H2O (MASH) to constrain the stability of hydrous phases in Earth's lower mantle. Phase identification in run products by synchrotron powder diffraction reveals a consistent set of stability relations for the high-pressure, dense hydrous silicate phases D and H. Experiments show that aluminous phase D is stable to ~ 55 GPa. Aluminous phase H becomes stable at ~ 40 GPa and remains stable to higher pressures throughout the lower mantle depth range in both model peridotitic and basaltic lithologies. Preliminary FEG-probe analyses indicate that Phase H is alumina-rich at ~ 50 GPa, with only 5 to 10 wt% each of MgO and SiO2. Variations in ambient unit cell volumes show that Mg-perovskite becomes more aluminous with pressure throughout the pressure range studied, and that Phase H may become more Mg- and Si-rich with pressure. We also find that at pressures above ~ 90 GPa stishovite is replaced in Si-rich compositions by seifertite, at which point there is a corresponding increase in the Al-content of phase H. The melting curves of MASH compositions have been determined using thermal perturbations in power versus temperature curves, and are observed to be shallow with dT/dP slopes of ~ 4K/GPa. Our results show that hydrated peridotitic or basaltic compositions in the lower mantle should be partially molten at all depths along an adiabatic mantle geotherm. Aluminous Phase H will be stable in colder, hydrated subducting slabs, potentially to the core-mantle boundary. Thus, aluminous phase H is the primary vessel for transport of hydrogen to the deepest mantle, but hydrous silicate melt will be the host of hydrogen at ambient mantle temperatures.

Thermodynamic properties of hydrate phases immersed in ice phase

NASA Astrophysics Data System (ADS)

Belosludov, V. R.; Subbotin, O. S.; Krupskii, D. S.; Ikeshoji, T.; Belosludov, R. V.; Kawazoe, Y.; Kudoh, J.

2006-01-01

Thermodynamic properties and the pressure of hydrate phases immersed in the ice phase with the aim to understand the nature of self-preservation effect of methane hydrate in the framework of macroscopic and microscopic molecular models was studied. It was show that increasing of pressure is happen inside methane hydrate phases immersed in the ice phase under increasing temperature and if the ice structure does not destroy, the methane hydrate will have larger pressure than ice phase. This is because of the thermal expansion of methane hydrate in a few times larger than ice one. The thermal expansion of the hydrate is constrained by the thermal expansion of ice because it can remain in a region of stability within the methane hydrate phase diagram. The utter lack of preservation behavior in CS-II methane- ethane hydrate can be explain that the thermal expansion of ethane-methane hydrate coincide with than ice one it do not pent up by thermal expansion of ice. The pressure and density during the crossing of interface between ice and hydrate was found and dynamical and thermodynamic stability of this system are studied in accordance with relation between ice phase and hydrate phase.

Ab initio study on structural stability of uranium carbide

NASA Astrophysics Data System (ADS)

Sahoo, B. D.; Joshi, K. D.; Gupta, Satish C.

2013-06-01

First principles calculations have been performed using plane wave pseudopotential and full potential linearized augmented plane wave (FP-LAPW) methods to analyze structural, elastic and dynamic stability of UC under hydrostatic compression. Our calculations within pseudopotential method suggest that the rocksalt (B1) structure will transform to body centered orthorhombic (bco) structure at ˜21.5 GPa. The FP-LAPW calculations put this transition at 23 GPa. The transition pressures determined from our calculations though agree reasonably with the experimental value of 27 GPa, the high pressure bco structure suggested by theory differs slightly from the experimentally reported pseudo bco phase. The elastic stability analysis of B1 phase suggests that the B1 to bco transition is driven by the failure of C44 modulus. This finding is further substantiated by the lattice dynamic calculations which demonstrate that the B1 phase becomes dynamically unstable around the transition pressure and the instability is of long wavelength nature.

Anomalous perovskite PbRuO3 stabilized under high pressure

PubMed Central

Cheng, J.-G.; Kweon, K. E.; Zhou, J.-S.; Alonso, J. A.; Kong, P.-P.; Liu, Y.; Jin, Changqing; Wu, Junjie; Lin, Jung-Fu; Larregola, S. A.; Yang, Wenge; Shen, Guoyin; MacDonald, A. H.; Manthiram, Arumugam; Hwang, G. S.; Goodenough, John B.

2013-01-01

Perovskite oxides ABO3 are important materials used as components in electronic devices. The highly compact crystal structure consists of a framework of corner-shared BO6 octahedra enclosing the A-site cations. Because of these structural features, forming a strong bond between A and B cations is highly unlikely and has not been reported in the literature. Here we report a pressure-induced first-order transition in PbRuO3 from a common orthorhombic phase (Pbnm) to an orthorhombic phase (Pbn21) at 32 GPa by using synchrotron X-ray diffraction. This transition has been further verified with resistivity measurements and Raman spectra under high pressure. In contrast to most well-studied perovskites under high pressure, the Pbn21 phase of PbRuO3 stabilized at high pressure is a polar perovskite. More interestingly, the Pbn21 phase has the most distorted octahedra and a shortest Pb—Ru bond length relative to the average Pb—Ru bond length that has ever been reported in a perovskite structure. We have also simulated the behavior of the PbRuO3 perovskite under high pressure by first principles calculations. The calculated critical pressure for the phase transition and evolution of lattice parameters under pressure match the experimental results quantitatively. Our calculations also reveal that the hybridization between a Ru:t2g orbital and an sp hybrid on Pb increases dramatically in the Pbnm phase under pressure. This pressure-induced change destabilizes the Pbnm phase to give a phase transition to the Pbn21 phase where electrons in the overlapping orbitals form bonding and antibonding states along the shortest Ru—Pb direction at P > Pc. PMID:24277807

First-principles study of the elastic and thermodynamic properties of thorium hydrides at high pressure

NASA Astrophysics Data System (ADS)

Xiao-Lin, Zhang; Yuan-Yuan, Wu; Xiao-Hong, Shao; Yong, Lu; Ping, Zhang

2016-05-01

The high pressure behaviors of Th4H15 and ThH2 are investigated by using the first-principles calculations based on the density functional theory (DFT). From the energy-volume relations, the bct phase of ThH2 is more stable than the fcc phase at ambient conditions. At high pressure, the bct ThH2 and bcc Th4H15 phases are more brittle than they are at ambient pressure from the calculated elastic constants and the Poisson ratio. The thermodynamic stability of the bct phase ThH2 is determined from the calculated phonon dispersion. In the pressure domain of interest, the phonon dispersions of bcc Th4H15 and bct ThH2 are positive, indicating the dynamical stability of these two phases, while the fcc ThH2 is unstable. The thermodynamic properties including the lattice vibration energy, entropy, and specific heat are predicted for these stable phases. The vibrational free energy decreases with the increase of the temperature, and the entropy and the heat capacity are proportional to the temperature and inversely proportional to the pressure. As the pressure increases, the resistance to the external pressure is strengthened for Th4H15 and ThH2. Project supported by the Long-Term Subsidy Mechanism from the Ministry of Finance and the Ministry of Education of China.

Dynamical stability of Fe-H in the Earth's mantle and core regions.

PubMed

Isaev, Eyvaz I; Skorodumova, Natalia V; Ahuja, Rajeev; Vekilov, Yuri K; Johansson, Börje

2007-05-29

The core extends from the depth of 2,900 km to the center of the Earth and is composed mainly of an iron-rich alloy with nickel, with 10% of the mass comprised of lighter elements like hydrogen, but the exact composition is uncertain. We present a quantum mechanical first-principles study of the dynamical stability of FeH phases and their phonon densities of states at high pressure. Our free-energy calculations reveal a phonon-driven stabilization of dhcp FeH at low pressures, thus resolving the present contradiction between experimental observations and theoretical predictions. Calculations reveal a complex phase diagram for FeH under pressure with a dhcp --> hcp --> fcc sequence of structural transitions.

Dynamical stability of Fe-H in the Earth's mantle and core regions

PubMed Central

Isaev, Eyvaz I.; Skorodumova, Natalia V.; Ahuja, Rajeev; Vekilov, Yuri K.; Johansson, Börje

2007-01-01

The core extends from the depth of 2,900 km to the center of the Earth and is composed mainly of an iron-rich alloy with nickel, with 10% of the mass comprised of lighter elements like hydrogen, but the exact composition is uncertain. We present a quantum mechanical first-principles study of the dynamical stability of FeH phases and their phonon densities of states at high pressure. Our free-energy calculations reveal a phonon-driven stabilization of dhcp FeH at low pressures, thus resolving the present contradiction between experimental observations and theoretical predictions. Calculations reveal a complex phase diagram for FeH under pressure with a dhcp → hcp → fcc sequence of structural transitions. PMID:17483486

Structural stability of methane hydrate at high pressures

USGS Publications Warehouse

Shu, J.; Chen, X.; Chou, I-Ming; Yang, W.; Hu, Jiawen; Hemley, R.J.; Mao, Ho-kwang

2011-01-01

The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil cells. The diffraction data for types II (sII) and H (sH) were refined to the known structures with space groups Fd3m and P63/mmc, respectively. Upon compression, sI methane hydrate transforms to the sII phase at 120 MPa, and then to the sH phase at 600 MPa. The sII methane hydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methane hydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm3m structure and ice VII (Pn3m). The results highlight the role of guest (CH4)-host (H2O) interactions in the stabilization of the hydrate structures under pressure.

Continuous and discontinuous phase transitions in the evolution of a polygenic trait under stabilizing selective pressure

NASA Astrophysics Data System (ADS)

Fierro, Annalisa; Cocozza, Sergio; Monticelli, Antonella; Scala, Giovanni; Miele, Gennaro

2017-06-01

The presence of phenomena analogous to phase transition in Statistical Mechanics has been suggested in the evolution of a polygenic trait under stabilizing selection, mutation and genetic drift. By using numerical simulations of a model system, we analyze the evolution of a population of N diploid hermaphrodites in random mating regime. The population evolves under the effect of drift, selective pressure in form of viability on an additive polygenic trait, and mutation. The analysis allows to determine a phase diagram in the plane of mutation rate and strength of selection. The involved pattern of phase transitions is characterized by a line of critical points for weak selective pressure (smaller than a threshold), whereas discontinuous phase transitions, characterized by metastable hysteresis, are observed for strong selective pressure. A finite-size scaling analysis suggests the analogy between our system and the mean-field Ising model for selective pressure approaching the threshold from weaker values. In this framework, the mutation rate, which allows the system to explore the accessible microscopic states, is the parameter controlling the transition from large heterozygosity ( disordered phase) to small heterozygosity ( ordered one).

Synthesis and high (pressure, temperature) stability of ZnTiO3 polymorphs studied by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Bernert, T.; Ruiz-Fuertes, J.; Bayarjargal, L.; Winkler, B.

2015-05-01

The phase-purity of ilmenite-type ZnTiO3 prepared by the ceramic method was investigated in dependence of the conditions during ball milling. The previously proposed addition of 2 ml ethanol to the starting materials led to a significant contamination of the product phase after a subsequent sintering process at 1073 K. However, by omitting ethanol this synthesis route led to a phase-pure sample of ZnTiO3 as confirmed by X-ray powder diffraction and Raman spectroscopy. High-temperature high-pressure experiments gave an ilmenite-type to perovskite-type phase boundary with a slope of dT/dP∼-135 K GPa-1 crossing ambient temperature conditions at ∼ 24 GPa in good agreement with previous calculations. Room-temperature high-pressure Raman spectroscopy experiments have shown the stability of the ilmenite-type phase up to a pressure of at least 38.5 GPa, the highest pressure applied in this study, indicating the presence of a kinetic barrier in this phase transition. The synthesis of ferroelectric LiNbO3-type ZnTiO3 was confirmed by second harmonic generation.

Quasicrystals at extreme conditions: The role of pressure in stabilizing icosahedral Al 63Cu 24Fe 13 at high temperature

DOE PAGES

Stagno, Vincenzo; Bindi, Luca; Park, Changyong; ...

2015-11-20

Icosahedrite, the first natural quasicrystal with composition Al 63Cu 24Fe 13, was discovered in several grains of the Khatyrka meteorite, a unique CV3 carbonaceous chondrite. The presence in the meteorite fragments of icosahedrite strictly associated with high-pressure phases like ahrensite and stishovite indicates a formation conditions at high pressures and temperatures, likely during an impact-induced shock occurred in contact with the reducing solar nebula gas. In contrast, previous experimental studies on the stability of synthetic icosahedral AlCuFe, which were limited to ambient pressure, indicated incongruent melting at ~1123 K, while high-pressure experiments carried out at room temperature showed structural stabilitymore » up to about 35 GPa. These data are insufficient to experimentally constrain the formation and stability of icosahedrite under extreme conditions. Here we present the results of in situ high pressure experiments using diamond anvil cells of the compressional behavior of synthetic icosahedrite up to ~50 GPa at room temperature. Simultaneous high P-T experiments have been also carried out using both laser-heated diamond anvil cells combined with in situ synchrotron X-ray diffraction (at ~42 GPa) and multi-anvil apparatus (at 21 GPa) to investigate the structural evolution of icosahedral Al 63Cu 24Fe 13 and crystallization of possible coexisting phases. The results demonstrate that the quasiperiodic symmetry of icosahedrite is retained over the entire experimental pressure range explored. In addition, we show that pressure acts to stabilize the icosahedral symmetry at temperatures much higher than previously reported. Based on our experimental study, direct crystallization of Al-Cu-Fe quasicrystals from an unusual Al-Cu-rich melt would be possible but limited to a narrow temperature range beyond which crystalline phases would form, like those observed in the Khatyrka meteorite. Here, an alternative mechanism would consist in late formation of the quasicrystal after crystallization and solid-solid reaction of Al-rich phases. In both cases, linking our results with observations in nature, quasicrystals are expected to preserve their structure even after hypervelocity impacts that involve simultaneous high pressures and temperatures, thus proving their cosmic stability.« less

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

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

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

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

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

Expert monitoring and verbal feedback as sources of performance pressure.

PubMed

Buchanan, John J; Park, Inchon; Chen, Jing; Mehta, Ranjana K; McCulloch, Austin; Rhee, Joohyun; Wright, David L

2018-05-01

The influence of monitoring-pressure and verbal feedback on the performance of the intrinsically stable bimanual coordination patterns of in-phase and anti-phase was examined. The two bimanual patterns were produced under three conditions: 1) no-monitoring, 2) monitoring-pressure (viewed by experts), and 3) monitoring-pressure (viewed by experts) combined with verbal feedback emphasizing poor performance. The bimanual patterns were produced at self-paced movement frequencies. Anti-phase coordination was always less stable than in-phase coordination across all three conditions. When performed under conditions 2 and 3, both bimanual patterns were performed with less variability in relative phase across a wide range of self-paced movement frequencies compared to the no-monitoring condition. Thus, monitoring-pressure resulted in performance stabilization rather than degradation and the presence of verbal feedback had no impact on the influence of monitoring pressure. The current findings are inconsistent with the predictions of explicit monitoring theory; however, the findings are consistent with studies that have revealed increased stability for the system's intrinsic dynamics as a result of attentional focus and intentional control. The results are discussed within the contexts of the dynamic pattern theory of coordination, explicit monitoring theory, and action-focused theories as explanations for choking under pressure. Copyright © 2018. Published by Elsevier B.V.

High-pressure NaCl-phase of tetrahedral compounds

NASA Astrophysics Data System (ADS)

Soma, T.; -Matsuo Kagaya, H.

1984-04-01

The phase transition of tetrahedral compounds such as GaP, InP, ZnS, ZnSe, ZnTe and CdTe under pressure is investigated from the electronic theory of solids by using our recently presented binding force, which includes mainly covalent interactions in the pseudopotential formalism and partially ionic interactions. The partially ionic forces give the important contributions to the high-pressure phase and stabilize the NaCl-type structure for the high-pressure phase of these compounds, although not reported for GaP experimentally. Then, the numerical results such as the transition pressure, the volume-discontinuity, the transition heat with respect to the pressure-induced phase transition from the zinc-blende-to the NaCl-type lattice are obtained theoretically.

Creating Binary Cu–Bi Compounds via High-Pressure Synthesis: A Combined Experimental and Theoretical Study

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

Clarke, Samantha M.; Amsler, Maximilian; Walsh, James P. S.

Exploration beyond the known phase space of thermodynamically stable compounds into the realm of metastable materials is a frontier of materials chemistry. The application of high pressure in experiment and theory provides a powerful vector by which to explore this uncharted phase space, allowing discovery of complex new structures and bonding in the solid state. We harnessed this approach for the Cu–Bi system, where the realization of new phases offers potential for exotic properties such as superconductivity. This potential is due to the presence of bismuth, which, by virtue of its status as one of the heaviest stable elements, formsmore » a critical component in emergent materials such as superconductors and topological insulators. To fully investigate and understand the Cu–Bi system, we welded theoretical predictions with experiment to probe the Cu–Bi system under high pressures. By employing the powerful approach of in situ X-ray diffraction in a laser-heated diamond anvil cell (LHDAC), we thoroughly explored the high-pressure and high-temperature (high-PT) phase space to gain insight into the formation of intermetallic compounds at these conditions. We employed density functional theory (DFT) calculations to calculate a pressure versus temperature phase diagram, which correctly predicts that CuBi is stabilized at lower pressures than Cu11Bi7, and allows us to uncover the thermodynamic contributions responsible for the stability of each phase. Detailed comparisons between the NiAs structure type and the two high-pressure Cu–Bi phases, Cu11Bi7 and CuBi, reveal the preference for elemental segregation within the Cu–Bi phases, and highlight the unique channels and layers formed by ordered Cu vacancies. The electron localization function from DFT calculations account for the presence of these “voids” as a manifestation of the lone pair orientation on the Bi atoms. Our study demonstrates the power of joint experimental–computational work in exploring the chemistry occurring at high-PT conditions. The existence of multiple high-pressure-stabilized phases in the Cu–Bi binary system, which can be readily identified with in situ techniques, offers promise for other systems in which no ambient pressure phases are known to exist.« less

System for stabilizing cable phase delay utilizing a coaxial cable under pressure

NASA Technical Reports Server (NTRS)

Clements, P. A. (Inventor)

1974-01-01

Stabilizing the phase delay of signals passing through a pressurizable coaxial cable is disclosed. Signals from an appropriate source at a selected frequency, e.g., 100 MHz, are sent through the controlled cable from a first cable end to a second cable end which, electrically, is open or heavily mismatched at 100 MHz, thereby reflecting 100 MHz signals back to the first cable end. Thereat, the phase difference between the reflected-back signals and the signals from the source is detected by a phase detector. The output of the latter is used to control the flow of gas to or from the cable, thereby controlling the cable pressure, which in turn affects the cable phase delay.

The high-pressure phase transitions of hydroxides

NASA Astrophysics Data System (ADS)

Nishi, M.; Kuwayama, Y.; Tsuchiya, J.; Tsuchiya, T.; Irifune, T.

2017-12-01

The discovery of new high-pressure hydrous minerals has important implications for understanding the structure, dynamics, and evolution of the Earth, since hydrogen significantly affects the physical properties and stabilities of Earth's constituent minerals. Whereas hydrous minerals commonly dehydrate under pressures of around a few tens of gigapascals (GPa) and at temperature around 1,500 K, those with CaCl2-type crystal structure, MgSiO4H2 phase H, δ-AlOOH and ɛ-FeOOH, are known to be stable at pressures corresponding to the lower mantle. However, although the CaCl2-type hydroxides were suggested to form a solid solution owing to their similar crystal structure, there are few experimental studies on the stability of the hydroxide in such multicomponent. Moreover, ab initio calculations have predicted that some CaCl2-type hydroxides transform to pyrite-type structure at higher pressures. Here, we conducted high pressure-temperature experiments on pure AlOOH, FeOOH, and their solid solutions, with the aid of these first-principles predictions. We use in situ X-ray measurements in conjunction with a multi-anvil apparatus to study the high-pressure behaviour of hydroxides in the multicomponent system under middle lower mantle conditions. Solid solutions in wide compositional ranges between CaCl2-type δ-AlOOH and ɛ-FeOOH were recognized from X-ray diffraction patterns. Also, unit cell volume of FeOOH and (Al,Fe)OOH significantly decreased accompanied with the spin transition of iron at 50 GPa. Thus, the wide compositional ranges in CaCl2-type hydroxide are maintained beyond the depth of the middle lower mantle, where the spin transition of iron occurs. We used a laser-heated diamond anvil cell in order to study the stability of AlOOH and FeOOH at higher pressures above 70 GPa. We observed that ɛ-FeOOH transforms to the pyrite-type structure at above 80 GPa, which is consistent with the theoretical prediction. At conditions above 190 GPa and 2,500 K, we observed the phase transition of δ-AlOOH to its higher pressure phase at above 170 GPa although further experimental study should be required to determine the precise structure. Based on these experimental and theoretical results, the stability and phase transitions of hydrous phases in the lower mantle will be discussed.

The Formation and Stability of Carbonic Acid on Outer Solar System Bodies

NASA Technical Reports Server (NTRS)

Peeters, Z.; Hudson, R. L.; Moore, M. H.; Lewis, Ariel

2009-01-01

The radiation chemistry, thermal stability, and vapor pressure of solid-phase carbonic acid (H2CO3) have been studied with mid-infrared spectroscopy. A new procedure for measuring this molecule's radiation stability has been used to obtain intrinsic IR band strengths and half-lives for radiolytic destruction. Results are compared to literature values. We report, for the first time, measurements of carbonic acid's vapor pressure and its heat of sublimation. We also report the first observation of a chemical reaction involving solid-phase carbonic acid. Possible applications of these findings are discussed, with an emphasis on the outer Solar System.

Phase transitions in the system CaCO3 at high P and T determined by in situ vibrational spectroscopy in diamond anvil cells and first-principles simulations

NASA Astrophysics Data System (ADS)

Koch-Müller, Monika; Jahn, Sandro; Birkholz, Natalie; Ritter, Eglof; Schade, Ulrich

2016-09-01

The stability of the high-pressure CaCO3 calcite (cc)-related polymorphs was studied in experiments that were performed in conventional diamond anvil cells (DAC) at room temperature as a function of pressure up to 30 GPa as well as in internally heated diamond anvil cells (DAC-HT) at pressures and temperatures up to 20 GPa and 800 K. To probe structural changes, we used Raman and FTIR spectroscopy. For the latter, we applied conventional and synchrotron mid-infrared as well as synchrotron far-infrared radiation. Within the cc-III stability field (2.2-15 GPa at room temperature, e.g., Catalli and Williams in Phys Chem Miner 32(5-6):412-417, 2005), we observed in the Raman spectra consistently three different spectral patterns: Two patterns at pressures below and above 3.3 GPa were already described in Pippinger et al. (Phys Chem Miner 42(1):29-43, 2015) and assigned to the phase transition of cc-IIIb to cc-III at 3.3 GPa. In addition, we observed a clear change between 5 and 6 GPa that is independent of the starting material and the pressure path and time path of the experiments. This apparent change in the spectral pattern is only visible in the low-frequency range of the Raman spectra—not in the infrared spectra. Complementary electronic structure calculations confirm the existence of three distinct stability regions of cc-III-type phases at pressures up to about 15 GPa. By combining experimental and simulation data, we interpret the transition at 5-6 GPa as a re-appearance of the cc-IIIb phase. In all types of experiments, we confirmed the transition from cc-IIIb to cc-VI at about 15 GPa at room temperature. We found that temperature stabilizes cc-VI to lower pressure. The reaction cc-IIIb to cc-VI has a negative slope of -7.0 × 10-3 GPa K-1. Finally, we discuss the possibility of the dense cc-VI phase being more stable than aragonite at certain pressure and temperature conditions relevant to the Earth's mantle.

Structural phase stability in nanocrystalline titanium to 161 GPa

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

Velisavljevic, Nenad; Jacobsen, Matthew K.; Vohra, Yogesh K.

2014-09-16

Nanocrystalline titanium (nc-Ti) metal was investigated up to 161 GPa at room temperature using a diamond anvil cell. X-ray diffraction and electrical resistance techniques were used to investigate the compressibility and structural phase stability. nc-Ti is observed to undergo three structural phase transitions at high pressures, starting with α → ω at 10GPa and followed by ω → γ at 127GPa and γ → δ at 140GPa. The observed structural phase transitions, as well as compressibility, are consistent with previously reported values for coarse grained Ti (c-Ti). The high pressure experiments on nc-Ti samples do no show any significant variationmore » of the α → ω transition pressure under varying nonhydrostatic conditions. This is in sharp contrast to c-Ti, where a significant decrease in the α → ω transition pressure is observed under increasing nonhydrostatic conditions. As a result, this would indicate that the decrease in grain size in nano grained titanium makes the α → ω phase transition less sensitive to shear stresses as compared to bulk or c-Ti.« less

Ab initio study of phase stability of NaZr{sub 2}(PO{sub 4}){sub 3} under pressure

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

Chinnappan, Ravi; Kaur, Gurpreet; Panigrahi, B. K.

2016-05-23

The elastic constants of NaZr{sub 2}(PO{sub 4}){sub 3} were computed as a function of pressure through Density Functional Theory calculations. The behavior of elastic constants show that the rhombohedral (R-3c) NaZr{sub 2}(PO{sub 4}){sub 3} becomes unstable above 8 GPa and is driven by softening of C{sub 44} through one of the Born stability criteria. High pressure equation of state and enthalpy show further that the ambient rhombohedral (R-3c)) NaZr{sub 2}(PO{sub 4}){sub 3} transforms first to another rhombohedral (R3) phase and subsequently to LiZr{sub 2}(PO{sub 4}){sub 3}-type orthorhombic phase at pressures above 6 and 8 GPa respectively which are in agreement with recentmore » X-ray diffraction study.« less

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)CO 3] 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)CO 3 system at deep-mantle conditions including the chemical dissociation to (Mg,Fe)O+CO 2, the occurrence of the tetrahedrally-coordinated carbonates based on CO 4 structural units, and various high-pressure phase transitions. Here we have studied the phase stability and compressional behavior of (Mg,Fe)CO 3 carbonates upmore » 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)CO 3 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

Synthesis of the new compound CaFe(CO 3) 2 and experimental constraints on the (Ca,Fe)CO 3 join

NASA Astrophysics Data System (ADS)

Davidson, Paula M.; Symmes, Gregory H.; Cohen, Barbara A.; Reeder, Richard J.; Lindsley, Donald H.

1993-12-01

Synthesis of the new (disordered) compound CaFe(CO 3) 2 has been achieved with the use of Fe-substituted CaCO 3(Cc ss) + Ca-substituted FeCO 3(Sid ss) as starting materials, and high CO 2 pressures. High pressure (20-30 kbar) is needed to stabilize FeCO 3 to sufficiently high temperatures for disordered CaFe(CO 3) 2 to form. Experiments provide reversed compositions of coexisting disordered phases in the CaFe join and locate the solvus temperature for CaFe(C) 3) 2 between 815 and 845°C at 30 kbars. Calculated phase relations predict that the stability of ordered CaFe(CO 3) 2 is limited to T < ˜450°C by the breakdown to Cc ss + Sid ss. A comparison of the unit-cell volume measured for disordered CaFe(CO 3) 2 vs. that estimated for ordered CaFe(CO 3) 2 suggests that increasing pressure stabilizes the disordered phase.

Stability and Solid Solutions of Hydrous Alumino-Silicates in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Panero, W. R.; Caracas, R.

2017-12-01

The degree to which the Earth's mantle stores and cycles water in excess of the storage capacity of nominally anhydrous minerals is dependent upon the stability of hydrous phases under mantle-relevant pressures, temperatures, and compositions. Two hydrous phases, phase D and phase H are stable to the pressures and temperatures of the Earth's lower mantle, suggesting that the Earth's lower mantle may participate in the cycling of water. Each phase has a wide solid solution series between MgSi2O6H2-Al2SiO6H2 and MgSiO4H2-2δAlOOH-SiO2, respectively, yet most work addresses end-member compositions for analysis of stability and elastic properties. We present the results of density functional theory calculations on the stability, structure, bonding, partitioning, and elasticity of hydrous phases D and H in the Al2O3-SiO2-MgO-H2O system, addressing the solid solution series through a statistical sampling of site occupancy and calculation of the partition function from the grand canonical ensemble. We find that the addition of Al to the endmember compositions stabilizes each phase to higher temperatures through additional configurational entropy. We further find that solid solutions tend not to undergo hydrogen-bond symmetrization as is found in the end member compositions as a result of non-symmetric bonding environments.

Description of intraoral pressures on sub-palatal space in young adult patients with normal occlusion.

PubMed

Fuentes, Ramón; Engelke, Wilfried; Flores, Tania; Navarro, Pablo; Borie, Eduardo; Curiqueo, Aldo; Salamanca, Carlos

2015-01-01

Under normal conditions, the oral cavity presents a perfect system of equilibrium between teeth, soft tissues and tongue. The equilibrium of soft tissues forms a closed capsular matrix, generating differences with the atmospheric environment. This difference is known as intraoral pressure. Negative intraoral pressure is fundamental to the stabilization of the soft palate and tongue, reducing neuromuscular activity for the permeability of the respiratory tract. Thus, the aim of this study was to describe the variations of intraoral pressure of the sub-palatal space (SPS) under different physiological conditions and biofunctional phases. A case series was conducted with 20 individuals aged between 18 and 25. The intraoral pressures were measured through a system of cannulae connected to a digital pressure meter in the SPS during seven biofunctional phases. Descriptive statistics were used based on the mean and standard deviation. The data recorded pressure variations under physiological conditions, reaching 65 mbar as the intraoral peak in forced inspiration. In the swallowing phase, peaks reached -91.9 mbar. No pressure variations were recorded in terms of atmospheric changes with the mouth open and semi-open. The data obtained during the swallowing and forced inspiration phases indicated forced lingual activity. In the swallowing phase, the adequate position of the tongue creates negative intraoral pressure, which represents a fundamental mechanism for the physical stabilization of the soft palate. This information could contribute to subsequent research into the treatment of primary roncopathies.

Phase Stability of Epsilon and Gamma HNIW (CL-20) at High-Pressure and Temperature

NASA Astrophysics Data System (ADS)

Gump, Jared

2007-06-01

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, and 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. Theoretical calculations have been performed for a variety of explosive ingredients including CL-20, but it was noted that no experimental measurements existed for comparison with the theoretical bulk modulus calculated for CL-20. Therefore, the phase stabilities of epsilon and gamma 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 5GPa and 175^oC, respectively. No phase change (from the starting epsilon phase) was observed under hydrostatic compression up to 6.3 GPa at ambient temperature. Under ambient pressure the epsilon phase was determined to be stable to a temperature of 120^oC. When heating above 125^oC the gamma phase appeared and it remained stable until thermal decomposition occurred above 150^oC. The gamma phase exhibits a phase change upon compression at both ambient temperature and 140^oC. Pressure -- volume data for the epsilon and gamma phase at ambient temperature and the epsilon phase at 75^oC were fit to the Birch-Murnaghan formalism to obtain isothermal equations of state.

Proton conducting ceramic membranes for hydrogen separation

DOEpatents

Elangovan, S [South Jordan, UT; Nair, Balakrishnan G [Sandy, UT; Small, Troy [Midvale, UT; Heck, Brian [Salt Lake City, UT

2011-09-06

A multi-phase proton conducting material comprising a proton-conducting ceramic phase and a stabilizing ceramic phase. Under the presence of a partial pressure gradient of hydrogen across the membrane or under the influence of an electrical potential, a membrane fabricated with this material selectively transports hydrogen ions through the proton conducting phase, which results in ultrahigh purity hydrogen permeation through the membrane. The stabilizing ceramic phase may be substantially structurally and chemically identical to at least one product of a reaction between the proton conducting phase and at least one expected gas under operating conditions of a membrane fabricated using the material. In a barium cerate-based proton conducting membrane, one stabilizing phase is ceria.

High pressure phase transitions and compressibilities of Er2Zr2O7 and Ho2Zr2O7

NASA Astrophysics Data System (ADS)

Zhang, F. X.; Lang, M.; Becker, U.; Ewing, R. C.; Lian, J.

2008-01-01

Phase stability and compressibility of rare earth zirconates with the defect-fluorite structure were investigated by in situ synchrotron x-ray diffraction. A sluggish defect-fluorite to a cotunnitelike phase transformation occurred at pressures of ˜22 and ˜30GPa for Er2Zr2O7 and Ho2Zr2O7, respectively. Enhanced compressibility was found for the high pressure phase as a result of increasing cation coordination number and cation-anion bond length.

Equation of state, phase stability, and phase transformations of uranium-6 wt. % niobium under high pressure and temperature

NASA Astrophysics Data System (ADS)

Zhang, Jianzhong; Vogel, Sven; Brown, Donald; Clausen, Bjorn; Hackenberg, Robert

2018-05-01

In-situ time-of-flight neutron diffraction experiments were conducted on the uranium-niobium alloy with 6 wt. % Nb (U-6Nb) at pressures up to 4.7 GPa and temperatures up to 1073 K. Upon static compression at room temperature, the monoclinic structure of U-6Nb (α″ U-6Nb) remains stable up to the highest experimental pressure. Based on the pressure-volume measurements at room temperature, the least-squares fit using the finite-strain equation of state (EOS) yields an isothermal bulk modulus of B0 = 127 ± 2 GPa for the α″-phase of U-6Nb. The calculated zero-pressure bulk sound speed from this EOS is 2.706 ± 0.022 km/s, which is in good agreement with the linear extrapolation of the previous Hugoniot data above 12 GPa for α″ U-6Nb, indicating that the dynamic response under those shock-loading conditions is consistent with the stabilization of the initial monoclinic phase of U-6Nb. Upon heating at ambient and high pressures, the metastable α″ U-6Nb exhibits complex transformation paths leading to the diffusional phase decomposition, which are sensitive to applied pressure, stress state, and temperature-time path. These findings provide new insight into the behavior of atypical systems such as U-Nb and suggest that the different U-Nb phases are separated by rather small energies and hence highly sensitive to compositional, thermal, and mechanical perturbations.

Metastable phase transformation and hcp-ω transformation pathways in Ti and Zr under high hydrostatic pressures

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

Gao, Lei; Ding, Xiangdong, E-mail: dingxd@mail.xjtu.edu.cn, E-mail: ekhard@esc.cam.ac.uk; Sun, Jun

2016-07-18

The energy landscape of Zr at high hydrostatic pressure suggests that its transformation behavior is strongly pressure dependent. This is in contrast to the known transition mechanism in Ti, which is essentially independent of hydrostatic pressure. Generalized solid-state nudged elastic band calculations at constant pressure shows that α-Zr transforms like Ti only at the lowest pressure inside the stability field of ω-phase. Different pathways apply at higher pressures where the energy landscape contains several high barriers so that metastable states are expected, including the appearance of a transient bcc phase at ca. 23 GPa. The global driving force for the hcp-ωmore » transition increases strongly with increasing pressure and reaches 23.7 meV/atom at 23 GPa. Much of this energy relates to the excess volume of the hcp phase compared with its ω phase.« less

Equation of state and pressure induced amorphization of beta-boron from X-ray measurements up to 100 GPa.

PubMed

Sanz, Delia Nieto; Loubeyre, Paul; Mezouar, Mohamed

2002-12-09

The equation of state of boron has been measured up to 100 GPa by single-crystal x-ray diffraction with helium as the pressure transmitting medium. Rhombohedral beta-boron is the stable structure up to 100 GPa under hydrostatic conditions. Nonhydrostatic stress stabilizes a different rhombohedral structure. At about 100 GPa a pressure-induced amorphization is observed. The amorphous phase can be quenched to ambient pressure. An explanation is proposed based on the different stability under pressure between intraicosahedra and intericosahedra bonds.

Understanding decomposition and encapsulation energies of structure I and II clathrate hydrates

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ohmura, Ryo

2016-10-01

When compressed with water or ice under high pressure and low temperature conditions, some gases form solid gas hydrate inclusion compounds which have higher melting points than ice under those pressures. In this work, we study the balance of the guest-water and water-water interaction energies that lead to the formation of the clathrate hydrate phases. In particular, molecular dynamics simulations with accurate water potentials are used to study the energetics of the formation of structure I (sI) and II (sII) clathrate hydrates of methane, ethane, and propane. The dissociation enthalpy of the clathrate hydrate phases, the encapsulation enthalpy of methane, ethane, and propane guests in the corresponding phases, and the average bonding enthalpy of water molecules are calculated and compared with accurate calorimetric measurements and previous classical and quantum mechanical calculations, when available. The encapsulation energies of methane, ethane, and propane guests stabilize the small and large sI and sII hydrate cages, with the larger molecules giving larger encapsulation energies. The average water-water interactions are weakened in the sI and sII phases compared to ice. The relative magnitudes of the van der Waals potential energy in ice and the hydrate phases are similar, but in the ice phase, the electrostatic interactions are stronger. The stabilizing guest-water "hydrophobic" interactions compensate for the weaker water-water interactions and stabilize the hydrate phases. A number of common assumptions regarding the guest-cage water interactions are used in the van der Waals-Platteeuw statistical mechanical theory to predict the clathrate hydrate phase stability under different pressure-temperature conditions. The present calculations show that some of these assumptions may not accurately reflect the physical nature of the interactions between guest molecules and the lattice waters.

Understanding decomposition and encapsulation energies of structure I and II clathrate hydrates.

PubMed

Alavi, Saman; Ohmura, Ryo

2016-10-21

When compressed with water or ice under high pressure and low temperature conditions, some gases form solid gas hydrate inclusion compounds which have higher melting points than ice under those pressures. In this work, we study the balance of the guest-water and water-water interaction energies that lead to the formation of the clathrate hydrate phases. In particular, molecular dynamics simulations with accurate water potentials are used to study the energetics of the formation of structure I (sI) and II (sII) clathrate hydrates of methane, ethane, and propane. The dissociation enthalpy of the clathrate hydrate phases, the encapsulation enthalpy of methane, ethane, and propane guests in the corresponding phases, and the average bonding enthalpy of water molecules are calculated and compared with accurate calorimetric measurements and previous classical and quantum mechanical calculations, when available. The encapsulation energies of methane, ethane, and propane guests stabilize the small and large sI and sII hydrate cages, with the larger molecules giving larger encapsulation energies. The average water-water interactions are weakened in the sI and sII phases compared to ice. The relative magnitudes of the van der Waals potential energy in ice and the hydrate phases are similar, but in the ice phase, the electrostatic interactions are stronger. The stabilizing guest-water "hydrophobic" interactions compensate for the weaker water-water interactions and stabilize the hydrate phases. A number of common assumptions regarding the guest-cage water interactions are used in the van der Waals-Platteeuw statistical mechanical theory to predict the clathrate hydrate phase stability under different pressure-temperature conditions. The present calculations show that some of these assumptions may not accurately reflect the physical nature of the interactions between guest molecules and the lattice waters.

Combined effects of Sr substitution and pressure on the ground states in CaFe2As2

NASA Astrophysics Data System (ADS)

Knöner, S.; Gati, E.; Köhler, S.; Wolf, B.; Tutsch, U.; Ran, S.; Torikachvili, M. S.; Bud'ko, S. L.; Canfield, P. C.; Lang, M.

2016-10-01

We present a detailed study of the combined effects of Sr substitution and hydrostatic pressure on the ground-state properties of CaFe2As2 . Measurements of the electrical resistance and magnetic susceptibility, both at ambient and finite pressure P ≤2 GPa, were performed on Ca1 -xSrxFe2As2 single crystals grown out of Sn flux. We find that by Sr substitution the transition temperature to the magnetic/structural phase is enhanced and therefore a higher pressure is needed to suppress the transition to lowest temperature. In addition, the transition to the collapsed tetragonal phase is found at a pressure, which is distinctly higher than in the pure compound. This implies that the stability ranges of both phases shift on the pressure-axis upon doping, but the latter one with a higher rate. These observations suggest the possibility of separating the two phase lines, which intersect already at elevated temperatures for x =0 and low Sr concentration levels. For x =0.177 , we find strong evidence that both phases remain separated down to the lowest temperature and that a zero-resistance state emerges in this intermediate pressure window. This observation indicates that Sr substitution combined with hydrostatic pressure provides another route for stabilizing superconductivity in CaFe2As2 . Our results are consistent with the notion that (i) preserving the fluctuations associated with the structural-magnetic transition to low temperatures is vital for superconductivity to form in this material and that (ii) the nonmagnetic collapsed tetragonal phase is detrimental for superconductivity.

The A-B transition in superfluid helium-3 under confinement in a thin slab geometry

PubMed Central

Zhelev, N.; Abhilash, T. S.; Smith, E. N.; Bennett, R. G.; Rojas, X.; Levitin, L.; Saunders, J.; Parpia, J. M.

2017-01-01

The influence of confinement on the phases of superfluid helium-3 is studied using the torsional pendulum method. We focus on the transition between the A and B phases, where the A phase is stabilized by confinement and a spatially modulated stripe phase is predicted at the A–B phase boundary. Here we discuss results from superfluid helium-3 contained in a single 1.08-μm-thick nanofluidic cavity incorporated into a high-precision torsion pendulum, and map the phase diagram between 0.1 and 5.6 bar. We observe only small supercooling of the A phase, in comparison to bulk or when confined in aerogel, with evidence for a non-monotonic pressure dependence. This suggests that an intrinsic B-phase nucleation mechanism operates under confinement. Both the phase diagram and the relative superfluid fraction of the A and B phases, show that strong coupling is present at all pressures, with implications for the stability of the stripe phase. PMID:28671184

Non-equilibrium phase stabilization versus bubble nucleation at a nanoscale-curved Interface

NASA Astrophysics Data System (ADS)

Schiffbauer, Jarrod; Luo, Tengfei

Using continuum dynamic van der Waals theory in a radial 1D geometry with a Lennard-Jones fluid model, we investigate the nature of vapor bubble nucleation near a heated, nanoscale-curved convex interface. Vapor bubble nucleation and growth are observed for interfaces with sufficiently large radius of curvature while phase stabilization of a superheated fluid layer occurs at interfaces with smaller radius. The hypothesis that the high Laplace pressure required for stable equilibrium of very small bubbles is responsible for phase stability is tested by effectively varying the parameter which controls liquid-vapor surface tension. In doing so, the liquid-vapor surface tension- hence Laplace pressure-is shown to have limited effect on phase stabilization vs. bubble nucleation. However, the strong dependence of nucleation on leading-order momentum transport, i.e. viscous dissipation, near the heated inner surface is demonstrated. We gratefully acknowledge ND Energy for support through the ND Energy Postdoctoral Fellowship program and the Army Research Office, Grant No. W911NF-16-1-0267, managed by Dr. Chakrapani Venanasi.

Slope stability of bioreactor landfills during leachate injection: effects of heterogeneous and anisotropic municipal solid waste conditions.

PubMed

Giri, Rajiv K; Reddy, Krishna R

2014-03-01

In bioreactor landfills, leachate recirculation can significantly affect the stability of landfill slope due to generation and distribution of excessive pore fluid pressures near side slope. The current design and operation of leachate recirculation systems do not consider the effects of heterogeneous and anisotropic nature of municipal solid waste (MSW) and the increased pore gas pressures in landfilled waste caused due to leachate recirculation on the physical stability of landfill slope. In this study, a numerical two-phase flow model (landfill leachate and gas as immiscible phases) was used to investigate the effects of heterogeneous and anisotropic nature of MSW on moisture distribution and pore-water and capillary pressures and their resulting impacts on the stability of a simplified bioreactor landfill during leachate recirculation using horizontal trench system. The unsaturated hydraulic properties of MSW were considered based on the van Genuchten model. The strength reduction technique was used for slope stability analyses as it takes into account of the transient and spatially varying pore-water and gas pressures. It was concluded that heterogeneous and anisotropic MSW with varied unit weight and saturated hydraulic conductivity significantly influenced the moisture distribution and generation and distribution of pore fluid pressures in landfill and considerably reduced the stability of bioreactor landfill slope. It is recommended that heterogeneous and anisotropic MSW must be considered as it provides a more reliable approach for the design and leachate operations in bioreactor landfills.

Structural stability, electronic structure and mechanical properties of alkali gallium hydrides AGaH{sub 4} (A = Li, Na)

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

Santhosh, M.; Rajeswarapalanichamy, R., E-mail: rrpalanichamy@gmail.com; Manikandan, M.

2016-05-06

Ab initio calculations are performed to investigate the structural stability, electronic structure and mechanical properties of alkali gallium hydrides AGaH{sub 4} (A = Li, Na) for three different crystal structures, namely tetragonal (P42{sub 1}c), tetragonal (P4{sub 2}/nmc) and monoclinic (P2{sub 1}/c). Among the considered structures, tetragonal (P42{sub 1}c) phase is found to be the most stable phase for these hydrides at normal pressure. A pressure induced structural phase transition from tetragonal (P42{sub 1}c) to tetragonal (P4{sub 2}/nmc) is observed. The electronic structure reveals that these hydrides are insulators. The calculated elastic constants indicate that these ternary imides are mechanically stablemore » at normal pressure.« less

Water adsorbate phases on ZnO and impact of vapor pressure on the equilibrium shape of nanoparticles

NASA Astrophysics Data System (ADS)

Kenmoe, Stephane; Biedermann, P. Ulrich

2018-02-01

ZnO nanoparticles are used as catalysts and have potential applications in gas-sensing and solar energy conversion. A fundamental understanding of the exposed crystal facets, their surface chemistry, and stability as a function of environmental conditions is essential for rational design and improvement of synthesis and properties. We study the stability of water adsorbate phases on the non-polar low-index (10 1 ¯ 0 ) and (11 2 ¯ 0 ) surfaces from low coverage to multilayers using ab initio thermodynamics. We show that phonon contributions and the entropies due to a 2D lattice gas at low coverage and multiple adsorbate configurations at higher coverage have an important impact on the stability range of water adsorbate phases in the (T,p) phase diagram. Based on this insight, we compute and analyze the possible growth mode of water films for pressures ranging from UHV via ambient conditions to high pressures and the impact of water adsorption on the equilibrium shape of nanoparticles in a humid environment. A 2D variant of the Wulff construction shows that the (10 1 ¯ 0 ) and (11 2 ¯ 0 ) surfaces coexist on 12-faceted prismatic ZnO nanoparticles in dry conditions, while in humid environment, the (10 1 ¯ 0 ) surface is selectively stabilized by water adsorption resulting in hexagonal prisms.

Stability of the high pressure phase Fe3S2 up to Earth's core pressures in the Fe-S-O and the Fe-S-Si systems

NASA Astrophysics Data System (ADS)

Zurkowski, C. C.; Chidester, B.; Davis, A.; Brauser, N.; Greenberg, E.; Prakapenka, V. B.; Campbell, A.

2017-12-01

Earth's core is comprised of an iron-nickel alloy that contains 5-15% of a light element component. The abundance and alloying capability of sulfur, silicon and oxygen in the bulk Earth make them important core alloy candidates; therefore, the high-pressure phase equilibria of the Fe-S-O and Fe-S-Si systems are relevant for understanding the possible chemistry of Earth's core. Previously, a Fe3S2 phase was recognized as a low-pressure intermediate phase in the Fe-FeS system that is stable from 14-21 GPa, but the structure of this phase has not been resolved. We report in-situ XRD and chemical analysis of recovered samples to further examine the stability and structure of Fe3S2 as it coexists with other phases in the Fe-S-O and Fe-S-Si systems. In situ high P-T synchrotron XRD experiments were conducted in the laser-heated diamond anvil cell to determine the equilibrium phases in Fe75S7O18 and Fe80S5Si15 compositions between 30 and 174 GPa and up to 3000 K. In the S,O-rich samples, an orthorhombic Fe3S2 phase coexists with hcp-Fe, Fe3S and FeO and undergoes two monoclinic distortions between 60 and 174 GPa. In the S,Si-rich samples, the orthorhombic Fe3S2 phase was observed up to 115 GPa. With increasing pressure, the Fe3S2 phase becomes stable to higher temperatures in both compositions, suggesting possible Fe3(S,O)2 or Fe3(S,Si)2 solid solutions. SEM analysis of a laser heated Fe75S7O18 sample recovered from 40 GPa and 1450 K confirms a Fe3(S,O)2 phase with O dissolved into the structure. Based on the current melting data in the Fe-S-O and Fe-S-Si systems, the Fe3(S,O)2 stability field intersects the solidus in the outer core and could be a possible liquidus phase in Fe,S,O-rich planetary cores, whereas Fe3S is the stable sulfide at outer core pressures in Fe,S,Si-rich systems.

Exploration of phase transition in ThS under pressure: An ab-initio investigation

NASA Astrophysics Data System (ADS)

Sahoo, B. D.; Mukherjee, D.; Joshi, K. D.; Kaushik, T. C.

2018-04-01

The ab-initio total energy calculations have been performed in thorium sulphide (ThS) to explore its high pressure phase stability. Our calculations predict a phase transformation from ambient rocksalt type structure (B1 phase) to a rhombohedral structure (R-3m phase) at ˜ 15 GPa and subsequently R-3m phase transforms to CsCl type structure (B2 phase) at ˜ 45 GPa. The first phase transition has been identified as second order type; whereas, the second transition is of first order type with volume discontinuity of 6.5%. The predicted high pressure R-3m phase is analogous to the experimentally observed hexagonal (distorted fcc) phase (Benedict et al., J. Less-Common Met., 1984) above 20 GPa. Further, using these calculations we have derived the equation of state which has been utilized to determine various physical quantities such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus at ambient conditions.

First principles study of structural stability, electronic structure and mechanical properties of ReN and TcN

NASA Astrophysics Data System (ADS)

Rajeswarapalanichamy, R.; Kavitha, M.; Sudha Priyanga, G.; Iyakutti, K.

2015-03-01

The crystal structure, structural stability, electronic and mechanical properties of ReN and TcN are investigated using first principles calculations. We have considered five different crystal structures: NaCl, zinc blende (ZB), NiAs, tungsten carbide (WC) and wurtzite (WZ). Among these ZB phase is found to be the lowest energy phase for ReN and TcN at normal pressure. Pressure induced structural phase transitions from ZB to WZ phase at 214 GPa in ReN and ZB to NiAs phase at 171 GPa in TcN are predicted. The electronic structure reveals that both ReN and TcN are metallic in nature. The computed elastic constants indicate that both the nitrides are mechanically stable. As ReN in NiAs phase has high bulk and shear moduli and low Poisson's ratio, it is found to be a potential ultra incompressible super hard material.

Chemical stabilization and high pressure synthesis of Ba-free Hg-based superconductors, (Hg,M)Sr2Ca(n-1)Cu(n)O(y)(n=1 to approximately 3)

NASA Technical Reports Server (NTRS)

Kishio, K.; Shimoyama, J.; Hahakura, S.; Kitazawa, K.; Yamaura, K.; Hiroi, Z.; Takano, M.

1995-01-01

A homologous series of new Hg-based HTSC compounds, (Hg,M)Sr2Ca(n - 1)Cu(n)P(y) with n = 1 to 3, have been synthesized. The stabilization of the pure phases have been accomplished by chemical doping of third elements such as M = Cr, Mo and Re. While the Hgl2O1(n = 1) phase was readily obtained in this way, it was necessary to simultaneously dope Y into the Ca site to stabilize the Hg1212(n = 2) phase. On the other hand, single-phase Y-free Hg1212(n = 2) and Hg1223 (n = 3) samples were synthesized only under a high pressure of 6 GPa. In sharp contrast to the Ba containing compounds, all the samples prepared in the present study have been quite stable during the synthesis and no deterioration in air has been observed after the preparation.

Stability of fluorite-type La 2Ce 2O 7 under extreme conditions

DOE PAGES

Zhang, F. X.; Tracy, C. L.; Lang, M.; ...

2016-03-03

Here, the structural stability of fluorite-type La 2Ce 2O 7 was studied at pressure up to ~40 GPa and under hydrothermal conditions (~1 GPa, 350 °C), respectively, using synchrotron x-ray diffraction (XRD) and Raman scattering measurements. XRD measurements indicated that fluorite-type La 2Ce 2O 7 is not stable at pressures greater than 22.6 GPa and slowly transforms to a high-pressure phase. The high-pressure phase is not stable and changes back to the fluorite-type structure when pressure is released. The La 2Ce 2O 7 fluorite is also not stable under hydrothermal conditions and begins to react with water at 200~250 °C.more » Both Raman and XRD results suggest that lanthanum hydroxide La(OH) 3 and La 3+-doped CeO 2 fluorite are the dominant products after hydrothermal treatment.« less

Exploring the coordination change of vanadium and structure transformation of metavanadate MgV2O6 under high pressure

PubMed Central

Tang, Ruilian; Li, Yan; Xie, Shengyi; Li, Nana; Chen, Jiuhua; Gao, Chunxiao; Zhu, Pinwen; Wang, Xin

2016-01-01

Raman spectroscopy, synchrotron angle-dispersive X-ray diffraction (ADXRD), first-principles calculations, and electrical resistivity measurements were carried out under high pressure to investigate the structural stability and electrical transport properties of metavanadate MgV2O6. The results have revealed the coordination change of vanadium ions (from 5+1 to 6) at around 4 GPa. In addition, a pressure-induced structure transformation from the C2/m phase to the C2 phase in MgV2O6 was detected above 20 GPa, and both phases coexisted up to the highest pressure. This structural phase transition was induced by the enhanced distortions of MgO6 octahedra and VO6 octahedra under high pressure. Furthermore, the electrical resistivity decreased with pressure but exhibited different slope for these two phases, indicating that the pressure-induced structural phase transitions of MgV2O6 was also accompanied by the obvious changes in its electrical transport behavior. PMID:27924843

First principles investigation of high pressure behavior of FeOOH-AlOOH-phase H (MgSiO4H2) system.

NASA Astrophysics Data System (ADS)

Tsuchiya, J.; Thompson, E. C.; Tsuchiya, T.; Nishi, M.; Kuwayama, Y.

2017-12-01

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. A numbers of researches have been conducted so far about the high pressure behaviors of DHMSs. In recent years, we found new DHMS, phase H, at lower mantle pressure condition and the solid solution between phase H and d-AlOOH has been proposed as the most important carrier of water in the deepest part of Earth's mantle (Tsuchiya 2013 GRL, Nishi et al. 2014 Nature Geo., Ohira et al. 2014 EPSL). However, those hydrous minerals are actually not denser than surrounding (dry) mantle minerals (Tsuchiya and Mookherjee 2015 Scientific Reports) and the gravitational stability in deeper part of the Earth is questionable. Therefore, the effects of denser element such as Fe on the stability of DHMS are intimately connected to the ability of transportation of water into Earth's deep interiors. In order to assess the effect of Fe on the phase relation of phase H and d-AlOOH, we first investigated the high pressure behavior of the end-member composition of this system, the e-FeOOH. We have found the new high pressure transformation of FeOOH in the lower mantle conditions both theoretically and experimentally(Nishi et al. 2017 Nature). Here we show high pressure structures and the physical properties of FeOOH-AlOOH-phase H system using first principles calculation and discuss the possible geophysical implications of these phases.

Polymorphism of paracetamol: relative stabilities of the monoclinic and orthorhombic phases inferred from topological pressure-temperature and temperature-volume phase diagrams.

PubMed

Espeau, Philippe; Céolin, René; Tamarit, Josep-Lluis; Perrin, Marc-Antoine; Gauchi, Jean-Pierre; Leveiller, Franck

2005-03-01

The thermodynamic relationships between the two known polymorphs of paracetamol have been investigated, and the subsequent pressure-temperature and temperature-volume phase diagrams were constructed using data from crystallographic and calorimetric measurements as a function of the temperature. Irrespective of temperature, monoclinic Form I and orthorhombic Form II are stable phases at ordinary and high pressures, respectively. The I and II phase regions in the pressure-temperature diagram are bordered by the I-II equilibrium curve, for which a negative slope (dp/dT approximately -0.3 MPa x K(-1)) was determined although it was not observed experimentally. This curve goes through the I-II-liquid triple point whose coordinates (p approximately 234 MPa, T approximately 505 K) correspond to the crossing point of the melting curves, for which dp/dT values of +3.75 MPa x K(-1) (I) and +3.14 MPa x K(-1) (II) were calculated from enthalpy and volume changes upon fusion. More generally, this case exemplifies how the stability hierarchy of polymorphs may be inferred from the difference in their sublimation curves, as topologically positioned with respect to each other, using the phase rule and simple inferences resorting to Gibbs equilibrium thermodynamics. Copyright 2004 Wiley-Liss, Inc. and the American Pharmacists Association.

High pressure–temperature phase diagram of 1,1-diamino-2,2-dinitroethylene (FOX-7)

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

Bishop, Matthew M.; Velisavljevic, Nenad; Chellappa, Raja

In this study, 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 boundarymore » (~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.« less

High pressure–temperature phase diagram of 1,1-diamino-2,2-dinitroethylene (FOX-7)

DOE PAGES

Bishop, Matthew M.; Velisavljevic, Nenad; Chellappa, Raja; ...

2015-08-27

In this study, 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 boundarymore » (~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.« less

Phenomenology of Polymorphism, III: p, TDiagram and Stability of Piracetam Polymorphs

NASA Astrophysics Data System (ADS)

Céolin, R.; Agafonov, V.; Louër, D.; Dzyabchenko, V. A.; Toscani, S.; Cense, J. M.

1996-02-01

The nootropic drug Piracetam is known to crystallize in three phases. In order to obtain their stability hierarchy from sublimation pressure inequalities, the drawing of a topologicalp,Tdiagram was attempted. For such a purpose and also for quality control, crystallographic and thermodynamic data were required. Powder X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) were used. Molecular energy calculations were performed. Phase I melts at 426 K (ΔfusH(I) = +180 J·g-1). Phase II transforms into Phase I at 399 K (Δ(II→I)H= +24 J·g-1). Phase III transforms into phase I at 392 K (Δ(III→I)H= +28 J·g-1) or melts at 412 K (ΔfusH(III) = +210 J·g-1). Thep,Tdiagram shows that phase I is stable at higher temperature and phase II at lower temperature, like phase III, which is stable under high pressure. At room temperature, phase II is the more stable form, and phase I the less stable one. This agrees with the spontaneous I → II transformation observed at 298 K within a few hours, and with lattice energies, calculated previously. Molecular energy calculations and crystal structure comparison show how intermolecular hydrogen bonds and H-bonded dimers, in phases II and III, may stabilize conformations higher in energy than those of the isolated molecule and of phase I.

Combined effects of Sr substitution and pressure on the ground states in CaFe 2 As 2

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

Knoner, S.; Gati, E.; Kohler, S.

2016-10-21

Here, we present a detailed study of the combined effects of Sr substitution and hydrostatic pressure on the ground-state properties of CaFe 2As 2. Measurements of the electrical resistance and magnetic susceptibility, both at ambient and finite pressure P ≤ 2 GPa, were performed on Ca 1–xSr xFe 2As 2 single crystals grown out of Sn flux. We find that by Sr substitution the transition temperature to the magnetic/structural phase is enhanced and therefore a higher pressure is needed to suppress the transition to lowest temperature. In addition, the transition to the collapsed tetragonal phase is found at a pressure,more » which is distinctly higher than in the pure compound. This implies that the stability ranges of both phases shift on the pressure-axis upon doping, but the latter one with a higher rate. These observations suggest the possibility of separating the two phase lines, which intersect already at elevated temperatures for x = 0 and low Sr concentration levels. For x = 0.177, we find strong evidence that both phases remain separated down to the lowest temperature and that a zero-resistance state emerges in this intermediate pressure window. This observation indicates that Sr substitution combined with hydrostatic pressure provides another route for stabilizing superconductivity in CaFe 2As 2. Lastly, our results are consistent with the notion that (i) preserving the fluctuations associated with the structural-magnetic transition to low temperatures is vital for superconductivity to form in this material and that (ii) the nonmagnetic collapsed tetragonal phase is detrimental for superconductivity.« less

Exploration of phase transition in Th2C under pressure: An Ab-initio investigation

NASA Astrophysics Data System (ADS)

Sahoo, B. D.; Joshi, K. D.; Kaushik, T. C.

2018-05-01

With the motivation of searching for new compounds in the Th-C system, we have performed ab initio evolutionary searches for all the stable compounds in this binary system in the pressure range of 0-100 GPa. We have found previously unknown, thermodynamically stable, composition Th2C along with experimentally known ThC, ThC2 and Th2C3 phases at 0 GPa. Interestingly at pressure of 13 GPa the predicted ground state orthorhombic (SG no. 59, Pmmn) phase of Th2C transforms to trigonal (SG no. 164, P-3m1) phase. We also find the mechanical and dynamical stability of both the phases. Further, the theoretically determined equation of state has been utilized to derive various physical quantities such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus of Pmmn phase at ambient conditions.

New High Pressure Phase of CaCO3: Implication for the Deep Diamond Formation

NASA Astrophysics Data System (ADS)

Mao, Z.; Li, X.; Zhang, Z.; Lin, J. F.; Ni, H.; Prakapenka, V.

2017-12-01

Surface carbon can be transported to the Earth's deep interior through sinking subduction slabs. Carbonates, including CaCO3, MgCO3 and MgCa(CO3)2, are important carbon carriers for the deep carbon cycle. Experimental studies on the phase stability of carbonates with coexisting mantle minerals at relevant pressure and temperature conditions are thus important for understanding the deep carbon cycle. In particular, recent petrological studies have revealed the evidence for the transportation of CaCO3 to the depth at least of the top lower mantle by analyzing the diamond inclusions. Yet the phase stability of CaCO3 at relevant pressure and temperature conditions of the top lower mantle is still unclear. Previous single-crystal study has shown that CaCO3 transforms from the CaCO3-III structure to CaCO3-VI at 15 GPa and 300 K. The CaCO3-VI is stable at least up to 40 GPa at 300 K. At high temperatures, CaCO3 in the aragonite structure will directly transform into the post-aragonite structure at 40 GPa. However, a recent theoretical study predicted a new phase of CaCO3 with a space group of P21/c between 32 and 48 GPa which is different from previous experimental results. In this study, we have investigated the phase stability of CaCO3 at high pressure-temperature conditions using synchrotron X-ray diffraction in laser-heated diamond anvil cells. We report the discovery of a new phase of CaCO3 at relevant pressure-temperature conditions of the top lower mantle which is consistent with previous theoretical predictions. This new phase is an important carrier for the transportation of carbon to the Earth's lower mantle and crucial for growing deep diamonds in the region.

Molecular Simulation of the Phase Diagram of Methane Hydrate: Free Energy Calculations, Direct Coexistence Method, and Hyperparallel Tempering.

PubMed

Jin, Dongliang; Coasne, Benoit

2017-10-24

Different molecular simulation strategies are used to assess the stability of methane hydrate under various temperature and pressure conditions. First, using two water molecular models, free energy calculations consisting of the Einstein molecule approach in combination with semigrand Monte Carlo simulations are used to determine the pressure-temperature phase diagram of methane hydrate. With these calculations, we also estimate the chemical potentials of water and methane and methane occupancy at coexistence. Second, we also consider two other advanced molecular simulation techniques that allow probing the phase diagram of methane hydrate: the direct coexistence method in the Grand Canonical ensemble and the hyperparallel tempering Monte Carlo method. These two direct techniques are found to provide stability conditions that are consistent with the pressure-temperature phase diagram obtained using rigorous free energy calculations. The phase diagram obtained in this work, which is found to be consistent with previous simulation studies, is close to its experimental counterpart provided the TIP4P/Ice model is used to describe the water molecule.

The phase diagram of water at negative pressures: virtual ices.

PubMed

Conde, M M; Vega, C; Tribello, G A; Slater, B

2009-07-21

The phase diagram of water at negative pressures as obtained from computer simulations for two models of water, TIP4P/2005 and TIP5P is presented. Several solid structures with lower densities than ice Ih, so-called virtual ices, were considered as possible candidates to occupy the negative pressure region of the phase diagram of water. In particular the empty hydrate structures sI, sII, and sH and another, recently proposed, low-density ice structure. The relative stabilities of these structures at 0 K was determined using empirical water potentials and density functional theory calculations. By performing free energy calculations and Gibbs-Duhem integration the phase diagram of TIP4P/2005 was determined at negative pressures. The empty hydrates sII and sH appear to be the stable solid phases of water at negative pressures. The phase boundary between ice Ih and sII clathrate occurs at moderate negative pressures, while at large negative pressures sH becomes the most stable phase. This behavior is in reasonable agreement with what is observed in density functional theory calculations.

B1-B2 phase transition mechanism and pathway of PbS under pressure

NASA Astrophysics Data System (ADS)

Adeleke, Adebayo A.; Yao, Yansun

2018-03-01

Experimental studies at finite Pressure-Temperature (P-T) conditions and a theoretical study at 0 K of the phase transition in lead sulphide (PbS) have been inconclusive. Many studies that have been done to understand structural transformation in PbS can broadly be classified into two main ideological streams—one with Pnma and another with Cmcm orthorhombic intermediate phase. To foster better understanding of this phenomenon, we present the result of the first-principles study of phase transition in PbS at finite temperature. We employed the particle swarm-intelligence optimization algorithm for the 0 K structure search and first-principles metadynamics simulations to study the phase transition pathway of PbS from the ambient pressure, 0 K Fm-3m structure to the high-pressure Pm-3m phase under experimentally achievable P-T conditions. Significantly, our calculation shows that both streams are achievable under specific P-T conditions. We further uncover new tetragonal and monoclinic structures of PbS with space group P21/c and I41/amd, respectively. We propose the P21/c and I41/amd as a precursor phase to the Pnma and Cmcm phases, respectively. We investigated the stability of the new structures and found them to be dynamically stable at their stability pressure range. Electronic structure calculations reveal that both P21/c and I41/amd phases are semiconducting with direct and indirect bandgap energies of 0.69(5) eV and 0.97(3) eV, respectively. In general, both P21/c and I41/amd phases were found to be energetically competitive with their respective orthorhombic successors.

MD simulations of phase stability of PuGa alloys: Effects of primary radiation defects and helium bubbles

DOE PAGES

Dremov, V. V.; Sapozhnikov, F. A.; Ionov, G. V.; ...

2013-05-14

We present classical molecular dynamics (MD) with Modified Embedded Atom Model (MEAM) simulations to investigate the role of primary radiation defects and radiogenic helium as factors affecting the phase stability of PuGa alloys in cooling–heating cycles at ambient pressure. The models of PuGa alloys equilibrated at ambient conditions were subjected to cooling–heating cycles in which they were initially cooled down to 100 K and then heated up to 500 K at ambient pressure. The rate of temperature change in the cycles was 10 K/ns. The simulations showed that the initial FCC phase of PuGa alloys undergo polymorphous transition in coolingmore » to a lower symmetry α'-phase. All the alloys undergo direct and reverse polymorphous transitions in the cooling–heating cycles. The alloys containing vacancies shift in both transitions to lower temperatures relative to the defect-free alloys. The radiogenic helium has much less effect on the phase stability compared to that of primary radiation defects (in spite of the fact that helium concentration is twice of that for the primary radiation defects). Lastly, this computational result agrees with experimental data on unconventional stabilization mechanism of PuGa alloys.« less

Pressure-magnetic field induced phase transformation in Ni{sub 46}Mn{sub 41}In{sub 13} Heusler alloy

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

Rama Rao, N. V., E-mail: nvrrao@dmrl.drdo.in; Manivel Raja, M.; Pandian, S.

2014-12-14

The effect of hydrostatic pressure and magnetic field on the magnetic properties and phase transformation in Ni{sub 46}Mn{sub 41}In{sub 13} Heusler alloy was investigated. Pressure (P)-magnetic field (H)-temperature (T) phase diagram has been constructed from experimental results. In the P–T contour of the phase diagram, the slope of the austenite-martensite phase boundary line appears positive (dT/dP > 0), while it appears negative (dT/dH < 0) in the H–T contour. The results revealed that pressure and magnetic field have opposite effect on phase stabilization. The combined effect of pressure and magnetic field on martensitic transition has led to two important findings: (i) pressure dependent shiftmore » of austenite start temperature (A{sub s}) is higher when larger field is applied, and (ii) field dependent shift of A{sub s} is lowered when a higher pressure is applied. The pressure and magnetic field dependent shift observed in the martensitic transformation has been explained on the basis of thermodynamic calculations. Curie temperature of the phases was found to increase with pressure at a rate of 0.6 K/kbar.« less

Phase equilibria in the nominally Al65Cu23Fe12 system at 3, 5 and 21 GPa: Implications for the quasicrystal-bearing Khatyrka meteorite

NASA Astrophysics Data System (ADS)

Stagno, Vincenzo; Bindi, Luca; Steinhardt, Paul J.; Fei, Yingwei

2017-10-01

Two of the three natural quasiperiodic crystals found in the Khatyrka meteorite show a composition within the Al-Cu-Fe system. Icosahedrite, with formula Al63Cu24Fe13, coexists with the new Al62Cu31Fe7 quasicrystal plus additional Al-metallic minerals such as stolperite (AlCu), kryachkoite [(Al,Cu)6(Fe,Cu)], hollisterite (AlFe3), khatyrkite (Al2Cu) and cupalite (AlCu), associated to high-pressure phases like ringwoodite/ahrensite, coesite, and stishovite. These high-pressure minerals represent the evidence that most of the Khatyrka meteoritic fragments formed at least at 5 GPa and 1200 °C, if not at more extreme conditions. On the other hand, experimental studies on phase equilibria within the representative Al-Cu-Fe system appear mostly limited to ambient pressure conditions, yet. This makes the interpretation of the coexisting mineral phases in the meteoritic sample quite difficult. We performed experiments at 3, 5 and 21 GPa and temperatures of 800-1500 °C using the multi-anvil apparatus to investigate the phase equilibria in the Al65Cu23Fe12 system representative of the first natural quasicrystal, icosahedrite. Our results, supported by single-crystal X-ray diffraction and analyses by scanning electron microscopy, confirm the stability of icosahedrite at high pressure and temperature along with additional coexisting Al-bearing phases representative of khatyrkite and stolperite as those found in the natural meteorite. One reversal experiment performed at 5 GPa and 1200 °C shows the formation of the icosahedral quasicrystal from a pure Al, Cu and Fe mixture, a first experimental synthesis of icosahedrite under those conditions. Pressure appears to not play a major role in the distribution of Al, Cu and Fe between the coexisting phases, icosahedrite in particular. Results from this study extend our knowledge on the stability of icosahedral AlCuFe at higher temperature and pressure than previously examined, and provide a new constraint on the stability of icosahedrite.

Plutonium Metallurgy

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

Freibert, Franz J.

2012-08-09

Due to its nuclear properties, Pu will remain a material of global interest well into the future. Processing, Structure, Properties and Performance remains a good framework for discussion of Pu materials science Self-irradiation and aging effects continue to be central in discussions of Pu metallurgy Pu in its elemental form is extremely unstable, but alloying helps to stabilize Pu; but, questions remain as to how and why this stabilization occurs. Which is true Pu-Ga binary phase diagram: US or Russian? Metallurgical issues such as solute coring, phase instability, crystallographic texture, etc. result in challenges to casting, processing, and properties modelingmore » and experiments. For Ga alloyed FCC stabilized Pu, temperature and pressure remain as variables impacting phase stability.« less

Method for stabilizing low-level mixed wastes at room temperature

DOEpatents

Wagh, A.S.; Singh, D.

1997-07-08

A method to stabilize solid and liquid waste at room temperature is provided comprising combining solid waste with a starter oxide to obtain a powder, contacting the powder with an acid solution to create a slurry, said acid solution containing the liquid waste, shaping the now-mixed slurry into a predetermined form, and allowing the now-formed slurry to set. The invention also provides for a method to encapsulate and stabilize waste containing cesium comprising combining the waste with Zr(OH){sub 4} to create a solid-phase mixture, mixing phosphoric acid with the solid-phase mixture to create a slurry, subjecting the slurry to pressure; and allowing the now pressurized slurry to set. Lastly, the invention provides for a method to stabilize liquid waste, comprising supplying a powder containing magnesium, sodium and phosphate in predetermined proportions, mixing said powder with the liquid waste, such as tritium, and allowing the resulting slurry to set. 4 figs.

Method for stabilizing low-level mixed wastes at room temperature

DOEpatents

Wagh, Arun S.; Singh, Dileep

1997-01-01

A method to stabilize solid and liquid waste at room temperature is provided comprising combining solid waste with a starter oxide to obtain a powder, contacting the powder with an acid solution to create a slurry, said acid solution containing the liquid waste, shaping the now-mixed slurry into a predetermined form, and allowing the now-formed slurry to set. The invention also provides for a method to encapsulate and stabilize waste containing cesium comprising combining the waste with Zr(OH).sub.4 to create a solid-phase mixture, mixing phosphoric acid with the solid-phase mixture to create a slurry, subjecting the slurry to pressure; and allowing the now pressurized slurry to set. Lastly, the invention provides for a method to stabilize liquid waste, comprising supplying a powder containing magnesium, sodium and phosphate in predetermined proportions, mixing said powder with the liquid waste, such as tritium, and allowing the resulting slurry to set.

Korean Red Ginseng Improves Blood Pressure Stability in Patients with Intradialytic Hypotension

PubMed Central

Chen, I-Ju; Chang, Ming-Yang; Chiao, Sheng-Lin; Chen, Jiun-Liang; Yu, Chun-Chen; Yang, Sien-Hung; Liu, Ju-Mei; Hung, Cheng-Chieh; Yang, Rong-Chi; Chang, Hui-Chi; Hsu, Chung-Hua; Fang, Ji-Tseng

2012-01-01

Introduction. Intradialytic hypotension (IDH) is a common complication during hemodialysis which may increase mortality risks. Low dose of Korean red ginseng (KRG) has been reported to increase blood pressure. Whether KRG can improve hemodynamic stability during hemodialysis has not been examined. Methods. The 8-week study consisted of two phases: observation phase and active treatment phase. According to prehemodialysis blood pressure (BP), 38 patients with IDH were divided into group A (BP ≥ 140/90 mmHg, n = 18) and group B (BP < 140/90 mmHg, n = 20). Patients were instructed to chew 3.5 gm KRG slices at each hemodialysis session during the 4-week treatment phase. Blood pressure changes, number of sessions disturbed by symptomatic IDH, plasma levels of vasoconstrictors, blood biochemistry, and adverse effects were recorded. Results. KRG significantly reduced the degree of blood pressure drop during hemodialysis (P < 0.05) and the frequency of symptomatic IDH (P < 0.05). More activation of vasoconstrictors (endothelin-1 and angiotensin II) during hemodialysis was found. The postdialytic levels of endothelin-1 and angiotensin II increased significantly (P < 0.01). Conclusion. Chewing KRG renders IDH patients better resistance to acute BP reduction during hemodialysis via activation of vasoconstrictors. Our results suggest that KRG could be an adjuvant treatment for IDH. PMID:22645630

High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure.

PubMed

Stavrou, Elissaios; Yao, Yansun; Zaug, Joseph M; Bastea, Sorin; Kalkan, Bora; Konôpková, Zuzana; Kunz, Martin

2016-08-12

Magnesium chloride (MgCl2) with the rhombohedral layered CdCl2-type structure (α-MgCl2) has been studied experimentally using synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy using a diamond-anvil cell up to 100 GPa at room temperature and theoretically using first-principles density functional calculations. The results reveal a pressure-induced second-order structural phase transition to a hexagonal layered CdI2-type structure (β-MgCl2) at 0.7 GPa: the stacking sequence of the Cl anions are altered resulting in a reduction of the c-axis length. Theoretical calculations confirm this phase transition sequence and the calculated transition pressure is in excellent agreement with the experiment. Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phase. According to our experimental results MgCl2 remains in a 2D layered phase up to 100 GPa and further, the 6-fold coordination of Mg cations is retained. Theoretical calculations of relative enthalpy suggest that this extensive pressure stability is due to a low enthalpy of the layered structure ruling out kinetic barrier effects. This observation is unusual, as it contradicts with the general structural behavior of highly compressed AB2 compounds.

High-pressure X-ray diffraction, Raman, and computational studies of MgCl 2 up to 1 Mbar: Extensive pressure stability of the β-MgCl 2 layered structure

DOE PAGES

Stavrou, Elissaios; Yao, Yansun; Zaug, Joseph M.; ...

2016-08-12

We studied magnesium chloride (MgCl 2) with the rhombohedral layered CdCl 2-type structure (α-MgCl 2), experimentally, using synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy using a diamond-anvil cell up to 100 GPa at room temperature and theoretically using first-principles density functional calculations. Our results reveal a pressure-induced second-order structural phase transition to a hexagonal layered CdI 2-type structure (β-MgCl 2) at 0.7 GPa: the stacking sequence of the Cl anions are altered resulting in a reduction of the c-axis length. Theoretical calculations confirm this phase transition sequence and the calculated transition pressure is in excellent agreement with the experiment.more » Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phase. According to our experimental results MgCl 2 remains in a 2D layered phase up to 100 GPa and further, the 6-fold coordination of Mg cations is retained. Theoretical calculations of relative enthalpy suggest that this extensive pressure stability is due to a low enthalpy of the layered structure ruling out kinetic barrier effects. Our observation is unusual, as it contradicts with the general structural behavior of highly compressed AB 2 compounds.« less

Phase stability of iron germanate, FeGeO3, to 127 GPa

NASA Astrophysics Data System (ADS)

Dutta, R.; Tracy, S. J.; Stan, C. V.; Prakapenka, V. B.; Cava, R. J.; Duffy, T. S.

2018-04-01

The high-pressure behavior of germanates is of interest as these compounds serve as analogs for silicates of the deep Earth. Current theoretical and experimental studies of iron germanate, FeGeO3, are limited. Here, we have examined the behavior of FeGeO3 to 127 GPa using the laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. Upon compression at room temperature, the ambient-pressure clinopyroxene phase transforms to a disordered triclinic phase [FeGeO3 (II)] at 18 GPa in agreement with earlier studies. An additional phase transition to FeGeO3 (III) occurs above 54 GPa at room temperature. Laser-heating experiments ( 1200-2200 K) were conducted at three pressures (33, 54, and 123 GPa) chosen to cover the stability regions of different GeO2 polymorphs. In all cases, we observe that FeGeO3 dissociates into GeO2 + FeO at high pressure and temperature conditions. Neither the perovskite nor the post-perovskite phase was observed up to 127 GPa at ambient or high temperatures. The results are consistent with the behavior of FeSiO3, which also dissociates into a mixture of the oxides (FeO + SiO2) at least up to 149 GPa.

On the Stability of c-BN-Reinforcing Particles in Ceramic Matrix Materials

PubMed Central

Wolfrum, Anne-Kathrin; Michaelis, Alexander; Herrmann, Mathias

2018-01-01

Cubic boron nitride (c-BN) composites produced at high pressures and temperatures are widely used as cutting tool materials. The advent of new, effective pressure-assisted densification methods, such as spark plasma sintering (SPS), has stimulated attempts to produce these composites at low pressures. Under low-pressure conditions, however, transformation of c-BN to the soft hexagonal BN (h-BN) phase can occur, with a strong deterioration in hardness and wear. In the present work, the influence of secondary phases (B2O3, Si3N4, and oxide glasses) on the transformation of c-BN was studied in the temperature range between 1100 °C and 1575 °C. The different heat treated c-BN particles and c-BN composites were analyzed by SEM, X-ray diffraction, and Raman spectroscopy. The transformation mechanism was found to be kinetically controlled solution–diffusion–precipitation. Given a sufficiently low liquid phase viscosity, the transformation could be observed at temperatures as low as 1200 °C for the c-BN–glass composites. In contrast, no transformation was found at temperatures up to 1575 °C when no liquid oxide phase is present in the composite. The results were compared with previous studies concerning the c-BN stability and the c-BN phase diagram. PMID:29414847

High pressure behaviour of uranium dicarbide (UC{sub 2}): Ab-initio study

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

Sahoo, B. D., E-mail: bdsahoo@barc.gov.in; Mukherjee, D.; Joshi, K. D.

2016-08-28

The structural stability of uranium dicarbide has been examined under hydrostatic compression employing evolutionary structure search algorithm implemented in the universal structure predictor: evolutionary Xtallography (USPEX) code in conjunction with ab-initio electronic band structure calculation method. The ab-initio total energy calculations involved for this purpose have been carried out within both generalized gradient approximations (GGA) and GGA + U approximations. Our calculations under GGA approximation predict the high pressure structural sequence of tetragonal → monoclinic → orthorhombic for this material with transition pressures of ∼8 GPa and 42 GPa, respectively. The same transition sequence is predicted by calculations within GGA + U also with transition pressuresmore » placed at ∼24 GPa and ∼50 GPa, respectively. Further, on the basis of comparison of zero pressure equilibrium volume and equation of state with available experimental data, we find that GGA + U approximation with U = 2.5 eV describes this material better than the simple GGA approximation. The theoretically predicted high pressure structural phase transitions are in disagreement with the only high experimental study by Dancausse et al. [J. Alloys. Compd. 191, 309 (1993)] on this compound which reports a tetragonal to hexagonal phase transition at a pressure of ∼17.6 GPa. Interestingly, during lowest enthalpy structure search using USPEX, we do not see any hexagonal phase to be closer to the predicted monoclinic phase even within 0.2 eV/f. unit. More experiments with varying carbon contents in UC{sub 2} sample are required to resolve this discrepancy. The existence of these high pressure phases predicted by static lattice calculations has been further substantiated by analyzing the elastic and lattice dynamic stability of these structures in the pressure regimes of their structural stability. Additionally, various thermo-physical quantities such as equilibrium volume, bulk modulus, Debye temperature, thermal expansion coefficient, Gruneisen parameter, and heat capacity at ambient conditions have been determined from these calculations and compared with the available experimental data.« less

Structural phase transition, electronic structure and optical properties of half Heusler alloys LiBeZ (Z = As, Sb)

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

Amudhavalli, A.; Rajeswarapalanichamy, R., E-mail: rajeswarapalanichamy@gmail.com

2016-05-23

Ab initio calculations are performed to investigate the structural stability, electronic structure, mechanical properties and optical properties of half Heusler alloys (LiBeAs and LiBeSb) for three different phases of zinc blende crystal structure. Among the considered phases, α- phase is found to be the most stable phase for these alloys at normal pressure. A pressure induced structural phase transition from α-phase to β- phase is observed for LiBeAs. The electronic structure reveals that these alloys are semiconductors. The optical properties confirm that these alloys are semiconductor in nature.

Gas-Liquid Flows and Phase Separation

NASA Technical Reports Server (NTRS)

McQuillen, John

2004-01-01

Common issues for space system designers include:Ability to Verify Performance in Normal Gravity prior to Deployment; System Stability; Phase Accumulation & Shedding; Phase Separation; Flow Distribution through Tees & Manifolds Boiling Crisis; Heat Transfer Coefficient; and Pressure Drop.The report concludes:Guidance similar to "A design that operates in a single phase is less complex than a design that has two-phase flow" is not always true considering the amount of effort spent on pressurizing, subcooling and phase separators to ensure single phase operation. While there is still much to learn about two-phase flow in reduced gravity, we have a good start. Focus now needs to be directed more towards system level problems .

Ion-beam-induced magnetic and structural phase transformation of Ni-stabilized face-centered-cubic Fe films on Cu(100)

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

Gloss, Jonas; Institute of Physical Engineering, Faculty of Mechanical Engineering, Brno University of Technology, Technická 2, 616 69 Brno; Shah Zaman, Sameena

2013-12-23

Metastable face-centered cubic (fcc) Fe/Cu(100) thin films are good candidates for ion-beam magnetic patterning due to their magnetic transformation upon ion-beam irradiation. However, pure fcc Fe films undergo spontaneous transformation when their thickness exceeds 10 ML. This limit can be extended to approximately 22 ML by deposition of Fe at increased CO background pressures. We show that much thicker films can be grown by alloying with Ni for stabilizing the fcc γ phase. The amount of Ni necessary to stabilize nonmagnetic, transformable fcc Fe films in dependence on the residual background pressure during the deposition is determined and a phasemore » diagram revealing the transformable region is presented.« less

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

DOE PAGES

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

2017-05-08

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

Pressure, temperature, and electric field dependence of phase transformations in niobium modified 95/5 lead zirconate titanate

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

Dong, Wen D.; Carlos Valadez, J.; Gallagher, John A.

2015-06-28

Ceramic niobium modified 95/5 lead zirconate-lead titanate (PZT) undergoes a pressure induced ferroelectric to antiferroelectric phase transformation accompanied by an elimination of polarization and a volume reduction. Electric field and temperature drive the reverse transformation from the antiferroelectric to ferroelectric phase. The phase transformation was monitored under pressure, temperature, and electric field loading. Pressures and temperatures were varied in discrete steps from 0 MPa to 500 MPa and 25 °C to 125 °C, respectively. Cyclic bipolar electric fields were applied with peak amplitudes of up to 6 MV m{sup −1} at each pressure and temperature combination. The resulting electric displacement–electric field hysteresis loops weremore » open “D” shaped at low pressure, characteristic of soft ferroelectric PZT. Just below the phase transformation pressure, the hysteresis loops took on an “S” shape, which split into a double hysteresis loop just above the phase transformation pressure. Far above the phase transformation pressure, when the applied electric field is insufficient to drive an antiferroelectric to ferroelectric phase transformation, the hysteresis loops collapse to linear dielectric behavior. Phase stability maps were generated from the experimental data at each of the temperature steps and used to form a three dimensional pressure–temperature–electric field phase diagram.« less

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.

Titanium α-ω phase transformation pathway and a predicted metastable structure

DOE PAGES

Zarkevich, Nickolai A.; Johnson, Duane D.

2016-01-15

A titanium is a highly utilized metal for structural lightweighting and its phases, transformation pathways (transition states), and structures have scientific and industrial importance. Using a proper solid-state nudged elastic band method employing two climbing images combined with density functional theory DFT + U methods for accurate energetics, we detail the pressure-induced α (ductile) to ω (brittle) transformation at the coexistence pressure. We also find two transition states along the minimal-enthalpy path and discover a metastable body-centered orthorhombic structure, with stable phonons, a lower density than the end-point phases, and decreasing stability with increasing pressure.

Phase diagram and transformations of iron pentacarbonyl to nm layered hematite and carbon-oxygen polymer under pressure

DOE PAGES

Ryu, Young Jay; Kim, Minseob; Yoo, Choong -Shik

2015-10-12

In this study, we present the phase diagram of Fe(CO) 5, consisting of three molecular polymorphs (phase I, II and III) and an extended polymeric phase that can be recovered at ambient condition. The phase diagram indicates a limited stability of Fe(CO) 5 within a pressure-temperature dome formed below the liquid- phase II- polymer triple point at 4.2 GPa and 580 K. The limited stability, in turn, signifies the temperature-induced weakening of Fe-CO back bonds, which eventually leads to the dissociation of Fe-CO at the onset of the polymerization of CO. The recovered polymer is a composite of novel nm-lamellarmore » layers of crystalline hematite Fe 2O 3 and amorphous carbon-oxygen polymers. These results, therefore, demonstrate the synthesis of carbon-oxygen polymer by compressing Fe(CO) 5, which advocates a novel synthetic route to develop atomistic composite materials by compressing organometallic compounds.« less

Raman studies of nanocomposites catalysts: temperature and pressure effects of CeAl, CeMn and NiAl oxides

NASA Astrophysics Data System (ADS)

da Silva, Antonio N.; Neto, Antonio B. S.; Oliveira, Alcemira C.; Junior, Manoel C.; Junior, Jose A. L.; Freire, Paulo T. C.; Filho, Josué M.; Oliveira, Alcineia C.; Lang, Rossano

2018-06-01

High temperature and pressure effects on the physicochemical properties of binary oxides catalysts were investigated. The nanocomposites catalysts comprising of CeAl, CeMn and NiAl were characterized through various physicochemical techniques. A study of the temperature and pressure induced phenomena monitored by Raman spectroscopy was proposed and discussed. Spectral modifications of the Raman modes belonging to the CeMn suggest structural changes in the solid due to the MnO2 phase oxidation with increasing temperature. The thermal expansion and lattice anharmonicity effects were observed on CeMn due to lack of stability of the lattice vacancies. The CeAl and NiAl composites presented crystallographic stability at low temperatures however, undertake a phase transformation of NiO/Al2O3 into NiAl2O4, mostly without any deformation in its structure with increasing the temperature. It was also inferred that the binary oxides are more stables in comparison with monoxides. Detailed pressure-dependent Raman measurements of the T2g phonon mode of CeMn and NiAl revealed that the pressure contributes to modify bonds length and reduces the particles sizes of the solids. On the contrary, high pressure on CeAl sample improved the stability with addition of Al2O3 in the CeO2 lattice. The results then suggest a good stability of CeAl and NiAl composite catalysts at high pressure and low temperature and show how to prospect of tuning the catalysis for surface reactions entirely through in situ spectroscopic investigations means.

Chemical stabilization and high pressure synthesis of Ba-free Hg-based superconductors, (Hg,M)Sr{sub 2}Ca{sub n-1}Cu{sub n}O{sub y}(N=1{approximately}3)

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

Kishio, K.; Shimoyama, J.; Hahakura, S.

1994-12-31

A homologous series of new Hg-based HTSC compounds, (Hg,M)Sr{sub 2}Ca{sub n-1}Cu{sub n}O{sub y} with n=1 to 3, have been synthesized. The stabilization of the pure phases have been accomplished by chemical doping of third elements such as M=Cr, Mo and Re. While the Hg1201(n=1) phase was readily obtained in this way, it was necessary to simultaneously dope Y into the Ca site to stabilize the Hg1212(n=2) phase. On the other hand, single-phase Y-free Hg1212(n=2) and Hg1223(n=3) samples were synthesized only under a high pressure of 6 GPa. In sharp contrast to the Ba-containing compounds, all the samples prepared in themore » present study have been quite stable during the synthesis and no deterioration in air has been observed after the preparation.« less

Studies on the structural stability of Co2P2O7 under pressure

NASA Astrophysics Data System (ADS)

Wang, W. P.; Pang, H.; Jin, M. L.; Shen, X.; Yao, Y.; Wang, Y. G.; Li, Y. C.; Li, X. D.; Jin, C. Q.; Yu, R. C.

2018-05-01

The crystal structural evolution of Co2P2O7 was studied by using in situ high pressure angle dispersive x-ray diffraction with synchrotron radiation. The results demonstrate that the α phase of Co2P2O7 goes through a partially irreversible structural transformation to β phase under pressure. The pressure is conductive to reduce the longest Cosbnd O bond length of the α phase, and then more uniform Cosbnd O bonds and regular hexagonal arrangement of CoO6 octahedra of the β phase are favored. According to the Birch-Murnaghan equation, the fitted bulk modulus B0 is 158.1(±5.6) GPa for α phase and 276.5(±6.5) GPa for β phase. Furthermore, the first-principles calculations show that these two phases of Co2P2O7 have almost equal total energies, and also have similar band structures and spin-polarized density of states at their ground states. This may be the reason why these two phases of Co2P2O7 can coexist in the pressure released state. It is found that the band gap energies decrease with increasing pressure for both phases.

Synthesis of monoclinic IrTe 2 under high pressure and its physical properties

DOE PAGES

Li, X.; Yan, J. -Q.; Singh, D. J.; ...

2015-10-12

In a pressure-temperature (P-T) diagram for synthesizing IrTe 2 compounds, the well-studied trigonal (H) phase with the CdI 2-type structure is stable at low pressures. The superconducting cubic (C) phase can be synthesized under higher temperatures and pressures. A rhombohedral phase with the crystal structure similar to the C phase can be made at ambient pressure; but the phase contains a high concentration of Ir deficiency. Here, we report that a rarely studied monoclinic (M) phase can be stabilized in narrow ranges of pressure and temperature in this P-T diagram. Moreover, the peculiar crystal structure of the M-IrTe 2 eliminatesmore » the tendency to form Ir-Ir dimers found in the H phase. The M phase has been fully characterized by structural determination and measurements of electrical resistivity, thermoelectric power, DC magnetization, and specific heat. These physical properties have been compared with those in the H and C phases of Ir 1-xTe 2. Finally, we present magnetic and transport properties and specific heat of the M-IrTe 2 can be fully justified by calculations with the density-functional theory.« less

Stability of CO2 hydrate under very high pressure and low temperature

NASA Astrophysics Data System (ADS)

Hirai, H.; Honda, M.; Kawamura, T.; Yamamoto, Y.; Yagi, T.

2009-12-01

CO2 hydrate is a clathrate compound and the crystal structure type is sI at low pressure. CO2-reduction in the atmosphere is one of the most urgent subjects for mankind. Some technical developments to seclude CO2 as CO2 hydrate in ocean floor have been proceeded. Looking around the solar system, existence of CO2 hydrate in and beneath Martian permafrost has been predicted from spacecraft probes and theoretical studies. Thus, its stability and properties under high pressures and low temperatures are of great interest for fundamental understanding of clathrate hydrate, for the ocean sequestration technology, and for planetary science. CO2 hydrate exhibits characteristic properties different from those of other gas hydrate such as methane hydrate. For example, phase boundary between hydrate and gas + water for many gas hydrates shows positive slope in pressure versus temperature field, and the gas hydrates are kept at pressures up to several GPa at room temperature. On the other hand, for CO2 hydrate, the phase boundary turns to negative slope from positive one at a certain critical point [Nakano et al., 1998], and it can exist only at low temperature regions. And, a theoretical study predicted that CO2 hydrate decompose at low temperature region [Longhi, 2005]. In this study, high pressure and low temperature experiments were performed to examine stability and phase changes of CO2 hydrate using diamond anvil cell in a pressure range from 0.1 to 2.5 GPa and a the temperature range from 65 to 265 K. X-ray diffractometry and Raman spectroscopy revealed that the known phase boundary was extended into lower temperature region, and that CO2 hydrate was kept at low temperature regions at least 65 K despite the theoretical prediction of decomposition. References [1] S. Nakano, M. Moritoki, K. Ohgaki, J. Chem. Eng. Data, 43, 807 (1998). [2] J. Longhi, Geochim. Cosmochim. Acta, 69, 529 (2005)

Physicochemical properties and storage stability of soybean protein nanoemulsions prepared by ultra-high pressure homogenization.

PubMed

Xu, Jing; Mukherjee, Dipaloke; Chang, Sam K C

2018-02-01

This study investigated the effects of the ultrahigh pressure homogenization (pressure, protein concentration, oil phase fraction, pH, temperature, and ionic strength) and storage on the properties of nanoemulsions (100-500nm range), which were stabilized by laboratory-prepared soybean protein isolate (SPI), β-conglycinin (7S) and glycinin (11S). The nanoemulsions made with SPI, 7S and 11S proteins exhibited considerable stability over various ionic strengths (0-500mM NaCl), pH (<4 or >7), thermal treatments (30-60°C) and storage (0-45days). The far-UV spectra of SPI, 7S, 11S dispersions, and SPI-, 7S-, 11S protein-stabilized nanoemulsions were analyzed for the protein structural changes following lipid removal. The ultra-high pressure homogenization changed the secondary structure of SPI, 7S, 11S proteins in the nanoemulsions, and enhanced their stability. This study demonstrated that SPI, 7S, and 11S proteins can be used as effective emulsifiers in nanoemulsions prepared by ultra-high pressure homogenization. Copyright © 2017. Published by Elsevier Ltd.

First principles study on Fe based ferromagnetic quaternary Heusler alloys

NASA Astrophysics Data System (ADS)

Amudhavalli, A.; Rajeswarapalanichamy, R.; Iyakutti, K.

2017-11-01

The study of stable half-metallic ferromagnetic materials is important from various fundamental and application points of view in condensed matter Physics. Structural phase stability, electronic structure, mechanical and magnetic properties of Fe-based quaternary Heusler alloys XX‧YZ (X = Co, Ni; X‧ = Fe; Y = Ti; Z = Si, Ge, As) for three different phases namely α, β and γ phases of LiMgPdSn crystal structure have been studied by density functional theory with generalized gradient approximation formulated by Perdew, Burke and Ernzerhof (GGA-PBE) and the Hubbard formalism (GGA-PBE + U). This work aims to identify the ferromagnetic and half-metallic properties of XX‧YZ (X = Co, Ni, X‧ = Fe; Y = Ti; Z = Si, Ge, As) quaternary Heusler alloys. The predicted phase stability shows that α-phase is found to be the lowest energy phase at ambient pressure. A pressure-induced structural phase transition is observed in CoFeTiSi, CoFeTiGe, CoFeTiAs, NiFeTiSi, NiFeTiGe and NiFeTiAs at the pressures of 151.6 GPa, 33.7 GPa, 76.4 GPa, 85.3 GPa, 87.7 GPa and 96.5 GPa respectively. The electronic structure reveals that these materials are half metals at normal pressure whereas metals at high pressure. The investigation of electronic structure and magnetic properties are performed to reveal the underlying mechanism of half metallicity. The spin polarized calculations concede that these quaternary Heusler compounds may exhibit the potential candidate in spintronics application. The magnetic moments for these quaternary Heusler alloys in all the three different phases (α, β and γ) are estimated.

Structural transformations in Ge{sub 2}Sb{sub 2}Te{sub 5} under high pressure and temperature

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

Mio, A. M.; Privitera, S., E-mail: stefania.privitera@imm.cnr.it; D'Arrigo, G.

2015-08-14

The structural transformations occurring in Ge{sub 2}Sb{sub 2}Te{sub 5} films heated at temperature up to 400 °C, and under hydrostatic pressure up to 12 GPa, have been investigated through in-situ X ray diffraction measurements. The adopted experimental conditions are close to those experienced by the phase change material during the SET (crystallization)/RESET (amorphization) processes in a nonvolatile memory device. The compression enhances the thermal stability of the amorphous phase, which remains stable up to 180 °C at 8 GPa and to 230 °C at 12 GPa. The structure of the crystalline phases is also modified, with the formation of a CsCl-type structure instead of rock-salt andmore » of a GeS-type structure at the temperature at which usually the trigonal stable phase is formed. Overall, the stability of the stable phase appears to be more affected by the compression. We argue that the presence of weak bonds associated to the van der Waals gaps is a determining factor for the observed reduced stability.« less

Solid phase stability of molybdenum under compression: Sound velocity measurements and first-principles calculations

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

Zhang, Xiulu; Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology, 621010 Mianyang, Sichuan; Liu, Zhongli

2015-02-07

The high-pressure solid phase stability of molybdenum (Mo) has been the center of a long-standing controversy on its high-pressure melting. In this work, experimental and theoretical researches have been conducted to check its solid phase stability under compression. First, we performed sound velocity measurements from 38 to 160 GPa using the two-stage light gas gun and explosive loading in backward- and forward-impact geometries, along with the high-precision velocity interferometry. From the sound velocities, we found no solid-solid phase transition in Mo before shock melting, which does not support the previous solid-solid phase transition conclusion inferred from the sharp drops of themore » longitudinal sound velocity [Hixson et al., Phys. Rev. Lett. 62, 637 (1989)]. Then, we searched its structures globally using the multi-algorithm collaborative crystal structure prediction technique combined with the density functional theory. By comparing the enthalpies of body centered cubic structure with those of the metastable structures, we found that bcc is the most stable structure in the range of 0–300 GPa. The present theoretical results together with previous ones greatly support our experimental conclusions.« less

Equation of state and electron localisation in fcc lithium

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

Frost, Mungo; Levitan, Abraham L.; Sun, Peihao

We present an improved equation of state for the high-pressure fcc phase of lithium with ambient temperature experimental data, extending the pressure range of previous studies to 36 GPa. Accompanying density functional theory calculations, which reproduce the experimental equation of state, show that with increasing density the phase diverges from a nearly free electron metal. At the high pressure limit of its stability fcc lithium exhibits enhanced electron density on the octahedral interstices with a high degree of localisation.

Equation of state and electron localisation in fcc lithium

DOE PAGES

Frost, Mungo; Levitan, Abraham L.; Sun, Peihao; ...

2018-02-14

We present an improved equation of state for the high-pressure fcc phase of lithium with ambient temperature experimental data, extending the pressure range of previous studies to 36 GPa. Accompanying density functional theory calculations, which reproduce the experimental equation of state, show that with increasing density the phase diverges from a nearly free electron metal. At the high pressure limit of its stability fcc lithium exhibits enhanced electron density on the octahedral interstices with a high degree of localisation.

Pressure induced phase transitions in ceramic compounds containing tetragonal zirconia

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

Sparks, R.G.; Pfeiffer, G.; Paesler, M.A.

Stabilized tetragonal zirconia compounds exhibit a transformation toughening process in which stress applied to the material induces a crystallographic phase transition. The phase transition is accompanied by a volume expansion in the stressed region thereby dissipating stress and increasing the fracture strength of the material. The hydrostatic component of the stress required to induce the phase transition can be investigated by the use of a high pressure technique in combination with Micro-Raman spectroscopy. The intensity of Raman lines characteristic for the crystallographic phases can be used to calculate the amount of material that has undergone the transition as a functionmore » of pressure. It was found that pressures on the order of 2-5 kBar were sufficient to produce an almost complete transition from the original tetragonal to the less dense monoclinic phase; while a further increase in pressure caused a gradual reversal of the transition back to the original tetragonal structure.« less

Shape evolution of a core-shell spherical particle under hydrostatic pressure.

PubMed

Colin, Jérôme

2012-03-01

The morphological evolution by surface diffusion of a core-shell spherical particle has been investigated theoretically under hydrostatic pressure when the shear modulii of the core and shell are different. A linear stability analysis has demonstrated that depending on the pressure, shear modulii, and radii of both phases, the free surface of the composite particle may be unstable with respect to a shape perturbation. A stability diagram finally emphasizes that the roughness development is favored in the case of a hard shell with a soft core.

Determination of pore-scale hydrate phase equilibria in sediments using lab-on-a-chip technology.

PubMed

Almenningen, Stian; Flatlandsmo, Josef; Kovscek, Anthony R; Ersland, Geir; Fernø, Martin A

2017-11-21

We present an experimental protocol for fast determination of hydrate stability in porous media for a range of pressure and temperature (P, T) conditions. Using a lab-on-a-chip approach, we gain direct optical access to dynamic pore-scale hydrate formation and dissociation events to study the hydrate phase equilibria in sediments. Optical pore-scale observations of phase behavior reproduce the theoretical hydrate stability line with methane gas and distilled water, and demonstrate the accuracy of the new method. The procedure is applicable for any kind of hydrate transitions in sediments, and may be used to map gas hydrate stability zones in nature.

Structural and electronic properties of the alkali metal incommensurate phases

NASA Astrophysics Data System (ADS)

Woolman, Gavin; Naden Robinson, Victor; Marqués, Miriam; Loa, Ingo; Ackland, Graeme J.; Hermann, Andreas

2018-05-01

Under pressure, the alkali elements sodium, potassium, and rubidium adopt nonperiodic structures based on two incommensurate interpenetrating lattices. While all elements form the same "host" lattice, their "guest" lattices are all distinct. The physical mechanism that stabilizes these phases is not known, and detailed calculations are challenging due to the incommensurability of the lattices. Using a series of commensurate approximant structures, we tackle this issue using density functional theory calculations. In Na and K, the calculations prove accurate enough to reproduce not only the stability of the host-guest phases, but also the complicated pressure dependence of the host-guest ratio and the two guest-lattice transitions. We find Rb-IV to be metastable at all pressures, and suggest it is a high-temperature phase. The electronic structure of these materials is unique: they exhibit two distinct, coexisting types of electride behavior, with both fully localized pseudoanions and electrons localized in 1D wells in the host lattice, leading to low conductivity. While all phases feature pseudogaps in the electronic density of states, the perturbative free-electron picture applies to Na, but not to K and Rb, due to significant d -orbital population in the latter.

Phase relations of iron and iron nickel alloys up to 300 GPa: Implications for composition and structure of the Earth's inner core

NASA Astrophysics Data System (ADS)

Kuwayama, Yasuhiro; Hirose, Kei; Sata, Nagayoshi; Ohishi, Yasuo

2008-09-01

We have investigated the phase relations of iron and iron-nickel alloys with 18 to 50 wt.% Ni up to over 300 GPa using a laser-heated diamond-anvil cell. The synchrotron X-ray diffraction measurements show the wide stability of hcp-iron up to 301 GPa and 2000 K and 319 GPa and 300 K without phase transition to dhcp, orthorhombic, or bcc phases. On the other hand, the incorporation of nickel has a remarkable effect on expanding the stability field of fcc phase. The geometry of the temperature-composition phase diagram of iron-nickel alloys suggests that the hcp-fcc-liquid triple point is located at 10 to 20 wt.% Ni at the pressure of the inner core boundary. The fcc phase could crystallize depending on the nickel and silicon contents in the Earth's core, both of which are fcc stabilizer.

Phase transition and equation of state of dense hydrous silica up to 63 GPa: DENSE HYDROUS PURE SILICA

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

Nisr, C.; Leinenweber, K.; Prakapenka, V.

Although it has previously been considered to be essentially anhydrous, Al-free stishovite can contain up to ~1.3 wt % of H2O, perhaps through the direct substitution ( math formula), according to recent studies. Yet the stability of such substitution and its impact on the properties of silica and rutile-structured hydrous phases (such as δ-AlOOH and phase H) are unknown at the conditions of the deeper mantle. We have synthesized hydrous and anhydrous Al-free stishovite samples at 723 K and 9 GPa, and 1473 K and 10 GPa, respectively. Synchrotron X-ray diffraction patterns show that the unit cell volume of hydrousmore » stishovite is 1.3% greater than that of anhydrous stishovite at 1 bar, suggesting significant incorporation of OH in the crystal structure (3.2 ± 0.5 wt % H2O). At 300 K, we found a lower and broader transition pressure from rutile type to CaCl2 type (28–42 GPa) in hydrous dense silica. We also found that hydrous silica polymorphs are more compressible than their anhydrous counterparts. After the phase transition, the unit cell volume of hydrous silica becomes the same as that of anhydrous silica, showing that the proton incorporation through a direct substitution can be further stabilized at high pressure. The lower pressure transition and the pressure stabilization of the proton incorporation in silica would provide ways to transport and store water in the lower mantle in silica-rich heterogeneities, such as subducted oceanic crust.« less

Pressure-induced superconductivity in CaC2

PubMed Central

Li, Yan-Ling; Luo, Wei; Zeng, Zhi; Lin, Hai-Qing; Mao, Ho-kwang; Ahuja, Rajeev

2013-01-01

Carbon can exist as isolated dumbbell, 1D chain, 2D plane, and 3D network in carbon solids or carbon-based compounds, which attributes to its rich chemical binding way, including sp-, sp2-, and sp3-hybridized bonds. sp2-hybridizing carbon always captures special attention due to its unique physical and chemical property. Here, using an evolutionary algorithm in conjunction with ab initio method, we found that, under compression, dumbbell carbon in CaC2 can be polymerized first into 1D chain and then into ribbon and further into 2D graphite sheet at higher pressure. The C2/m structure transforms into an orthorhombic Cmcm phase at 0.5 GPa, followed by another orthorhombic Immm phase, which is stabilized in a wide pressure range of 15.2–105.8 GPa and then forced into MgB2-type phase with wide range stability up to at least 1 TPa. Strong electron–phonon coupling λ in compressed CaC2 is found, in particular for Immm phase, which has the highest λ value (0.562–0.564) among them, leading to its high superconducting critical temperature Tc (7.9∼9.8 K), which is comparable with the 11.5 K value of CaC6. Our results show that calcium not only can stabilize carbon sp2 hybridization at a larger range of pressure but also can contribute in superconducting behavior, which would further ignite experimental and theoretical interest in alkaline–earth metal carbides to uncover their peculiar physical properties under extreme conditions. PMID:23690580

Pressure induced structural phase transition from NaCl-type (B1) to CsCl-type (B2) structure in sodium chloride

NASA Astrophysics Data System (ADS)

Jain, Aayushi; Dixit, R. C.

2018-05-01

Pressure induced structural phase transition of NaCl-type (B1) to CsCl-type (B2) structure in Sodium Chloride NaCl are presented. An effective interionic interaction potential (EIOP) with 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 is reported here. The reckon value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are compatible as compared with reported data. The variations of elastic constants and their combinations with pressure follow ordered behavior. The present approach has also succeeded in predicting the Born and relative stability criteria.

Phase stability of iron germanate, FeGeO 3, to 127 GPa

DOE PAGES

Dutta, R.; Tracy, S. J.; Stan, C. V.; ...

2017-11-15

The high-pressure behavior of germanates is of interest as these compounds serve as analogs for silicates of the deep Earth. Current theoretical and experimental studies of iron germanate, FeGeO 3, are limited. Here in this paper, we have examined the behavior of FeGeO 3 to 127 GPa using the laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. Upon compression at room temperature, the ambient-pressure clinopyroxene phase transforms to a disordered triclinic phase [FeGeO 3 (II)] at ~ 18 GPa in agreement with earlier studies. An additional phase transition to FeGeO 3 (III) occurs above 54 GPa atmore » room temperature. Laser-heating experiments (~ 1200–2200 K) were conducted at three pressures (33, 54, and 123 GPa) chosen to cover the stability regions of different GeO 2 polymorphs. In all cases, we observe that FeGeO 3 dissociates into GeO 2 + FeO at high pressure and temperature conditions. Neither the perovskite nor the post-perovskite phase was observed up to 127 GPa at ambient or high temperatures. The results are consistent with the behavior of FeSiO 3, which also dissociates into a mixture of the oxides (FeO + SiO 2) at least up to 149 GPa.« less

Pressure-induced amorphization of charge ordered spinel AlV{sub 2}O{sub 4} at low temperature

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

Malavi, Pallavi S., E-mail: malavips@barc.gov.in; Karmakar, S., E-mail: malavips@barc.gov.in; Sharma, S. M.

2014-04-24

Structural properties of charge ordered spinel AlV{sub 2}O{sub 4} have been investigated under high pressure at low temperature (80K) by synchrotron based x-ray diffraction measurements. It is observed that upon increasing pressure the structure becomes progressively disordered due to the distortion of the AlO{sub 4} tetrahedral unit and undergoes amorphization above ∼12 GPa. While releasing pressure, the rhombohedral phase is only partially recovered at a much lower pressure (below 5 GPa). Within the stability of the rhombohedral phase, the distortion in the vanadium heptamer increases monotonically with pressure, suggesting enhanced charge ordering. This result is in sharp contrast with themore » recent observation of pressure-induced frustration in the charge ordered state leading to structural transition to the cubic phase at room temperature [JPCM 25, 292201, 2013].« less

Dynamics of face and annular seals with two-phase flow

NASA Technical Reports Server (NTRS)

Hughes, William F.; Basu, Prithwish; Beatty, Paul A.; Beeler, Richard M.; Lau, Stephen

1989-01-01

A detailed study was made of face and annular seals under conditions where boiling, i.e., phase change of the leaking fluid, occurs within the seal. Many seals operate in this mode because of flashing due to pressure drop and/or heat input from frictional heating. High pressure, water pumps, industrial chemical pumps, and cryogenic pumps are mentioned as a few of many applications. The initial motivation was the LOX-GOX seals for the space shuttle main engine, but the study was expanded to include any face or annular seal where boiling occurs. Some of the distinctive behavior characteristics of two-phase seals were discussed, particularly their axial stability. While two-phase seals probably exhibit instability to disturbances of other degrees of freedom such as wobble, etc., under certain conditions, such analyses are too complex to be treated at present. Since an all liquid seal (with parallel faces) has a neutral axial stiffness curve, and is stabilized axially by convergent coning, other degrees of freedom stability analyses are necessary. However, the axial stability behavior of the two-phase seal is always a consideration no matter how well the seal is aligned and regardless of the speed. Hence, axial stability is thought of as the primary design consideration for two-phase seals and indeed the stability behavior under sub-cooling variations probably overshadows other concerns. The main thrust was the dynamic analysis of axial motion of two-phase face seals, principally the determination of axial stiffness, and the steady behavior of two-phase annular seals. The main conclusions are that seals with two-phase flow may be unstable if improperly balanced. Detailed theoretical analyses of low (laminar) and high (turbulent) leakage seals are presented along with computer codes, parametric studies, and in particular a simplified PC based code that allows for rapid performance prediction. A simplified combined computer code for the performance prediction over the laminar and turbulent ranges of a two-phase seal is described and documented. The analyses, results, and computer codes are summarized.

Phase relations of Fe Ni alloys at high pressure and temperature

NASA Astrophysics Data System (ADS)

Mao, Wendy L.; Campbell, Andrew J.; Heinz, Dion L.; Shen, Guoyin

2006-04-01

Using a diamond anvil cell and double-sided laser-heating coupled with synchrotron X-ray diffraction, we determined phase relations for three compositions of Fe-rich FeNi alloys in situ at high pressure and high temperature. We studied Fe with 5, 15, and 20 wt.% Ni to 55, 62, and 72 GPa, respectively, at temperatures up to ˜3000 K. Ni stabilizes the face-centered cubic phase to lower temperatures and higher pressure, and this effect increases with increasing pressure. Extrapolation of our experimental results for Fe with 15 wt.% Ni suggests that the stable phase at inner core conditions is hexagonal close packed, although if the temperature at the inner core boundary is higher than ˜6400 K, a two phase outer region may also exist. Comparison to previous laser-heated diamond anvil cell studies demonstrates the importance of kinetics even at high temperatures.

First principles study of structural and magnetic properties of transition metal nitrides TMN (TM = Cr, Mn)

NASA Astrophysics Data System (ADS)

Rajeswarapalanichamy, R.; Amudhavalli, A.; Manikandan, M.; Kavitha, M.; Iyakutti, K.

2017-09-01

The structural stability of chromium nitride (CrN) and manganese nitride (MnN) is investigated among four different structures, namely, NaCl (Fm3m), zinc blende (F4-3m), orthorhombic (Pnma) and tetragonal (I4/mmm). It is found that the most stable phase is the zinc blende phase for CrN and MnN. The structural phase transition from zinc blende to orthorhombic phase is predicted at high pressure. At normal pressure, CrN and MnN are found to be antiferromagnetic. As the pressure is increased, antiferromagnetic-to-nonmagnetic phase transition is observed at the pressures of 169.5 GPa in CrN and 206 GPa in MnN. The elastic constants obey the Born-Huang criteria, suggesting that they are mechanically stable. The calculated B/G values indicate that CrN and MnN are ductile in nature.

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

Ferreira, A. S.; Rovani, P. R.; Lima, J. C. de, E-mail: joao.cardoso.lima@ufsc.br

A nanostructured Ti{sub 50}Ni{sub 25}Fe{sub 25} phase (B2) was formed by mechanical alloying and its structural stability was studied as a function of pressure. The changes were followed by X-ray diffraction. The B2 phase was observed up to 7 GPa; for larger pressures, the B2 phase transformed into a trigonal/hexagonal phase (B19) that was observed up to the highest pressure used (18 GPa). Besides B2 and B19, elemental Ni or a SS-(Fe,Ni) and FeNi{sub 3} were observed. With decompression, the B2 phase was recovered. Using in situ angle-dispersive X-ray diffraction patterns, the single line method was applied to obtain the apparent crystallitemore » size and the microstrain for both the B2 and the B19 phases as a function of the applied pressure. Values of the bulk modulus for the B2, B19, elemental Ni or SS-(Fe,Ni) and FeNi{sub 3} phases were obtained by fitting the pressure dependence of the volume to a Birch–Murnaghan equation of state (BMEOS)« less

Ab initio molecular dynamic study of solid-state transitions of ammonium nitrate

PubMed Central

Yu, Hongyu; Duan, Defang; Liu, Hanyu; Yang, Ting; Tian, Fubo; Bao, Kuo; Li, Da; Zhao, Zhonglong; Liu, Bingbing; Cui, Tian

2016-01-01

High-pressure polymorphism and phase transitions have wide ranging consequences on the basic properties of ammonium nitrate. However, the phase diagram of ammonium nitrate at high pressure and high temperature is still under debate. This study systematically investigates the phase transitions and structural properties of ammonium nitrate at a pressure range of 5–60 GPa and temperature range of 250–400 K by ab initio molecular dynamics simulations. Two new phases are identified: one corresponds to the experimentally observed phase IV’ and the other is named AN-X. Simultaneously, the lattice strains play a significant role in the formation and stabilization of phase IV’, providing a reasonable explanation for experimental observation of phase IV-IV’ transition which only appears under nonhydrostatic pressure. In addition, 12 O atoms neighboring the NH (N atom in ammonium cation) atom are selected as reference system to clearly display the tanglesome rotation of ammonium cation. PMID:26754622

Calcium with the β-tin structure at high pressure and low temperature

PubMed Central

Li, Bing; Ding, Yang; Yang, Wenge; Wang, Lin; Zou, Bo; Shu, Jinfu; Sinogeikin, Stas; Park, Changyong; Zou, Guangtian; Mao, Ho-kwang

2012-01-01

Using synchrotron high-pressure X-ray diffraction at cryogenic temperatures, we have established the phase diagram for calcium up to 110 GPa and 5–300 K. We discovered the long-sought for theoretically predicted β-tin structured calcium with I41/amd symmetry at 35 GPa in a s mall low-temperature range below 10 K, thus resolving the enigma of absence of this lowest enthalpy phase. The stability and relations among various distorted simple-cubic phases in the Ca-III region have also been examined and clarified over a wide range of high pressures and low temperatures. PMID:23012455

Dolomite III: A new candidate lower mantle carbonate

NASA Astrophysics Data System (ADS)

Mao, Zhu; Armentrout, Matt; Rainey, Emma; Manning, Craig E.; Dera, Przemyslaw; Prakapenka, Vitali B.; Kavner, Abby

2011-11-01

Dolomite is a major constituent of subducted carbonates; therefore evaluation of its phase stability and equation of state at high pressures and temperatures is important for understanding the deep Earth carbon cycle. X-ray diffraction experiments in the diamond anvil cell show that Ca0.988Mg0.918Fe0.078Mn0.016(CO3)2 dolomite transforms to dolomite-II at ∼17 GPa and 300 K and then upon laser-heating transforms to a new monoclinic phase (dolomite-III), that is observed between 36 and 83 GPa. Both high-pressure polymorphs are stable up to 1500 K, indicating that addition of minor Fe stabilizes dolomite to Earth's deep-mantle conditions.

Structural stability, dynamical stability, thermoelectric properties, and elastic properties of GeTe at high pressure

NASA Astrophysics Data System (ADS)

Kagdada, Hardik L.; Jha, Prafulla K.; Śpiewak, Piotr; Kurzydłowski, Krzysztof J.

2018-04-01

The stability of GeTe in rhombohedral (R 3 m ), face centred cubic (F m 3 m ), and simple cubic (P m 3 m ) phases has been studied using density functional perturbation theory. The rhombohedral phase of GeTe is dynamically stable at 0 GPa, while F m 3 m and P m 3 m phases are stable at 3.1 and 33 GPa, respectively. The pressure-dependent phonon modes are observed in F m 3 m and P m 3 m phases at Γ and M points, respectively. The electronic and the thermoelectric properties have been investigated for the stable phases of GeTe. The electronic band gap for rhombohedral and F m 3 m phases of GeTe has been observed as 0.66 and 0.17 eV, respectively, while the P m 3 m phase shows metallic behavior. We have used the Boltzmann transport equation under a rigid band approximation and constant relaxation time approximation as implemented in boltztrap code for the calculation of thermoelectric properties of GeTe. The metallic behavior of P m 3 m phase gives a very low value of Seebeck coefficient compared to the other two phases as a function of temperature and the chemical potential μ. It is observed that the rhombohedral phase of GeTe exhibits higher thermoelectric performance. Due to the metallic nature of P m 3 m phase, negligible thermoelectric performance is observed compared to R 3 m and F m 3 m -GeTe. The calculated lattice thermal conductivities are low for F m 3 m -GeTe and high for R 3 m -GeTe. At the relatively higher temperature of 1350 K, the figure of merit ZT is found to be 0.7 for rhombohedral GeTe. The elastic constants satisfy the Born stability criteria for all three phases. The rhombohedral and F m 3 m phases exhibits brittleness and the P m 3 m phase shows ductile nature.

A locally conservative stabilized continuous Galerkin finite element method for two-phase flow in poroelastic subsurfaces

NASA Astrophysics Data System (ADS)

Deng, Q.; Ginting, V.; McCaskill, B.; Torsu, P.

2017-10-01

We study the application of a stabilized continuous Galerkin finite element method (CGFEM) in the simulation of multiphase flow in poroelastic subsurfaces. The system involves a nonlinear coupling between the fluid pressure, subsurface's deformation, and the fluid phase saturation, and as such, we represent this coupling through an iterative procedure. Spatial discretization of the poroelastic system employs the standard linear finite element in combination with a numerical diffusion term to maintain stability of the algebraic system. Furthermore, direct calculation of the normal velocities from pressure and deformation does not entail a locally conservative field. To alleviate this drawback, we propose an element based post-processing technique through which local conservation can be established. The performance of the method is validated through several examples illustrating the convergence of the method, the effectivity of the stabilization term, and the ability to achieve locally conservative normal velocities. Finally, the efficacy of the method is demonstrated through simulations of realistic multiphase flow in poroelastic subsurfaces.

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

Benzocaine polymorphism: pressure-temperature phase diagram involving forms II and III.

PubMed

Gana, Inès; Barrio, Maria; Do, Bernard; Tamarit, Josep-Lluís; Céolin, René; Rietveld, Ivo B

2013-11-18

Understanding the phase behavior of an active pharmaceutical ingredient in a drug formulation is required to avoid the occurrence of sudden phase changes resulting in decrease of bioavailability in a marketed product. Benzocaine is known to possess three crystalline polymorphs, but their stability hierarchy has so far not been determined. A topological method and direct calorimetric measurements under pressure have been used to construct the topological pressure-temperature diagram of the phase relationships between the solid phases II and III, the liquid, and the vapor phase. In the process, the transition temperature between solid phases III and II and its enthalpy change have been determined. Solid phase II, which has the highest melting point, is the more stable phase under ambient conditions in this phase diagram. Surprisingly, solid phase I has not been observed during the study, even though the scarce literature data on its thermal behavior appear to indicate that it might be the most stable one of the three solid phases. Copyright © 2013 Elsevier B.V. All rights reserved.

Communication: phase transitions, criticality, and three-phase coexistence in constrained cell models.

PubMed

Nayhouse, Michael; Kwon, Joseph Sang-Il; Orkoulas, G

2012-05-28

In simulation studies of fluid-solid transitions, the solid phase is usually modeled as a constrained system in which each particle is confined to move in a single Wigner-Seitz cell. The constrained cell model has been used in the determination of fluid-solid coexistence via thermodynamic integration and other techniques. In the present work, the phase diagram of such a constrained system of Lennard-Jones particles is determined from constant-pressure simulations. The pressure-density isotherms exhibit inflection points which are interpreted as the mechanical stability limit of the solid phase. The phase diagram of the constrained system contains a critical and a triple point. The temperature and pressure at the critical and the triple point are both higher than those of the unconstrained system due to the reduction in the entropy caused by the single occupancy constraint.

Stabilization of scandium terephthalate MOFs against reversible amorphization and structural phase transition by guest uptake at extreme pressure.

PubMed

Graham, Alexander J; Banu, Ana-Maria; Düren, Tina; Greenaway, Alex; McKellar, Scott C; Mowat, John P S; Ward, Kenneth; Wright, Paul A; Moggach, Stephen A

2014-06-18

Previous high-pressure experiments have shown that pressure-transmitting fluids composed of small molecules can be forced inside the pores of metal organic framework materials, where they can cause phase transitions and amorphization and can even induce porosity in conventionally nonporous materials. Here we report a combined high-pressure diffraction and computational study of the structural response to methanol uptake at high pressure on a scandium terephthalate MOF (Sc2BDC3, BDC = 1,4-benzenedicarboxylate) and its nitro-functionalized derivative (Sc2(NO2-BDC)3) and compare it to direct compression behavior in a nonpenetrative hydrostatic fluid, Fluorinert-77. In Fluorinert-77, Sc2BDC3 displays amorphization above 0.1 GPa, reversible upon pressure release, whereas Sc2(NO2-BDC)3 undergoes a phase transition (C2/c to Fdd2) to a denser but topologically identical polymorph. In the presence of methanol, the reversible amorphization of Sc2BDC3 and the displacive phase transition of the nitro-form are completely inhibited (at least up to 3 GPa). Upon uptake of methanol on Sc2BDC3, the methanol molecules are found by diffraction to occupy two sites, with preferential relative filling of one site compared to the other: grand canonical Monte Carlo simulations support these experimental observations, and molecular dynamics simulations reveal the likely orientations of the methanol molecules, which are controlled at least in part by H-bonding interactions between guests. As well as revealing the atomistic origin of the stabilization of these MOFs against nonpenetrative hydrostatic fluids at high pressure, this study demonstrates a novel high-pressure approach to study adsorption within a porous framework as a function of increasing guest content, and so to determine the most energetically favorable adsorption sites.

Synthesis and Stability of Lanthanum Superhydrides

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

Geballe, Zachary M.; Liu, Hanyu; Mishra, Ajay K.

Recent theoretical calculations predict that megabar pressure stabilizes very hydrogen-rich simple compounds having new clathrate-like structures and remarkable electronic properties including room-temperature superconductivity. X-ray diffraction and optical studies demonstrate that superhydrides of lanthanum can be synthesized with La atoms in an fcc lattice at 170 GPa upon heating to about 1000 K. The results match the predicted cubic metallic phase of LaH10 having cages of thirty-two hydrogen atoms surrounding each La atom. Upon decompression, the fcc-based structure undergoes a rhombohedral distortion of the La sublattice. The superhydride phases consist of an atomic hydrogen sublattice with H-H distances of about 1.1more » Å, which are close to predictions for solid atomic metallic hydrogen at these pressures. With stability below 200 GPa, the superhydride is thus the closest analogue to solid atomic metallic hydrogen yet to be synthesized and characterized.« less

Thermal properties and phase transition in the fluoride, (NH{sub 4}){sub 3}SnF{sub 7}

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

Kartashev, A.V.; Astafijev Krasnoyarsk State Pedagogical University, 660049 Krasnoyarsk; Gorev, M.V.

2016-05-15

Calorimetric, dilatometric and differential thermal analysis studies were performed on (NH{sub 4}){sub 3}SnF{sub 7} for a wide range of temperatures and pressures. Large entropy (δS{sub 0}=22 J/mol K) and elastic deformation (δ(ΔV/V){sub 0}=0.89%) jumps have proven that the Pa-3↔Pm-3m phase transition is a strong first order structural transformation. A total entropy change of ΔS{sub 0}=32.5 J/mol K is characteristic for the order–disorder phase transition, and is equal to the sum of entropy changes in the related material, (NH{sub 4}){sub 3}TiF{sub 7}, undergoing transformation between the two cubic phases through the intermediate phases. Hydrostatic pressure decreases the stability of the highmore » temperature Pm-3m phase in (NH{sub 4}){sub 3}SnF{sub 7}, contrary to (NH{sub 4}){sub 3}TiF{sub 7}, characterised by a negative baric coefficient. The effect of experimental conditions on the chemical stability of (NH{sub 4}){sub 3}SnF{sub 7} was observed. - Graphical abstract: Strong first order structural transformation Pa-3↔Pm-3m in (NH{sub 4}){sub 3}SnF{sub 7} is associated with very large total entropy change of ΔS{sub 0}=32.5 J/mol K characteristic for the ordering processes and equal to the sum of entropy changes in the related (NH{sub 4}){sub 3}TiF{sub 7} undergoing transformation between the same two cubic phases through the intermediate phases. - Highlights: • (NH{sub 4}){sub 3}SnF{sub 7} undergoes strong first order Pa-3↔Pm-3m phase transition. • Anomalous behaviour of ΔC{sub p} and ΔV/V exists far below phase transition temperature. • Structural distortions are accompanied by huge total entropy change ΔS≈Rln50. • High pressure strongly increases the stability of Pa-3 phase in (NH{sub 4}){sub 3}SnF{sub 7}. • Entropy of the Pa-3↔Pm-3m phase transition does not depend on pressure.« less

First-principles calculations of high-pressure iron-bearing monoclinic dolomite and single-cation carbonates with internally-consistent Hubbard U

NASA Astrophysics Data System (ADS)

Solomatova, N. V.; Asimow, P. D.

2017-12-01

It has been proposed that iron has a significant effect on the relative stability of carbonate phases at high pressures, possibly even stabilizing double-cation carbonates (e.g., dolomite) with respect to single-cation carbonates (e.g., magnesite, aragonite and siderite). X-ray diffraction experiments have shown that dolomite transforms at 35 GPa to a high-pressure polymorph that is stable to decomposition; however, there has been disagreement on the structure of the high-pressure phase [1,2]. Ab initio calculations interfaced with an evolutionary structure prediction algorithm demonstrated that a C2/c polymorph of pure CaMg(CO3)2 dolomite is more stable than previously reported structures [3]. In this study, we calculate the relative enthalpies up to 80 GPa for a set of carbonate phases including Fe-bearing solutions and endmembers, using the generalized gradient approximation and a Hubbard U parameter calculated through linear response theory to accurately characterize the electronic structure of Fe. When calculated with a constant U of 4 eV, the spin transition pressure of (Mg,Fe)CO3 agrees well with experiments, whereas an internally-consistent U overestimates the spin transition pressure by 50 GPa. However, whether we use constant or internally-consistent U values, a higher iron concentration increases the stability field of dolomite C2/c with respect to single-cation carbonate assemblages, but iron-free dolomite is not stable with respect to single-cation carbonates at any pressure. Thus, high-pressure polymorphs of Fe-bearing dolomite could in fact represent an important reservoir for carbon storage within oxidized sections of Earth's mantle. [1] Mao, Z. et al. (2011) Geophysical Research Letters, 38. [2] Merlini, M. et al. (2012) Proceedings of the National Academy of Sciences, 109, 13509-13514. [3] Solomatova, N. V. and Asimow, P. D. (2017) American Mineralogist, 102, 210-215.

High pressure structural behavior of YGa2: A combined experimental and theoretical study

NASA Astrophysics Data System (ADS)

Sekar, M.; Shekar, N. V. Chandra; Babu, R.; Sahu, P. Ch.; Sinha, A. K.; Upadhyay, Anuj; Singh, M. N.; Babu, K. Ramesh; Appalakondaiah, S.; Vaitheeswaran, G.; Kanchana, V.

2015-03-01

High pressure structural stability studies were carried out on YGa2 (AlB2 type structure at NTP, space group P6/mmm) up to a pressure of 35 GPa using both laboratory based rotating anode and synchrotron X-ray sources. An isostructural transition with reduced c/a ratio, was observed at 6 GPa and above 17.5 GPa, the compound transformed to orthorhombic structure. Bulk modulus B0 for the parent and high pressure phases were estimated using Birch-Murnaghan and modified Birch-Murnaghan equation of state. Electronic structure calculations based on projector augmented wave method confirms the experimentally observed two high pressure structural transitions. The calculations also reveal that the 'Ga' networks remains as two dimensional in the high pressure isostructural phase, whereas the orthorhombic phase involves three dimensional networks of 'Ga' atoms interconnected by strong covalent bonds.

Stresses and pressures at the quartz-to-coesite phase transformation in shear deformation experiments

NASA Astrophysics Data System (ADS)

Richter, B.; Stünitz, H.; Heilbronner, R.

2016-11-01

Coesite was found in quartz aggregates, experimentally deformed at confining pressures of 1.0-1.5 GPa and temperatures between 600°C and 900°C. The confining pressure (Pc) and, in most cases, the mean stress (σm) of the experiments were below those of the quartz-to-coesite phase transformation. Yet coesite formed when the maximum principal stress (σ1) was within the P-T range of the coesite stability field. In one sample, the euhedral coesite grains were corroded indicating that coesite started to transform back to quartz. It is inferred that this sample started to deform with σ1 above the quartz-to-coesite phase transformation and, with ongoing deformation, σ1 decreased to values in the quartz stability field due to strain weakening. In all cases, σ1 triggered the quartz-to-coesite reaction as well as the reverse reaction, suggesting that σ1 is the critical parameter for the quartz-to-coesite transformation—not Pc or σm. With progressive deformation, the coesite laths rotated toward the shear plane as more rigid particles with the sense of shear. In case of back reaction, new quartz grains exhibit no systematic crystallographic relationship with respect to old coesite. The experiments cover different degrees of pressure "overstepping," different temperatures, and different experimental durations at P and T, and deformation always enhances the reaction kinetics. The observation that σ1 is critical for a pressure-dependent phase transformation (also for reversals) poses questions for the thermodynamic treatment of such phase transformations.

Epitaxial bain paths and metastable phases of tetragonal iron and manganese

NASA Astrophysics Data System (ADS)

Ma, Hong

2002-04-01

Epitaxial Bain paths and metastable states of tetragonal Fe and Mn have been studied by first-principles total-energy calculations using the full-potential linearized-augmented-plane-wave method. The main accomplishments are as follows. (1) We have performed the first ever EBP calculation of tetragonal antiferromagnetic (AF) Mn showing that when grown epitaxially on Pd(001), the AF Mn film is strained gamma-Mn, but grown on V(001) the film is strained delta-Mn, which could not be determined using the available crystallographic and elastic data because they were obtained from unstrained states. (2) We have calculated the EBP's of Fe at zero pressure in four magnetic phases, i.e., ferromagnetic (FM), nonmagnetic (NM), type-I antiferromagnetic (AF1), and type-II antiferromagnetic (AF2), which show that the AF2 is the phase of the bulk of epitaxial Fe films on Cu(001) and it is unstable for [110] and [010] shears in the (001) plane, but it can be stabilized by epitaxy on Cu(001). (3)We have unified and simplified the theory of elasticity under hydrostatic pressure p at zero temperature using the Gibbs free energy G, rather than the energy E. The minima of G, but not E, with respect to strains at the equilibrium structure give the zero temperature elastic constants; the stability of a phase at p is then determined by the same Born stability conditions used at p = 0 when applied to the elastic constants from G. The EBP's of FM Fe under hydrostatic pressure show that the bcc phase exists up to 1500 kbar. A bct phase is shown to come into existence at 1300 kbar and becomes stable at 1825 kbar and above. (4) Based on this dissertation research five papers have been published in refereed journals.

The depolarization performances of 0.97PbZrO3-0.03Ba(Mg1/3Nb2/3)O3 ceramics under hydrostatic pressure

NASA Astrophysics Data System (ADS)

Su, Rigu; Nie, Hengchang; Liu, Zhen; Peng, Ping; Cao, Fei; Dong, Xianlin; Wang, Genshui

2018-02-01

Several 0.97PbZrO3-0.03Ba(Mg1/3Nb2/3)O3 (0.97PZ-0.03BMN) ceramics were prepared via the columbite precursor method. Their microstructures and pressure-dependent ferroelectric and depolarization performances were then studied. The X-ray diffraction patterns of ground and fresh samples indicate that a main rhombohedral symmetry crystal structure is present in the bulk and that it sits alongside a trace quantity of an orthorhombic antiferroelectric phase that results from the effect of grinding on the surface. The remanent polarization (Pr) of the 0.97PZ-0.03BMN reached 32.4 μC/cm2 at 4.5 kV/mm and ambient pressure. In an in situ pressure-induced current measurement, more than 91% of the retained Pr of the pre-poled sample was released when the pressure was increased from 194 MPa to 238 MPa. That this pressure-driven depolarization should be attributed to the pressure-induced ferroelectric-antiferroelectric phase transition is supported by the emergence of double P-E loops at high hydrostatic pressures. Moreover, the 0.97PZ-0.03BMN ceramics exhibit no temperature-induced phase transitions and little related polarization loss up to 125 °C, which suggests that Pr has excellent thermal stability. The sharp depolarization behavior at low pressures and excellent temperature stability reveal that our 0.97PZ-0.03BMN ceramics exhibit superior performances in mechanical-electrical energy conversion applications.

Pressure-induced structural phase transition in transition metal carbides TMC (TM = Ru, Rh, Pd, Os, Ir, Pt): a DFT study

NASA Astrophysics Data System (ADS)

Manikandan, M.; Rajeswarapalanichamy, R.; Iyakutti, K.

2018-03-01

First-principles calculations based on density functional theory was performed to analyse the structural stability of transition metal carbides TMC (TM = Ru, Rh, Pd, Os, Ir, Pt). It is observed that zinc-blende phase is the most stable one for these carbides. Pressure-induced structural phase transition from zinc blende to NiAs phase is predicted at the pressures of 248.5 GPa, 127 GPa and 142 GPa for OsC, IrC and PtC, respectively. The electronic structure reveals that RuC exhibits a semiconducting behaviour with an energy gap of 0.7056 eV. The high bulk modulus values of these carbides indicate that these metal carbides are super hard materials. The high B/G value predicts that the carbides are ductile in their most stable phase.

A Rotational Pressure-Correction Scheme for Incompressible Two-Phase Flows with Open Boundaries

PubMed Central

Dong, S.; Wang, X.

2016-01-01

Two-phase outflows refer to situations where the interface formed between two immiscible incompressible fluids passes through open portions of the domain boundary. We present several new forms of open boundary conditions for two-phase outflow simulations within the phase field framework, as well as a rotational pressure correction based algorithm for numerically treating these open boundary conditions. Our algorithm gives rise to linear algebraic systems for the velocity and the pressure that involve only constant and time-independent coefficient matrices after discretization, despite the variable density and variable viscosity of the two-phase mixture. By comparing simulation results with theory and the experimental data, we show that the method produces physically accurate results. We also present numerical experiments to demonstrate the long-term stability of the method in situations where large density contrast, large viscosity contrast, and backflows occur at the two-phase open boundaries. PMID:27163909

Suppression of the ferromagnetic order in the Heusler alloy Ni{sub 50}Mn{sub 35}In{sub 15} by hydrostatic pressure

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

Salazar Mejía, C., E-mail: Catalina.Salazar@cpfs.mpg.de; Mydeen, K.; Naumov, P.

2016-06-27

We report on the effect of hydrostatic pressure on the magnetic and structural properties of the shape-memory Heusler alloy Ni{sub 50}Mn{sub 35}In{sub 15}. Magnetization and x-ray diffraction experiments were performed at hydrostatic pressures up to 5 GPa using diamond anvil cells. Pressure stabilizes the martensitic phase, shifting the martensitic transition to higher temperatures, and suppresses the ferromagnetic austenitic phase. Above 3 GPa, where the martensitic-transition temperature approaches the Curie temperature in the austenite, the magnetization shows no longer indications of ferromagnetic ordering. We further find an extended temperature region with a mixture of martensite and austenite phases, which directly relates to themore » magnetic properties.« less

High pressure study of Pu(0.92)Am(0.08) binary alloy.

PubMed

Klosek, V; Griveau, J C; Faure, P; Genestier, C; Baclet, N; Wastin, F

2008-07-09

The phase transitions (by means of x-ray diffraction) and electrical resistivity of a Pu(0.92)Am(0.08) binary alloy were determined under pressure (up to 2 GPa). The evolution of atomic volume with pressure gives detailed information concerning the degree of localization of 5f electronic states and their delocalization process. A quasi-linear V = f(P) dependence reflects subtle modifications of the electronic structure when P increases. The electrical resistivity measurements reveal the very high stability of the δ phase for pressures less than 0.7 GPa, since no martensitic-like transformation occurs at low temperature. Remarkable electronic behaviours have also been observed. Finally, resistivity curves have shown the temperature dependence of the phase transformations together with unexpected kinetic effects.

First principles study of pressure induced polymorphic phase transition in trimethylamine

NASA Astrophysics Data System (ADS)

Abraham, B. Moses; Vaitheeswaran, G.

2018-04-01

The pressure induced variations on the crystal structure of various polymorphs of Trimethyamine (TMA-I, TMA-II, TMAIII) has been studied theoretically using first principles calculations up to 5 GPa. The obtained equilibrium lattice parameters using standard PBE-GGA functional for the ambient and high pressure phases are found to be in good agreement with the experimental values. We calculated the enthalpies of each phase to assess their relative stability. Our results also supports the existence of additional phase transitions of TMA into two new polymorphs under external pressure. The TMA-I to TMA-II transition is found to occur at 1.41 GPa and the TMA-II to TMA-III transition at 3.33 GPa. The electronic band structure calculations using Tran Blaha-modified Becke Johnson (TB-mBJ) potential show that these polymorphs of TMA are indirect band gap insulators.

Stability and superconducting properties of GaH5 at high pressure

NASA Astrophysics Data System (ADS)

Ning, Yan-Li; Yang, Wen-Hua; Zang, Qing-Jun; Lu, Wen-Cai

2017-11-01

Using genetic algorithm (GA) method combined with first-principles calculations, the structures, dynamical and thermodynamic stabilities of GaH5 were studied. The calculated results suggested that at the pressure range 150-400 GPa, the P21/m phase of GaH5 is the most favorable phase and dynamically stable, but thermodynamically it is unstable and can decompose into GaH3 and H2. The superconducting property of GaH5 was further calculated, and the predicted superconducting transformation temperature Tc of GaH5 P21/m phase is about 35.63 K at 250 GPa. Besides, we compared the GaH5 and GaH3 superconducting properties, and found that GaH3-Pm-3n structure has a larger DOS near Fermi level than GaH5-P21/m structure, which may be the main reason causing higher Tc of GaH3 than GaH5.

High-Pressure Phase Transition of Iron: A Combined Magnetic Remanence and Mössbauer Study

NASA Astrophysics Data System (ADS)

Wei, Qingguo; McCammon, Catherine; Gilder, Stuart Alan

2017-12-01

We measured Mössbauer spectra and the acquisition of saturation isothermal remanent magnetization in alternating steps on the same sample of polycrystalline, multidiron metal powder in a diamond anvil cell across the body centered cubic (bcc) to hexagonal closed packed (hcp) phase transition at room temperature up to 19.2 GPa. Within the bcc stability field indicated by the presence of magnetic hyperfine splitting, saturation remanent magnetization and sextet area were well correlated during compression and decompression. The areas and dips of the outer (first and sixth) and middle (second and fifth) components of the sextet changed in relative proportion as a function of pressure, which was attributed to rotation of the magnetization direction perpendicular to the gamma-ray source. Sextet peaks disappeared above ˜15 GPa, yet magnetic remanence persisted. Magnetic remanence intensity divided by the fractional area of the sextet, taken to represent bcc Fe, attained maxima at pressures near the boundaries of the hysteretic transition, which we attribute to strain-related magnetostriction effects associated with a distorted bcc-hcp phase. Magnetic remanence observed within the hcp stability field, as defined by the absence of sextet peaks, could be due to a previously described, distorted bcc-hcp phase whose hyperfine field was below detection limits of Mössbauer spectroscopy. Our study suggests that distorted bcc-hcp Fe holds magnetic remanence and leaves open the possibility that this phase carries magnetic remanence into the pressure range where only pure hcp Fe is considered stable.

Comparison between thermochemical and phase stability data for the quartz-coesite-stishovite transformations

NASA Technical Reports Server (NTRS)

Weaver, J. S.; Chipman, D. W.; Takahashi, T.

1979-01-01

Phase stability and elasticity data have been used to calculate the Gibbs free energy, enthalpy, and entropy changes at 298 K and 1 bar associated with the quartz-coesite and coesite-stishovite transformations in the system SiO2. For the quartz-coesite transformation, these changes disagree by a factor of two or three with those obtained by calorimetric techniques. The phase boundary for this transformation appears to be well determined by experiment; the discrepancy, therefore, suggests that the calorimetric data for coesite are in error. Although the calorimetric and phase stability data for the coesite-stishovite transformation yield the same transition pressure at 298 K, the phase-boundary slopes disagree by a factor of two. At present, it is not possible to determine which of the data are in error. Thus serious inconsistencies exist in the thermodynamic data for the polymorphic transformations of silica.

Phase transition thermodynamics of bisphenols.

PubMed

Costa, José C S; Dávalos, Juan Z; Santos, Luís M N B F

2014-10-16

Herein we have studied, presented, and analyzed the phase equilibria thermodynamics of a bisphenols (BP-A, BP-E, BP-F, BP-AP, and BP-S) series. In particular, the heat capacities, melting temperatures, and vapor pressures at different temperatures as well as the standard enthalpies, entropies, and Gibbs energies of phase transition (fusion and sublimation) were experimentally determined. Also, we have presented the phase diagrams of each bisphenol derivative and investigated the key parameters related to the thermodynamic stability of the condensed phases. When all the bisphenol derivatives are compared at the same conditions, solids BP-AP and BP-S present lower volatilities (higher Gibbs energy of sublimation) and high melting temperatures due to the higher stability of their solid phases. Solids BP-A and BP-F present similar stabilities, whereas BP-E is more volatile. The introduction of -CH3 groups in BP-F (giving BP-E and BP-A) leads an entropic differentiation in the solid phase, whereas in the isotropic liquids the enthalpic and entropic differentiations are negligible.

Stability of the body-centred-cubic phase of iron in the Earth's inner core.

PubMed

Belonoshko, Anatoly B; Ahuja, Rajeev; Johansson, Börje

2003-08-28

Iron is thought to be the main constituent of the Earth's core, and considerable efforts have therefore been made to understand its properties at high pressure and temperature. While these efforts have expanded our knowledge of the iron phase diagram, there remain some significant inconsistencies, the most notable being the difference between the 'low' and 'high' melting curves. Here we report the results of molecular dynamics simulations of iron based on embedded atom models fitted to the results of two implementations of density functional theory. We tested two model approximations and found that both point to the stability of the body-centred-cubic (b.c.c.) iron phase at high temperature and pressure. Our calculated melting curve is in agreement with the 'high' melting curve, but our calculated phase boundary between the hexagonal close packed (h.c.p.) and b.c.c. iron phases is in good agreement with the 'low' melting curve. We suggest that the h.c.p.-b.c.c. transition was previously misinterpreted as a melting transition, similar to the case of xenon, and that the b.c.c. phase of iron is the stable phase in the Earth's inner core.

Nature of phase transitions in crystalline and amorphous GeTe-Sb2Te3 phase change materials.

PubMed

Kalkan, B; Sen, S; Clark, S M

2011-09-28

The thermodynamic nature of phase stabilities and transformations are investigated in crystalline and amorphous Ge(1)Sb(2)Te(4) (GST124) phase change materials as a function of pressure and temperature using high-resolution synchrotron x-ray diffraction in a diamond anvil cell. The phase transformation sequences upon compression, for cubic and hexagonal GST124 phases are found to be: cubic → amorphous → orthorhombic → bcc and hexagonal → orthorhombic → bcc. The Clapeyron slopes for melting of the hexagonal and bcc phases are negative and positive, respectively, resulting in a pressure dependent minimum in the liquidus. When taken together, the phase equilibria relations are consistent with the presence of polyamorphism in this system with the as-deposited amorphous GST phase being the low entropy low-density amorphous phase and the laser melt-quenched and high-pressure amorphized GST being the high entropy high-density amorphous phase. The metastable phase boundary between these two polyamorphic phases is expected to have a negative Clapeyron slope. © 2011 American Institute of Physics

Optical and Raman microspectroscopy of nitrogen and hydrogen mixtures at high pressures

NASA Astrophysics Data System (ADS)

Ciezak, Jennifer; Jenkins, T.; Hemley, R.

2009-06-01

Extended phases of molecular solids formed from simple molecules have led to polymeric materials under extreme conditions with advanced optical, mechanical and energetic properties. Although the existence of extended phases has been demonstrated in N2, CO and CO2, recovery of the materials to ambient conditions has posed considerable difficulty. Recent molecular dynamics simulations have predicted that the addition of hydrogen to nitrogen may increase the stability of the cubic-gauche nitrogen polymer and thereby offer the possibility of synthesis at lower pressures and temperatures. Here we present optical and Raman microspectroscopy measurements performed on nitrogen and hydrogen mixtures to 85 GPa. To pressures of 30 GPa, large deviations in the internal molecular stretching modes of the mixtures relative to those of the pure material reveal unusual phase behavior. After an unusual phase separation near 35 GPa, a phase assemblage of consisting of a phase rich in both nitrogen and hydrogen, a phase of relatively amorphous nitrogen and a mixture of the two is observed. Near this pressure, Raman bands attributed to the N-N single bonded stretch were observed.

Mechanical Stability Criterion, Triple-Phase Condition, and Pressure Differences of Matter Condensed in a Porous Matrix.

PubMed

Setzer, Max J.

2001-03-01

In contrast to the triple-point condition of bulk material, condensed matter in porous media can coexist stably as liquid, solid, and vapor over a wide temperature range. The necessary conditions are found by a thermodynamic approach starting with the potential which reflects the grand canonical distribution and is characterized by heat and matter exchange. The other parameters are volume and surface. Therefore, it is designated the free mechanical potential. General expressions for mechanical stability are given. On condensation and melting the nonwetting phases vanish. These are thermodynamically stable phase transitions. For the opposing effects evaporation and fusion, an energy barrier must be transgressed either by nucleation or by intrusion as discussed here. These are metastable states. Phase transitions are the conditions which limit the triple-phase region. Within this region high negative pressures are generated in the unfrozen liquid independent of the pore size where it exists. The findings are applied to water in the disperse matrix of hardened cement paste. They are the basis for "micro ice lens pumping". Copyright 2001 Academic Press.

Curvature induced phase stability of an intensely heated liquid

NASA Astrophysics Data System (ADS)

Sasikumar, Kiran; Liang, Zhi; Cahill, David G.; Keblinski, Pawel

2014-06-01

We use non-equilibrium molecular dynamics simulations to study the heat transfer around intensely heated solid nanoparticles immersed in a model Lennard-Jones fluid. We focus our studies on the role of the nanoparticle curvature on the liquid phase stability under steady-state heating. For small nanoparticles we observe a stable liquid phase near the nanoparticle surface, which can be at a temperature well above the boiling point. Furthermore, for particles with radius smaller than a critical radius of 2 nm we do not observe formation of vapor even above the critical temperature. Instead, we report the existence of a stable fluid region with a density much larger than that of the vapor phase. We explain the stability in terms of the Laplace pressure associated with the formation of a vapor nanocavity and the associated effect on the Gibbs free energy.

Stability characteristics of a single-phase free convection loop

NASA Technical Reports Server (NTRS)

Creveling, H. F.; De Paz, J. F.; Baladi, J. Y.; Schoenhals, R. J.

1975-01-01

Experiments investigating the stability characteristics of a single-phase free convection loop are reported. Results of the study confirm the contention made by previous workers that instabilities near the thermodynamic critical point can occur for ordinary fluids as well as those with unusual behavior in the near-critical region. Such a claim runs counter to traditional beliefs, but it is supported by the observation of such instabilities for water at atmospheric pressure and moderate temperatures in the present work.

Anomalous behaviour of thermodynamic properties at successive phase transitions in (NH4)3GeF7

NASA Astrophysics Data System (ADS)

Bogdanov, Evgeniy V.; Kartashev, Andrey V.; Pogoreltsev, Evgeniy I.; Gorev, Mikhail V.; Laptash, Natalia M.; Flerov, Igor N.

2017-12-01

Heat capacity, thermal dilatation, susceptibility to hydrostatic pressure and dielectric properties associated with succession of three phase transitions below room temperature in double fluoride salt (NH4)3GeF7 were studied. A possible transformation into the parent Pm-3m cubic phase was not observed up to the decomposition of compound. Nonferroelectric nature of structural distortions was confirmed. The DTA under pressure studies revealed a high temperature stability of two phases: P4/mbm and Pbam. The entropies of the phase transitions agree well with the model of structural distortions. Analysis of the thermal properties associated with the individual phase transitions in the framework of thermodynamic equations has shown a high reliability of the data obtained.

Melting relations of model lherzolite in the system CaO-MgO-Al2O3-SiO2 at 2.4-3.4 GPa and the generation of komatiites

NASA Astrophysics Data System (ADS)

Gudfinnsson, Gudmundur H.; Presnall, Dean C.

1996-12-01

Isobarically invariant phase relations in the CaO-MgO-Al2O3-SiO2 system (CMAS) involving the lherzolite phase assemblage in equilibrium with liquid have been determined at 2.4-3.4 GPa. These phase relations form the solidus of model lherzolite in the CMAS system. Our data, which include determinations of all phase compositions, are in excellent agreement with the 3.0 and 4.0 GPa points of Milholland and Presnall [1991] and Davis and Schairer [1965], respectively. The invariant transition on the P-T solidus curve from spinel- to garnet-lherzolite at 3.0 GPa, 1575°C [Milholland and Presnall, 1991], is confirmed, but we observe that the theoretically required temperature depression on the solidus curve at this point is not experimentally detectable. Composition trends along the solidus take a sharp turn at the transition. In the spinel-lherzolite stability field, melt compositions become increasingly Fo-normative and less En-normative with increasing pressure, but become less Fo-normative and more pyroxenitic as pressure increases in the garnet-lherzolite stability field. Calculated melting reactions indicate that forsterite is in reaction relationship with the melt up to 3.0 GPa. Orthopyroxene is also in reaction relationship at pressures higher than just over 2.8 GPa and is the only phase in reaction relationship with the melt in the garnet-lherzolite stability field. Comparison of the normative compositions and the CaO/Al2O3 values of the komatiites of Gorgona Island and of the Reliance Formation in Zimbabwe with the compositions of liquids along the solidus of model lherzolite in the CMAS system indicates that the former komatiites were generated at pressures close to 3.7 GPa and the latter at close to 4.5 GPa, assuming that the melt generation occurred in the presence of the complete garnet-lherzolite assemblage.

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.

X-ray diffraction and spectroscopy study of nano-Eu 2O 3 structural transformation under high pressure

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

Yu, Zhenhai; Wang, Qinglin; Ma, Yanzhang

Nanoscale materials exhibit properties that are quite distinct from those of bulk materials because of their size restricted nature. Here, we investigated the high-pressure structural stability of cubic (C-type) nano-Eu2O3 using in situ synchrotron X-ray diffraction (XRD), Raman and luminescence spectroscopy, and impedance spectra techniques. Our high-pressure XRD experimental results revealed a pressure-induced structural phase transition in nano-Eu2O3 from the C-type phase (space group: Ia-3) to a hexagonal phase (A-type, space group: P-3m1). Our reported transition pressure (9.3 GPa) in nano-Eu2O3 is higher than that of the corresponding bulk-Eu2O3 (5.0 GPa), which is contrary to the preceding reported experimental result.more » After pressure release, the A-type phase of Eu2O3 transforms into a new monoclinic phase (B-type, space group: C2/m). Compared with bulk-Eu2O3, C-type and A-type nano-Eu2O3 exhibits a larger bulk modulus. Our Raman and luminescence findings and XRD data provide consistent evidence of a pressure-induced structural phase transition in nano-Eu2O3. To our knowledge, we have performed the first high-pressure impedance spectra investigation on nano-Eu2O3 to examine the effect of the structural phase transition on its transport properties. We propose that the resistance inflection exhibited at ~12 GPa results from the phase boundary between the C-type and A-type phases. Besides, we summarized and discussed the structural evolution process by the phase diagram of lanthanide sesquioxides (Ln2O3) under high pressure.« less

Microstructure of calcite deformed by high-pressure torsion: An X-ray line profile study

NASA Astrophysics Data System (ADS)

Schuster, Roman; Schafler, Erhard; Schell, Norbert; Kunz, Martin; Abart, Rainer

2017-11-01

Calcite aggregates were deformed to high strain using high-pressure torsion and applying confining pressures of 1-6 GPa and temperatures between room temperature and 450 °C. The run products were characterized by X-ray diffraction, and key microstructural parameters were extracted employing X-ray line profile analysis. The dominant slip system was determined as r { 10 1 bar 4 } ⟨ 2 bar 021 ⟩ with edge dislocation character. The resulting dislocation density and the size of the coherently scattering domains (CSD) exhibit a systematic dependence on the P-T conditions of deformation. While high pressure generally impedes recovery through reducing point defect mobility, the picture is complicated by pressure-induced phase transformations in the CaCO3 system. Transition from the calcite stability field to those of the high-pressure polymorphs CaCO3-II, CaCO3-III and CaCO3-IIIb leads to a change of the microstructural evolution with deformation. At 450 °C and pressures within the calcite stability field, dislocation densities and CSD sizes saturate at shear strains exceeding 10 in agreement with earlier studies at lower pressures. In the stability field of CaCO3-II, the dislocation density exhibits a more complex behavior. Furthermore, at a given strain and strain rate, the dislocation density increases and the CSD size decreases with increasing pressure within the stability fields of either calcite or of the high-pressure polymorphs. There is, however, a jump from high dislocation densities and small CSDs in the upper pressure region of the calcite stability field to lower dislocation densities and larger CSDs in the low-pressure region of the CaCO3-II stability field. This jump is more pronounced at higher temperatures and less so at room temperature. The pressure influence on the deformation-induced evolution of dislocation densities implies that pressure variations may change the rheology of carbonate rocks. In particular, a weakening is expected to occur at the transition from the calcite to the CaCO3-II stability field, if aragonite does not form.

Phase transitions in MgSiO3 at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Ono, S.

2017-12-01

As olivine, pyroxene and garnet are major minerals in the upper mantle, understanding the dynamics and evolution of the mantle requires knowledge of MgSiO3, which is an end-member of pyroxene. Therefore, phase relations in MgSiO3 have been repeatedly investigated by a number of authors. However, the transition sequence of the MgSiO3 mineral remains as yet unconfirmed. The discrepancy among researchers is likely due to the accuracy of phase boundary determinations related with the stability field of two phases, wadsleyite + stishovite or ringwoodite + stishovite.High-pressure experiments were carried out using multi-anvil high-pressure apparatus installed at the synchrotron facilities of KEK and SPring-8 in Japan. Experimental details were described elsewhere [e.g., 1,2]. A mixture of the powdered MgSiO3 and gold was used. Experimental pressures were determined from the unit cell volumes of gold. All recovered samples were investigated by an electron microprobe analyzer to identify the stable phase in each experimental run.Experimental runs were performed at pressures between 15 and 21 GPa. Two types of recovered samples, single (MgSiO3) and two phases (Mg2SiO4 + SiO2), were confirmed. The single phase was high-pressure clinoenstatite or akimotoite, and two phases were wadsleyite + stishovite or ringwoodite + stishovite. According to experimental data, two reaction boundaries were determined. The reaction boundary between high-pressure clinoenstatite and wadsleyite + stishovite has a positive dP/dT gradient, 0.0064 GPa/K [3]. In contrast, the reaction boundary between ringwoodite + stishovite and akimotoite has a negative dP/dT gradient, -0.0012 GPa/K [4]. This study indicates that the stability field of wadsleyite + stishovite expands to a low temperature region corresponding to the P-T path in the subducted slab. Moreover, a triple point of wadsleyite + stishovite-ringwoodite + stishovite-akimotoite is located at a temperature slightly lower than the geotherm. These experimental results can reconcile the inconsistency recorded between previous studies regarding the phase relation in MgSiO3.[1] Ono et al., Phys. Chem. Minerals, 40, 811-816 (2013)[2] Ono et al., Phys. Earth Planet. Inter., 264, 1-6 (2017)[3] Ono et al., (under review)[4] Ono et al., Phys. Chem. Minerals, 44, 425-430 (2017)

Prediction of new high pressure structural sequence in thorium carbide: A first principles study

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

Sahoo, B. D., E-mail: bdsahoo@barc.gov.in; Joshi, K. D.; Gupta, Satish C.

2015-05-14

In the present work, we report the detailed electronic band structure calculations on thorium monocarbide. The comparison of enthalpies, derived for various phases using evolutionary structure search method in conjunction with first principles total energy calculations at several hydrostatic compressions, yielded a high pressure structural sequence of NaCl type (B1) → Pnma → Cmcm → CsCl type (B2) at hydrostatic pressures of ∼19 GPa, 36 GPa, and 200 GPa, respectively. However, the two high pressure experimental studies by Gerward et al. [J. Appl. Crystallogr. 19, 308 (1986); J. Less-Common Met. 161, L11 (1990)] one up to 36 GPa and other up to 50 GPa, onmore » substoichiometric thorium carbide samples with carbon deficiency of ∼20%, do not report any structural transition. The discrepancy between theory and experiment could be due to the non-stoichiometry of thorium carbide samples used in the experiment. Further, in order to substantiate the results of our static lattice calculations, we have determined the phonon dispersion relations for these structures from lattice dynamic calculations. The theoretically calculated phonon spectrum reveal that the B1 phase fails dynamically at ∼33.8 GPa whereas the Pnma phase appears as dynamically stable structure around the B1 to Pnma transition pressure. Similarly, the Cmcm structure also displays dynamic stability in the regime of its structural stability. The B2 phase becomes dynamically stable much below the Cmcm to B2 transition pressure. Additionally, we have derived various thermophysical properties such as zero pressure equilibrium volume, bulk modulus, its pressure derivative, Debye temperature, thermal expansion coefficient and Gruneisen parameter at 300 K and compared these with available experimental data. Further, the behavior of zero pressure bulk modulus, heat capacity and Helmholtz free energy has been examined as a function temperature and compared with the experimental data of Danan [J. Nucl. Mater. 57, 280 (1975)].« less

Experimental and analytical study of stability characteristics of natural circulation boiling water reactors during startup transient

NASA Astrophysics Data System (ADS)

Woo, Kyoungsuk

Two-phase natural circulation loops are unstable at low pressure operating conditions. New reactor design relying on natural circulation for both normal and abnormal core cooling is susceptible to different types of flow instabilities. In contrast to forced circulation boiling water reactor (BWR), natural circulation BWR is started up without recirculation pumps. The tall chimney placed on the top of the core makes the system susceptible to flashing during low pressure start-up. In addition, the considerable saturation temperature variation may induce complicated dynamic behavior driven by thermal non-equilibrium between the liquid and steam. The thermal-hydraulic problems in two-phase natural circulation systems at low pressure and low power conditions are investigated through experimental methods. Fuel heat conduction, neutron kinetics, flow kinematics, energetics and dynamics that govern the flow behavior at low pressure, are formulated. A dimensionless analysis is introduced to obtain governing dimensionless groups which are groundwork of the system scaling. Based on the robust scaling method and start-up procedures of a typical natural circulation BWR, the simulation strategies for the transient with and without void reactivity feedback is developed. Three different heat-up rates are applied to the transient simulations to study characteristics of the stability during the start-up. Reducing heat-up rate leads to increase in the period of flashing-induced density wave oscillation and decrease in the system pressurization rate. However, reducing the heat-up rate is unable to completely prevent flashing-induced oscillations. Five characteristic regions of stability are discovered at low pressure conditions. They are stable single-phase, flashing near the separator, intermittent oscillation, sinusoidal oscillation and low subcooling stable regions. Stability maps were acquired for system pressures ranging 100 kPa to 400 kPa. According to experimental investigation, the flow becomes stable below a certain heat flux regardless of the inlet subcooling at the core and system pressure. At higher heat flux, unstable phenomena were indentified within a certain range of inlet subcooling. The unstable region diminishes as the system pressure increases. In natural circulation BWRs, the significant gravitational pressure drop over the tall chimney section induces a Type-I instability. The Type-I instability becomes especially important during low power and pressure conditions during reactor start-up. Under these circumstances the effect of pressure variations on the saturation enthalpy becomes significant. An experimental study shows that the flashing phenomenon in the adiabatic chimney section is dominant during the start-up of a natural circulation BWR. Since flashing occurs outside the core, nuclear feedback effects on the stability are small. Furthermore, the thermal-hydraulic oscillation period is much longer than power fluctuation period caused by void reactivity feedback. In the natural circulation system increasing the inlet restriction reduces the natural circulation flow rate, shifting the unstable region to higher inlet subcooling.

Pressure effect on the structural, phonon, elastic and thermodynamic properties of L12 phase RH3TA: First-principles calculations

NASA Astrophysics Data System (ADS)

Wang, Leini; Jian, Zhang; Ning, Wei

2018-06-01

The phonon, elastic and thermodynamic properties of L12 phase Rh3Ta have been investigated by the density functional theory (DFT) approach combined with the quasi-harmonic approximation model. The results of the phonon band structure show that L12 phase Rh3Ta possesses dynamical stability in the pressure range from 0-80 GPa due to the absence of imaginary frequencies. The pressure dependences with the elastic constants Cij, shear modulus G, bulk modulus B, Young’s modulus Y, Poisson’s ratio and B/G ratio have been analyzed. The results of the elastic properties studies show that L12 phase Rh3Ta compound is mechanically stable and possesses a higher hardness, improved ductility and plasticity under higher pressures. The pressure and temperature relationship of the thermodynamic properties, such as the Debye temperature ΘD, heat capacity Cp, thermal expansion coefficient α and the Grüneisen parameter γ are predicted by the quasi-harmonic Debye model in a wide pressure (0-80 GPa) and temperature (0-750 K) ranges.

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

High-pressure phase transition and phase diagram of gallium arsenide

NASA Astrophysics Data System (ADS)

Besson, J. M.; Itié, J. P.; Polian, A.; Weill, G.; Mansot, J. L.; Gonzalez, J.

1991-09-01

Under hydrostatic pressure, cubic GaAs-I undergoes phase transitions to at least two orthorhombic structures. The initial phase transition to GaAs-II has been investigated by optical-transmittance measurements, Raman scattering, and x-ray absorption. The structure of pressurized samples, which are retrieved at ambient, has been studied by x-ray diffraction and high-resolution diffraction microscopy. Various criteria that define the domain of stability of GaAs-I are examined, such as the occurrence of crystalline defects, the local variation in atomic coordination number, or the actual change in crystal structure. These are shown not to occur at the same pressure at 300 K, the latter being observable only several GPa above the actual thermodynamic instability pressure of GaAs-I. Comparison of the evolution of these parameters on increasing and decreasing pressure locates the thermodynamic transition region GaAs-I-->GaAs-II at 12+/-1.5 GPa and at 300 K that is lower than generally reported. The use of thermodynamic relations around the triple point, and of regularities in the properties of isoelectronic and isostructural III-V compounds, yields a phase diagram for GaAs which is consistent with this value.

A Study of the Stability Mechanism of the Dispersed Particle Gel Three-Phase Foam Using the Interfacial Dilational Rheology Method.

PubMed

Yao, Xue; Yi, Ping; Zhao, Guang; Sun, Xin; Dai, Caili

2018-04-28

The dispersed particle gel (DPG) three-phase foam is a novel profile control and flooding system. The stability mechanism of the DPG three-phase foam was studied using an interfacial dilational rheology method. The results show that the elastic modulus of the DPG three-phase foam is up to 14 mN/m, which is much higher than the traditional foam. The increase in interface elasticity produces significantly positive effects on foam stability. Emphasis is given to the influences of frequency, temperature, pressure, and concentration on the viscoelasticity and interfacial adsorption of DPG particles, which change the modules of the foam interface and have a significant effect on foam stability. In addition, the microstructure of the DPG three-phase foam was observed. A viscoelastic shell is formed by the aggregation of the DPG particles on the interface. The irreversible adsorption gives the interface high elasticity and mechanical strength. The electrostatic repulsion between particles increases the spacing between bubbles. The combined effects of these factors give the interface higher mechanical strength, slow down the film drainage, effectively prevent gas permeation, and significantly improve the foam stability.

A Study of the Stability Mechanism of the Dispersed Particle Gel Three-Phase Foam Using the Interfacial Dilational Rheology Method

PubMed Central

Yi, Ping; Zhao, Guang; Sun, Xin; Dai, Caili

2018-01-01

The dispersed particle gel (DPG) three-phase foam is a novel profile control and flooding system. The stability mechanism of the DPG three-phase foam was studied using an interfacial dilational rheology method. The results show that the elastic modulus of the DPG three-phase foam is up to 14 mN/m, which is much higher than the traditional foam. The increase in interface elasticity produces significantly positive effects on foam stability. Emphasis is given to the influences of frequency, temperature, pressure, and concentration on the viscoelasticity and interfacial adsorption of DPG particles, which change the modules of the foam interface and have a significant effect on foam stability. In addition, the microstructure of the DPG three-phase foam was observed. A viscoelastic shell is formed by the aggregation of the DPG particles on the interface. The irreversible adsorption gives the interface high elasticity and mechanical strength. The electrostatic repulsion between particles increases the spacing between bubbles. The combined effects of these factors give the interface higher mechanical strength, slow down the film drainage, effectively prevent gas permeation, and significantly improve the foam stability. PMID:29710805

High-pressure phase transition and elastic behavior of aluminum compound semiconductors

NASA Astrophysics Data System (ADS)

Singh, R. K.; Singh, Sadhna

1992-01-01

A three-body-force-potential approach, developed earlier [Phys. Rev. B 39, 671 (1989)] for III-V compound semiconductors, has been extended to describe the high-pressure phase transition and elastic behavior of the remaining members (AlAs, AlSb, and AlP) of this family. We have obtained a reasonably better agreement between our theoretical (10.2, 6.6, and 18.0 GPa) and experimental (12.0, 8.3, and 14.0-17.0 GPa) results on the phase-transition pressures, respectively, in Al compounds (AlAs, AlSb, and AlP) than those obtained by Chelikowsky (31.0, 10.2, and 45.0 GPa) and by Zhang and Cohen (7.6, 5.6, and 9.3 GPa). The volume collapses and transition heats are also in good agreement with their experimental results available only in AlSb and they are comparable to those obtained by earlier workers. The variations of the second-order elastic constants with pressure have shown systematic trends in all Al compounds similar to those observed in other compounds of zinc-blende structure. The present approach has also succeeded in predicting the relative stability and satisfying the Born stability criterion. The slight disagreements have been ascribed to the exclusion of covalency effects.

High pressure homogenization to improve the stability of casein - hydroxypropyl cellulose aqueous systems.

PubMed

Ye, Ran; Harte, Federico

2014-03-01

The effect of high pressure homogenization on the improvement of the stability hydroxypropyl cellulose (HPC) and micellar casein was investigated. HPC with two molecular weights (80 and 1150 kDa) and micellar casein were mixed in water to a concentration leading to phase separation (0.45% w/v HPC and 3% w/v casein) and immediately subjected to high pressure homogenization ranging from 0 to 300 MPa, in 100 MPa increments. The various dispersions were evaluated for stability, particle size, turbidity, protein content, and viscosity over a period of two weeks and Scanning Transmission Electron Microscopy (STEM) at the end of the storage period. The stability of casein-HPC complexes was enhanced with the increasing homogenization pressure, especially for the complex containing high molecular weight HPC. The apparent particle size of complexes was reduced from ~200nm to ~130nm when using 300 MPa, corresponding to the sharp decrease of absorbance when compared to the non-homogenized controls. High pressure homogenization reduced the viscosity of HPC-casein complexes regardless of the molecular weight of HPC and STEM imagines revealed aggregates consistent with nano-scale protein polysaccharide interactions.

High pressure homogenization to improve the stability of casein - hydroxypropyl cellulose aqueous systems

PubMed Central

Ye, Ran; Harte, Federico

2013-01-01

The effect of high pressure homogenization on the improvement of the stability hydroxypropyl cellulose (HPC) and micellar casein was investigated. HPC with two molecular weights (80 and 1150 kDa) and micellar casein were mixed in water to a concentration leading to phase separation (0.45% w/v HPC and 3% w/v casein) and immediately subjected to high pressure homogenization ranging from 0 to 300 MPa, in 100 MPa increments. The various dispersions were evaluated for stability, particle size, turbidity, protein content, and viscosity over a period of two weeks and Scanning Transmission Electron Microscopy (STEM) at the end of the storage period. The stability of casein-HPC complexes was enhanced with the increasing homogenization pressure, especially for the complex containing high molecular weight HPC. The apparent particle size of complexes was reduced from ~200nm to ~130nm when using 300 MPa, corresponding to the sharp decrease of absorbance when compared to the non-homogenized controls. High pressure homogenization reduced the viscosity of HPC-casein complexes regardless of the molecular weight of HPC and STEM imagines revealed aggregates consistent with nano-scale protein polysaccharide interactions. PMID:24159250

Solid state stability and solubility of triethylenetetramine dihydrochloride.

PubMed

Henriet, Théo; Gana, Inès; Ghaddar, Carine; Barrio, Maria; Cartigny, Yohann; Yagoubi, Najet; Do, Bernard; Tamarit, Josep-Lluis; Rietveld, Ivo B

2016-09-10

The API triethylenetetramine dihydrochloride used as an alternative treatment of Wilson's disease is sensitive to water and it exhibits polymorphism. As this may become an issue for the drug formulation, the physical stability has been studied by differential scanning calorimetry, high-pressure thermal analysis, dynamic vapor sorption, and X-ray diffraction as a function of temperature. In addition, high-pressure liquid chromatography and mass spectrometry have been used to study the purity and chemical stability of the API. A pressure-temperature phase diagram of the pure compound has been constructed and it can be concluded that form II is monotropic in relation to form I, which is the only stable solid. The solubilities of the different solid forms have been determined with the help of a temperature - composition phase diagram. The API is very soluble, at 20° C about 10% of the saturated solution with respect to the dihydrate consists of API and the solubility of the pure form I is twice as high. Moreover, it has been shown that at 20°C, a relative humidity above 40% induces the formation of the dihydrate and at 70% a saturated solution appears. At higher temperatures, the formation of the dihydrate appears at lower relative humidity values. A clear link has been established between the API's chemical stability, its physical stability and the relative humidity in the air. Humidity levels above 40% are detrimental to the quality of the API. Copyright © 2016 Elsevier B.V. All rights reserved.

Surface thermodynamic analysis of fluid confined in a cone and comparison with the sphere-plate and plate-plate geometries.

PubMed

Zargarzadeh, Leila; Elliott, Janet A W

2013-10-22

The behavior of pure fluid confined in a cone is investigated using thermodynamic stability analysis. Four situations are explained on the basis of the initial confined phase (liquid/vapor) and its pressure (above/below the saturation pressure). Thermodynamic stability analysis (a plot of the free energy of the system versus the size of the new potential phase) reveals whether the phase transition is possible and, if so, the number and type (unstable/metastable/stable) of equilibrium states in each of these situations. Moreover we investigated the effect of the equilibrium contact angle and the cone angle (equivalent to the confinement's surface separation distance) on the free energy (potential equilibrium states). The results are then compared to our previous study of pure fluid confined in the gap between a sphere and a flat plate and the gap between two flat plates.1 Confined fluid behavior of the four possible situations (for these three geometries) can be explained in a unified framework under two categories based on only the meniscus shape (concave/convex). For systems with bulk-phase pressure imposed by a reservoir, the stable coexistence of pure liquid and vapor is possible only when the meniscus is concave.

Vapor pressures, thermodynamic stability, and fluorescence properties of three 2,6-alkyl naphthalenes.

PubMed

Santos, Ana Filipa L O M; Oliveira, Juliana A S A; Ribeiro da Silva, Maria D M C; Monte, Manuel J S

2016-03-01

This work reports the experimental determination of relevant thermodynamic properties and the characterization of luminescence properties of the following polycyclic aromatic hydrocarbons (PAHs): 2,6-diethylnaphthalene, 2,6-diisopropylnaphthalene and 2,6-di-tert-butylnaphthalene. The standard (p(o) = 0.1 MPa) molar enthalpies of combustion, ΔcHm(o), of the three compounds were determined using static bomb combustion calorimetry. The vapor pressures of the crystalline phase of 2,6-diisopropylnaphthalene and 2,6-di-tert-butylnaphthalene were measured at different temperatures using the Knudsen effusion method and the vapor pressures of both liquid and crystalline phases of 2,6-diethylnaphthalene were measured by means of a static method. The temperatures and the molar enthalpies of fusion of the three compounds were determined using differential scanning calorimetry. The gas-phase molar heat capacities and absolute entropies of the three 2,6-dialkylnaphthalenes studied were determined computationally. The thermodynamic stability of the compounds in both the crystalline and gaseous phases was evaluated by the determination of the Gibbs energies of formation and compared with the ones reported in the literature for 2,6-dimethylnaphthalene. From fluorescence spectroscopy measurements, the optical properties of the compounds studied and of naphthalene were evaluated in solution and in the solid state. Copyright © 2015 Elsevier Ltd. All rights reserved.

Phase boundary between cubic B1 and rhombohedral structures in (Mg,Fe)O magnesiowüstite determined by in situ X-ray diffraction measurements

NASA Astrophysics Data System (ADS)

Dymshits, Anna M.; Litasov, Konstantin D.; Shatskiy, Anton; Chanyshev, Artem D.; Podborodnikov, Ivan V.; Higo, Yuji

2018-01-01

The phase relations and equation of state of (Mg0.08Fe0.92)O magnesiowüstite (Mw92) have been studied using the Kawai-type high-pressure apparatus coupled with synchrotron radiation. To determine the phase boundary between the NaCl-type cubic (B1) and rhombohedral ( rB1) structures in Mw92, in situ X-ray observations were carried out at pressures of 0-35 GPa and temperatures of 300-1473 K. Au and MgO were used as the internal pressure markers and metallic Fe as oxygen fugacity buffer. The phase boundary between B1 and rB1 structures was described by a linear equation P (GPa) = 1.6 + 0.033 × T (K). The Clapeyron slope (d P/d T) determined in this study is close to that obtained at pressures above 70 GPa but steeper than that obtained for FeO. An addition of MgO to FeO structure expands the stability field of the rB1 phase to lower pressures and higher temperatures. Thus, the rB1 phase may be stabilized with respect to the B1 phase at a lower pressures. The pressure-volume-temperature equation of state of B1-Mw92 was determined up to 30 GPa and 1473 K. Fitting the hydrostatic compression data up to 30 GPa with the Birch-Murnaghan equation of state (EoS) yielded: unit cell volume ( V 0, T0), 79.23 ± 4 Å3; bulk modulus ( K 0, T0), 183 ± 4 GPa; its pressure derivative ( K' T ), 4.1 ± 0.4; (∂ K 0, T /∂ T) = -0.029 ± 0.005 GPa K‒1; a = 3.70 ± 0.27 × 10-5 K-1 and b = 0.47 ± 0.49 × 10-8 K-2, where α0, T = a + bT is the volumetric thermal expansion coefficient. The obtained bulk modulus of Mw92 is very close to the value expected for stoichiometric iron-rich (Mg,Fe)O. This result confirms the idea that the bulk modulus of (Mg,Fe)O is greatly affected by the actual defect structure, caused by either Mg2+ or vacancies.

Phase relations in the Fe-Ni-Cr-S system and the sulfidation of an austenitic stainless steel

NASA Technical Reports Server (NTRS)

Jacob, K. T.; Rao, D. B.; Nelson, H. G.

1977-01-01

The stability fields of various sulfide phases that form on Fe-Cr, Fe-Ni, Ni-Cr and Fe-Cr-Ni alloys were developed as a function of temperature and the partial pressure of sulfur. The calculated stability fields in the ternary system were displayed on plots of log P sub S sub 2 versus the conjugate extensive variable which provides a better framework for following the sulfidation of Fe-Cr-Ni alloys at high temperatures. Experimental and estimated thermodynamic data were used in developing the sulfur potential diagrams. Current models and correlations were employed to estimate the unknown thermodynamic behavior of solid solutions of sulfides and to supplement the incomplete phase diagram data of geophysical literature. These constructed stability field diagrams were in excellent agreement with the sulfide phases and compositions determined during a sulfidation experiment.

Enhanced power factor via the control of structural phase transition in SnSe

PubMed Central

Yu, Hulei; Dai, Shuai; Chen, Yue

2016-01-01

Tin selenide has attracted much research interest due to its unprecedentedly high thermoelectric figure of merit (ZT). For real applications, it is desirable to increase the ZT value in the lower-temperature range, as the peak ZT value currently exists near the melting point. It is shown in this paper that the structural phase transition plays an important role in boosting the ZT value of SnSe in the lower-temperature range, as the Cmcm phase is found to have a much higher power factor than the Pnma phase. Furthermore, hydrostatic pressure is predicted to be extremely effective in tuning the phase transition temperature based on ab-initio molecular dynamic simulations; a remarkable decrease in the phase transition temperature is found when a hydrostatic pressure is applied. Dynamical stabilities are investigated based on phonon calculations, providing deeper insight into the pressure effects. Accurate band structures are obtained using the modified Becke-Johnson correction, allowing reliable prediction of the electrical transport properties. The effects of hydrostatic pressure on the thermal transport properties are also discussed. Hydrostatic pressure is shown to be efficient in manipulating the transport properties via the control of phase transition temperature in SnSe, paving a new path for enhancing its thermoelectric efficiency. PMID:27193260

Evaluation of Next Generation Thermal Stability-Improving Additives for JP-8, Phase 1, Thermal Stability Impact Characterization

DTIC Science & Technology

2012-04-01

time , crystal frequency, temperature, and headspace oxygen concentration. 41 Approved for public release; distribution unlimited. C-4. Fuels: In...at ambient pressure. At this point the heater, which is set at 140 °C, is turned on and computer data acquisition is begun. The run time , crystal frequency

Microfluidic generation of particle-stabilized water-in-water emulsions

NASA Astrophysics Data System (ADS)

Abbasi, Niki; Navi, Maryam; Tsai, Scott

2017-11-01

We present a microfluidic platform that generates particle-stabilized water-in-water emulsions, using an aqueous two-phase system (ATPS) of polyethylene glycol (PEG) and Dextran (DEX). DEX droplets are generated passively at a flow focusing junction, in a continuous phase of PEG and carboxylated particles, using weak hydrostatic pressure to drive the flow. As DEX droplets travel inside the microfluidic device, carboxylated particles partition to the interface of the droplets. The number of particles partitioning to the interface of droplets increases as the droplets migrate downstream in the microchannel. As a result, the DEX droplets become stabilized against coalescence. We study the coverage and stability of the DEX droplets further downstream inside a reservoir, by changing the carboxylated particle concentration and the particle size. We anticipate that particle-stabilized water-in-water emulsions may have important biotechnological applications, due to their intrinsic biocompatibility compared to traditional particle-stabilized water-in-oil emulsions, for example for cell encapsulation.

New Stability Field of Jeffbenite (ex-"TAPP"): Possibility of Super-Deep Origin

NASA Astrophysics Data System (ADS)

Anzolini, C.; Drewitt, J.; Lord, O. T.; Walter, M. J.; Nestola, F.

2016-12-01

Jeffbenite is a new tetragonal phase with garnet-like stoichiometry (Nestola et al., 2016) previously referred to as TAPP (Tetragonal Almandine-Pyrope Phase), which is found exclusively in nature as inclusions in super-deep diamonds and may provide key information about their depth of formation. Nevertheless, whether jeffbenite forms as a primary phase in the transition zone (TZ) or in the lower mantle (LM), or is the product of retrogression from high-pressure mantle phases is still controversial. At present two possibilities are proposed for its formation: 1) entrapment as a primary mineral by diamond in the upper mantle at pressures up to 13 GPa (Armstrong & Walter, 2012); 2) retrograde formation from a bridgmanite or a majoritic garnet below 13 GPa (Armstrong & Walter, 2012; Brenker et al., 2002; Harte & Hudson, 2013). The only previously experimentally determined stability field for jeffbenite is that of Armstrong & Walter (2012), which provides a maximum pressure for jeffbenite stability of 13 GPa ( 390 km) at 1700 K. This suggested that jeffbenite is a sub-lithospheric mineral, but ruled out direct incorporation of jeffbenite into diamond at the TZ-LM boundary. These results were obtained on a Ti-rich jeffbenite, which is usually found as part of composite inclusions, and not on a Ti-free jeffbenite, which occurs as single-phase inclusions in diamonds. We therefore performed new laser heated diamond-anvil cell experiments from 5 to 30 GPa on a Ti-free jeffbenite, in order to determine the role that TiO2 plays in its stability field and to determine if jeffbenite can be directly incorporated into diamond in the TZ or LM. Our preliminary results indicate that the absence of TiO2 extends the stability field of jeffbenite to higher pressures than previously determined. This work was supported by Fondazione CaRiPaRo, NERC Grant NE/M000419/1 to MJW, NERC Fellowship Grant NE/J018945/1 to OTL and ERC-2012-StG 307322 to FN. Armstrong, L.S. & Walter, M.J. (2012) Eur J Mineral, 24:587-597. Brenker, F.E., Stachel, T., Harris, J.W. (2002) Earth Planet Sci Lett, 198:1-9. Harte & Hudson (2013) Proceedings of 10th International Kimberlite Conference, 235-253. Nestola, F., Burnham, A.D., Peruzzo, L., Tauro, L., Alvaro, M., Walter, M.J., Gunter, M., Anzolini, C., Kohn, S.C. (2016) Mineral Mag, DOI: 10.1180/minmag.2016.080.059

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

Ukita, Masaya, E-mail: uktia.masaya@f.mbox.nagoya-u.ac.jp; Toyoura, Kazuaki; Nakamura, Atsutomo

The thermodynamic phase stabilities of calcite and aragonite have been investigated from lattice vibrational analyses based on first-principles calculations. Different pressure dependences in phonon feature were found between the two polymorphs, suggesting different physical origins of the pressure-induced phase transitions. In the most stable phase in calcite (calcite I), an imaginary phonon mode consisting of rotation of CO{sub 3} ions with slight displacement of Ca ions appears at the F point in the Brillouin zone above 0.8 GPa. Such a soft mode means that external pressure induces the lattice-dynamical instability of calcite I leading to the phase transition to calcite II.more » On the other hand, the origin of the phase transition in aragonite is not due to such a lattice-dynamical instability. The estimated thermodynamical properties indicate that a first-order phase transition occurs between aragonite and post-aragonite at 34.7 GPa, coinciding with the reported experimental value at room temperature (35 GPa).« less

Experimental and Theoretical Investigations on d and f Electron Systems under High Pressure

NASA Astrophysics Data System (ADS)

Gupta, Satish C.; Joshi, K. D.; Banerjee, S.

2008-07-01

The pressure-induced electron transfer from sp to d band in transition elements, and spd to f band in the light actinides significantly influences the stability of crystal structures in these metals. Although α → ω → β phase transition with increasing pressure in group IV transition elements is well documented, the β → ω transition under pressure has not been reported until recently. Our experimental study on the β-stabilized Zr-20Nb alloy reveals that it transforms to ω phase on shock compression, whereas this transition is not seen in a hydrostatic pressure condition. The platelike morphology of ω formed under shock compression is in contrast to the fine particle morphology seen in this system under thermal treatment, which clearly indicates that the mechanism of the β → ω transformation under shock treatment involves a large shear component. In this article, we have analyzed why the ω → β transition pressures in Ti, Zr, and Hf do not follow the trend implied by the principle of corresponding states. Our analysis shows that the ω → β transition depends on how the increased d population caused by the sp → d transfer of electron is distributed among various d substates. In Th, we have analyzed the role of 5f electrons in determining the mechanical stability of fcc and bct structures under hydrostatic compressions. Our analysis shows that the fcc to bct transition in this metal, which has been reported by high-pressure experiments, occurs because of softening of the tetragonal shear modulus C' = ( C 11 - C 12)/2 under compression. From the total energy calculated as a function of specific volume, we have determined the 0 K isotherm, which is then used to deduce the shock Hugoniot. The theoretical Hugoniot compares well with the experimental data.

Thermal stability of simple tetragonal and hexagonal diamond germanium

DOE PAGES

Huston, Larissa Q.; Johnson, Brett C.; Haberl, Bianca; ...

2017-11-07

Here, exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursormore » materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3 ± 0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44 ± 0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications.« less

Thermal stability of simple tetragonal and hexagonal diamond germanium

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

Huston, Larissa Q.; Johnson, Brett C.; Haberl, Bianca

Here, exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursormore » materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3 ± 0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44 ± 0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications.« less

Petalite under pressure: Elastic behavior and phase stability

DOE PAGES

Ross, Nancy L.; Zhao, Jing; Slebodnick, Carla; ...

2015-04-01

The lithium aluminosilicate mineral petalite (LiAlSi 4O 10) has been studied using high-pressure single-crystal X-ray diffraction (HP-XRD) up to 5 GPa. Petalite undergoes two pressure-induced first-order phase transitions, never reported in the literature, at ca. 1.5 and 2.5 GPa. The first of these transforms the low-pressure α-phase of petalite (P2/c) to an intermediate β-phase that then fully converts to the high-pressure β-phase at ca. 2.5 GPa. The α→β transition is isomorphic and is associated with a commensurate modulation that triples the unit cell volume. Analysis of the HP-XRD data show that although the fundamental features of the petalite structure aremore » retained through this transition, there are subtle alterations in the internal structure of the silicate double-layers in the β-phase relative to the α-phase. Measurement of the unit cell parameters of petalite as a function of pressure, and fitting of the data with 3rd order Birch-Murnaghan equations of state, has provided revised elastic constants for petalite. The bulk moduli of the α and β-phases are 49(1) and 35(3) GPa, respectively. These values indicate that the compressibility of the- phase of petalite lies between the alkali feldpsars and alkali feldspathoids, whereas the β-phase has a compressibility more comparable with layered silicates. Structure analysis has shown that the compression of the -phase is facilitated by the rigid body movement of the Si 2O 7 units from which the silicate double-layers are constructed.« less

Anisotropy of the ferromagnetic L10 phase in the Mn-Al-C alloys induced by high-pressure spark plasma sintering

NASA Astrophysics Data System (ADS)

Tyrman, Muriel; Ahmim, Smail; Pasko, Alexandre; Etgens, Victor; Mazaleyrat, Frédéric; Quetel-Weben, Simon; Perrière, Loïc; Guillot, Ivan

2018-05-01

The metastable τ-phase of MnAl equi-atomic compound belongs to a family of ferromagnetic alloys with L10 crystal structure. Stabilization of the phase by adding 2 at. % using manganese carbide (Mn23C6) enhances the magnetization in relation with the increase in lattice volume. It is thus a promising candidate for rare-earth-free permanent magnets. Coercivity of Mn-Al-C alloys being still weak, there is an interest to see to which extend sintering/transformation of the ɛ-phase by Spark Plasma Sintering (SPS) can increase the coercivity and the anisotropy. The structural and the magnetic properties were studied for samples sintered at 550 °C under uniaxial pressure of 100, 200, 300 and 400 MPa. Coercivity, remanence and anistotropy appears with the sintering pressure. The high pressure applied while sintering produces preferential orientation of the flake-shaped grains which influences the remanence.

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

Alvarado, Andrew; Attapattu, Jeevake; Zhang, Yi

Zinc oxide (ZnO) undergoes a pressure-induced structural transition from its normal ambient-pressure wurtzite (WZ) phase to a rocksalt (RS) phase around 10 GPa. A recent experiment shows that the high-pressure RS ZnO phase can be recovered and stabilized at ambient conditions, which raises exciting prospects of expanding the range of properties of ZnO. For a fundamental understanding of the RS ZnO phase, we have performed first-principles calculations to determine its electronic, phonon, and thermodynamic properties at high (20 GPa) and ambient (0 GPa) pressure. Furthermore, we have calculated its electrical and thermal transport properties, which allow an evaluation of itsmore » thermoelectric figure of merit ZT at different temperature and doping levels. Our calculations show that the ambient-pressure RS ZnO phase can reach ZT values of 0.25 to 0.3 under both n-type and p-type doping in a large temperature range of 400 K to 800 K, which is considerably lower than the temperature range of 1400 K to 1600 K where WZ ZnO reaches similar ZT values. Lastly, these results establish RS ZnO as a promising material for thermoelectric devices designed to operate at temperatures desirable for many heat recovery applications.« less

Stability hierarchy between Piracetam forms I, II, and III from experimental pressure-temperature diagrams and topological inferences.

PubMed

Toscani, Siro; Céolin, René; Minassian, Léon Ter; Barrio, Maria; Veglio, Nestor; Tamarit, Josep-Lluis; Louër, Daniel; Rietveld, Ivo B

2016-01-30

The trimorphism of the active pharmaceutical ingredient piracetam is a famous case of polymorphism that has been frequently revisited by many researchers. The phase relationships between forms I, II, and III were ambiguous because they seemed to depend on the heating rate of the DSC and on the history of the samples or they have not been observed at all (equilibrium II-III). In the present paper, piezo-thermal analysis and high-pressure differential thermal analysis have been used to elucidate the positions of the different solid-solid and solid-liquid equilibria. The phase diagram, involving the three solid phases, the liquid phase and the vapor phase, has been constructed. It has been shown that form III is the high-pressure, low-temperature form and the stable form at room temperature. Form II is stable under intermediary conditions and form I is the low pressure, high temperature form, which possesses a stable melting point. The present paper demonstrates the strength of the topological approach based on the Clapeyron equation and the alternation rule when combined with high-pressure measurements. Copyright © 2015 Elsevier B.V. All rights reserved.

High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

NASA Astrophysics Data System (ADS)

Bishop, M. M.; Chellappa, R. S.; Liu, Z.; Preston, D. N.; Sandstrom, M. M.; Dattelbaum, D. M.; Vohra, Y. K.; Velisavljevic, N.

2014-05-01

1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and α → β (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → (~210 °C), with the δ phase being stable up to ~251 °C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 °C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa.

Differential Stability of Dimeric and Monomeric Cytochrome c Oxidase Exposed to Elevated Hydrostatic Pressure†

PubMed Central

Staničová, Jana; Sedlák, Erik; Musatov, Andrej; Robinson, Neal C.

2007-01-01

Detergent-solubilized dimeric and monomeric cytochrome c oxidase (CcO) have significantly different quaternary stability when exposed to 2−3 kbar of hydrostatic pressure. Dimeric, dodecyl maltoside-solubilized cytochrome c oxidase is very resistant to elevated hydrostatic pressure with almost no perturbation of its quaternary structure or functional activity after release of pressure. In contrast to the stability of dimeric CcO, 3 kbar of hydrostatic pressure triggers multiple structural and functional alterations within monomeric cytochrome c oxidase. The perturbations are either irreversible or slowly reversible since they persist after the release of high pressure. Therefore, standard biochemical analytical procedures could be used to quantify the pressure-induced changes after the release of hydrostatic pressure. The electron transport activity of monomeric cytochrome c oxidase decreases by as much as 60% after exposure to 3 kbar of hydrostatic pressure. The irreversible loss of activity occurs in a time- and pressure-dependent manner. Coincident with the activity loss is a sequential dissociation of four subunits as detected by sedimentation velocity, high-performance ion-exchange chromatography, and reversed-phase and SDS–PAGE subunit analysis. Subunits VIa and VIb are the first to dissociate followed by subunits III and VIIa. Removal of subunits VIa and VIb prior to pressurization makes the resulting 11-subunit form of CcO even more sensitive to elevated hydrostatic pressure than monomeric CcO containing all 13 subunits. However, dimeric CcO, in which the association of VIa and VIb is stabilized, is not susceptible to pressure-induced inactivation. We conclude that dissociation of subunit III and/or VIIa must be responsible for pressure-induced inactivation of CcO since VIa and VIb can be removed from monomeric CcO without significant activity loss. These results are the first to clearly demonstrate an important structural role for the dimeric form of cytochrome c oxidase, i.e., stabilization of its quaternary structure. PMID:17530783

High-pressure phase relations and thermodynamic properties of CaAl 4Si 2O 11 CAS phase

NASA Astrophysics Data System (ADS)

Akaogi, M.; Haraguchi, M.; Yaguchi, M.; Kojitani, H.

2009-03-01

Phase relations in CaAl4Si2O11 were examined at 12-23 GPa and 1000-1800 °C by multianvil experiments. A three-phase mixture of grossular, kyanite and corundum is stable below about 13 GPa at 1000-1800 °C. At higher pressure and at temperature below about 1200 °C, a mixture of grossular, stishovite and corundum is stable, indicating the decomposition of kyanite. Above about 1200 °C, CaAl4Si2O11 CAS phase is stable at pressure higher than about 13 GPa. The triple point is placed at 14.7 GPa and 1280 °C. The equilibrium boundary of formation of CAS phase from the mixture of grossular, kyanite and corundum has a small negative slope, and that from the mixture of grossular, stishovite and corundum has a strongly negative slope, while the decomposition boundary of kyanite has a small positive slope. Enthalpies of the transitions were measured by high-temperature drop-solution calorimetry. The enthalpy of formation of CaAl4Si2O11 CAS phase from the mixture of grossular, kyanite and corundum was 139.5 ± 15.6 kJ/mol, and that from the mixture of grossular, stishovite and corundum was 94.2 ± 15.4 kJ/mol. The transition boundaries calculated using the measured enthalpy data were consistent with those determined by the high-pressure experiments. The boundaries in this study are placed about 3 GPa higher in pressure and about 200 °C lower in temperature than those by Zhai and Ito [Zhai, S., Ito, E., 2008. Phase relations of CaAl4Si2O11 at high-pressure and high-temperature with implications for subducted continental crust into the deep mantle. Phys. Earth Planet. Inter. 167, 161-167]. Combining the thermodynamic data measured in this study with those in the literature, dissociation boundary of CAS phase into a mixture of Ca-perovskite, corundum and stishovite and that of grossular into Ca-perovskite plus corundum were calculated to further constrain the stability field of CAS phase. The result suggests that the stability of CAS phase would be limited at the bottom of transition zone and top of the lower mantle, when sediments are subducted into the deep mantle. It is also suggested that CAS phase may be stable at the depth of the upper part of the lower mantle, when partial melting of basalt occurs at the depth.

Structural phase transitions in Bi2Se3 under high pressure

PubMed Central

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

2015-01-01

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. PMID:26522818

Structural phase transitions in Bi 2Se 3 under high pressure

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

Yu, Zhenhai; Gu, Genda; Wang, Lin

2015-11-02

Raman spectroscopy and angle dispersive X-ray diffraction (XRD) experiments of bismuth selenide (Bi 2Se 3) 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 Bi 2Se 3 crystallizes into body-centered tetragonal structures rather than the recently reported disordered body-centered cubic (BCC) phase. Furthermore, first principles theoretical calculationsmore » favor the viewpoint that the I4/mmm phase Bi 2Se 3 can be stabilized under high pressure (>30 GPa). Remarkably, the Raman spectra of Bi 2Se 3 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 Bi 2Se 3 may explain why Bi 2Se 3 shows different structural behavior than isocompounds Bi 2Te 3 and Sb 2Te 3.« less

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

Halevy, I.; Zamir, G; Winterrose, M

The phase stability of a commercial purity (Ti-CP), high purity (Ti-HP) and Ti-6Al-4V alloy were investigated in a diamond anvil cell up to 32 GPa and 298 K using a polychromatic X-ray beam. The Ti-CP and Ti-HP shown the same HCP (c/a {approx} 0.632) to Hexagonal (c/a {approx} 1.63) non reversible martensitic transition at about 9 GPa. The as received Ti-6Al-4V shows a very low relative volume fraction {beta}-Ti/{alpha}-Ti. No phase changes were observed in the Ti-6Al-4V alloy in the pressure range of this study. The {alpha} phase of the Ti-6Al-4V shows monotonic volume cell pressure dependence. This volume changemore » is reversible and non-hysteretic. The cell of the a phase recovered its original volume when the pressure was released.« less

The phase diagrams of KCaF3 and NaMgF3 by ab initio simulations

NASA Astrophysics Data System (ADS)

Jakymiw, Clément; Vočadlo, Lidunka; Dobson, David P.; Bailey, Edward; Thomson, Andrew R.; Brodholt, John P.; Wood, Ian G.; Lindsay-Scott, Alex

2018-04-01

ABF3 compounds have been found to make valuable low-pressure analogues for high-pressure silicate phases that are present in the Earth's deep interior and that may also occur in the interiors of exoplanets. The phase diagrams of two of these materials, KCaF3 and NaMgF3, have been investigated in detail by static ab initio computer simulations based on density functional theory. Six ABF3 polymorphs were considered, as follows: the orthorhombic perovskite structure (GdFeO3-type; space group Pbnm); the orthorhombic CaIrO3 structure ( Cmcm; commonly referred to as the "post-perovskite" structure); the orthorhombic Sb2S3 and La2S3 structures (both Pmcn); the hexagonal structure previously suggested in computer simulations of NaMgF3 ( P63/ mmc); the monoclinic structure found to be intermediate between the perovskite and CaIrO3 structures in CaRhO3 ( P21/ m). Volumetric and axial equations of state of all phases considered are presented. For KCaF3, as expected, the perovskite phase is shown to be the most thermodynamically stable at atmospheric pressure. With increasing pressure, the relative stability of the KCaF3 phases then follows the sequence: perovskite → La2S3 structure → Sb2S3 structure → P63/ mmc structure; the CaIrO3 structure is never the most stable form. Above about 2.6 GPa, however, none of the KCaF3 polymorphs are stable with respect to dissociation into KF and CaF2. The possibility that high-pressure KCaF3 polymorphs might exist metastably at 300 K, or might be stabilised by chemical substitution so as to occur within the standard operating range of a multi-anvil press, is briefly discussed. For NaMgF3, the transitions to the high-pressure phases occur at pressures outside the normal range of a multi-anvil press. Two different sequences of transitions had previously been suggested from computer simulations. With increasing pressure, we find that the relative stability of the NaMgF3 phases follows the sequence: perovskite → CaIrO3 structure → Sb2S3 structure → P63/ mmc structure. However, only the perovskite and CaIrO3 structures are stable with respect to dissociation into NaF and MgF2.

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.

The phase diagram of ammonium nitrate.

PubMed

Chellappa, Raja S; Dattelbaum, Dana M; Velisavljevic, Nenad; Sheffield, Stephen

2012-08-14

The pressure-temperature (P-T) phase diagram of ammonium nitrate (AN) [NH(4)NO(3)] has been determined using synchrotron x-ray diffraction (XRD) and Raman spectroscopy measurements. Phase boundaries were established by characterizing phase transitions to the high temperature polymorphs during multiple P-T measurements using both XRD and Raman spectroscopy measurements. At room temperature, the ambient pressure orthorhombic (Pmmn) AN-IV phase was stable up to 45 GPa and no phase transitions were observed. AN-IV phase was also observed to be stable in a large P-T phase space. The phase boundaries are steep with a small phase stability regime for high temperature phases. A P-V-T equation of state based on a high temperature Birch-Murnaghan formalism was obtained by simultaneously fitting the P-V isotherms at 298, 325, 446, and 467 K, thermal expansion data at 1 bar, and volumes from P-T ramping experiments. Anomalous thermal expansion behavior of AN was observed at high pressure with a modest negative thermal expansion in the 3-11 GPa range for temperatures up to 467 K. The role of vibrational anharmonicity in this anomalous thermal expansion behavior has been established using high P-T Raman spectroscopy.

The phase diagram of ammonium nitrate

NASA Astrophysics Data System (ADS)

Chellappa, Raja S.; Dattelbaum, Dana M.; Velisavljevic, Nenad; Sheffield, Stephen

2012-08-01

The pressure-temperature (P-T) phase diagram of ammonium nitrate (AN) [NH4NO3] has been determined using synchrotron x-ray diffraction (XRD) and Raman spectroscopy measurements. Phase boundaries were established by characterizing phase transitions to the high temperature polymorphs during multiple P-T measurements using both XRD and Raman spectroscopy measurements. At room temperature, the ambient pressure orthorhombic (Pmmn) AN-IV phase was stable up to 45 GPa and no phase transitions were observed. AN-IV phase was also observed to be stable in a large P-T phase space. The phase boundaries are steep with a small phase stability regime for high temperature phases. A P-V-T equation of state based on a high temperature Birch-Murnaghan formalism was obtained by simultaneously fitting the P-V isotherms at 298, 325, 446, and 467 K, thermal expansion data at 1 bar, and volumes from P-T ramping experiments. Anomalous thermal expansion behavior of AN was observed at high pressure with a modest negative thermal expansion in the 3-11 GPa range for temperatures up to 467 K. The role of vibrational anharmonicity in this anomalous thermal expansion behavior has been established using high P-T Raman spectroscopy.

Quasi-dynamic pressure and temperature initiated β<-->δ solid phase transitions in HMX

NASA Astrophysics Data System (ADS)

Zaug, Joseph M.; Farber, Daniel L.; Craig, Ian M.; Blosch, Laura L.; Shuh, David K.; Hansen, Donald W.; Aracne-Ruddle, Chantel M.

2000-04-01

The phase transformation of β-HMX (>0.5% RDX) to δ phase has been studied for over twenty years and more recently with an high-contrast optical second harmonic generation technique. Shock studies of the plastic binder composites of HMX have indicated that the transition is perhaps irreversible, a result that concurs with the static pressure results published by F. Goetz et al. [1] in 1978. However, the stability field favors the β polymorph over δ as pressure is increased (up to 5.4 GPa) along any thermodynamically reasonable isotherm. In this experiment, strict control of pressure and temperature is maintained while x-ray and optical diagnostics are applied to monitor the conformational dynamics of HMX. Unlike the temperature induced β→δ transition, the pressure induced is heterogeneous in nature. The 1 bar 25 °C δ→β transition is not immediate, occuring over tens of hours. Transition points and kinetics are path dependent and consequently this paper describes our work in progress.

Development of a Predictive Model for the Stabilizer Concentration Estimation in Microreservoir Transdermal Drug Delivery Systems Using Lipophilic Pressure-Sensitive Adhesives as Matrix/Carrier.

PubMed

Chenevas-Paule, Clémence; Wolff, Hans-Michael; Ashton, Mark; Schubert, Martin; Dodou, Kalliopi

2017-05-01

Microreservoir-type transdermal drug delivery systems (MTDDS) can prevent drug crystallization; however, no current predictive model considers the impact of drug load and hydration on their physical stability. We investigated MTDDS films containing polyvinylpyrrolidone (PVP) as polymeric drug stabilizer in lipophilic pressure-sensitive adhesive (silicone). Medicated and unmedicated silicone films with different molar N-vinylpyrrolidone:drug ratios were prepared and characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, scanning electron microscopy, microscopy, dynamic vapor sorption (DVS), and stability testing for 4 months at different storage conditions. Homogeneously distributed drug-PVP associates were observed when nonaqueous emulsions, containing drug-PVP (inner phase) and silicone adhesive (outer phase), were dried to films. DVS data were essential to predict physical stability at different humidities. A predictive thermodynamic model was developed based on drug-polymer hydrogen-bonding interactions, using the Hoffman equation, to estimate the drug-PVP ratio needed to obtain stable MTDDS and to evaluate the impact of humidity on their physical stability. This new approach considers the impact of polymorphism on drug solubility by using easily accessible experimental data (T m and DVS) and avoids uncertainties associated with the solubility parameter approach. In conclusion, a good fit of predicted and experimental data was observed. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

The stability of a crystal with diamond structure for patchy particles with tetrahedral symmetry.

PubMed

Noya, Eva G; Vega, Carlos; Doye, Jonathan P K; Louis, Ard A

2010-06-21

The phase diagram of model anisotropic particles with four attractive patches in a tetrahedral arrangement has been computed at two different values of the range of the potential, with the aim of investigating the conditions under which a diamond crystal can be formed. We find that the diamond phase is never stable for our longer-ranged potential. At low temperatures and pressures, the fluid freezes into a body-centered-cubic solid that can be viewed as two interpenetrating diamond lattices with a weak interaction between the two sublattices. Upon compression, an orientationally ordered face-centered-cubic crystal becomes more stable than the body-centered-cubic crystal, and at higher temperatures, a plastic face-centered-cubic phase is stabilized by the increased entropy due to orientational disorder. A similar phase diagram is found for the shorter-ranged potential, but at low temperatures and pressures, we also find a region over which the diamond phase is thermodynamically favored over the body-centered-cubic phase. The higher vibrational entropy of the diamond structure with respect to the body-centered-cubic solid explains why it is stable even though the enthalpy of the latter phase is lower. Some preliminary studies on the growth of the diamond structure starting from a crystal seed were performed. Even though the diamond phase is never thermodynamically stable for the longer-ranged model, direct coexistence simulations of the interface between the fluid and the body-centered-cubic crystal and between the fluid and the diamond crystal show that at sufficiently low pressures, it is quite probable that in both cases the solid grows into a diamond crystal, albeit involving some defects. These results highlight the importance of kinetic effects in the formation of diamond crystals in systems of patchy particles.

Polymorphism and thermodynamic ground state of silver fulminate studied from van der Waals density functional calculations

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

Yedukondalu, N.; Vaitheeswaran, G., E-mail: gvsp@uohyd.ernet.in

2014-06-14

Silver fulminate (AgCNO) is a primary explosive, which exists in two polymorphic phases, namely, orthorhombic (Cmcm) and trigonal (R3{sup ¯}) forms at ambient conditions. In the present study, we have investigated the effect of pressure and temperature on relative phase stability of the polymorphs using planewave pseudopotential approaches based on Density Functional Theory (DFT). van der Waals interactions play a significant role in predicting the phase stability and they can be effectively captured by semi-empirical dispersion correction methods in contrast to standard DFT functionals. Based on our total energy calculations using DFT-D2 method, the Cmcm structure is found to bemore » the preferred thermodynamic equilibrium phase under studied pressure and temperature range. Hitherto Cmcm and R3{sup ¯} phases denoted as α- and β-forms of AgCNO, respectively. Also a pressure induced polymorphic phase transition is seen using DFT functionals and the same was not observed with DFT-D2 method. The equation of state and compressibility of both polymorphic phases were investigated. Electronic structure and optical properties were calculated using full potential linearized augmented plane wave method within the Tran-Blaha modified Becke-Johnson potential. The calculated electronic structure shows that α, β phases are indirect bandgap insulators with a bandgap values of 3.51 and 4.43 eV, respectively. The nature of chemical bonding is analyzed through the charge density plots and partial density of states. Optical anisotropy, electric-dipole transitions, and photo sensitivity to light of the polymorphs are analyzed from the calculated optical spectra. Overall, the present study provides an early indication to experimentalists to avoid the formation of unstable β-form of AgCNO.« less

A fresh look at dense hydrogen under pressure. IV. Two structural models on the road from paired to monatomic hydrogen, via a possible non-crystalline phase

NASA Astrophysics Data System (ADS)

Labet, Vanessa; Hoffmann, Roald; Ashcroft, N. W.

2012-02-01

In this paper, we examine the transition from a molecular to monatomic solid in hydrogen over a wide pressure range. This is achieved by setting up two models in which a single parameter δ allows the evolution from a molecular structure to a monatomic one of high coordination. Both models are based on a cubic Bravais lattice with eight atoms in the unit cell; one belongs to space group Pabar 3, the other to space group Rbar 3m. In Pabar 3 one moves from effective 1-coordination, a molecule, to a simple cubic 6-coordinated structure but through a very special point (the golden mean is involved) of 7-coordination. In Rbar 3m, the evolution is from 1 to 4 and then to 3 to 6-coordinate. If one studies the enthalpy as a function of pressure as these two structures evolve (δ increases), one sees the expected stabilization of minima with increased coordination (moving from 1 to 6 to 7 in the Pabar 3 structure, for instance). Interestingly, at some specific pressures, there are in both structures relatively large regions of phase space where the enthalpy remains roughly the same. Although the structures studied are always higher in enthalpy than the computationally best structures for solid hydrogen - those emerging from the Pickard and Needs or McMahon and Ceperley numerical laboratories - this result is suggestive of the possibility of a microscopically non-crystalline or "soft" phase of hydrogen at elevated pressures, one in which there is a substantial range of roughly equi-enthalpic geometries available to the system. A scaling argument for potential dynamic stabilization of such a phase is presented.

The Pressure-Temperature Phase Diagram of Metacetamol and Its Comparison to the Phase Diagram of Paracetamol.

PubMed

Barrio, Maria; Huguet, Judit; Rietveld, Ivo B; Robert, Benoît; Céolin, René; Tamarit, Josep-Lluis

2017-06-01

Understanding the polymorphic behavior of active pharmaceutical ingredients is important for formulation purposes and regulatory reasons. Metacetamol is an isomer of paracetamol and it similarly exhibits polymorphism. In the present article, it has been found that one of the polymorphs of metacetamol is only stable under increased pressure, which has led to the conclusion that metacetamol like paracetamol is a monotropic system under ordinary (= laboratory) conditions and that it becomes enantiotropic under pressure with the I-II-L triple point coordinates for metacetamol T I-II-L  = 535 ± 10 K and P I-II-L  = 692 ± 70 MPa. However, whereas for paracetamol the enantiotropy under pressure can be foreseen, because the metastable polymorph is denser, in the case of metacetamol this is not possible, as the metastable polymorph is less dense than the stable one. The existence of the stability domain for the less dense polymorph of metacetamol can only be demonstrated by the construction of the topological phase diagram as presented in this article. It is a delicate interplay between the specific volume differences and the enthalpy differences causing the stability domain of the less dense polymorph to be sandwiched between the denser polymorph and the liquid. Metacetamol shares this behavior with bicalutamide and fluoxetine nitrate. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Stability of Electrodeposition at Solid-Solid Interfaces and Implications for Metal Anodes

NASA Astrophysics Data System (ADS)

Ahmad, Zeeshan; Viswanathan, Venkatasubramanian

2017-08-01

We generalize the conditions for stable electrodeposition at isotropic solid-solid interfaces using a kinetic model which incorporates the effects of stresses and surface tension at the interface. We develop a stability diagram that shows two regimes of stability: a previously known pressure-driven mechanism and a new density-driven stability mechanism that is governed by the relative density of metal in the two phases. We show that inorganic solids and solid polymers generally do not lead to stable electrodeposition, and provide design guidelines for achieving stable electrodeposition.

Electronic and thermodynamic properties of layered Hf2Sfrom first-principles calculations

NASA Astrophysics Data System (ADS)

Nandadasa, Chandani; Yoon, Mina; Kim, Seong-Gon; Erwin, Steve; Kim, Sungho; Kim, Sung Wng; Lee, Kimoon

Theoretically we explored two stable phases of inorganic fullerene-like structure of the layered dihafnium sulfide (Hf2 S) . We investigated structural and electronic properties of the two phases of Hf2 S by using first-principles calculations. Our calculation identifies experimentally observed anti-NbS2 structure of Hf2 S . Our electronic calculation results indicate that the density of states of anti- NbS2 structure of Hf2 S at fermi level is less than that of the other phase of Hf2 S . To study the relative stability of different phases at finite temperature Helmholtz free energies of two phases are obtained using density functional theory and density functional perturbation theory. The free energy of the anti-NbS2 structure of Hf2 S always lies below the free energy of the other phase by confirming the most stable structure of Hf2 S . The phonon dispersion, phonon density of states including partial density of states and total density of states are obtained within density functional perturbation theory. Our calculated zero-pressure phonon dispersion curves confirm that the thermodynamic stability of Hf2 S structures. For further investigation of thermodynamic properties, the temperature dependency of thermal expansion, heat capacities at constant pressure and volume are evaluated within the quasiharmonic approximations (QHA).

Superfluid helium 2 liquid-vapor phase separation: Technology assessment

NASA Technical Reports Server (NTRS)

Lee, J. M.

1984-01-01

A literature survey of helium 2 liquid vapor phase separation is presented. Currently, two types of He 2 phase separators are being investigated: porous, sintered metal plugs and the active phase separator. The permeability K(P) shows consistency in porous plug geometric characterization. Both the heat and mass fluxes increase with K(P). Downstream pressure regulation to adjust for varying heat loads and both temperatures is possible. For large dynamic heat loads, the active phase separator shows a maximum heat rejection rate of up to 2 W and bath temperature stability of 0.1 mK. Porous plug phase separation performance should be investigated for application to SIRTF and, in particular, that plugs of from 10 to the minus ninth square centimeters to 10 to the minus eighth square centimeters in conjunction with downstream pressure regulation be studied.

Iron-Nickel alloy in the Earth's core

NASA Astrophysics Data System (ADS)

Lin, Jung-Fu; Heinz, Dion L.; Campbell, Andrew J.; Devine, James M.; Mao, Wendy L.; Shen, Guoyin

2002-05-01

The phase relations of an Fe10wt%Ni alloy were investigated in a diamond anvil cell up to 86 GPa and 2382 K. Adding nickel into iron stabilizes the fcc phase to higher pressures and lower temperatures compared to pure iron, and a region of two-phase coexistence between fcc and hcp phases is observed. Iron with up to 10 wt% nickel is likely to be in the hcp structure under inner core conditions. The axial ratio (c/a) of hcp-Fe10wt%Ni has a weak pressure dependence, but it increases substantially with increasing temperature. The extrapolated c/a ratio at ~5700 K and ~86 GPa is approximately 1.64, lower than a theoretically predicted value of nearly 1.7 for hcp-Fe at 5700 K and inner-core pressure. A lower c/a ratio should have an effect on the longitudinal anisotropy of the hcp phase, and hence, may influence the interpretation of the seismic wave anisotropy of the inner core.

Pressure induced structural phase transition in solid oxidizer KClO3: A first-principles study

NASA Astrophysics Data System (ADS)

Yedukondalu, N.; Ghule, Vikas D.; Vaitheeswaran, G.

2013-05-01

High pressure behavior of potassium chlorate (KClO3) has been investigated from 0 to 10 GPa by means of first principles density functional theory calculations. The calculated ground state parameters, transition pressure, and phonon frequencies using semiempirical dispersion correction scheme are in excellent agreement with experiment. It is found that KClO3 undergoes a pressure induced first order phase transition with an associated volume collapse of 6.4% from monoclinic (P21/m) → rhombohedral (R3m) structure at 2.26 GPa, which is in good accord with experimental observation. However, the transition pressure was found to underestimate (0.11 GPa) and overestimate (3.57 GPa) using local density approximation and generalized gradient approximation functionals, respectively. Mechanical stability of both the phases is explained from the calculated single crystal elastic constants. In addition, the zone center phonon frequencies have been calculated using density functional perturbation theory at ambient as well as at high pressure and the lattice modes are found to soften under pressure between 0.6 and 1.2 GPa. The present study reveals that the observed structural phase transition leads to changes in the decomposition mechanism of KClO3 which corroborates with the experimental results.

Pressure induced structural phase transition in solid oxidizer KClO3: a first-principles study.

PubMed

Yedukondalu, N; Ghule, Vikas D; Vaitheeswaran, G

2013-05-07

High pressure behavior of potassium chlorate (KClO3) has been investigated from 0 to 10 GPa by means of first principles density functional theory calculations. The calculated ground state parameters, transition pressure, and phonon frequencies using semiempirical dispersion correction scheme are in excellent agreement with experiment. It is found that KClO3 undergoes a pressure induced first order phase transition with an associated volume collapse of 6.4% from monoclinic (P2(1)/m) → rhombohedral (R3m) structure at 2.26 GPa, which is in good accord with experimental observation. However, the transition pressure was found to underestimate (0.11 GPa) and overestimate (3.57 GPa) using local density approximation and generalized gradient approximation functionals, respectively. Mechanical stability of both the phases is explained from the calculated single crystal elastic constants. In addition, the zone center phonon frequencies have been calculated using density functional perturbation theory at ambient as well as at high pressure and the lattice modes are found to soften under pressure between 0.6 and 1.2 GPa. The present study reveals that the observed structural phase transition leads to changes in the decomposition mechanism of KClO3 which corroborates with the experimental results.

Pitfalls and feedback when constructing topological pressure-temperature phase diagrams

NASA Astrophysics Data System (ADS)

Ceolin, R.; Toscani, S.; Rietveld, Ivo B.; Barrio, M.; Tamarit, J. Ll.

2017-04-01

The stability hierarchy between different phases of a chemical compound can be accurately reproduced in a topological phase diagram. This type of phase diagrams may appear to be the result of simple extrapolations, however, experimental complications quickly increase in the case of crystalline trimorphism (and higher order polymorphism). To ensure the accurate positioning of stable phase domains, a topological phase diagram needs to be consistent. This paper gives an example of how thermodynamic feedback can be used in the topological construction of phase diagrams to ensure overall consistency in a phase diagram based on the case of piracetam crystalline trimorphism.

First principles study of structural, electronic and optical properties of polymorphic forms of Rb 2Te

NASA Astrophysics Data System (ADS)

Alay-e-Abbas, S. M.; Shaukat, A.

2011-05-01

First-principles density functional theory calculations have been performed for structural, electronic and optical properties of three polymorphic forms of rubidium telluride. Our calculations show that the sequence of pressure induced phase transitions for Rb 2Te is Fm3¯m → Pnma → P6 3/mmc which is governed by the coordination numbers of the anions. From our calculated low transition pressure value for the Fm3¯m phase to the Pnma phase transition of Rb 2Te, the experimentally observed meta-stability of Fm3¯m phase at ambient conditions seems reasonable. The electronic band structure has been calculated for all the three phases and the change in the energy band gap is discussed for the transitioning phases. The energy band gaps obtained for the three phases of Rb 2Te decrease on going from the meta-stable phase to the high-pressure phases. Total and partial density of states for the polymorphs of Rb 2Te has been computed to elucidate the contribution of various atomic states on the electronic band structure. Furthermore, optical properties for all the polymorphic forms have been presented in form of the complex dielectric function.

Energetic metastable high-pressure phases of CO

NASA Astrophysics Data System (ADS)

Barbee, Troy W., III

1996-03-01

First-row elements present some of the best possibilities for storing chemical energy in metastable structures because of their strong bonding and light mass. Recent calculations have predicted(Mailhiot, Yang, and McMahan, Phys. Rev. B 46), 14419 (1992). that under pressure, molecular nitrogen should undergo a transition to a polymeric structure which should be metastable and energetic at ambient pressure. Because carbon monoxide is isoelectronic to N_2, the phase diagram of CO is quite similar to that of nitrogen. Observations of chemical reactions in solid CO under pressure have been made,(Katz, Schiferl, and Mills, J. Phys. Chem. 88), 3176 (1984). and the products (C_3O_2) have been recovered at ambient pressure. I will present calculations of the high-pressure stability and metastability for several candidate structures for CO at high pressure, as well as the energy stored in the metastable C_3O2 at ambient pressure. This work was performed under the auspices of the U.S. DOE by LLNL under contract No. W--7405--ENG--48.

Toward pressure-induced multiferroicity in PrMn2O5

NASA Astrophysics Data System (ADS)

Peng, W.; Balédent, V.; Chattopadhyay, S.; Lepetit, M.-B.; Yahia, G.; Colin, C. V.; Gooch, M. J.; Pasquier, C. R.; Auban-Senzier, P.; Greenblatt, M.; Foury-Leylekian, P.

2017-08-01

The series of multiferroics R Mn2O5 is extensively studied for its quasicollinear spin arrangement, which results in an electrical polarization according to the exchange-striction model. Variations of the interatomic distances modified by the external pressure can strongly influence the multiferroic properties. Understanding this influence is of great importance, especially for the future realization of multiferroic devices. As PrMn2O5 is paraelectric at ambient pressure, it is the most suitable candidate to search for pressure induced multiferroicity. In this paper, we report the emergence of a new pressure induced magnetic phase in PrMn2O5 determined by powder neutron diffraction under pressure. This new magnetic phase presenting at relatively low pressure becomes completely exclusive at 8 GPa. The determination of its magnetic structure has thus been possible for the first time. More importantly, the magnetic structure stabilized under pressure should induce a strong spontaneous electric polarization due to the nearly perfect collinearity of the Mn3 + and Mn4 + spins.

Thermodynamic Effects on Phase Stabilities and Structural Properties of TiO2 from the First-principles

NASA Astrophysics Data System (ADS)

Aoki, Yuta; Saito, Susumu

2013-03-01

Titanium dioxide (TiO2) is one of the most representative photocatalytic materials and much attention is focused on understanding and improvement of its photocatalytic activity. At the same time, TiO2 is known to be a highly polymorphic material and as many as eleven crystal phases have been identified so far. It is expected that TiO2 show various photocatalytic properties depending on crystal phases. However, relative stabilities of these identified phases are still controversial. In order to clarify the thermodynamic phase stabilities of TiO2, we obtain the free energies of its several representative phases, rutile, anatase, brookite, and TiO2-II within the framework of the density-functional theory using the pseudopotential method. We calculate both the static energy and the contribution of phonons to the free energy through the quasiharmonic approximation for each phase. It is found that treatment of semicore electrons in constructing the pseudopotential of the Ti atom significantly affects the relative phase stabilities. From the phase diagram obtained, we find that the anatase phase is the most stable at lower temperature and pressure. We also discuss the thermodynamic effects on structural properties such as thermal expansion. We acknowledge the financial supports from the Global Center-of-Excellence Program by MEXT, Japan through the Nanoscience and Quantum Physics Project of Tokyo Institute of Technology, and the Elements Science and Technology Project by MEXT.

Existence, stability, and nonlinear dynamics of detached Bridgman growth states under zero gravity

NASA Astrophysics Data System (ADS)

Yeckel, Andrew; Derby, Jeffrey J.

2011-01-01

A thermocapillary model is used to study the existence, stability, and nonlinear dynamics of detached melt crystal growth in a vertical Bridgman system under zero gravity conditions. The model incorporates time-dependent heat, mass, and momentum transport, and accounts for temperature-dependent surface tension effects at the menisci bounding the melt. The positions of the menisci and phase-change boundary are computed to satisfy the conservation laws rigorously. A rich bifurcation structure in gap width versus pressure difference is uncovered, demarcating conditions under which growth with a stable gap is feasible. Thermal effects shift the bifurcation diagram to a slightly different pressure range, but do not alter its general structure. Necking and freeze-off are shown to be two different manifestations of the same instability mechanism. Supercooling of melt at the meniscus and low thermal gradients in the melt ahead of the crystal-melt-gas triple phase line, either of which may be destabilizing, are both observed under some conditions. The role of wetting and growth angles in dynamic shape stability is clarified.

Pressure-induced stable BeN4 as a high-energy density material

NASA Astrophysics Data System (ADS)

Zhang, Shoutao; Zhao, Ziyuan; Liu, Lulu; Yang, Guochun

2017-10-01

Polynitrogens are the ideal rocket fuels or propellants. Due to strong triple N≡N bond in N2, the direct polymerization of nitrogen is rather difficult (i.e. extreme high temperature and high pressure). However, the use of nitrides as precursors or the reaction of N2 with other elements has been proved to be an effective way to obtain polynitrogens. Here, with assistance of the advanced first-principles swarm-intelligence structure searches, we found that P 1 bar -BeN4, containing infinite zigzag-like polymeric nitrogen chains, can be synthesized by compressing the mixture of Be3N2 and N2 at 25.4 GPa, which is greatly lower than 110 GPa for synthesizing cubic gauche nitrogen and other polynitrogen compounds (e.g. bulk CNO at 52 GPa and SN4 at 49 GPa). Its structural stability can be attributed to the coexistence of ionic Be-N and covalent N-N bonds. Intriguingly, this phase has high kinetic stability and remains metastable at ambient pressure. The exceptional properties, including high energy density (3.60 kJ g-1), high nitrogen content (86.1%), high dynamical stability, and low polymerization pressure, make P 1 bar -structured BeN4 a promising high energy material. Infinite nitrogen chains in P 1 bar -BeN4 transform to N10 rings network in P21/c phase at 115.1 GPa. P 1 bar -BeN4 is metallic, while P21/c-BeN4 is an insulator.

Stability of the accelerated expansion in nonlinear electrodynamics

NASA Astrophysics Data System (ADS)

Sharif, M.; Mumtaz, Saadia

2017-02-01

This paper is devoted to the phase space analysis of an isotropic and homogeneous model of the universe by taking a noninteracting mixture of the electromagnetic and viscous radiating fluids whose viscous pressure satisfies a nonlinear version of the Israel-Stewart transport equation. We establish an autonomous system of equations by introducing normalized dimensionless variables. In order to analyze the stability of the system, we find corresponding critical points for different values of the parameters. We also evaluate the power-law scale factor whose behavior indicates different phases of the universe in this model. It is concluded that the bulk viscosity as well as electromagnetic field enhances the stability of the accelerated expansion of the isotropic and homogeneous model of the universe.

Accurate critical pressures for structural phase transitions of group IV, III-V, and II-VI compounds from the SCAN density functional

NASA Astrophysics Data System (ADS)

Shahi, Chandra; Sun, Jianwei; Perdew, John P.

2018-03-01

Most of the group IV, III-V, and II-VI compounds crystallize in semiconductor structures under ambient conditions. Upon application of pressure, they undergo structural phase transitions to more closely packed structures, sometimes metallic phases. We have performed density functional calculations using projector augmented wave (PAW) pseudopotentials to determine the transition pressures for these transitions within the local density approximation (LDA), the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and the strongly constrained and appropriately normed (SCAN) meta-GGA. LDA underestimates the transition pressure for most of the studied materials. PBE under- or overestimates in many cases. SCAN typically corrects the errors of LDA and PBE for the transition pressure. The accuracy of SCAN is comparable to that of computationally expensive methods like the hybrid functional HSE06, the random phase approximation (RPA), and quantum Monte Carlo (QMC), in cases where calculations with these methods have been reported, but at a more modest computational cost. The improvement from LDA to PBE to SCAN is especially clearcut and dramatic for covalent semiconductor-metal transitions, as for Si and Ge, where it reflects the increasing relative stabilization of the covalent semiconducting phases under increasing functional sophistication.

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

Alvarado, Andrew; Attapattu, Jeevake; Zhang, Yi

Zinc oxide (ZnO) undergoes a pressure-induced structural transition from its normal ambient-pressure wurtzite (WZ) phase to a rocksalt (RS) phase around 10 GPa. A recent experiment shows that the high-pressure RS ZnO phase can be recovered and stabilized at ambient conditions, which raises exciting prospects of expanding the range of properties of ZnO. For a fundamental understanding of the RS ZnO phase, we have performed first-principles calculations to determine its electronic, phonon, and thermodynamic properties at high (20 GPa) and ambient (0 GPa) pressure. Furthermore, we have calculated its electrical and thermal transport properties, which allow an evaluation of its thermoelectric figure ofmore » merit ZT at different temperature and doping levels. Our calculations show that the ambient-pressure RS ZnO phase can reach ZT values of 0.25 to 0.3 under both n-type and p-type doping in a large temperature range of 400 K to 800 K, which is considerably lower than the temperature range of 1400 K to 1600 K where WZ ZnO reaches similar ZT values. These results establish RS ZnO as a promising material for thermoelectric devices designed to operate at temperatures desirable for many heat recovery applications.« less

Thermoelectric properties of rocksalt ZnO from first-principles calculations

DOE PAGES

Alvarado, Andrew; Attapattu, Jeevake; Zhang, Yi; ...

2015-10-22

Zinc oxide (ZnO) undergoes a pressure-induced structural transition from its normal ambient-pressure wurtzite (WZ) phase to a rocksalt (RS) phase around 10 GPa. A recent experiment shows that the high-pressure RS ZnO phase can be recovered and stabilized at ambient conditions, which raises exciting prospects of expanding the range of properties of ZnO. For a fundamental understanding of the RS ZnO phase, we have performed first-principles calculations to determine its electronic, phonon, and thermodynamic properties at high (20 GPa) and ambient (0 GPa) pressure. Furthermore, we have calculated its electrical and thermal transport properties, which allow an evaluation of itsmore » thermoelectric figure of merit ZT at different temperature and doping levels. Our calculations show that the ambient-pressure RS ZnO phase can reach ZT values of 0.25 to 0.3 under both n-type and p-type doping in a large temperature range of 400 K to 800 K, which is considerably lower than the temperature range of 1400 K to 1600 K where WZ ZnO reaches similar ZT values. Lastly, these results establish RS ZnO as a promising material for thermoelectric devices designed to operate at temperatures desirable for many heat recovery applications.« less

Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped Bi-2223 and Ag/Bi-2223 systems

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Luo, J. S.; Maroni, V. A.

1995-02-01

Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made in the lead-doped Bi-2223 superconducting system in the temperature range 700-815°C by means of an oxygen titration technique that employs an yttria-stabilized zirconia electrolyte. The results of our studies indicate that processing or annealing lead-doped Bi-2223 at temperatures ranging from 750 to 815°C and at oxygen partial pressures ranging from ∼ 0.02 to 0.2 atm should preserve Bi-2223 as essentially single-phase material. Thermodynamic assessments of the partial molar quantities ΔS¯( O2) andΔH¯( O2) indicate that the plateau regions in the plot of oxygen partial pressure versus oxygen stoichiometry ( x) can be represented by the diphasic CuOCu 2O system. In accord with the EMF measurements, it was found that lead-doped Bi-2223 in a silver sheath is stable at 815°C for oxygen partial pressures between 0.02 and 0.13 atm.

Numerical and experimental study of the dynamics of a superheated jet

NASA Astrophysics Data System (ADS)

Sinha, Avick; Gopalakrishnan, Shivasubramanian; Balasubramanian, Sridhar

2015-11-01

Flash-boiling is a phenomenon where a liquid experiences low pressures in a system resulting in it getting superheated. The sudden drop in pressures results in accelerated expansion and violent vapour formation. Understanding the physics behind the jet disintegration and flash-boiling phenomenon is still an open problem, with applications in automotive and aerospace combustors. The behaviour of a flash-boiling jet is highly dependent on the input parameters, inlet temperature and pressure. In the present study, the external (outside nozzle) and the internal (inside nozzle) flow characteristics of the two-phase flow has been studied numerically and experimentally. The phase change from liquid to vapour takes place over a finite period of time, modeled sing Homogeneous Relaxation Model (HRM). In order to validate the numerical results, controlled experiments were performed. Optical diagnostic techniques such as Particle Image Velocimetry (PIV) and Shadowgraphy were used to study the flow characteristics. Spray angle, penetration depth, droplet spectra were obtained which provides a better understanding of the break-up mechanism. Linear stability analysis is performed to study the stability characteristics of the jet.

Ab Initio Study of the Structure and Stability of High-Pressure Iron-Bearing Dolomite

NASA Astrophysics Data System (ADS)

Solomatova, N. V.; Asimow, P. D.

2016-12-01

Carbon is subducted into the mantle primarily in the form of metasomatically calcium-enriched basaltic rock, calcified serpentinites and carbonaceous ooze, all of which often contain dolomite. End-member CaMg(CO3)2 dolomite typically breaks down upon compression into two carbonates at 5-6 GPa in the temperature range of 800-1200 K [1]. However, high-pressure X-ray diffraction experiments have recently shown that the presence of iron may be sufficient to stabilize high-pressure dolomite over single-cation carbonates above 35 GPa [2,3]. The structure and equation of state of high-pressure dolomite phases have been debated, creating a need for theoretical calculations. Using density functional theory interfaced with a genetic algorithm that predicts crystal structures (USPEX), we have found a monoclinic phase with space group C2/c. The C2/c structure has a lower energy than previously reported dolomite structures at relevant pressures. It is possible that this phase is not achieved experimentally due to a large energy barrier and a correspondingly large required volume drop, resulting in the transformation to metastable dolomite II. We calculate the equation of state of trigonal dolomite, dolomite III and monoclinic C2/c dolomite to 80 GPa with 0 and 50 mol% CaFe(CO3)2 and compare their enthalpies to single-carbonate assemblages. Although end-member C2/c CaMg(CO3)2 dolomite is not stable relative to single-cation carbonates, C2/c CaMg0.5Fe0.5(CO3)2 is preferred over single-cation carbonates at high pressures. Thus, iron-bearing C2/c dolomite may be an important host phase for carbon in slabs subducted into the lower mantle. [1] Shirasaka, M., et al. (2002) American Mineralogist, 87, 922-930. [2] Mao, Z. et al. (2011) Geophysical Research Letters, 38. [3] Merlini, M. et al. (2012) Proceedings of the National Academy of Sciences, 109, 13509-13514.

High-pressure high-temperature stability of hcp-Ir xOs 1-x (x = 0.50 and 0.55) alloys

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

Yusenko, Kirill V.; Bykova, Elena; Bykov, Maxim

2016-12-23

Hcp-Ir 0.55Os 0.45 and hcp-Ir 0.50Os 0.50 alloys were synthesised by thermal decomposition of single-source precursors in hydrogen atmosphere. Both alloys correspond to a miscibility gap in the Ir–Os binary phase diagram and therefore are metastable at ambient conditions. An in situ powder X-ray diffraction has been used for a monitoring a formation of hcp-Ir0.55Os0.45 alloy from (NH 4) 2[Ir 0.55Os 0.45Cl 6] precursor. A crystalline intermediate compound and nanodimentional metallic particles with a large concentration of defects has been found as key intermediates in the thermal decomposition process in hydrogen flow. High-temperature stability of titled hcp-structured alloys has beenmore » investigated upon compression up to 11 GPa using a multi-anvil press and up to 80 GPa using laser-heated diamond-anvil cells to obtain a phase separation into fcc + hcp mixture. Compressibility curves at room temperature as well as thermal expansion at ambient pressure and under compression up to 80 GPa were collected to obtain thermal expansion coefficients and bulk moduli. hcp-Ir 0.55Os 0.45 alloy shows bulk moduli B0 = 395 GPa. Thermal expansion coefficients were estimated as α = 1.6·10 -5 K -1 at ambient pressure and α = 0.3·10 -5 K -1 at 80 GPa. Obtained high-pressure high-temperature data allowed us to construct the first model for pressure-dependent Ir–Os phase diagram.« less

Phase diagrams of nonionic foam films: construction by means of disjoining pressure versus thickness curves.

PubMed

Stubenrauch, Cosima; Kashchiev, Dimo; Strey, Reinhard

2004-12-01

The thickness h of foam films can be measured as a function of the disjoining pressure Pi using a thin film pressure balance. Experimental Pi-h curves of foam films stabilized with nonionic surfactants measured at various concentrations resemble the p-V(m) isotherms of real gases measured at various temperatures (p is the pressure and V(m) is the molar volume of the gas). This observation led us to adopt the van der Waals approach for describing real gases to thin foam films, where the thickness h takes the role of V(m) and the disjoining pressure Pi replaces the ordinary pressure p. Our analysis results in a phase diagram for a thin foam film with spinodal, binodal as well as a critical point. The thicker common black film corresponds to the gas phase and the compact Newton black film for which the two surfaces are in direct contact corresponds to the dense liquid. We show that the tuning parameter for the phase behavior of the film is the surface charge density, which means that Pi-h curves should not be referred to as isotherms. In addition to the equilibrium properties the driving force for the phase transition from a common black film to a Newton black film or vice versa is calculated. We discuss how this transition can be controlled experimentally.

Cu--Pd--M hydrogen separation membranes

DOEpatents

Do{hacek over }an, Omer N; Gao, Michael C; Young, Rongxiang Hu; Tafen, De Nyago

2013-12-17

The disclosure provides an H2 separation membrane comprised of an allow having the composition Cu.Sub.(100-x-y)Pd.sub.xM.sub.y, where x is from about 35 to about 50 atomic percent and where y is from greater than 0 to about 20 atomic percent, and where M consists of magnesium, yttrium, aluminum, titanium, lanthanum, or combinations thereof. The M elements act as strong stabilizers for the B2 phase of the allow, and extend the critical temperature of the alloy for a given hydrogen concentration and pressure. Due to the phase stabilization and the greater temperature range over which a B2 phase can be maintained, the allow is well suited for service as a H2 separation membrane, particularly when applicable conditions are established or cycled above about 600.degree. C. over the course of expected operations. In certain embodiments, the B2 phase comprises at least 60 estimated volume percent of the allow at a steady-state temperature of 400.degree. C. The B2 phase stability is experimentally validated through HT-XRD.

Atmospheric Dynamics on Venus, Jupiter, and Saturn: An Observational and Analytical Study

NASA Technical Reports Server (NTRS)

Bridger, Alison; Magalhaes, Julio A.; Young, Richard E.

2000-01-01

Determining the static stability of Jupiter's atmosphere below the visible cloud levels is important for understanding the dynamical modes by which energy and momentum are transported through Jupiter's deep troposphere. The Galileo Probe Atmospheric Structure Investigation (ASI) employed pressure and temperature sensors to directly measure these state variables during the parachute-descent phase, which started at a pressure (p) of 0.4 bars and ended at p= 22 bars. The internal temperature of the probe underwent large temperature fluctuations which significantly exceeded design specifications. Corrections for these anomalous interior temperatures have been evaluated based on laboratory data acquired after the mission using the flight spare hardware. The corrections to the pressure sensor readings was particularly large and the uncertainties in the atmospheric pressures derived from the p sensor measurements may still be significant. We have sought to estimate the formal uncertainties in the static stability derived from the p and T sensor measurements directly and to devise means of assessing the static stability of Jupiter's atmosphere which do not rely on the p sensor data.

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

NASA Astrophysics Data System (ADS)

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

2015-01-01

High-pressure phase transformations between the polymorphic forms I, II, III, and IIIb of CaCO3 were investigated by analytical in situ high-pressure high-temperature experiments on oriented single-crystal samples. All experiments at non-ambient conditions were carried out by means of Raman scattering, X-ray, and synchrotron diffraction techniques using diamond-anvil cells in the pressure range up to 6.5 GPa. The composite-gasket resistive heating technique was applied for all high-pressure investigations at temperatures up to 550 K. High-pressure Raman spectra reveal distinguishable characteristic spectral differences located in the wave number range of external modes with the occurrence of band splitting and shoulders due to subtle symmetry changes. Constraints from in situ observations suggest a stability field of CaCO3-IIIb at relatively low temperatures adjacent to the calcite-II field. Isothermal compression of calcite provides the sequence from I to II, IIIb, and finally, III, with all transformations showing volume discontinuities. Re-transformation at decreasing pressure from III oversteps the stability field of IIIb and demonstrates the pathway of pressure changes to determine the transition sequence. Clausius-Clapeyron slopes of the phase boundary lines were determined as: Δ P/Δ T = -2.79 ± 0.28 × 10-3 GPa K-1 (I-II); +1.87 ± 0.31 × 10-3 GPa K-1 (II/III); +4.01 ± 0.5 × 10-3 GPa K-1 (II/IIIb); -33.9 ± 0.4 × 10-3 GPa K-1 (IIIb/III). The triple point between phases II, IIIb, and III was determined by intersection and is located at 2.01(7) GPa/338(5) K. The pathway of transition from I over II to IIIb can be interpreted by displacement with small shear involved (by 2.9° on I/II and by 8.2° on II/IIIb). The former triad of calcite-I corresponds to the [20-1] direction in the P21/ c unit cell of phase II and to [101] in the pseudomonoclinic C setting of phase IIIb. Crystal structure investigations of triclinic CaCO3-III at non-ambient pressure-temperature conditions confirm the reported structure, and the small changes associated with the variation in P and T explain the broad stability of this structure with respect to variations in P and T. PVT equation of state parameters was determined from experimental data points in the range of 2.20-6.50 GPa at 298-405 K providing = 87.5(5.1) GPa, ( δK T/ δT) P = -0.21(0.23) GPa K-1, α 0 = 0.8(21.4) × 10-5 K-1, and α 1 = 1.0(3.7) × 10-7 K-1 using a second-order Birch-Murnaghan equation of state formalism.

High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

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

Bishop, M. M.; Chellappa, R. S.; Liu, Z.

Here, 1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and β → γ (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → δ (~210 °C),more » with the δ phase being stable up to ~251 degree C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 degree C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa..« less

Modeling the Capillary Pressure for the Migration of the Liquid Phase in Granular Solid-Liquid-Vapor Systems: Application to the Control of the Composition Profile in W-Cu FGM Materials

NASA Astrophysics Data System (ADS)

Missiaen, Jean-Michel; Raharijaona, Jean-Joël; Delannay, Francis

2016-11-01

A model is developed to compute the capillary pressure for the migration of the liquid phase out or into a uniform solid-liquid-vapor system. The capillary pressure is defined as the reduction of the overall interface energy per volume increment of the transferred fluid phase. The model takes into account the particle size of the solid particle aggregate, the packing configuration (coordination number, porosity), the volume fractions of the different phases, and the values of the interface energies in the system. The model is used for analyzing the stability of the composition profile during processing of W-Cu functionally graded materials combining a composition gradient with a particle size gradient. The migration pressure is computed with the model in two stages: (1) just after the melting of copper, i.e., when sintering and shape accommodation of the W particle aggregate can still be neglected and (2) at high temperature, when the system is close to full density with equilibrium particle shape. The model predicts well the different stages of liquid-phase migration observed experimentally.

High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

DOE PAGES

Bishop, M. M.; Chellappa, R. S.; Liu, Z.; ...

2014-05-07

Here, 1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and β → γ (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → δ (~210 °C),more » with the δ phase being stable up to ~251 degree C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 degree C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa..« less

Stabilizing detached Bridgman melt crystal growth: Model-based nonlinear feedback control

NASA Astrophysics Data System (ADS)

Yeckel, Andrew; Daoutidis, Prodromos; Derby, Jeffrey J.

2012-12-01

The dynamics and operability limits of a nonlinear-proportional-integral controller designed to stabilize detached vertical Bridgman crystal growth are studied. The manipulated variable is the pressure difference between upper and lower vapor spaces, and the controlled variable is the gap width at the triple-phase line. The controller consists of a model-based nonlinear component coupled with a standard proportional-integral controller. The nonlinear component is based on a capillary model of shape stability. Perturbations to gap width, pressure difference, wetting angle, and growth angle are studied under both shape stable and shape unstable conditions. The nonlinear-PI controller allows a wider operating range of gain than a standard PI controller used alone, is easier to tune, and eliminates solution multiplicity from closed-loop operation.

Mechanism of gas saturated oil viscosity anomaly near to phase transition point

NASA Astrophysics Data System (ADS)

Suleimanov, Baghir A.; Abbasov, Elkhan M.; Sisenbayeva, Marziya R.

2017-01-01

The article presents experimental studies of the phase behavior by the flash liberation test and of the viscosity of the live oil at different pressures. Unlike the typical studies at the pressure near the saturation pressure, the measurements were conducted at a relatively small pressure increment of 0.08-0.25 MPa. The viscosity anomaly was discovered experimentally near to the phase transition point in the range of the pressure levels P/Pb = 1-1.14 (Pb—bubble point pressure) and shows that it decreases about 70 times in comparison to the viscosity at the reservoir pressure. It was found that the bubble point pressure decreases significantly (up to 36%) with surfactant addition. Furthermore, the viscosity of the live oil at the surfactant concentration of 5 wt. % decreases almost 37 times in comparison to the viscosity at the reservoir pressure. The mechanism of observed effects was suggested based on the formation of the stable subcritical gas nuclei and associated slippage effect. The mechanism for the stabilization of the subcritical nuclei by the combined action of the surface and electrical forces, as well as the morphology of the formed nanobubbles, was considered. The model for determining the oil viscosity taking into account the slippage effect was suggested.

Lattice dynamics, elasticity and magnetic abnormality in ordered crystalline alloys Fe3Pt at high pressures

NASA Astrophysics Data System (ADS)

Cheng, Tai-min; Yu, Guo-Liang; Su, Yong; Ge, Chong-Yuan; Zhang, Xin-Xin; Zhu, Lin; Li, Lin

2018-05-01

The ordered crystalline Invar alloy Fe3Pt is in a special magnetic critical state, under which the lattice dynamic stability of the system is extremely sensitive to external pressures. We studied the pressure dependence of enthalpy and magnetism of Fe3Pt in different crystalline alloys by using the first-principles projector augmented-wave method based on the density functional theory. Results show that the P4/mbm structure is the ground state structure and is more stable relative to other structures at pressures below 18.54 GPa. The total magnetic moments of L12, I4/mmm and DO22 structures decrease rapidly with pressure and oscillate near the ferromagnetic collapse critical pressure. At the pressure of 43 GPa, the ferrimagnetic property in DO22 structure becomes apparently strengthened and its volume increases rapidly. The lattice dynamics calculation for L12 structures at high pressures shows that the spontaneous magnetization of the system in ferromagnetic states induces the softening of the transverse acoustic phonon TA1 (M), and there exists a strong spontaneous volume magnetostriction at pressures below 26.95 GPa. Especially, the lattice dynamics stability is sensitive to pressure, in the pressure range between the ferromagnetic collapse critical pressure (41.9 GPa) and the magnetism completely disappearing pressure (57.25 GPa), and near the pressure of phase transition from L12 to P4/mbm structure (27.27 GPa). Moreover, the instability of magnetic structure leads to a prominent elastic modulus oscillation, and the spin polarizability of electrons near the Fermi level is very sensitive to pressures in that the pressure range. The pressure induces the stability of the phonon spectra of the system at pressures above 57.25 GPa.

Raman spectroscopic study of calcite III to aragonite transformation under high pressure and high temperature

NASA Astrophysics Data System (ADS)

Liu, Chuanjiang; Zheng, Haifei; Wang, Duojun

2017-10-01

In our study, a series of Raman experiments on the phase transition of calcite at high pressure and high temperature were investigated using a hydrothermal diamond anvil cell and Raman spectroscopy technique. It was found that calcite I transformed to calcite II and calcite III at pressures of 1.62 and 2.12 GPa and room temperature. With increasing temperature, the phase transition of calcite III to aragonite occurred. Aragonite was retained upon slowly cooling of the system, indicating that the transition of calcite III to aragonite was irreversible. Based on the available data, the phase boundary between calcite III and aragonite was determined by the following relation: P(GPa) = 0.013 × T(°C) + 1.22 (100°C ≤ T ≤ 170°C). It showed that the transition pressure linearly rose with increasing temperature. A better understanding of the stability of calcite III and aragonite is of great importance to further explore the thermodynamic behavior of carbonates and carbon cycling in the mantle.

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.

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.

Effect of pressure on the superconducting {ital T}{sub {ital c}} of lanthanum

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

Tissen, V.G.; Ponyatovskii, E.G.; Nefedova, M.V.

1996-04-01

The effect of pressure on the superconducting transition temperature {ital T}{sub {ital c}} of La was studied up to 50 GPa. {ital T}{sub {ital c}}({ital P}) shows a rather complicated variation with a discontinuous increase in {ital T}{sub {ital c}} at about 2.2 GPa due to the first-order phase transition from dhcp to fcc structure. At about 5.4 GPa a sharp peak is observed due to the soft-mode phase transition from fcc to the distorted fcc structure and two broad maxima are found within the stability region of the distorted fcc structure around 12 and 39 GPa. Some differences betweenmore » these and previous low-pressure data for metastable fcc La are noticed. The results are discussed in connection with pressure-induced structural phase transitions found in earlier x-ray-diffraction experiments and band-structure calculations giving evidences for van Hove singularities in the density of states. {copyright} {ital 1996 The American Physical Society.}« less

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

Manikandan, M.; Santhosh, M.; Rajeswarapalanichamy, R., E-mail: rrpalanichamy@gmail.com

Ab initio calculations are performed to investigate the structural stability, electronic structure and mechanical properties of actinide carbides AnC (An=U, Np) for three different crystal structures, namely NaCl, CsCl and ZnS. Among the considered structures, NaCl structure is found to be the most stable structure for these carbides at normal pressure. A pressure induced structural phase transition from NaCl to ZnS is observed. The electronic structure reveals that these carbides are metals. The calculated elastic constants indicate that these carbides are mechanically stable at normal pressure.

Elasticity of phase-Pi (Al3Si2O7(OH)3) - A hydrous aluminosilicate phase

NASA Astrophysics Data System (ADS)

Peng, Ye; Mookherjee, Mainak; Hermann, Andreas; Bajgain, Suraj; Liu, Songlin; Wunder, Bernd

2017-08-01

Phase-Pi (Al3Si2O7(OH)3) is an aluminosilicate hydrous mineral and is likely to be stable in hydrated sedimentary layers of subducting slabs. Phase-Pi is likely to be stable between the depths of 60 and 200 km and is likely to transport water into the Earth's interior. Here, we use first principles simulations based on density functional theory to explore the crystal structure at high-pressure, equation of state, and full elastic stiffness tensor as a function of pressure. We find that the pressure volume results could be described by a finite strain fit with V0 , K0 , and K0‧ being 310.3 Å3, 133 GPa, and 3.6 respectively. At zero pressure, the full elastic stiffness tensor shows significant anisotropy with the diagonal principal components C11 , C22 , and C33 being 235, 292, 266 GPa respectively, the diagonal shear C44 , C55 , and C66 being 86, 92, and 87 GPa respectively, and the off-diagonal stiffness C12 , C13 , C14 ,C15 , C16 , C23 , C24 , C25 , C26 , C34 , C35 , C36 , C45 , C46 , and C56 being 73, 78, 6, -30, 15, 61, 17, 2, 1, -13, -15, 6, 3, 1, and 3 GPa respectively. The zero pressure, shear modulus, G0 and its pressure derivative, G0 ‧ are 90 GPa and 1.9 respectively. Upon compression, hydrogen bonding in phase-Pi shows distinct behavior, with some hydrogen bonds weakening and others strengthening. The latter eventually undergo symmetrization, at pressure greater (>40 GPa) than the thermodynamic stability of phase-Pi. Full elastic constant tensors indicate that phase-Pi is very anisotropic with AVP ∼22.4% and AVS ∼23.7% at 0 GPa. Our results also indicate that the bulk sound velocity of phase-Pi is slower than that of the high-pressure hydrous aluminosilicate phase, topaz-OH.

What do a foam film and a real gas have in common?

PubMed

Stubenrauch, Cosima

2005-01-01

The stability of well-drained quasistatic foam films (thickness <100 nm) is usually discussed in terms of surface forces, which create an excess pressure normal to the film interfaces, called the disjoining pressure pi The disjoining pressure is the sum of repulsive electrostatic (pi(elec)), attractive van der Waals (pi(vdW)), and repulsive steric (pi(sr)) forces on the assumption that structural forces can be neglected. On the basis of these forces two different types of thin foam films are distinguished, namely common black films (CBF), which are mainly stabilized by pi(elec), and Newton black films (NBF), the stability of which is determined by pi(sr),With a thin-film pressure balance (TFPB) the thickness h of a foam film can be measured as a function of the applied pressure from which the disjoining pressure pi can be calculated. A thorough analysis of the results published so far reveals that the pi-h curves of nonionic surfactants measured at different surfactant concentrations resemble p-V(m) isotherms of a real gas measured at different temperatures. On the basis of these observations the van der Waals description of a real gas can be applied to foam films and a phase diagram for a foam film was constructed using the Maxwell construction.

Silicate garnet studies at high pressures: A view into the Earth's mantle

NASA Astrophysics Data System (ADS)

Conrad, Pamela Gales

Silicate garnets are an abundant component in the Earth's upper mantle and transition zone. Therefore, an understanding of garnet behavior under the pressure and temperature conditions of the mantle is critical to the development of models for mantle mineralogy and dynamics. Work from three projects is presented in this report. Each investigation explores an aspect of silicate garnet behavior under high pressures. Moreover, each investigation was made possible by state-of-the-art methods that have previously been unavailable. Brillouin scattering was used to determine the elastic constants and aggregate elastic moduli of three end-member garnets at high pressures in a diamond anvil cell. These are the first high-pressure measurements of the elastic constants of end-member silicate garnets by direct measurement of acoustic velocities. The results indicate that the pressure dependence of silicate garnet elastic constants varies with composition. Therefore, extrapolation from measurements on mixed composition garnets is not possible. A new method of laser heating minerals in a diamond anvil cell has made possible the determination of the high-pressure and high-temperature stability of almandine garnet. This garnet does not transform to a silicate perovskite phase as does pyrope garnet, but it decomposes to its constituent oxides: FeO, Alsb2Osb3, and SiOsb2. These results disprove an earlier prediction that ferrous iron may expand the stability field of garnet to the lower mantle. The present results demonstrate that this is not the case. The third topic is a presentation of the results of a new technique for studying inclusions in mantle xenoliths with synchrotron X-ray microdiffraction. The results demonstrate the importance of obtaining structural as well as chemical information on inclusions within diamonds and other high-pressure minerals. An unusual phase with garnet composition is investigated and several other phases are identified from a suite of natural diamonds that are thought to have a lower mantle origin.

Effect of Al on stability of DHMS up to the uppermost lower mantle

NASA Astrophysics Data System (ADS)

Xu, C.; Inoue, T.

2017-12-01

Water plays an important role on Earth. It influences the physical and chemical property of minerals and melts, which further effects the evolution of the Earth. A series of dense hydrous magnesium silicate (DHMS) phases such as phase A (PhA), phase E (PhE), superhydrous phase B (SUB) and phase D (PhD) have been suggested as potential water carriers to transition zone and even to the lower mantle under the conditions present in the cold subducting slabs [e.g. Kawamoto, 2004; Komabayashi and Omori, 2006]. Because of its importance, the DHMS have been widely studied by using different starting materials in MgO-SiO2-H2O system. Recently, the newly reported Al-PhD is stable at temperatures up to 2,000 °C at 26 GPa, which indicates aluminum increases stability regions of DHMS [e.g. Pamato et al., 2015]. To systematically study the effect of Al on the stability of hydrous phases, we use Kawai-type high pressure apparatus to investigate nature clinochlore, which contains about 15 wt% H2O and about 14 wt% Al2O3. The Al-bearing hydrous PhE, SUB and PhD were observed with P-T increasing. Following the P-T path of cold subduction, the phase assemblage PhE + PhD is stable at 14-23 GPa, and even a trace of PhE is detected at 1150°C and 25 GPa coexisting with PhD. The phase SUB is stable between 16-22 GPa coexisting with PhE + PhD. Following the P-T path of hot subduction, the phase assemblage PhE + Gt is observed at 14-18 GPa coexisting with fluid or melt. The phase assemblage SUB + PhD is stable at 18-25 GPa, which may extend to higher pressures and temperatures. Therefore, it is obvious that Al enhances the stabilities of these three hydrous minerals, which are stable even in the hot subducting conditions. On the other hand, the Al substitution mechanism in PhE, SUB and PhD were clarified according to chemical compositional relationship between Mg, Si, Al. This shows that they can hold a significant amount of H (water) in their structure. Our results may indicate that the wide stabilities of Al-bearing DHMS increase the chance of water transportation to deeper mantle after antigorite (serpentine) decomposition at the shallow region of the subduction zone.

First-principles study on the phase transitions, crystal stabilities and thermodynamic properties of TiN under high pressure

NASA Astrophysics Data System (ADS)

Sun, Xinjun; Liu, Changdong; Guo, Yongliang; Sun, Deyan; Ke, Xuezhi

2018-03-01

The structural and thermodynamic properties of titanium nitride (TiN) have been investigated by merging first-principles calculations and particle-swarm algorithm. The three phases are identified for TiN, including the B1, the P63 / mmc, and the B2 phases. A new phase of anti-TiP structure with the space group P63 / mmc has been predicted. The calculated phase transition from the B1 to the P63 / mmc occurs at 270 GPa. The vibrational, elastic, and thermodynamic properties for the three phases have been calculated and discussed.

New transformations between crystalline and amorphous ice

NASA Technical Reports Server (NTRS)

Hemley, R. J.; Chen, L. C.; Mao, H. K.

1989-01-01

High-pressure optical and spectroscopic techniques were used to obtain directly the ice I(h) - hda-ice transformation in a diamond-anvil cell, and the stability of the amorphous form is examined as functions of pressure and temperature. It is demonstrated that hda-ice transforms abruptly at 4 GPa and 77 K to a crystalline phase close in structure to orientationally disordered ice-VII and to a more highly ordered, ice-VIII-like structure at higher temperatures. This is the first time that an amorphous solid is observed to convert to a crystalline solid at low temperatures by compression alone. Phase transitions of this type may be relevant on icy planetary satellites, and there may also be implications for the high-pressure behavior of silica.

Tuning the Adsorption-Induced Phase Change in the Flexible Metal–Organic Framework Co(bdp)

DOE PAGES

Taylor, Mercedes K.; Runčevski, Tomče; Oktawiec, Julia; ...

2016-11-02

Metal–organic frameworks that flex to undergo structural phase changes upon gas adsorption are promising materials for gas storage and separations, and achieving synthetic control over the pressure at which these changes occur is crucial to the design of such materials for specific applications. To this end, a new family of materials based on the flexible metal–organic framework Co(bdp) (bdp 2– = 1,4-benzenedipyrazolate) has been prepared via the introduction of fluorine, deuterium, and methyl functional groups on the bdp 2– ligand, namely, Co(F-bdp), Co(p-F 2-bdp), Co(o-F 2-bdp), Co(D 4-bdp), and Co(p-Me 2-bdp). These frameworks are isoreticular to the parent framework andmore » exhibit similar structural flexibility, transitioning from a low-porosity, collapsed phase to high-porosity, expanded phases with increasing gas pressure. Powder X-ray diffraction studies reveal that fluorination of the aryl ring disrupts edge-to-face π–π interactions, which work to stabilize the collapsed phase at low gas pressures, while deuteration preserves these interactions and methylation strengthens them. In agreement with these observations, high-pressure CH 4 adsorption isotherms show that the pressure of the CH 4-induced framework expansion can be systematically controlled by ligand functionalization, as materials without edge-to-face interactions in the collapsed phase expand at lower CH 4 pressures, while frameworks with strengthened edge-to-face interactions expand at higher pressures. This work puts forth a general design strategy relevant to many other families of flexible metal–organic frameworks, which will be a powerful tool in optimizing these phase-change materials for industrial applications.« less

In situ 3D-X-ray diffraction tracking of individual grains of olivine during high-pressure/ high-temperature phase transitions

NASA Astrophysics Data System (ADS)

Rosa, A. D.; Merkel, S.; Ghosh, S.; Hilairet, N.; Perrillat, J.; Mezouar, N.; Vaughan, G.

2013-12-01

The series of phase transitions between olivine, wadsleyite and ringwoodite play an essential role for large scale dynamical processes in the Earth mantle. Detailed knowledge of the microscopic mechanism at the origin of these high-pressure and high-temperature phase transformations is useful to connect global seismic observations and geodynamics. Indeed, the textures of these phases can be induced either during mantle flow or during the phase transformations and they greatly affect the characteristics of seismic wave propagation. Here, we present a new design of diamond anvil cell experiments to collect three-dimensional diffraction images and track individual grains inside a polycristalline sample at high pressure and high temperature. The instrumentation includes a new resistively heated diamond anvil cell developed at beamline ID27 of the ESRF which provided stable and homogenous temperature condition over more than 24 hours. In our experiments, the pressure is first increased up to 12 GPa at a constant temperature of T = 800 K. The temperature is then further increased to 1300 K to reach the stability field of the high-pressure polymorph. Upon further compression the transformation of olivine to its high-pressure polymorph is successfully monitored. At each pressure-temperature step and while the sample is transforming the crystallographic parameters, the orientations and positions of grains within the sample are tracked in situ using three-dimensional X-ray diffraction. This will provide important information on the micromechanical properties of olivine including orientation statistics, orientation relations between parent and daughter phases, and transformation textures at different stages of the phase transition. This in turn will help in interpreting the geophysical observations. Details of the experimental and analytical approach used in this study will be given.

Crystal structure, equation of state, and elasticity of phase H (MgSiO4H2) at Earth's lower mantle pressures.

PubMed

Tsuchiya, Jun; Mookherjee, Mainak

2015-10-23

Dense hydrous magnesium silicate (DHMS) phases play a crucial role in transporting water in to the Earth's interior. A newly discovered DHMS, phase H (MgSiO4H2), is stable at Earth's lower mantle, i.e., at pressures greater than 30 GPa. Here we report the crystal structure and elasticity of phase H and its evolution upon compression. Using first principles simulations, we have explored the relative energetics of the candidate crystal structures with ordered and disordered configurations of magnesium and silicon atoms in the octahedral sites. At conditions relevant to Earth's lower mantle, it is likely that phase H is able to incorporate a significant amount of aluminum, which may enhance the thermodynamic stability of phase H. The sound wave velocities of phase H are ~2-4% smaller than those of isostructural δ-AlOOH. The shear wave impedance contrast due to the transformation of phase D to a mixture of phase H and stishovite at pressures relevant to the upper part of the lower mantle could partly explain the geophysical observations. The calculated elastic wave velocities and anisotropies indicate that phase H can be a source of significant seismic anisotropy in the lower mantle.

Dramatic changes in the electronic structure upon transition to the collapsed tetragonal phase in CaFe 2As 2

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

Dhaka, R. S.; Jiang, Rui; Ran, S.

2014-01-31

We use angle-resolved photoemission spectroscopy and density functional theory calculations to study the electronic structure of CaFe 2As 2 in the collapsed tetragonal (CT) phase. This unusual phase of iron arsenic high-temperature superconductors was hard to measure as it exists only under pressure. By inducing internal strain, via the postgrowth thermal treatment of single crystals, we were able to stabilize the CT phase at ambient pressure. We find significant differences in the Fermi surface topology and band dispersion data from the more common orthorhombic-antiferromagnetic or tetragonal-paramagnetic phases, consistent with electronic structure calculations. The top of the hole bands sinks belowmore » the Fermi level, which destroys the nesting present in parent phases. The absence of nesting in this phase, along with an apparent loss of Fe magnetic moment, are now clearly experimentally correlated with the lack of superconductivity in this phase.« less

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.

Tin sulfides and tin selenides at ambient and high pressure conditions

NASA Astrophysics Data System (ADS)

Nguyen Cong, Kien; Gonzalez, Joseph; Steele, Brad; Oleynik, Ivan

The application of high pressure promotes unusual chemical bonding in condensed phase resulting in the synthesis of novel materials, which may be recoverable in metastable states at ambient conditions. First-principles evolutionary crystal structure search is performed to explore novel tin sulfide (SnxSy) and tin selenide (SnxSy) crystals with the goal to discover novel photovoltaic and thermoelectric materials. Variable stoichiometry searches at various pressures are performed and the phase diagrams are constructed in the range of pressures 0-100 GPa, which include both the thermodynamically stable and lowest enthalpy metastable structures. Several new structures are identified and their dynamical stability is investigated. To help experimental synthesis of these novel compounds, Raman spectra and XRD patterns are also calculated. These new materials are also investigated to identify those with promising photovoltaic and thermoelectric properties.

Publisher's Note: High-temperature superconductivity stabilized by electron-hole interband coupling in collapsed tetragonal phase of KFe 2 As 2 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 KFe 2As 2 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 T c finds a maximum onset value of 7 K near 2 GPa, in contrast to previous reports that find a minimum T c and reversal of pressure dependence at this pressure. Upon applying higher pressures, this T c is diminished until a sudden drastic enhancement occurs coincident with a first-order structural phasemore » 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 KFe 2As 2 is substantially enhanced by the presence of nested electron and hole pockets, providing the key ingredient of high-T c superconductivity in iron pnictide superconductors.« less

Synthesis and characterization of some low and negative thermal expansion materials

NASA Astrophysics Data System (ADS)

Varga, Tamas

2005-12-01

The high-pressure behavior of several negative thermal expansion materials was studied by different methods. In-situ high-pressure x-ray and neutron diffraction studies on several compounds of the orthorhombic Sc 2W3O12 structure revealed an unusual "bulk modulus collapse" at the orthorhombic to monoclinic phase transition. In some members of the A2M3O12 family, a second phase transition and/or pressure-induced amorphization were also seen at higher pressure. The mechanism for volume contraction on compression is different from that on heating. A combined in-situ high pressure x-ray diffraction and absorption spectroscopic study has been carried out for the first time. The pressure-induced amorphization in cubic ZrW2O8 and ZrMo 2O8 was studied by following the changes in the local coordination environments of the metals. A significant change in the average tungsten coordination was found in ZrW2O8, and a less pronounced change in the molybdenum coordination in ZrMo2O8 on amorphization. A kinetically frustrated phase transition to a high-pressure crystalline phase or a kinetically hindered decomposition, are likely driving forces of the amorphization. A complementary ex-situ study confirmed the greater distortion of the framework tetrahedra in ZrW2O8, and revealed a similar distortion of the octahedra in both compounds. The possibility of stabilizing the low thermal expansion high-temperature structure in AM2O7 compounds to lower temperatures through stuffing of ZrP2O7 was explored. Although the phase transition temperature was suppressed in MIxZr 1-xMIIIxP2O7 compositions, the chemical modification employed was not successful in stabilizing the high-temperature structure to around room temperature. An attempt has been made to control the thermal expansion properties in materials of the (MIII0.5MV 0.5)P2O7-type through the choice of the metal cations and through manipulating the ordering of the cations by different heat treatment conditions. Although controlled heat treatment resulted in only short-range cation ordering, the choice of the MIII cation had a marked effect on the thermal expansion behavior of the materials. Different grades of fluorinert were examined as pressure-transmitting media for high-pressure diffraction studies. All of the fluorinerts studied became nonhydrostatic at relatively low pressures (˜1 GPa).

Dielectric Study of the Phase Transitions in [P(CH3)4]2CuY4 (Y = Cl, Br)

NASA Astrophysics Data System (ADS)

Gesi, Kazuo

2002-05-01

Phase transitions in [P(CH3)4]2CuY4 (Y = Cl, Br) have been studied by dielectric measurements. In [P(CH3)4]2CuCl4, a slight break and a discontinuous jump on the dielectric constant vs. temperature curve are seen at the normal-incommensurate and the incommensurate-commensurate phase transitions, respectively. A small peak of dielectric constant along the b-direction exists just above the incommensurate-to-commensurate transition temperature. The anisotropic dielectric anomalies of [P(CH3)4]2CuBr4 at phase transitions were measured along the three crystallographic axes. The pressure-temperature phase diagram of [P(CH3)4]2CuCl4 was determined. The initial pressure coefficients of the normal-to-incommensurate and the incommensurate-to-commensurate transition temperatures are 0.19 K/MPa and 0.27 K/MPa, respectively. The incommensurate phase in [P(CH3)4]2CuCl4 disappears at a triple point which exists at 335 MPa and 443 K. The stability and the pressure effects of the incommensurate phases are much different among the four [Z(CH3)4]2CuY4 crystals (Z = N, P; Y = Cl, Br).

Decomposition of silicon carbide at high pressures and temperatures

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

Daviau, Kierstin; Lee, Kanani K. M.

We measure the onset of decomposition of silicon carbide, SiC, to silicon and carbon (e.g., diamond) at high pressures and high temperatures in a laser-heated diamond-anvil cell. We identify decomposition through x-ray diffraction and multiwavelength imaging radiometry coupled with electron microscopy analyses on quenched samples. We find that B3 SiC (also known as 3C or zinc blende SiC) decomposes at high pressures and high temperatures, following a phase boundary with a negative slope. The high-pressure decomposition temperatures measured are considerably lower than those at ambient, with our measurements indicating that SiC begins to decompose at ~ 2000 K at 60more » GPa as compared to ~ 2800 K at ambient pressure. Once B3 SiC transitions to the high-pressure B1 (rocksalt) structure, we no longer observe decomposition, despite heating to temperatures in excess of ~ 3200 K. The temperature of decomposition and the nature of the decomposition phase boundary appear to be strongly influenced by the pressure-induced phase transitions to higher-density structures in SiC, silicon, and carbon. The decomposition of SiC at high pressure and temperature has implications for the stability of naturally forming moissanite on Earth and in carbon-rich exoplanets.« less

Effects of Phase Transformations and Dynamic Material Strength on Hydrodynamic Instability Evolution in Metals

NASA Astrophysics Data System (ADS)

Opie, Saul

Hydrodynamic phenomena such as the Rayleigh-Taylor (RT) and Richtmyer-Meshkov (RM) instabilities can be described by exponential/linear growth of surface perturbations at a bimaterial interface when subjected to constant/impulsive acceleration. A challenge in designing systems to mitigate or exploit these effects is the lack of accurate material models at large dynamic strain rates and pressures. In particular, little stress-strain constitutive information at large strain rates and pressures is available for transient material phases formed at high pressures, and the continuum effect the phase transformation process has on the instability evolution. In this work, a phase-aware isotropic strength model is developed and partially validated with a novel RM-based instability experiment in addition to existing data from the literature. With the validated material model additional simulations are performed to provide insight into to the role that robust material constitutive behavior (e.g., pressure, temperature, rate dependence) has on RM instability and how RM instability experiments can be used to characterize and validated expected material behavior. For phase aware materials, particularly iron in this work, the simulations predict a strong dependence on the Atwood number that single phase materials do not have. At Atwood numbers close to unity, and pressures in the high pressure stability region, the high pressure phase dominates the RM evolution. However, at Atwood numbers close to negative one, the RM evolution is only weakly affected by the high-pressure phase even for shocks well above the phase transformation threshold. In addition to RM evolution this work looks at the closely related shock front perturbation evolution. Existing analytical models for isentropic processes in gases and liquids are modified for metal equation of states and plastic behavior for the first time. It is found that the presence of a volume collapsing phase transformation with increased pressure causes shock front perturbations to decay sooner, while plastic strength has the opposite effect which is significantly different from the effect viscosity has. These results suggest additional experimental setups to validate material models, or relevant material parameters that can be optimized for system design objectives, e.g., minimize feed through perturbations in inertial confinement fusion capsules.

Effect of lipid viscosity and high-pressure homogenization on the physical stability of "Vitamin E" enriched emulsion.

PubMed

Alayoubi, Alaadin; Abu-Fayyad, Ahmed; Rawas-Qalaji, Mutasem M; Sylvester, Paul W; Nazzal, Sami

2015-01-01

Recently there has been a growing interest in vitamin E for its potential use in cancer therapy. The objective of this work was therefore to formulate a physically stable parenteral lipid emulsion to deliver higher doses of vitamin E than commonly used in commercial products. Specifically, the objectives were to study the effects of homogenization pressure, number of homogenizing cycles, viscosity of the oil phase, and oil content on the physical stability of emulsions fortified with high doses of vitamin E (up to 20% by weight). This was done by the use of a 27-run, 4-factor, 3-level Box-Behnken statistical design. Viscosity, homogenization pressure, and number of cycles were found to have a significant effect on particle size, which ranged from 213 to 633 nm, and on the percentage of vitamin E remaining emulsified after storage, which ranged from 17 to 100%. Increasing oil content from 10 to 20% had insignificant effect on the responses. Based on the results it was concluded that stable vitamin E rich emulsions could be prepared by repeated homogenization at higher pressures and by lowering the viscosity of the oil phase, which could be adjusted by blending the viscous vitamin E with medium-chain triglycerides (MCT).

Stabilization of ammonia-rich hydrate inside icy planets.

PubMed

Naden Robinson, Victor; Wang, Yanchao; Ma, Yanming; Hermann, Andreas

2017-08-22

The interior structure of the giant ice planets Uranus and Neptune, but also of newly discovered exoplanets, is loosely constrained, because limited observational data can be satisfied with various interior models. Although it is known that their mantles comprise large amounts of water, ammonia, and methane ices, it is unclear how these organize themselves within the planets-as homogeneous mixtures, with continuous concentration gradients, or as well-separated layers of specific composition. While individual ices have been studied in great detail under pressure, the properties of their mixtures are much less explored. We show here, using first-principles calculations, that the 2:1 ammonia hydrate, (H 2 O)(NH 3 ) 2 , is stabilized at icy planet mantle conditions due to a remarkable structural evolution. Above 65 GPa, we predict it will transform from a hydrogen-bonded molecular solid into a fully ionic phase O 2- ([Formula: see text]) 2 , where all water molecules are completely deprotonated, an unexpected bonding phenomenon not seen before. Ammonia hemihydrate is stable in a sequence of ionic phases up to 500 GPa, pressures found deep within Neptune-like planets, and thus at higher pressures than any other ammonia-water mixture. This suggests it precipitates out of any ammonia-water mixture at sufficiently high pressures and thus forms an important component of icy planets.

Stability Improvement of High-Pressure-Ratio Turbocharger Centrifugal Compressor by Asymmetric Flow Control-Part I: Non-Axisymmetrical Flow in Centrifugal Compressor.

PubMed

Yang, Mingyang; Zheng, Xinqian; Zhang, Yangjun; Bamba, Takahiro; Tamaki, Hideaki; Huenteler, Joern; Li, Zhigang

2013-03-01

This is Part I of a two-part paper documenting the development of a novel asymmetric flow control method to improve the stability of a high-pressure-ratio turbocharger centrifugal compressor. Part I focuses on the nonaxisymmetrical flow in a centrifugal compressor induced by the nonaxisymmetrical geometry of the volute while Part II describes the development of an asymmetric flow control method to avoid the stall on the basis of the characteristic of nonaxisymmetrical flow. To understand the asymmetries, experimental measurements and corresponding numerical simulation were carried out. The static pressure was measured by probes at different circumferential and stream-wise positions to gain insights about the asymmetries. The experimental results show that there is an evident nonaxisymmetrical flow pattern throughout the compressor due to the asymmetric geometry of the overhung volute. The static pressure field in the diffuser is distorted at approximately 90 deg in the rotational direction of the volute tongue throughout the diffuser. The magnitude of this distortion slightly varies with the rotational speed. The magnitude of the static pressure distortion in the impeller is a function of the rotational speed. There is a significant phase shift between the static pressure distributions at the leading edge of the splitter blades and the impeller outlet. The numerical steady state simulation neglects the aforementioned unsteady effects found in the experiments and cannot predict the phase shift, however, a detailed asymmetric flow field structure is obviously obtained.

Surface Stability and Growth Kinetics of Compound Semiconductors: An Ab Initio-Based Approach

PubMed Central

Kangawa, Yoshihiro; Akiyama, Toru; Ito, Tomonori; Shiraishi, Kenji; Nakayama, Takashi

2013-01-01

We review the surface stability and growth kinetics of III-V and III-nitride semiconductors. The theoretical approach used in these studies is based on ab initio calculations and includes gas-phase free energy. With this method, we can investigate the influence of growth conditions, such as partial pressure and temperature, on the surface stability and growth kinetics. First, we examine the feasibility of this approach by comparing calculated surface phase diagrams of GaAs(001) with experimental results. In addition, the Ga diffusion length on GaAs(001) during molecular beam epitaxy is discussed. Next, this approach is systematically applied to the reconstruction, adsorption and incorporation on various nitride semiconductor surfaces. The calculated results for nitride semiconductor surface reconstructions with polar, nonpolar, and semipolar orientations suggest that adlayer reconstructions generally appear on the polar and the semipolar surfaces. However, the stable ideal surface without adsorption is found on the nonpolar surfaces because the ideal surface satisfies the electron counting rule. Finally, the stability of hydrogen and the incorporation mechanisms of Mg and C during metalorganic vapor phase epitaxy are discussed. PMID:28811438

Lipid order, saturation and surface property relationships: a study of human meibum saturation.

PubMed

Mudgil, Poonam; Borchman, Douglas; Yappert, Marta C; Duran, Diana; Cox, Gregory W; Smith, Ryan J; Bhola, Rahul; Dennis, Gary R; Whitehall, John S

2013-11-01

Tear film stability decreases with age however the cause(s) of the instability are speculative. Perhaps the more saturated meibum from infants may contribute to tear film stability. The meibum lipid phase transition temperature and lipid hydrocarbon chain order at physiological temperature (33 °C) decrease with increasing age. It is reasonable that stronger lipid-lipid interactions could stabilize the tear film since these interactions must be broken for tear break up to occur. In this study, meibum from a pool of adult donors was saturated catalytically. The influence of saturation on meibum hydrocarbon chain order was determined by infrared spectroscopy. Meibum is in an anhydrous state in the meibomian glands and on the surface of the eyelid. The influence of saturation on the surface properties of meibum was determined using Langmuir trough technology. Saturation of native human meibum did not change the minimum or maximum values of hydrocarbon chain order so at temperatures far above or below the phase transition of human meibum, saturation does not play a role in ordering or disordering the lipid hydrocarbon chains. Saturation did increase the phase transition temperature in human meibum by over 20 °C, a relatively high amount. Surface pressure-area studies showing the late take off and higher maximum surface pressure of saturated meibum compared to native meibum suggest that the saturated meibum film is quite molecularly ordered (stiff molecular arrangement) and elastic (molecules are able to rearrange during compression and expansion) compared with native meibum films which are more fluid agreeing with the infrared spectroscopic results of this study. In saturated meibum, the formation of compacted ordered islands of lipids above the surfactant layer would be expected to decrease the rate of evaporation compared to fluid and more loosely packed native meibum. Higher surface pressure observed with films of saturated meibum compared to native meibum suggests greater film stability especially under the high shear stress of a blink. Copyright © 2013 Elsevier Ltd. All rights reserved.

High pressure study of a highly energetic nitrogen-rich carbon nitride, cyanuric triazide

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

Laniel, Dominique; Desgreniers, Serge; Downie, Laura E.

Cyanuric triazide (CTA), a nitrogen-rich energetic material, was compressed in a diamond anvil cell up to 63.2 GPa. Samples were characterized by x-ray diffraction, Raman, and infrared spectroscopy. A phase transition occurring between 29.8 and 30.7 GPa was found by all three techniques. The bulk modulus and its pressure derivative of the low pressure phase were determined by fitting the 300 K isothermal compression data to the Birch-Murnaghan equation of state. Due to the strong photosensitivity of CTA, synchrotron generated x-rays and visible laser radiation both lead to the progressive conversion of CTA into a two dimensional amorphous C=N network,more » starting from 9.2 GPa. As a result of the conversion, increasingly weak and broad x-ray diffraction lines were recorded from crystalline CTA as a function of pressure. Hence, a definite structure could not be obtained for the high pressure phase of CTA. Results from infrared spectroscopy carried out to 40.5 GPa suggest the high pressure formation of a lattice built of tri-tetrazole molecular units. The decompression study showed stability of the high pressure phase down to 13.9 GPa. Finally, two CTA samples, one loaded with neon and the other with nitrogen, used as pressure transmitting media, were laser-heated to approximately 1100 K and 1500 K while compressed at 37.7 GPa and 42.0 GPa, respectively. In both cases CTA decomposed resulting in amorphous compounds, as recovered at ambient conditions.« less

On the mechanical stability of the body-centered cubic phase and the emergence of a metastable cI16 phase in classical hard sphere solids

NASA Astrophysics Data System (ADS)

Warshavsky, Vadim B.; Ford, David M.; Monson, Peter A.

2018-01-01

The stability of the body-centered cubic (bcc) solid phase of classical hard spheres is of intrinsic interest and is also relevant to the development of perturbation theories for bcc solids of other model systems. Using canonical ensemble Monte Carlo, we simulated systems initialized in a perfect bcc lattice at various densities in the solid region. We observed that the systems rapidly evolved into one of four structures that then persisted for the duration of the simulation. Remarkably, one of these structures was identified as cI16, a cubic crystalline structure with 16 particles in the unit cell, which has recently been observed experimentally in lithium and sodium solids at high pressures. The other three structures do not exhibit crystalline order but are characterized by common patterns in the radial distribution function and bond-orientational order parameter distribution; we refer to them as bcc-di, with i ranging from 1 to 3. We found similar outcomes when employing any of the three single occupancy cell (SOC) restrictions commonly used in the literature. We also ran long constant-pressure simulations with box shape fluctuations initiated from bcc and cI16 initial configurations. At lower pressures, all the systems evolved to defective face-centered cubic (fcc) or hexagonal close-packed (hcp) structures. At higher pressures, most of the systems initiated as bcc evolved to cI16 with some evolving to defective fcc/hcp. High pressure systems initiated from cI16 remained in that structure. We computed the chemical potential of cI16 using the Einstein crystal reference method and found that it is higher than that of fcc by ˜0.5kT-2.5kT over the pressure range studied, with the difference increasing with pressure. We find that the undistorted bcc solid, even with constant-volume and SOC restrictions applied, is so mechanically unstable that it is unsuitable for consideration as a metastable phase or as a reference system for studying bcc phases of other systems. On the other hand, cI16 is a mechanically stable structure that can spontaneously emerge from a bcc starting point but it is thermodynamically metastable relative to fcc or hcp.

Structure and Stability of High-Pressure Dolomite with Implications for the Earth's Deep Carbon Cycle

NASA Astrophysics Data System (ADS)

Solomatova, N. V.; Asimow, P. D.

2014-12-01

Carbon is subducted into the mantle primarily in the form of metasomatically calcium-enriched basaltic rock, calcified serpentinites and carbonaceous ooze. The fate of these carbonates in subduction zones is not well understood. End-member CaMg(CO3)2 dolomite typically breaks down into two carbonates at 2-7 GPa, which may further decompose to oxides and CO2-bearing fluid. However, high-pressure X-ray diffraction experiments have recently shown that the presence of iron may be sufficient to stabilize dolomite I to high pressures, allowing the transformation to dolomite II at 17 GPa and subsequently to dolomite III at 35 GPa [1][2]. Such phases may be a principal host for deeply subducted carbon. The structure and equation of state of these high-pressure phases is debated and the effect of varying concentrations of iron is unknown, creating a need for theoretical calculations. Here we compare calculated dolomite structures to experimentally observed phases. Using the Vienna ab-initio simulation package (VASP) interfaced with a genetic algorithm that predicts crystal structures (USPEX), a monoclinic phase with space group 5 ("dolomite sg5") was found for pure end-member dolomite. Dolomite sg5 has a lower energy than reported dolomite structures and an equation of state that resembles that of dolomite III. It is possible that dolomite sg5 is not achieved experimentally due to a large energy barrier and a correspondingly large required volume drop, resulting in the transformation to metastable dolomite II. Due to the complex energy landscape for candidate high-pressure dolomite structures, it is likely that several competing polymorphs exist. Determining the behavior of high-pressure Ca-Mg-Fe(-Mn) dolomite phases in subduction environments is critical for our understanding of the Earth's deep carbon cycle and supercell calculations with Fe substitution are in progress. [1] Mao, Z., Armentrout, M., Rainey, E., Manning, C. E., Dera, P., Prakapenka, V. B., and Kavner, A. (2011). Dolomite III: A new candidate lower mantle carbonate. Geophy. Res. Lett., 38(22). [2] Merlini, M., Crichton, W. A., Hanfland, M., Gemmi, M., Müller, H., Kupenko, I., and Dubrovinsky, L. (2012). Structures of dolomite at ultrahigh pressure and their influence on the deep carbon cycle. Proc. Nat. Acad. Sci., 109(34), 13509-13514.

The stability of anhydrous phase B, Mg14Si5O24, at mantle transition zone conditions

NASA Astrophysics Data System (ADS)

Yuan, Liang; Ohtani, Eiji; Shibazaki, Yuki; Ozawa, Shin; Jin, Zhenmin; Suzuki, Akio; Frost, Daniel J.

2018-06-01

The stability of anhydrous phase B, Mg14Si5O24, has been determined in the pressure range of 14-21 GPa and the temperature range of 1100-1700 °C with both normal and reversal experiments using multi-anvil apparatus. Our results demonstrate that anhydrous phase B is stable at pressure-temperature conditions corresponding to the shallow depth region of the mantle's transition zone and it decomposes into periclase and wadsleyite at greater depths. The decomposition boundary of anhydrous phase B into wadsleyite and periclase has a positive phase transition slope and can be expressed by the following equation: P(GPa) = 7.5 + 6.6 × 10-3 T (°C). This result is consistent with a recent result on the decomposition boundary of anhydrous phase B (Kojitani et al., Am Miner 102:2032-2044, 2017). However, our phase boundary deviates significantly from this previous study at temperatures < 1400 °C. Subducting carbonates may be reduced at depths > 250 km, which could contribute ferropericlase (Mg, Fe)O or magnesiowustite (Fe, Mg)O into the deep mantle. Incongruent melting of hydrous peridotite may also produce MgO-rich compounds. Anh-B could form in these conditions due to reactions between Mg-rich oxides and silicates. Anh-B might provide a new interpretation for the origin of diamonds containing ferropericlase-olivine inclusions and chromitites which have been found to have ultrahigh-pressure characteristics. We propose that directly touching ferropericlase-olivine inclusions found in natural diamonds might be the retrogressive products of anhydrous phase B decomposing via the reaction (Mg,Fe)14Si5O24 (Anh-B) = (Mg,Fe)2SiO4 (olivine) + (Mg,Fe)O (periclase). This decomposition may occur during the transportation of the host diamonds from their formation depths of < 500 km in the upper part of the mantle transition zone to the surface.

The stability of anhydrous phase B, Mg14Si5O24, at mantle transition zone conditions

NASA Astrophysics Data System (ADS)

Yuan, Liang; Ohtani, Eiji; Shibazaki, Yuki; Ozawa, Shin; Jin, Zhenmin; Suzuki, Akio; Frost, Daniel J.

2017-12-01

The stability of anhydrous phase B, Mg14Si5O24, has been determined in the pressure range of 14-21 GPa and the temperature range of 1100-1700 °C with both normal and reversal experiments using multi-anvil apparatus. Our results demonstrate that anhydrous phase B is stable at pressure-temperature conditions corresponding to the shallow depth region of the mantle's transition zone and it decomposes into periclase and wadsleyite at greater depths. The decomposition boundary of anhydrous phase B into wadsleyite and periclase has a positive phase transition slope and can be expressed by the following equation: P(GPa) = 7.5 + 6.6 × 10-3 T (°C). This result is consistent with a recent result on the decomposition boundary of anhydrous phase B (Kojitani et al., Am Miner 102:2032-2044, 2017). However, our phase boundary deviates significantly from this previous study at temperatures < 1400 °C. Subducting carbonates may be reduced at depths > 250 km, which could contribute ferropericlase (Mg, Fe)O or magnesiowustite (Fe, Mg)O into the deep mantle. Incongruent melting of hydrous peridotite may also produce MgO-rich compounds. Anh-B could form in these conditions due to reactions between Mg-rich oxides and silicates. Anh-B might provide a new interpretation for the origin of diamonds containing ferropericlase-olivine inclusions and chromitites which have been found to have ultrahigh-pressure characteristics. We propose that directly touching ferropericlase-olivine inclusions found in natural diamonds might be the retrogressive products of anhydrous phase B decomposing via the reaction (Mg,Fe)14Si5O24 (Anh-B) = (Mg,Fe)2SiO4 (olivine) + (Mg,Fe)O (periclase). This decomposition may occur during the transportation of the host diamonds from their formation depths of < 500 km in the upper part of the mantle transition zone to the surface.

High-pressure phase transitions of strontianite

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Phase Transitions in the system CaCO3 at high P and T determined by in-situ Vibrational Spectroscopy in Diamond-Anvil-Cells

NASA Astrophysics Data System (ADS)

Koch-Mueller, M.; Jahn, S.; Birkholz, N.; Schade, U.

2013-12-01

Carbonates are the most abundant carbon-bearing minerals on Earth. They can be transported into the upper and lower mantle via subduction processes. Knowledge of the stability of solid carbonates adapting different structures with increasing pressure and temperature is therefore of great importance to understand the structure and dynamics of the Earth. Even for the very simple system CaCO3, the phase relations at high pressure and temperature are only poorly understood. It has been known for many years that calcite (cc) can adopt different structures with increasing pressure (e.g. Bridgman, 1939: cc-I to III; Tyburczy and Ahrens, 1986: cc-VI). But only recently Merlini et al. (2012) were able to solve the crystal structures of some of these high pressure polymoprhs namely cc-III, cc-IIIb and cc-VI. They report that cc-VI has a higher density then aragonite under the same conditions. To study the stability of the CaCO3-polymorphs, experiments were performed in conventional diamond anvil cells (DAC) at ambient temperatures as a function of pressure up to 30 GPa as well as in internally heated diamond anvil cells (DAC-HT) in the pressure range 9 to 20 GPa and temperatures up to 800 K. As probe for the structural changes we used conventional mid-infrared-, synchrotron far-infrared- and Raman-spectroscopy. Within the cc-III stability field (3 to 15 GPa at room temperature, e.g. Catalli and Williams, 2005) we observed in all types of experiments consistently two different spectral patterns: one at lower P < 5 GPa and another at P > 5 < 15 GPa independent on the starting material and the pressure- and time-path of the experiments. Whether these P-induced structural changes may be linked to the above mentioned different structures of cc-III is not yet clear. Also, in all types of experiments we confirmed the transition of cc-III to cc-VI at about 15 GPa at room temperature. Merlini et al. (2012) speculated that temperature may stabilize the structures of cc-III to lower pressure and surprisingly we found the same for the cc-III to cc-VI transition. The reaction has a negative slope of about -0.007 GPa/K. Thus, under the P, T- conditions of the Earth's mantle cc-VI may be stabilized towards lower pressure replacing aragonite in some parts of the mantle. References Bridgman P.W. (1939) Am J Sci, 237, 7 - 18. Catalli K. and Williams Q. (2005) Am Mineral, 90, 1679 - 1682. Merlini M. (2012) EPSL, 333-334, 265 - 271. Tyburczy J. A. and Ahrens T. J. (1986) J Geophysical Research, 91, 4730 - 4744.

Stability of Pseudobrookite-Type Titanium Oxides

NASA Technical Reports Server (NTRS)

Xirouchakis, Dimistrios

2002-01-01

Orthorhombic, (Bbmm), (Al, Fe, Cr, Ti)(sub 2) TiO5-(Mg, Fe)Ti2O5 solid solutions (pseudobrookites, s.l.) are found either as an oxidation product of ilmenite and/or spinel or a primary crystallizing phase in igneous and metamorphic rocks on Earth (e.g., basalt flows, crustal and mantle xenoliths, hornfels), and basaltic rocks on the Moon. Moreover, orthorhombic oxides are often part of the crystalline matrix in glass/ceramics with useful applications, and play a major role in the industrial production of TiO2. To fully exploit the potential of these compounds as petrogenetic indicators and/or useful materials we need to quantitatively understand the factors controlling their properties and stability, and thus, to extrapolate beyond the calibrating experiments. For that purpose, we need to combine thermochemistry, phase equilibrium, and in situ P-V-T-cation disorder experimental data that presently either are incomplete or lacking. Perhaps, the most complete data set is that for MgTi2O5 (karrooite) which allows the calibration of models for the Gibbs free energy of the MgTi2O5 as a function of pressure, temperature, and the Mg2+-Ti4+ distribution between the two nonequivalent octahedral sites. Consequently, the effect of cation disorder on MgTi2O5 stability, and the phase relations among MgTi2O5, other titanium oxides, and silicate minerals can be examined. Calculated phase relations in the Mg-Ti-Si-O system and phase equilibrium experiments in Fe-bearing compositions suggest that pseudobrookite-type oxides may be a more common in rocks than previously realized. However, homogeneous and heterogeneous equilibria, and crystallization paths likely affect their stability. For example, isobaric increases in temperature favor disordering and thus entropy-stabilization, in contrast, isothermal increases in pressure have the opposite effect. Although, currently, the potential effect of composition to cation disorder cannot be fully explored, it appears that enrichment in trivalent cations probably enhances entropy-stabilization and thus may increase the stability of (Al, Fe, Cr, Ti)-rich pseudobrookites relative to that of (Mg, Fe)-rich ones. In addition, high-temperature, nearly isothermal, decompression paths of olivine+orthopyroxene+oxide assemblages may favor pseudobrookites (s.l.) over rutile and/or ilmenite, in contrast, cooling at low pressures seems to favor ilmenite and/or rutile. In the case of crustal and mantle xenoliths, the presence or absence of orthorhombic oxides is probably controlled by reactions with olivine, orthopyroxene, ilmenite, and rutile. In oceanic mantle xenoliths such reactions may also involve a TiO2-enriched but not SiO2-enriched melt/fluid, because pseudobrookites (s.l.) would react with the SiO2-enriched melt/fluid to form orthopyroxene and rutile. Parenthetically, experiments and model calculations in the Mg-Ti-Si-O system suggest that low degree partial melting of low-TiO2 bulk compositions may produce Ti-enriched liquids in equilibrium with olivine, orthopyroxen ad=nd MgTi2O5, rutile or ilmenite.

Stability of Fe,Al-bearing bridgmanite in the lower mantle and synthesis of pure Fe-bridgmanite

PubMed Central

Ismailova, Leyla; Bykova, Elena; Bykov, Maxim; Cerantola, Valerio; McCammon, Catherine; Boffa Ballaran, Tiziana; Bobrov, Andrei; Sinmyo, Ryosuke; Dubrovinskaia, Natalia; Glazyrin, Konstantin; Liermann, Hanns-Peter; Kupenko, Ilya; Hanfland, Michael; Prescher, Clemens; Prakapenka, Vitali; Svitlyk, Volodymyr; Dubrovinsky, Leonid

2016-01-01

The physical and chemical properties of Earth’s mantle, as well as its dynamics and evolution, heavily depend on the phase composition of the region. On the basis of experiments in laser-heated diamond anvil cells, we demonstrate that Fe,Al-bearing bridgmanite (magnesium silicate perovskite) is stable to pressures over 120 GPa and temperatures above 3000 K. Ferric iron stabilizes Fe-rich bridgmanite such that we were able to synthesize pure iron bridgmanite at pressures between ~45 and 110 GPa. The compressibility of ferric iron–bearing bridgmanite is significantly different from any known bridgmanite, which has direct implications for the interpretation of seismic tomography data. PMID:27453945

Reconstructed phase spaces of intrinsic mode functions. Application to postural stability analysis.

PubMed

Snoussi, Hichem; Amoud, Hassan; Doussot, Michel; Hewson, David; Duchêne, Jacques

2006-01-01

In this contribution, we propose an efficient nonlinear analysis method characterizing postural steadiness. The analyzed signal is the displacement of the centre of pressure (COP) collected from a force plate used for measuring postural sway. The proposed method consists of analyzing the nonlinear dynamics of the intrinsic mode functions (IMF) of the COP signal. The nonlinear properties are assessed through the reconstructed phase spaces of the different IMFs. This study shows some specific geometries of the attractors of some intrinsic modes. Moreover, the volume spanned by the geometric attractors in the reconstructed phase space represents an efficient indicator of the postural stability of the subject. Experiments results corroborate the effectiveness of the method to blindly discriminate young subjects, elderly subjects and subjects presenting a risk of falling.

Capacity retention in hydrogen storage alloys

NASA Technical Reports Server (NTRS)

Anani, A.; Visintin, A.; Srinivasan, S.; Appleby, A. J.; Reilly, J. J.; Johnson, J. R.

1992-01-01

Results of our examination of the properties of several candidate materials for hydrogen storage electrodes and their relation to the decrease in H-storage capacity upon open-circuit storage over time are reported. In some of the alloy samples examined to date, only about 10 percent of the hydrogen capacity was lost upon storage for 20 days, while in others, this number was as high as 30 percent for the same period of time. This loss in capacity is attributed to two separate mechanisms: (1) hydrogen desorbed from the electrode due to pressure differences between the cell and the electrode sample; and (2) chemical and/or electrochemical degradation of the alloy electrode upon exposure to the cell environment. The former process is a direct consequence of the equilibrium dissociation pressure of the hydride alloy phase and the partial pressure of hydrogen in the hydride phase in equilibrium with that in the electrolyte environment, while the latter is related to the stability of the alloy phase in the cell environment. Comparison of the equilibrium gas-phase dissociation pressures of these alloys indicate that reversible loss of hydrogen capacity is higher in alloys with P(eqm) greater than 1 atm than in those with P(eqm) less than 1 atm.

Enhancement of Edge Stability with Lithium Wall Coatings in NSTX

NASA Astrophysics Data System (ADS)

Maingi, R.; Bell, R. E.; Leblanc, B. P.; Kaita, R.; Kaye, S. M.; Kugel, H. W.; Mansfield, D. K.; Osborne, T. H.

2008-11-01

ELM reduction or elimination while maintaining high confinement is essential for ITER, which has been designed for H-mode operation. Large ELMs are thought to be triggered by exceeding either edge current density and/or pressure gradient limits (peeling, ballooning modes). Stability calculations show that spherical tori should have access to higher pressure gradients and pedestal heights than higher R/a tokamaks, owing to access to second stability regimes[...1]. An ELM-free regime was recently observed in the NSTX following the application of lithium onto the graphite plasma facing components[......2]. ELMs were eliminated in phases[.....3], with the resulting pressure gradients and pedestal widths increasing substantially. Calculations with TRANSP have shown that the edge bootstrap current increased substantially, consistent with second stability access. These ELM-free discharges have a substantial improvement in energy confinement, up to the global βN˜ 5.5 limit. * Supported by US DOE DE-FG02-04ER54520, DE-AC-76CH03073, and DE-FC02-04ER54698. [.1] P. B. Snyder, et. al., Plasma Phys. Contr. Fusion 46 (2004) A131. [2] H. W. Kugel, et. al., Phys. Plasma 15 (2008) #056118. [3] D. M. Mansfield, et. al., J. Nucl. Materials (2009) submitted.

Electrical Resistivity of natural Marcasite at High-pressures

NASA Astrophysics Data System (ADS)

Parthasarathy, Gopalakrishnarao

2013-06-01

Marcasite is considered to be a common iron sulfide in reducing Martian sediments and may enclose microbial remains during growth and hence study of marcasite may have significance in the search for fossil life on Mars. The high-pressure phase stability investigations of marcasite are useful in understanding the sulfide mineralogy of Martian surface, affected by meteorite impacts. The sulfides were characterized by electron microprobe micro analyses (EPMA), powder X-ray diffraction, DTA, and FTIR spectroscopic measurements. The samples were powdered using a porcelain mortar and pestle. The chemical composition of the sample was determined by an electron probe micro-analyzer (EPMA). High-pressure electrical resistivity measurements were carried out on natural marcasite, and marcasite rich samples (Marcasite 95 mol % pyrite 5 mol %) up to 7 GPa. Marcasite sample shows a discontinuous decrease in the electrical resistivity at 5. 2 (+/- 0.5) GPa indicating a first order phase transition. The Differential thermal analyses and the Fourier transform infrared spectroscopic measurements on the pressure quenched sample shows the characteristics of pyrite, indicating the pressure induced marcasite-to -pyrite transition of the natural marcasite at 5. 2 (+/- 0.5) GPa. The observation of marcasite to pyrite phase transition may be useful in estimating the pressure experienced by shock events on the Martian surface as well as the meteorites where marcasite- pyrite phases coexist. Financial support from CSIR-SHORE-PSC0205.

A high-pressure van der Waals compound in solid nitrogen-helium mixtures

NASA Technical Reports Server (NTRS)

Vos, W. L.; Finger, L. W.; Hemley, R. J.; Hu, J. Z.; Mao, H. K.; Schouten, J. A.

1992-01-01

A detailed diamond anvil-cell study using synchrotron X-ray diffraction, Raman scattering, and optical microscopy has been conducted for the He-N system, with a view to the weakly-bound van der Waals molecule interactions that can be formed in the gas phase. High pressure is found to stabilize the formation of a stoichiometric, solid van der Waals compound of He(N2)11 composition which may exemplify a novel class of compounds found at high pressures in the interiors of the outer planets and their satellites.

Experimental investigation of condensation predictions for dust-enriched systems

NASA Astrophysics Data System (ADS)

Ustunisik, Gokce; Ebel, Denton S.; Walker, David; Boesenberg, Joseph S.

2014-10-01

Condensation models describe the equilibrium distribution of elements between coexisting phases (mineral solid solutions, silicate liquid, and vapor) in a closed chemical system, where the vapor phase is always present, using equations of state of the phases involved at a fixed total pressure (<1 bar) and temperature (T). The VAPORS code uses a CaO-MgO-Al2O3-SiO2 (CMAS) liquid model at T above the stability field of olivine, and the MELTS thermodynamics algorithm at lower T. Quenched high-T crystal + liquid assemblages are preserved in meteorites as Type B Ca-, Al-rich inclusions (CAIs), and olivine-rich ferromagnesian chondrules. Experimental tests of compositional regions within 100 K of the predicted T of olivine stability may clarify the nature of the phases present, the phase boundaries, and the partition of trace elements among these phases. Twenty-three Pt-loop equilibrium experiments in seven phase fields on twelve bulk compositions at specific T and dust enrichment factors tested the predicted stability fields of forsteritic olivine (Mg2SiO4), enstatite (MgSiO3), Cr-bearing spinel (MgAl2O4), perovskite (CaTiO3), melilite (Ca2Al2SiO7-Ca2Mg2Si2O7) and/or grossite (CaAl4O7) crystallizing from liquid. Experimental results for forsterite, enstatite, and grossite are in very good agreement with predictions, both in chemistry and phase abundances. On the other hand the stability of spinel with olivine, and stability of perovskite and gehlenite are quite different from predictions. Perovskite is absent in all experiments. Even at low oxygen fugacity (IW-3.4), the most TiO2-rich experiments do not crystallize Al-, Ti-bearing calcic pyroxene. The stability of spinel and olivine together is limited to a smaller phase field than is predicted. The melilite stability field is much larger than predicted, indicating a deficiency of current liquid or melilite activity models. In that respect, these experiments contribute to improving the data for calibrating thermodynamic models including MELTS.

Higher-order compositional modeling of three-phase flow in 3D fractured porous media based on cross-flow equilibrium

NASA Astrophysics Data System (ADS)

Moortgat, Joachim; Firoozabadi, Abbas

2013-10-01

Numerical simulation of multiphase compositional flow in fractured porous media, when all the species can transfer between the phases, is a real challenge. Despite the broad applications in hydrocarbon reservoir engineering and hydrology, a compositional numerical simulator for three-phase flow in fractured media has not appeared in the literature, to the best of our knowledge. In this work, we present a three-phase fully compositional simulator for fractured media, based on higher-order finite element methods. To achieve computational efficiency, we invoke the cross-flow equilibrium (CFE) concept between discrete fractures and a small neighborhood in the matrix blocks. We adopt the mixed hybrid finite element (MHFE) method to approximate convective Darcy fluxes and the pressure equation. This approach is the most natural choice for flow in fractured media. The mass balance equations are discretized by the discontinuous Galerkin (DG) method, which is perhaps the most efficient approach to capture physical discontinuities in phase properties at the matrix-fracture interfaces and at phase boundaries. In this work, we account for gravity and Fickian diffusion. The modeling of capillary effects is discussed in a separate paper. We present the mathematical framework, using the implicit-pressure-explicit-composition (IMPEC) scheme, which facilitates rigorous thermodynamic stability analyses and the computation of phase behavior effects to account for transfer of species between the phases. A deceptively simple CFL condition is implemented to improve numerical stability and accuracy. We provide six numerical examples at both small and larger scales and in two and three dimensions, to demonstrate powerful features of the formulation.

Neutron diffraction study, magnetic properties and thermal stability of YMn 2D 6 synthesized under high deuterium pressure

NASA Astrophysics Data System (ADS)

Paul-Boncour, V.; Filipek, S. M.; Dorogova, M.; Bourée, F.; André, G.; Marchuk, I.; Percheron-Guégan, A.; Liu, R. S.

2005-01-01

A new phase YMn 2D 6 was synthesized by submitting YMn 2 to 1.7 kbar deuterium pressure at 473 K. According to X-ray and neutron powder diffraction experiments, YMn 2D 6 crystallizes in the Fm3¯m space group with a=6.709(1) Å at 300 K. The Y and half of the Mn atoms occupy statistically the 8 c site whereas the other Mn atoms are located in 4 a site and surrounded by 6 D atoms (24 e). This corresponds to a K 2PtCl 6-type structure with a partially disordered substructure which can be written as [YMn]MnH 6. No ordered magnetic moment is observed in the NPD patterns and the magnetization measurements display a paramagnetic behavior. The study of the thermal stability by Differential Scanning Calorimetry and XRD experiments indicates that this phase decomposes in YD 2 and Mn at 625 K, and is more stable than YMn 2H 4.5.

Wettability and Flow Rate Impacts on Immiscible Displacement: A Theoretical Model

NASA Astrophysics Data System (ADS)

Hu, Ran; Wan, Jiamin; Yang, Zhibing; Chen, Yi-Feng; Tokunaga, Tetsu

2018-04-01

When a more viscous fluid displaces a less viscous one in porous media, viscous pressure drop stabilizes the displacement front against capillary pressure fluctuation. For this favorable viscous ratio conditions, previous studies focused on the front instability under slow flow conditions but did not address competing effects of wettability and flow rate. Here we study how this competition controls displacement patterns. We propose a theoretical model that describes the crossover from fingering to stable flow as a function of invading fluid contact angle θ and capillary number Ca. The phase diagram predicted by the model shows that decreasing θ stabilizes the displacement for θ≥45° and the critical contact angle θc increases with Ca. The boundary between corner flow and cooperative filling for θ < 45° is also described. This work extends the classic phase diagram and has potential applications in predicting CO2 capillary trapping and manipulating wettability to enhance gas/oil displacement efficiency.

Viscosity and stability of ultra-high internal phase CO2-in-water foams stabilized with surfactants and nanoparticles with or without polyelectrolytes.

PubMed

Xue, Zheng; Worthen, Andrew; Qajar, Ali; Robert, Isaiah; Bryant, Steven L; Huh, Chun; Prodanović, Maša; Johnston, Keith P

2016-01-01

To date, relatively few examples of ultra-high internal phase supercritical CO2-in-water foams (also referred to as macroemulsions) have been observed, despite interest in applications including "waterless" hydraulic fracturing in energy production. The viscosities and stabilities of foams up to 0.98 CO2 volume fraction were investigated in terms of foam bubble size, interfacial tension, and bulk and surface viscosity. The foams were stabilized with laurylamidopropyl betaine (LAPB) surfactant and silica nanoparticles (NPs), with and without partially hydrolyzed polyacrylamide (HPAM). For foams stabilized with mixture of LAPB and NPs, fine ∼70 μm bubbles and high viscosities on the order of 100 cP at>0.90 internal phase fraction were stabilized for hours to days. The surfactant reduces interfacial tension, and thus facilitates bubble generation and decreases the capillary pressure to reduce the drainage rate of the lamella. The LAPB, which is in the cationic protonated form, also attracts anionic NPs (and anionic HPAM in systems containing polymer) to the interface. The adsorbed NPs at the interface are shown to slow down Ostwald ripening (with or without polymer added) and increase foam stability. In systems with added HPAM, the increase in the bulk and surface viscosity of the aqueous phase further decreases the lamella drainage rate and inhibits coalescence of foams. Thus, the added polymer increases the foam viscosity by threefold. Scaling law analysis shows the viscosity of 0.90 volume fraction foams is inversely proportional to the bubble size. Copyright © 2015 Elsevier Inc. All rights reserved.

Postaragonite phases of CaCO3 at lower mantle pressures

NASA Astrophysics Data System (ADS)

Smith, Dean; Lawler, Keith V.; Martinez-Canales, Miguel; Daykin, Austin W.; Fussell, Zachary; Smith, G. Alexander; Childs, Christian; Smith, Jesse S.; Pickard, Chris J.; Salamat, Ashkan

2018-01-01

The stability, structure, and properties of carbonate minerals at lower mantle conditions have significant impact on our understanding of the global carbon cycle and the composition of the interior of the Earth. In recent years there has been significant interest in the behavior of carbonates at lower mantle conditions, specifically in their carbon hybridization, which has relevance for the storage of carbon within the deep mantle. Using high-pressure synchrotron x-ray diffraction in a diamond anvil cell coupled with direct laser heating of CaCO3 using a CO2 laser, we identify a crystalline phase of the material above 40 GPa—corresponding to a lower mantle depth of around 1000 km—which has first been predicted by ab initio structure predictions. The observed s p2 carbon hybridized species at 40 GPa is monoclinic with P 21/c symmetry and is stable up to 50 GPa, above which it transforms into a structure which cannot be indexed by existing known phases. A combination of ab initio random structure search (AIRSS) and quasiharmonic approximation (QHA) calculations are used to re-explore the relative phase stabilities of the rich phase diagram of CaCO3. Nudged elastic band (NEB) calculations are used to investigate the reaction mechanisms between relevant crystal phases of CaCO3 and we postulate that the mineral is capable of undergoing s p2-s p3 hybridization change purely in the P 21/c structure—forgoing the accepted postaragonite P m m n structure.

Thermal, optical, and dielectric properties of fluoride Rb2TaF7

NASA Astrophysics Data System (ADS)

Pogorel'tsev, E. I.; Mel'nikova, S. V.; Kartashev, A. V.; Gorev, M. V.; Flerov, I. N.; Laptash, N. M.

2017-05-01

The thermal, optical, and dielectric properties of fluoride Rb2TaF7 were investigated. It was observed that the variation in chemical pressure in fluorides A 2 +TaF7 caused by the cation substitution of rubidium for ammonium does not affect the ferroelastic nature of structural distortions, but leads to stabilization of the high- and low-temperature phases and enhancement of birefringence. The entropy of the phase transition P4/nmm ↔ Cmma is typical of the shift transformations, which is consistent with a model of the initial and distorted phase structures. The anisotropy of chemical pressure causes the change of signs of the anomalous strain and baric coefficient dT/ dp of Rb2TaF7 as compared with the values for its ammonium analog.

The structural phase diagram and oxygen equilibrium partial pressure of YBa 2Cu 3O 6+ x studied by neutron powder diffraction and gas volumetry

NASA Astrophysics Data System (ADS)

Andersen, N. H.; Lebech, B.; Poulsen, H. F.

1990-12-01

An experimental technique based on neutron powder diffraction and gas volumetry is presented and used to study the structural phase diagram of YBa 2Cu 3O 6+ x under equilibrium conditions in an extended part of ( x, T)-phase (0.15< x<0.92 and 25° C< T<725°C). Our experimental observations lend strong support to a recent two-dimensional anisotropic next-nearest-neighbour Ising model calculation (the ASYNNNI model) of the basal plane oxygen ordering based of first principle interaction parameters. Simultaneous measurements of the oxygen equilibrium partial pressure show anomalies, one of which proves the thermodynamic stability of the orthorhombic OII double cell structure. Striking similarity with predictions of recent model calculations support that another anomaly may be interpreted to result from local one-dimensional fluctuations in the distribution of oxygen atoms in the basal plane of tetragonal YBCO. Our pressure data also indicate that x=0.92 is a maximum obtainable oxygen concentration for oxygen pressures below 760 Torr.

Comparison of segmental spinal movement control in adolescents with and without idiopathic scoliosis using modified pressure biofeedback unit.

PubMed

Luo, Hong-Ji; Lin, Shi-Xiang; Wu, Shyi-Kuen; Tsai, Mei-Wun; Lee, Shwn-Jen

2017-01-01

Postural rehabilitation emphasizing on motor control training of segmental spinal movements has been proposed to effectively reduce the scoliotic spinal deformities in adolescent idiopathic scoliosis (AIS). However, information regarding the impairments of segmental spinal movement control involving segmental spinal stabilizers in adolescent idiopathic scoliosis remains limited. Examination of segmental spinal movement control may provide a window for investigating the features of impaired movement control specific to spinal segments that may assist in the development of physiotherapeutic management of AIS. To compare segmental spinal movement control in adolescents with and without idiopathic scoliosis using modified pressure biofeedback unit. Segmental spinal movement control was assessed in twenty adolescents with idiopathic scoliosis (AISG) and twenty healthy adolescents (CG) using a modified pressure biofeedback unit. Participants performed segmental spinal movements that primarily involved segmental spinal stabilizing muscles with graded and sustained muscle contraction against/off a pressure cuff from baseline to target pressures and then maintained for 1 min. Pressure data during the 1-minute maintenance phase were collected for further analysis. Pressure deviation were calculated and compared between groups. The AISG had significantly greater pressure deviations for all segmental spinal movements of cervical, thoracic, and lumbar spine than the CG. Pressure biofeedback unit was feasible for assessing segmental spinal movement control in AIS. AISG exhibited poorer ability to grade and sustain muscle activities for local movements of cervical, thoracic, and lumbar spine, suggesting motor control training of segmental spinal movements involving segmental spinal stabilizing muscles on frontal, sagittal, and transverse planes were required.

Pressure cell for investigations of solid-liquid interfaces by neutron reflectivity.

PubMed

Kreuzer, Martin; Kaltofen, Thomas; Steitz, Roland; Zehnder, Beat H; Dahint, Reiner

2011-02-01

We describe an apparatus for measuring scattering length density and structure of molecular layers at planar solid-liquid interfaces under high hydrostatic pressure conditions. The device is designed for in situ characterizations utilizing neutron reflectometry in the pressure range 0.1-100 MPa at temperatures between 5 and 60 °C. The pressure cell is constructed such that stratified molecular layers on crystalline substrates of silicon, quartz, or sapphire with a surface area of 28 cm(2) can be investigated against noncorrosive liquid phases. The large substrate surface area enables reflectivity to be measured down to 10(-5) (without background correction) and thus facilitates determination of the scattering length density profile across the interface as a function of applied load. Our current interest is on the stability of oligolamellar lipid coatings on silicon surfaces against aqueous phases as a function of applied hydrostatic pressure and temperature but the device can also be employed to probe the structure of any other solid-liquid interface.

Producing a lycopene nanodispersion: Formulation development and the effects of high pressure homogenization.

PubMed

Shariffa, Y N; Tan, T B; Uthumporn, U; Abas, F; Mirhosseini, H; Nehdi, I A; Wang, Y-H; Tan, C P

2017-11-01

The aim of this study was to develop formulations to produce lycopene nanodispersions and to investigate the effects of the homogenization pressure on the physicochemical properties of the lycopene nanodispersion. The samples were prepared by using emulsification-evaporation technique. The best formulation was achieved by dispersing an organic phase (0.3% w/v lycopene dissolved in dichloromethane) in an aqueous phase (0.3% w/v Tween 20 dissolved in deionized water) at a ratio of 1:9 by using homogenization process. The increased level of homogenization pressure to 500bar reduced the particle size and lycopene concentration significantly (p<0.05). Excessive homogenization pressure (700-900bar) resulted in large particle sizes with high dispersibility. The zeta potential and turbidity of the lycopene nanodispersion were significantly influenced by the homogenization pressure. The results from this study provided useful information for producing small-sized lycopene nanodispersions with a narrow PDI and good stability for application in beverage products. Copyright © 2017 Elsevier Ltd. All rights reserved.

High pressure phase transformation in uranium carbide: A first principle study

NASA Astrophysics Data System (ADS)

Sahoo, B. D.; Joshi, K. D.; Gupta, Satish C.

2013-02-01

First principles calculations have been carried out to analyze structural, elastic and dynamic stability, of UC under hydrostatic compression. The comparison of enthalpies of rocksalt type (B1) and body centered orthorhombic (bco) structures as a function of pressure suggests the B1 →bco transition at ˜ 23 GPa, in good agreement with experimental value of 27 GPa. From the lattice dynamic calculations we have determined the phonon dispersion relations for B1 phase at various compressions. It is found that TA phonon branch along Γ-X direction becomes imaginary around the transition pressure. Further, the phonon instability so caused is of long wavelength nature as it occurs near the Brillouin zone centre. This long wavelength phonon instability at the transition point indicates that the B1 →bco transition is driven by elastic failure (the vanishing of C44 modulus). Various physical quantities such as equilibrium volume, bulk modulus, pressure derivative of bulk modulus and elastic constants have been determined at zero pressure and compared with data available in literature.

Investigation of Thin Layered Cobalt Oxide Nano-Islands on Gold

NASA Astrophysics Data System (ADS)

Bajdich, Michal; Walton, Alex S.; Fester, Jakob; Arman, Mohammad A.; Osiecki, Jacek; Knudsen, Jan; Vojvodic, Aleksandra; Lauritsen, Jeppe V.

2015-03-01

Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER), but the synergistic effect of contact with gold is yet to be fully understood. The synthesis of three distinct types of thin-layered cobalt oxide nano-islands supported on a single crystal gold (111) substrate is confirmed by combination of STM and XAS methods. In this work, we present DFT+U theoretical investigation of above nano-islands using several previously known structural models. Our calculations confirm stability of two low-oxygen pressure phases: (a) rock-salt Co-O bilayer and (b) wurtzite Co-O quadlayer and single high-oxygen pressure phase: (c) O-Co-O trilayer. The optimized geometries agree with STM structures and calculated oxidation states confirm the conversion from Co2+ to Co3+ found experimentally in XAS. The O-Co-O trilayer islands have the structure of a single layer of CoOOH proposed to be the true active phase for OER catalyst. For that reason, the effect of water on the Pourbaix stabilities of basal planes and edge sites is fully investigated. Lastly, we also present the corresponding OER theoretical overpotentials.

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.

High-pressure/high-temperature polymorphs of energetic materials by first-principles simulations

NASA Astrophysics Data System (ADS)

Le, Nam; Schweigert, Igor

2017-06-01

Energetic molecular crystals exhibit complex phase diagrams that include solid-solid phase transitions, melting, and decomposition. Sorescu and Rice have recently demonstrated that first-principles molecular dynamics (MD) simulations based on dispersion-corrected density functional theory (DFT) can capture the α to γ phase transition in hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) on time scales of several picoseconds. Motivated by their work, we are using DFT-based MD to model the relative stability of solid phases in several molecular crystals. In this presentation, we report simulations of pentaerythritol tetranitrate (PETN) and 2,4,6-trinitrotoluene (TNT) under high pressures and temperatures and compare them with experimentally observed polymorphs. This work was supported by the U.S. Naval Research Laboratory via the National Research Council and by the Office of Naval Research through the U.S. Naval Research Laboratory.

A first-principles study on new high-pressure metastable polymorphs of MoO{sub 2}

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

Becker, Nils; Dronskowski, Richard; Jülich-Aachen Research Alliance

The pressure-dependence of the stabilities of several MoO{sub 2} phases has been investigated by density-functional theory (GGA/PBE/PAW). Out of a set of 15 MX{sub 2} structures, the [SnO{sub 2}(II)], [α-PbO{sub 2}], and a modified rutile structure type were identified as possible metastable MoO{sub 2} polymorphs based on the analysis of thermodynamic properties and dynamic stability. High-pressure calculations suggest an orthorhombic TiO{sub 2} structure, dubbed [ortho-TiO{sub 2}], as a high-pressure polymorph at around 25 GPa. Furthermore, we find that the previously reported rutile-type MoO{sub 2} may be understood as a modified rutile type similar to the [VO{sub 2}] structure. - Graphicalmore » abstract: First-principles electronic structure and thermochemical calculations reveal four structure candidates as possible metastable polymorphs of MoO{sub 2}. Most promising is a distorted rutile-type similar to the known [VO{sub 2}] structure. An orthorhombic polymorph is proposed as a high-pressure polymorph. Display Omitted - Highlights: • Three possible metastable structure candidates for MoO{sub 2}. • Undistorted rutile type is improbable, a new distorted rutile-type MoO{sub 2} was suggested. • Orthorhombic phase of MoO{sub 2} (ortho-TiO{sub 2} type) should form at 25 GPa. • ab initio thermochemical data provided for MoO{sub 2}.« less

Thermal Stability of Microstructure and Microhardness of Heterophase BCC-Alloys After Torsional Deformation on Bridgman Anvils

NASA Astrophysics Data System (ADS)

Ditenberg, I. A.; Tyumentsev, A. N.

2018-03-01

The results of investigations of thermal stability of microstructure and microhardness of alloys of the V-4Ti-4Cr and Mo-47Re systems, subjected to torsional deformation by high quasi-hydrostatic pressure at room temperature, are reported. It is shown that submicrocrystalline and nanocrystalline states, and the respective high values of microhardness, persist up to the upper bound ( 0.4 Tmelt) of the temperature interval of their recovery and polygonization in a single-phase state. The main factors ensuring thermal stability of highlydefective states in heterophase alloys are discussed.

Ab Initio High Pressure and Temperature Investigation on Cubic PbMoO3 Perovskite

NASA Astrophysics Data System (ADS)

Dar, Sajad Ahmad; Srivastava, Vipul; Sakalle, Umesh Kumar

2017-12-01

A combined high pressure and temperature investigation on recently reported cubic perovskite PbMoO3 have been performed within the most accurate density functional theory (DFT). The structure was found stable in cubic paramagnetic phase. The DFT calculated analytical and experimental lattice constant were found in good agreement. The analytical tolerance factor as well as the elastic properties further verifies the cubic stability for PbMoO3. The spin polarized electronic band structure and density of states presented metallic nature with symmetry in up and down states. The insignificant magnetic moment also confirms the paramagnetic nature for the compound. The high pressure elastic and mechanical study up to 35 GPa reveal the structural stability of the material in this pressure range. The compound was found to establish a ductile nature. The electrical conductivity obtained from the band structure results show a decreasing trend with increasing temperature. The temperature dependence of thermodynamic parameters such as specific heat ( C v), thermal expansion ( α) has also been evaluated.

THE EFFECT OF GAS HYDRATES DISSOCIATION AND DRILLING FLUIDS INVASION UPON BOREHOLE STABILITY IN OCEANIC GAS HYDRATES-BEARING SEDIMENT

NASA Astrophysics Data System (ADS)

Ning, F.; Wu, N.; Jiang, G.; Zhang, L.

2009-12-01

Under the condition of over-pressure drilling, the solid-phase and liquid-phase in drilling fluids immediately penetrate into the oceanic gas hydrates-bearing sediment, which causes the water content surrounding the borehole to increase largely. At the same time, the hydrates surrounding borehole maybe quickly decompose into water and gas because of the rapid change of temperature and pressure. The drilling practices prove that this two factors may change the rock characteristics of wellbore, such as rock strength, pore pressure, resistivity, etc., and then affect the logging response and evaluation, wellbore stability and well safty. The invasion of filtrate can lower the angle of friction and weaken the cohesion of hydrates-bearing sediment,which is same to the effect of invading into conventional oil and gas formation on borehole mechnical properties. The difference is that temperature isn’t considered in the invasion process of conventional formations while in hydrates-bearing sediments, it is a factor that can not be ignored. Temperature changes can result in hydrates dissociating, which has a great effect on mechanical properties of borehole. With the application of numerical simulation method, we studied the changes of pore pressure and variation of water content in the gas hydrates-bearing sediment caused by drilling fluid invasion under pressure differential and gas hydrate dissociation under temperature differential and analyzed their influence on borehole stability.The result of simulation indicated that the temperature near borehole increased quickly and changed hardly any after 6 min later. About 1m away from the borehole, the temperature of formation wasn’t affected by the temperature change of borehole. At the place near borehole, as gas hydrate dissociated dramatically and drilling fluid invaded quickly, the pore pressure increased promptly. The degree of increase depends on the permeability and speed of temperature rise of formation around bohole. If the formation has a low permeability and is heated quickly, the dissociated gas and water couldn’t flow away in time, which is likely to bring a hazard of excess pore pressure. Especially in the area near the wall of borehole, the increase degree of pore pressure is high than other area because the dissociation of gas hydrates is relatively violent and hydraulic gradient is bigger. We also studied the distribution of water saturation around borehole after 10min, 30min and 60min respectively. It revealed that along with the invasion of drilling fluid and dissociation of gas hydrate, the degree of water saturation increased gradually. The effect of gas hydrate dissociation and drilling fluids invasion on borehole stability is to weaken mechanical properties of wellbore and change the pore pressure, then changes the effective stress of gas hydrates-bearing sediment. So temperature, pressure in the borehole and filter loss of drilling fluids should be controlled strictly to prevent gas hydrates from decomposing largely and in order to keep the borehole stability in the gas hydrates-bearing formations.

Heating- and pressure-induced transformations in amorphous and hexagonal ice: A computer simulation study using the TIP4P/2005 model

NASA Astrophysics Data System (ADS)

Engstler, Justin; Giovambattista, Nicolas

2017-08-01

We characterize the phase behavior of glassy water by performing extensive out-of-equilibrium molecular dynamics simulations using the TIP4P/2005 water model. Specifically, we study (i) the pressure-induced transformations between low-density (LDA) and high-density amorphous ice (HDA), (ii) the pressure-induced amorphization (PIA) of hexagonal ice (Ih), (iii) the heating-induced LDA-to-HDA transformation at high pressures, (iv) the heating-induced HDA-to-LDA transformation at low and negative pressures, (v) the glass transition temperatures of LDA and HDA as a function of pressure, and (vi) the limit of stability of LDA upon isobaric heating and isothermal decompression (at negative pressures). These transformations are studied systematically, over a wide range of temperatures and pressures, allowing us to construct a P-T phase diagram for glassy TIP4P/2005 water. Our results are in qualitative agreement with experimental observations and with the P-T phase diagram obtained for glassy ST2 water that exhibits a liquid-liquid phase transition and critical point. We also discuss the mechanism for PIA of ice Ih and show that this is a two-step process where first, the hydrogen-bond network (HBN) is distorted and then the HBN abruptly collapses. Remarkably, the collapse of the HB in ice Ih occurs when the average molecular orientations order, a measure of the tetrahedrality of the HBN, is of the same order as in LDA, suggesting a common mechanism for the LDA-to-HDA and Ih-to-HDA transformations.

Heating- and pressure-induced transformations in amorphous and hexagonal ice: A computer simulation study using the TIP4P/2005 model.

PubMed

Engstler, Justin; Giovambattista, Nicolas

2017-08-21

We characterize the phase behavior of glassy water by performing extensive out-of-equilibrium molecular dynamics simulations using the TIP4P/2005 water model. Specifically, we study (i) the pressure-induced transformations between low-density (LDA) and high-density amorphous ice (HDA), (ii) the pressure-induced amorphization (PIA) of hexagonal ice (I h ), (iii) the heating-induced LDA-to-HDA transformation at high pressures, (iv) the heating-induced HDA-to-LDA transformation at low and negative pressures, (v) the glass transition temperatures of LDA and HDA as a function of pressure, and (vi) the limit of stability of LDA upon isobaric heating and isothermal decompression (at negative pressures). These transformations are studied systematically, over a wide range of temperatures and pressures, allowing us to construct a P-T phase diagram for glassy TIP4P/2005 water. Our results are in qualitative agreement with experimental observations and with the P-T phase diagram obtained for glassy ST2 water that exhibits a liquid-liquid phase transition and critical point. We also discuss the mechanism for PIA of ice I h and show that this is a two-step process where first, the hydrogen-bond network (HBN) is distorted and then the HBN abruptly collapses. Remarkably, the collapse of the HB in ice I h occurs when the average molecular orientations order, a measure of the tetrahedrality of the HBN, is of the same order as in LDA, suggesting a common mechanism for the LDA-to-HDA and I h -to-HDA transformations.

Prediction of novel alloy phases of Al with Sc or Ta

PubMed Central

Bilić, Ante; Gale, Julian D.; Gibson, Mark A.; Wilson, Nick; McGregor, Kathie

2015-01-01

Using the evolutionary optimization algorithm, as implemented in the USPEX crystal predictor program, and first principles total energy calculations, the compositional phase diagrams for Al-Sc and Al-Ta alloy systems at zero temperature and pressure have been calculated. In addition to the known binary intermetallic phases, new potentially stable alloys, AlSc3 and AlTa7, have been identified in the Al-poor region of the phase diagram. The dynamic and thermal stability of their lattices has been confirmed from the calculated vibrational normal mode spectra in the harmonic approximation. PMID:25950915

High pressure and multiferroics materials: a happy marriage

PubMed Central

Gilioli, Edmondo; Ehm, Lars

2014-01-01

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. 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. PMID:25485138

Solid Electrolytes and Photoelectrolysis

DTIC Science & Technology

1974-12-31

some DC and low-frequency AC measurements are made with molten NaNO, on both sides of the specimen. These molten - salt measurements have been in...transport properties. 1. Im3 phase. A metastable cubic phase of NaSbO, was obtained from high-pressure KSbO, by ion exchange in molten NaNO...sieves. As these latter structures are stabilized by water, they are unsuitable for solid electrolytes that are to be in contact with molten

Manipulating the stability of crystallographic and magnetic sub-lattices: A first-order magnetoelastic transformation in transition metal based Laves phase

DOE PAGES

Yibole, H.; Pathak, A. K.; Mudryk, Y.; ...

2018-05-24

A first-order magnetoelastic transition (FOMT) is found near the triple point between ferromagnetic, antiferromagnetic and paramagnetic phases in the magneto-chemical phase diagram of (Hf1-xNbx)Fe2 Laves phase system. We show that bringing different magnetic states to the edge of stability, both as a function of the chemical composition and under the influence of external stimuli, such as temperature, pressure and magnetic field, is essential to obtain and control FOMTs. Temperature dependent X-ray diffraction experiments reveal a discontinuity in the lattice parameter a and the unit cell volume without the change in the crystal symmetry at the FOMT. Under applied pressure, themore » transition temperature drastically shifts downward at a remarkable rate of –122 K/GPa. It is this first-order magnetic transition that leads to a negative thermal expansion (NTE) with average ΔV/(VΔT) ≈ –15 × 10 –6 K –1 observed over a 90 K broad temperature range, which is uncommon for magnetoelastic NTE materials. Density functional theory calculations and microstructural analyses demonstrate that the unusual broadness of the FOMT originates from phase separation between ferro- and antiferromagnetic phases, which in turn is rooted in partial segregation of Hf and Nb and a peculiar microstructure. In conclusion, this new understanding of the composition-structure-property relationships in transition metal based Laves phases is an essential step toward a better control and more precise tailoring of rich functionalities in this group of material.« less

Manipulating the stability of crystallographic and magnetic sub-lattices: A first-order magnetoelastic transformation in transition metal based Laves phase

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

Yibole, H.; Pathak, A. K.; Mudryk, Y.

A first-order magnetoelastic transition (FOMT) is found near the triple point between ferromagnetic, antiferromagnetic and paramagnetic phases in the magneto-chemical phase diagram of (Hf1-xNbx)Fe2 Laves phase system. We show that bringing different magnetic states to the edge of stability, both as a function of the chemical composition and under the influence of external stimuli, such as temperature, pressure and magnetic field, is essential to obtain and control FOMTs. Temperature dependent X-ray diffraction experiments reveal a discontinuity in the lattice parameter a and the unit cell volume without the change in the crystal symmetry at the FOMT. Under applied pressure, themore » transition temperature drastically shifts downward at a remarkable rate of –122 K/GPa. It is this first-order magnetic transition that leads to a negative thermal expansion (NTE) with average ΔV/(VΔT) ≈ –15 × 10 –6 K –1 observed over a 90 K broad temperature range, which is uncommon for magnetoelastic NTE materials. Density functional theory calculations and microstructural analyses demonstrate that the unusual broadness of the FOMT originates from phase separation between ferro- and antiferromagnetic phases, which in turn is rooted in partial segregation of Hf and Nb and a peculiar microstructure. In conclusion, this new understanding of the composition-structure-property relationships in transition metal based Laves phases is an essential step toward a better control and more precise tailoring of rich functionalities in this group of material.« less

Active Suppression of Instabilities in Engine Combustors

NASA Technical Reports Server (NTRS)

Kopasakis, George

2004-01-01

A method of feedback control has been proposed as a means of suppressing thermo-acoustic instabilities in a liquid- fueled combustor of a type used in an aircraft engine. The basic principle of the method is one of (1) sensing combustor pressure oscillations associated with instabilities and (2) modulating the rate of flow of fuel to the combustor with a control phase that is chosen adaptively so that the pressure oscillations caused by the modulation oppose the sensed pressure oscillations. The need for this method arises because of the planned introduction of advanced, lean-burning aircraft gas turbine engines, which promise to operate with higher efficiencies and to emit smaller quantities of nitrogen oxides, relative to those of present aircraft engines. Unfortunately, the advanced engines are more susceptible to thermoacoustic instabilities. These instabilities are hard to control because they include large dead-time phase shifts, wide-band noise characterized by amplitudes that are large relative to those of the instabilities, exponential growth of the instabilities, random net phase walks, and amplitude fluctuations. In this method (see figure), the output of a combustion-pressure sensor would be wide-band-pass filtered and then further processed to generate a control signal that would be applied to a fast-actuation valve to modulate the flow of fuel. Initially, the controller would rapidly take large phase steps in order to home in, within a fraction of a second, to a favorable phase region within which the instability would be reduced. Then the controller would restrict itself to operate within this phase region and would further restrict itself to operate within a region of stability, as long as the power in the instability signal was decreasing. In the phase-shifting scheme of this method, the phase of the control vector would be made to continuously bounce back and forth from one boundary of an effective stability region to the other. Computationally, this scheme would be implemented by the adaptive sliding phaser averaged control (ASPAC) algorithm, which requires very little detailed knowledge of the combustor dynamics. In the ASPAC algorithm, the power of the instability signal would be calculated from the wide-bandpass- filtered combustion-pressure signal and averaged over a period of time (typically of the order of a few hundredths of a second) corresponding to the controller updating cycle [not to be confused with the controller sampling cycle, which would be much shorter (typically of the order of 10(exp -4) second)].

Electronic structure of carbon dioxide under pressure and insights into the molecular-to-nonmolecular transition

PubMed Central

Shieh, Sean R.; Jarrige, Ignace; Wu, Min; Hiraoka, Nozomu; Tse, John S.; Mi, Zhongying; Kaci, Linada; Jiang, Jian-Zhong; Cai, Yong Q.

2013-01-01

Knowledge of the high-pressure behavior of carbon dioxide (CO2), an important planetary material found in Venus, Earth, and Mars, is vital to the study of the evolution and dynamics of the planetary interiors as well as to the fundamental understanding of the C–O bonding and interaction between the molecules. Recent studies have revealed a number of crystalline polymorphs (CO2-I to -VII) and an amorphous phase under high pressure–temperature conditions. Nevertheless, the reported phase stability field and transition pressures at room temperature are poorly defined, especially for the amorphous phase. Here we shed light on the successive pressure-induced local structural changes and the molecular-to-nonmolecular transition of CO2 at room temperature by performing an in situ study of the local electronic structure using X-ray Raman scattering, aided by first-principle exciton calculations. We show that the transition from CO2-I to CO2-III was initiated at around 7.4 GPa, and completed at about 17 GPa. The present study also shows that at ∼37 GPa, molecular CO2 starts to polymerize to an extended structure with fourfold coordinated carbon and minor CO3 and CO-like species. The observed pressure is more than 10 GPa below previously reported. The disappearance of the minority species at 63(±3) GPa suggests that a previously unknown phase transition within the nonmolecular phase of CO2 has occurred. PMID:24167283

Respiratory sinus arrhythmia stabilizes mean arterial blood pressure at high-frequency interval in healthy humans.

PubMed

Elstad, Maja; Walløe, Lars; Holme, Nathalie L A; Maes, Elke; Thoresen, Marianne

2015-03-01

Arterial blood pressure variations are an independent risk factor for end organ failure. Respiratory sinus arrhythmia (RSA) is a sign of a healthy cardiovascular system. However, whether RSA counteracts arterial blood pressure variations during the respiratory cycle remains controversial. We restricted normal RSA with non-invasive intermittent positive pressure ventilation (IPPV) to test the hypothesis that RSA normally functions to stabilize mean arterial blood pressure. Ten young volunteers were investigated during metronome-paced breathing and IPPV. Heart rate (ECG), mean arterial blood pressure and left stroke volume (finger arterial pressure curve) and right stroke volume (pulsed ultrasound Doppler) were recorded, while systemic and pulmonary blood flow were calculated beat-by-beat. Respiratory variations (high-frequency power, 0.15-0.40 Hz) in cardiovascular variables were estimated by spectral analysis. Phase angles and correlation were calculated by cross-spectral analysis. The magnitude of RSA was reduced from 4.9 bpm(2) (95% CI 3.0, 6.2) during metronome breathing to 2.8 bpm(2) (95% CI 1.1, 5.0) during IPPV (p = 0.03). Variations in mean arterial blood pressure were greater (2.3 mmHg(2) (95% CI 1.4, 3.9) during IPPV than during metronome breathing (1.0 mmHg(2) [95% CI 0.7, 1.3]) (p = 0.014). Respiratory variations in right and left stroke volumes were inversely related in the respiratory cycle during both metronome breathing and IPPV. RSA magnitude is lower and mean arterial blood pressure variability is greater during IPPV than during metronome breathing. We conclude that in healthy humans, RSA stabilizes mean arterial blood pressure at respiratory frequency.

Ferroelectricity in high-density H 2O ice

DOE PAGES

Caracas, Razvan; Hemley, Russell J.

2015-04-01

The origin of longstanding anomalies in experimental studies of the dense solid phases of H 2O ices VII, VIII, and X is examined using a combination of first-principles theoretical methods. We find that a ferroelectric variant of ice VIII is energetically competitive with the established antiferroelectric form under pressure. The existence of domains of the ferroelectric form within anti-ferroelectric ice can explain previously observed splittings in x-ray diffraction data. The ferroelectric form is stabilized by density and is accompanied by the onset of spontaneous polarization. Here, the presence of local electric fields triggers the preferential parallel orientation of the watermore » molecules in the structure, which could be stabilized in bulk using new high-pressure techniques.« less

A study of nonlinear dynamics of single- and two-phase flow oscillations

NASA Astrophysics Data System (ADS)

Mawasha, Phetolo Ruby

The dynamics of single- and two-phase flows in channels can be contingent on nonlinearities which are not clearly understood. These nonlinearities could be interfacial forces between the flowing fluid and its walls, variations in fluid properties, growth of voids, etc. The understanding of nonlinear dynamics of fluid flow is critical in physical systems which can undergo undesirable system operating scenarios such an oscillatory behavior which may lead to component failure. A nonlinear lumped mathematical model of a surge tank with a constant inlet flow into the tank and an outlet flow through a channel is derived from first principles. The model is used to demonstrate that surge tanks with inlet and outlet flows contribute to oscillatory behavior in laminar, turbulent, single-phase, and two-phase flow systems. Some oscillations are underdamped while others are self-sustaining. The mechanisms that are active in single-phase oscillations with no heating are presented using specific cases of simplified models. Also, it is demonstrated how an external mechanism such as boiling contributes to the oscillations observed in two-phase flow and gives rise to sustained oscillations (or pressure drop oscillations). A description of the pressure drop oscillation mechanism is presented using the steady state pressure drop versus mass flow rate characteristic curve of the heated channel, available steady state pressure drop versus mass flow rate from the surge tank, and the transient pressure drop versus mass flow rate limit cycle. Parametric studies are used to verify the theoretical pressure drop oscillations model using experimental data by Yuncu's (1990). The following contributions are unique: (1) comparisons of nonlinear pressure drop oscillation models with and without the effect of the wall thermal heat capacity and (2) comparisons of linearized pressure drop oscillation models with and without the effect of the wall thermal heat capacity to identify stability boundaries.

High-pressure stability, transformations, and vibrational dynamics of nitrosonium nitrate from synchrotron infrared and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Song, Yang; Hemley, Russell J.; Liu, Zhenxian; Somayazulu, Maddury; Mao, Ho-kwang; Herschbach, Dudley R.

2003-07-01

The properties of nitrosonium nitrate (NO+NO3-) were investigated following synthesis by laser heating of N2O and N2O4 under high pressures in a diamond anvil cell. Synchrotron infrared absorption spectra of NO+NO3- were measured at pressures up to 32 GPa at room temperature. Raman spectra were obtained at pressures up to 40 GPa at room temperature and up to 14 GPa at temperatures down to 80 K. For both lattice and intramolecular vibrational modes, a smooth evolution of spectral bands with pressure indicates that NO+NO3- forms a single phase over a broad range above 10 GPa, whereas marked changes, particularly evident in the Raman spectra at low temperature, indicate a phase transition occurs near 5 GPa. NO+NO3- could be recovered at atmospheric pressure and low temperature, persisting to 180 K. The Raman and IR spectroscopic data suggest that the NO+NO3- produced by laser heating of N2O followed by decompression may differ in structure or orientational order-disorder from that produced by autoionization of N2O4.

Pretest analysis document for Semiscale Test S-FS-1

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

Chen, T.H.

This report documents the pretest analysis calculation completed with the RELAP5/MOD2/CY21 code for Semiscale Test S-FS-1. The test will simulate the double-ended offset shear of the main steam line at the exit of the broken loop steam generator (downstream of the flow restrictor) and the subsequent plant recovery. The recovery portion of the test consists of a plant stabilization phase and a plant cooldown phase. The recovery procedures involve normal charging/letdown operation, pressurizer heater operation, secondary steam and feed of the unaffected steam generator, and pressurizer auxiliary spray. The test will be terminated after the unaffected steam generator and pressurizermore » pressures and liquid levels are stable, and the average priamry fluid temperature is stable at about 480 K (405/sup 0/F) for at least 10 minutes.« less

Laboratory Investigation of the Growth and Crystal Structure of Nitric Acid Hydrates by Transmission Electron Microscopy (TEM)

NASA Technical Reports Server (NTRS)

Blake, David F.; Chang, Sherwood (Technical Monitor)

1994-01-01

A great deal of recent laboratory work has focussed on the characterization of the nitric acid hydrates, thought to be present in type I Polar Stratospheric Clouds (PSCs). Phase relationships and vapor pressure measurements (1-3) and infrared characterizations (4-5) have been made. However, the observed properties of crystalline solids (composition, melting point, vapor pressure, surface reactivity, thermodynamic stability, extent of solid solution with other components, etc.) are controlled by their crystal structure. The only means of unequivocal structural identification for crystalline solids is diffraction (using electrons, X-rays, neutrons, etc.). Other observed properties of crystalline solids, such as their infrared spectra, their vapor pressure as a function of temperature, etc. yield only indirect information about what phases are present, their relative proportions, or whether they are crystalline or amorphous.

Carbon under extreme conditions: phase boundaries and electronic properties from first-principles theory.

PubMed

Correa, Alfredo A; Bonev, Stanimir A; Galli, Giulia

2006-01-31

At high pressure and temperature, the phase diagram of elemental carbon is poorly known. We present predictions of diamond and BC8 melting lines and their phase boundary in the solid phase, as obtained from first-principles calculations. Maxima are found in both melting lines, with a triple point located at approximately 850 GPa and approximately 7,400 K. Our results show that hot, compressed diamond is a semiconductor that undergoes metalization upon melting. In contrast, in the stability range of BC8, an insulator to metal transition is likely to occur in the solid phase. Close to the diamond/liquid and BC8/liquid boundaries, molten carbon is a low-coordinated metal retaining some covalent character in its bonding up to extreme pressures. Our results provide constraints on the carbon equation of state, which is of critical importance for devising models of Neptune, Uranus, and white dwarf stars, as well as of extrasolar carbon-rich planets.

Dynamics of face and annular seals with two-phase flow

NASA Technical Reports Server (NTRS)

Hughes, William F.; Basu, Prithwish; Beatty, Paul A.; Beeler, Richard M.; Lau, Stephen

1988-01-01

A detailed study was made of face and annular seals under conditions where boiling, i.e., phase change of the leaking fluid, occurs within the seal. Many seals operate in this mode because of flashing due to pressure drop and/or heat input from frictional heating. Some of the distinctive behavior characteristics of two phase seals are discussed, particularly their axial stability. The main conclusions are that seals with two phase flow may be unstable if improperly balanced. Detailed theoretical analyses of low (laminar) and high (turbulent) leakage seals are presented along with computer codes, parametric studies, and in particular a simplified PC based code that allows for rapid performance prediction: calculations of stiffness coefficients, temperature and pressure distributions, and leakage rates for parallel and coned face seals. A simplified combined computer code for the performance prediction over the laminar and turbulent ranges of a two phase flow is described and documented. The analyses, results, and computer codes are summarized.

Carbon under extreme conditions: Phase boundaries and electronic properties from first-principles theory

DOE PAGES

Correa, Alfredo A.; Bonev, Stanimir A.; Galli, Giulia

2006-01-23

At high pressure and temperature, the phase diagram of elemental carbon is poorly known. We present predictions of diamond and BC8 melting lines and their phase boundary in the solid phase, as obtained from first-principles calculations. Maxima are found in both melting lines, with a triple point located at ≈ 850 GPa and ≈ 7,400 K. Our results show that hot, compressed diamond is a semiconductor that undergoes metalization upon melting. In contrast, in the stability range of BC8, an insulator to metal transition is likely to occur in the solid phase. Close to the diamond/liquid and BC8/liquid boundaries, moltenmore » carbon is a low-coordinated metal retaining some covalent character in its bonding up to extreme pressures. Lastly, our results provide constraints on the carbon equation of state, which is of critical importance for devising models of Neptune, Uranus, and white dwarf stars, as well as of extrasolar carbon-rich planets.« less

High Pressure-Temperature Phase Diagram of 1,1-diamino-2,2-dinitroethylene

NASA Astrophysics Data System (ADS)

Bishop, Matthew; Chellappa, Raja; Liu, Zhenxian; Preston, Daniel; Sandstrom, Mary; Dattelbaum, Dana; Vohra, Yogesh; Velisavljevic, Nenad

2013-06-01

1,1-diamino-2,2-dinitroethelyne (FOX-7) is a less sensitive energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ) . In this study, we have investigated the high P-T stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra confirmed the known α --> β (110 °C) and β --> γ (160 °C) phase transitions; as well as, indicated an additional phase transition, γ --> δ (210°C), with the δ phase being stable up to 250 °C prior to melt/decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa revealed that the α --> β transition occurs at 180 °C, while β --> β + δ phase transition shifted to 300 °C with suppression of γ phase. Decomposition was observed above 325 °C. Based on multiple high P-T measurements, we have established the first high P-T phase diagram of FOX-7. This work was, in part, supported by the US DOE under contract No. DE-AC52-06NA25396 and Science Campaign 2 Program. MB acknowledges additional support from the NSF BD program. Use of NSLS (DE-AC02-98CH10886) beamline U2A (COMPRES, No.EAR01-35554, CDAC).

Local structure of solid Rb at megabar pressures

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

De Panfilis, S.; Gorelli, F.; Santoro, M.

2015-06-07

We have investigated the local and electronic structure of solid rubidium by means of x-ray absorption spectroscopy up to 101.0 GPa, thus doubling the maximum investigated experimental pressure. This study confirms the predicted stability of phase VI and was completed by the combination of two pivotal instrumental solutions. On one side, we made use of nanocrystalline diamond anvils, which, contrary to the more commonly used single crystal diamond anvils, do not generate sharp Bragg peaks (glitches) at specific energies that spoil the weak fine structure oscillations in the x-ray absorption cross section. Second, we exploited the performance of a state-of-the-artmore » x-ray focussing device yielding a beam spot size of 5 × 5 μm{sup 2}, spatially stable over the entire energy scan. An advanced data analysis protocol was implemented to extract the pressure dependence of the structural parameters in phase VI of solid Rb from 51.2 GPa up to the highest pressure. A continuous reduction of the nearest neighbour distances was observed, reaching about 6% over the probed pressure range. We also discuss a phenomenological model based on the Einstein approximation to describe the pressure behaviour of the mean-square relative displacement. Within this simplified scheme, we estimate the Grüneisen parameter for this high pressure Rb phase to be in the 1.3–1.5 interval.« less

The topological phase diagram of cimetidine: A case of overall monotropy.

PubMed

Céolin, R; Rietveld, I B

2017-03-01

Cimetidine is a histamine H 2 -receptor antagonist used against peptic ulcers. It is known to exhibit crystalline polymorphism. Forms A and D melt within 0.35 degrees from each other and the enthalpies of fusion are similar as well. The present paper demonstrates how to construct a pressure-temperature phase diagram with only calorimetric and volumetric data available. The phase diagram provides the stability domains and the phase equilibria for the phases A, D, the liquid and the vapor. Cimetidine is overall monotropic with form D the only stable solid phase. Copyright © 2016 Académie Nationale de Pharmacie. Published by Elsevier Masson SAS. All rights reserved.

Synthesis of Novel Extended Phases of Molecular Solids at High Pressures and Temperatures

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

Yoo, C; Evans, W; Cynn, H

2004-03-30

This study is for in-situ investigation of chemical bonding and molecular structure of low z-elements and simple molecular solids at high pressures and temperatures using 3rd-generation synchrotron x-ray diffraction. To understand the contribution of the empty d-electron orbital of Mg in relation to the formation of molecular solids like MgO, which is one of the important Earth lower mantle materials and MgB{sub 2}, which has recently been the focus of intense superconducting material research, we have performed double-sided laser heating experiments using a diamond anvil cell (DAC). Understanding the structural stability and the formation of the above Mg-compounds requires studyingmore » Mg itself as well as the relevant compounds. BL10XU at the Spring-8 was used to study phase stability and make accurate equation of state (EOS) determinations of Mg coupled with external heating and the double-sided laser heating technique. Monochromatic x-ray at 30 keV (0.4135 {angstrom}) was focused to about 40 {micro}m at the sample and the diffracted x-ray were recorded using a high-resolution image plate (3000 x 3000 pixels with a 0.1 mm resolution per pixel). EOS parameters for hcp and bcc Mg were determined by fitting to a Birch-Murnaghan equation. An isothermal compression of Mg at 300 K up to 100 GPa provides EOS parameters (B{sub 0}, B{sub 0}{prime}, and V{sub 0}) comparable for both hcp and bcc phases, which is similar to the cases for hcp and fcc phases measured in cobalt and xenon. Similar EOS parameters for both low and high pressure phases with a very small or no measurable volume discontinuity at the phase transition pressure suggests that the hcp-bcc structural transition of Mg may be driven by a stacking fault due to a shear instability as seen in xenon and cobalt. Compared to the recent estimation determined using a large volume press [1], our B{sub 0} is smaller by more than 10% suggesting that the difference may be due to non-hydrostatic conditions. The phase boundary of Mg up to 650 K was determined using external resistive heating in air. The results show a noticeable hysteresis during forward and backward transitions. The initial negative slope of the phase boundary agrees very well with the value predicted by theory[2]. Double-side laser heating at several pressures below 20 GPa with simultaneous in-situ x-ray diffraction indicates that hcp is the dominant stable phase and a double hexagonal close packed structure (dhcp) is not seen at high temperatures and high pressures, unlike the observations of recent studies of Mg using a large volume press, claiming dhcp below 20 GPa between 1350 and 1050 K. We suggest that the dhcp may appear as nonequilibrium phase induced by shear stress.« less

New Polymorph of Fe3O4 Stable at Core-Mantle Boundary Conditions

NASA Astrophysics Data System (ADS)

Greenberg, E.; Prakapenka, V. B.

2017-12-01

Magnetite Fe3O4 (and its high-pressure polymorphs) is one of the most studied iron bearing minerals. One reason for the interest in magnetite is that it contains both Fe2+ and Fe3+, which is especially important for understanding the physical and chemical properties of Earth's deep interior. Early studies on magnetite debated the nature of the structural phase transition at 35 GPa [1-4]. This high-pressure structure was shown to be of the CaTi2O4-type [5], but with Fe3+ occupying multiple sites. Furthermore, at pressures above 65 GPa a second structural transition to a Pmma space group was shown to take place [5], similar to that in Fe3-xTixO4 solid solution [6]. Other studies have focused on the P-T stability of Fe3O4. Early studies by Lazor et al. [7] predicted that Fe3O4 might disproportionate into FeO and h-Fe2O3 at 50 GPa. Other studies suggested that the high-pressure phase should be stable up to 100 GPa [3]. A more recent experimental study by Ricolleau and Fei [8] revealed that Fe3O4 is stable at least up to 103 GPa. Thus far, structural studies of Fe3O4 have been limited to pressures below 105 GPa. We have studied Fe3O4 up to pressures of 175 GPa and temperatures above 4000K, using diamond anvil cells in combination with synchrotron x-ray diffraction and an online pulsed laser-heating system to study the stability of Fe3O4 at relevant pressure-temperature conditions. Our results show that Fe3O4 is stable up to at least 176 GPa and 4200 K. We have discovered a new polymorph of Fe3O4 at these high P-T conditions. This new phase is stable in the pressure range of at least 100

The effect of relativity on stability of Copernicium phases, their electronic structure and mechanical properties

NASA Astrophysics Data System (ADS)

Čenčariková, Hana; Legut, Dominik

2018-05-01

The phase stability of the various crystalline structures of the super-heavy element Copernicium was determined based on the first-principles calculations with different levels of the relativistic effects. We utilized the Darwin term, mass-velocity, and spin-orbit interaction with the single electron framework of the density functional theory while treating the exchange and correlation effects using local density approximations. It is found that the spin-orbit coupling is the key component to stabilize the body-centered cubic (bcc) structure over the hexagonal closed packed (hcp) structure, which is in accord with Sol. Stat. Comm. 152 (2012) 530, but in contrast to Atta-Fynn and Ray (2015) [11], Gaston et al. (2007) [10], Papaconstantopoulos (2015) [9]. It seems that the main role here is the correct description of the semi-core relativistic 6p1/2 orbitals. The all other investigated structures, i.e. face-centered cubic (fcc) , simple cubic (sc) as well as rhombohedral (rh) structures are higher in energy. The criteria of mechanical stability were investigated based on the calculated elastic constants, identifying the phase instability of fcc and rh structures, but surprisingly confirm the stability of the energetically higher sc structure. In addition, the pressure-induced structural transition between two stable sc and bcc phases has been detected. The ground-state bcc structure exhibits the highest elastic anisotropy from single elements of the Periodic table. At last, we support the experimental findings that Copernicium is a metal.

Effect of Pore Pressure on Slip Failure of an Impermeable Fault: A Coupled Micro Hydro-Geomechanical Model

NASA Astrophysics Data System (ADS)

Yang, Z.; Juanes, R.

2015-12-01

The geomechanical processes associated with subsurface fluid injection/extraction is of central importance for many industrial operations related to energy and water resources. However, the mechanisms controlling the stability and slip motion of a preexisting geologic fault remain poorly understood and are critical for the assessment of seismic risk. In this work, we develop a coupled hydro-geomechanical model to investigate the effect of fluid injection induced pressure perturbation on the slip behavior of a sealing fault. The model couples single-phase flow in the pores and mechanics of the solid phase. Granular packs (see example in Fig. 1a) are numerically generated where the grains can be either bonded or not, depending on the degree of cementation. A pore network is extracted for each granular pack with pore body volumes and pore throat conductivities calculated rigorously based on geometry of the local pore space. The pore fluid pressure is solved via an explicit scheme, taking into account the effect of deformation of the solid matrix. The mechanics part of the model is solved using the discrete element method (DEM). We first test the validity of the model with regard to the classical one-dimensional consolidation problem where an analytical solution exists. We then demonstrate the ability of the coupled model to reproduce rock deformation behavior measured in triaxial laboratory tests under the influence of pore pressure. We proceed to study the fault stability in presence of a pressure discontinuity across the impermeable fault which is implemented as a plane with its intersected pore throats being deactivated and thus obstructing fluid flow (Fig. 1b, c). We focus on the onset of shear failure along preexisting faults. We discuss the fault stability criterion in light of the numerical results obtained from the DEM simulations coupled with pore fluid flow. The implication on how should faults be treated in a large-scale continuum model is also presented.

The stability of thermodynamically metastable phases in a Zr-Sn-Nb-Mo alloy: Effects of alloying elements, morphology and applied stress/strain

NASA Astrophysics Data System (ADS)

Yu, Hongbing; Yao, Zhongwen; Daymond, Mark R.

2017-09-01

In this paper, a dual phase Zr-Sn-Nb-Mb alloy was studied with TEM after thermal treatment and high-temperature tensile deformation. Plate and pressure tube material, manufactured through different processing routes, were used in this study. The overall average concentrations of Mo and Nb in the β phase are higher in the pressure tube than in the plate. It was revealed that these concentrations have significant effects on the subsequent stability of the β and ω phases as well as on the precipitation behavior of the α phase from the β phase. That is, the higher the concentrations, the more stable the β and ω phases are, and hence there is a reduced tendency for precipitation of α phase. Aging treatments cause the transformation of athermal ω to isothermal ω, as expected. The most striking finding is the product of the decomposition of the isothermal ω particles during aging treatment is determined as not being α phase, even though the structure of it is, as-yet, not fully determined. The non-uniform morphology of the β grains in the plate material provides us a unique opportunity to investigate the effects of morphology on the aging response of the β phase. It was found that thin β filaments suppress the precipitation of isothermal ω particles but enhance the precipitation of α phase at α/β interfaces. The effect of the Burgers orientation relationship between α and β grains on the precipitation of the α phase at the α/β interface is discussed. Applied high-temperature stress/strain has been found to enhance the decomposition of isothermal ω phase but suppress α precipitation inside the β grains. The suppression of α precipitation by applied stress/strain is discussed in terms of the ω assisted α precipitation. Implications of these findings for the in-service application of the alloy are discussed.

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 and growth of large crystallites, here the contribution of different phases could be better distinguished by analyzing the 3-dimensional distribution in the reciprocal space of the diffraction peaks. Laser heating experiments in the Fe-C-O system were conducted in the pressure range 20-140 GPa. The siderite stability field seems narrower than the previous investigations suggested. At least one of the extracted single crystal phases provides evidence of oxidation-reduction reactions.

Crystal structure of Earth's inner core: A first-principles study

NASA Astrophysics Data System (ADS)

Moustafa, S. G.; Schultz, A. J.; Zurek, E.; Kofke, D. A.

2017-12-01

Since the detection of the Earth's solid inner core (IC) by Lehmann in 1936, its composition and crystal structure (which are essential to understand Earth's evolution) have been controversial. While seismological measurements (e.g. PREM) can give a robust estimation of the density, pressure, and elasticity of the IC, they cannot be directly used to determine its composition and/or crystal structure. Experimentally, reaching the extreme IC conditions ( 330 GPa and 6000 K) and getting reliable measurements is very challenging. First-principles calculations provide a viable alternative that can work as a powerful investigative tool. Although several attempts have been made to assess phase stability at IC conditions computationally, they often use a low level of theory for electronic structure (e.g., classical force-field), adopt approximate methods (e.g., quasiharmonic approximation, fixed hcp-c/a), or do not consider finite-size effects. The study of phase stability using accurate first-principles methods is hampered in part by the difficulty of computing the free energy (FE), the central thermodynamic quantity that determines stability, while including anharmonic and finite-size effects. Additional difficulty related to the IC in particular is introduced by the dynamical instability of one of the IC candidate structures (bcc) at low temperature. Recently [1-3], we introduced a novel method (denoted as "harmonically mapped averaging", or HMA) to efficiently measure anharmonic properties (e.g. FE, pressure, elastic modulus) by molecular simulation, yielding orders of magnitude CPU speedup compared to conventional methods. We have applied this method to the hcp candidate phase of iron at the IC conditions, obtaining first-principles anharmonic FE values with unprecedented accuracy and precision [4]. We have now completed and report HMA calculations to assess the phase stability of all IC candidate phases (fcc/hcp/bcc). This knowledge is the prerequisite for interpreting the geophysical and geochemical constraints of the IC (e.g. anisotropy and low rigidity); which should be a key ingredient in the longstanding debate about the nature of the Earth's IC. References[1] 10.1103/PhysRevE.92.043303[2] 10.1021/acs.jctc.6b00018[3] 10.1021/acs.jctc.6b01082[4] 10.1103/PhysRevB.96.014117

High-calorific biogas production from anaerobic digestion of food waste using a two-phase pressurized biofilm (TPPB) system.

PubMed

Li, Yeqing; Liu, Hong; Yan, Fang; Su, Dongfang; Wang, Yafei; Zhou, Hongjun

2017-01-01

To obtain high calorific biogas via anaerobic digestion without additional upgrading equipment, a two-phase pressurized biofilm system was built up, including a conventional continuously stirred tank reactor and a pressurized biofilm anaerobic reactor (PBAR). Four different pressure levels (0.3, 0.6, 1.0 and 1.7MPa) were applied to the PBAR in sequence, with the organic loading rate maintained at 3.1g-COD/L/d. Biogas production, gas composition, process stability parameters were measured. Results showed that with the pressure increasing from 0.3MPa to 1.7MPa, the pH value decreased from 7.22±0.19 to 6.98±0.05, the COD removal decreased from 93.0±0.9% to 79.7±1.2% and the methane content increased from 80.5±1.5% to 90.8±0.8%. Biogas with higher calorific value of 36.2MJ/m 3 was obtained at a pressure of 1.7MPa. Pressure showed a significant effect on biogas production and gas quality in methanogenesis reactor. Copyright © 2016 Elsevier Ltd. All rights reserved.

Combustion Stability Characteristics of the Project Morpheus Liquid Oxygen / Liquid Methane Main Engine

NASA Technical Reports Server (NTRS)

Melcher, John C.; Morehead, Robert L.

2014-01-01

The project Morpheus liquid oxygen (LOX) / liquid methane (LCH4) main engine is a Johnson Space Center (JSC) designed 5,000 lbf-thrust, 4:1 throttling, pressure-fed cryogenic engine using an impinging element injector design. The engine met or exceeded all performance requirements without experiencing any in- ight failures, but the engine exhibited acoustic-coupled combustion instabilities during sea-level ground-based testing. First tangential (1T), rst radial (1R), 1T1R, and higher order modes were triggered by conditions during the Morpheus vehicle derived low chamber pressure startup sequence. The instability was never observed to initiate during mainstage, even at low power levels. Ground-interaction acoustics aggravated the instability in vehicle tests. Analysis of more than 200 hot re tests on the Morpheus vehicle and Stennis Space Center (SSC) test stand showed a relationship between ignition stability and injector/chamber pressure. The instability had the distinct characteristic of initiating at high relative injection pressure drop at low chamber pressure during the start sequence. Data analysis suggests that the two-phase density during engine start results in a high injection velocity, possibly triggering the instabilities predicted by the Hewitt stability curves. Engine ignition instability was successfully mitigated via a higher-chamber pressure start sequence (e.g., 50% power level vs 30%) and operational propellant start temperature limits that maintained \\cold LOX" and \\warm methane" at the engine inlet. The main engine successfully demonstrated 4:1 throttling without chugging during mainstage, but chug instabilities were observed during some engine shutdown sequences at low injector pressure drop, especially during vehicle landing.

Pressure-induced amorphization and collapse of magnetic order in the type-I clathrate Eu8Ga16Ge30

NASA Astrophysics Data System (ADS)

Mardegan, J. R. L.; Fabbris, G.; Veiga, L. S. I.; Adriano, C.; Avila, M. A.; Haskel, D.; Giles, C.

2013-10-01

We investigate the low temperature structural and electronic properties of the type-I clathrate Eu8Ga16Ge30 under pressure using x-ray powder diffraction (XRD), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD) techniques. The XRD measurements reveal a transition to an amorphous phase above 18 GPa. Unlike previous reports on other clathrate compounds, no volume collapse is observed prior to the crystalline-amorphous phase transition which takes place when the unit cell volume is reduced to 81% of its ambient pressure value. Fits of the pressure-dependent relative volume to a Murnaghan equation of state yield a bulk modulus B0=65±3 GPa and a pressure derivative B0'=3.3±0.5. The Eu L2-edge XMCD data shows quenching of the magnetic order at a pressure coincident with the crystalline-amorphous phase transition. This information along with the persistence of an Eu2+ valence state observed in the XANES spectra up to the highest pressure point (22 GPa) indicates that the suppression of XMCD intensity is due to the loss of long range magnetic order. When compared with other clathrates, the results point to the importance of guest ion-cage interactions in determining the mechanical stability of the framework structure and the critical pressure for amorphization. Finally, the crystalline structure is not found to recover after pressure release, resulting in an amorphous material that is at least metastable at ambient pressure and temperature.

Shock-activated reaction synthesis and high pressure response of titanium-based ternary carbide and nitride ceramics

NASA Astrophysics Data System (ADS)

Jordan, Jennifer Lynn

The objectives of this study were to (a) investigate the effect of shock activation of precursor powders for solid-state reaction synthesis of Ti-based ternary ceramics and (b) to determine the high pressure phase stability and Hugoniot properties of Ti3SiC2. Dynamically densified compacts of Ti, SiC, and graphite precursor powders and Ti and AlN precursor powders were used to study the shock-activated formation of Ti 3SiC2 and Ti2AlN ternary compounds, respectively, which are considered to be novel ceramics having high stiffness but low hardness. Gas gun and explosive loading techniques were used to obtain a range of loading conditions resulting in densification and activation. Measurements of fraction reacted as a function of time and temperature and activation energies obtained from DTA experiments were used to determine the degree of activation caused by shock compression and its subsequent effect on the reaction mechanisms and kinetics. In both systems, shock activation led to an accelerated rate of reaction at temperatures less than 1600°C and, above that temperature, it promoted the formation of almost 100% of the ternary compound. A kinetics-based mathematical model based on mass and thermal transport was developed to predict the effect of shock activation and reaction synthesis conditions that ensure formation of the ternary compounds. Model predictions revealed a transition temperature above which the reaction is taken over by the "run-away" combustion-type mode. The high pressure phase stability of pre-alloyed Ti 3SiC2 compound was investigated by performing Hugoniot shock and particle velocity measurements using the facilities at the National Institute for Materials Science (Tsukuba, Japan). Experiments performed at pressures of 95--120 GPa showed that the compressibility of Ti3SiC 2 at these pressures deviates from the previously reported compressibility of the material under static high pressure loading. The deviation in compressibility behavior is indicative of the transformation of the Ti3 SiC2 ceramic to a high pressure, high density phase.

High hydrostatic pressure inactivation of Lactobacillus plantarum cells in (O/W)-emulsions is independent from cell surface hydrophobicity and lipid phase parameters

NASA Astrophysics Data System (ADS)

Kafka, T. A.; Reitermayer, D.; Lenz, C. A.; Vogel, R. F.

2017-07-01

Inactivation efficiency of high hydrostatic pressure (HHP) processing of food is strongly affected by food matrix composition. We investigated effects of fat on HHP inactivation of spoilage-associated Lactobacillus (L.) plantarum strains using defined oil-in-water (O/W)-emulsion model systems. Since fat-mediated effects on HHP inactivation could be dependent on interactions between lipid phase and microbial cells, three major factors possibly influencing such interactions were considered, that is, cell surface hydrophobicity, presence and type of surfactants, and oil droplet size. Pressure tolerance varied noticeably among L. plantarum strains and was independent of cell surface hydrophobicity. We showed that HHP inactivation of all strains tended to be more effective in presence of fat. The observation in both, surfactant-stabilized and surfactant-free (O/W)-emulsion, indicates that cell surface hydrophobicity is no intrinsic pressure resistance factor. In contrast to the presence of fat per se, surfactant type and oil droplet size did not affect inactivation efficiency.

Novel Rubidium Poly-Nitrogen Energetic Materials

NASA Astrophysics Data System (ADS)

Huff, Ashley; Steele, Brad; Oleynik, Ivan

High-nitrogen content compounds are being actively explored with the goal of discovering new high-energy density materials with performance surpassing the conventional energetic materials such as HMX or RDX. Although pure polynitrogen compounds such as cg-N are predicted to deliver 10-fold increase in detonation pressure and detonation velocity of 30 km/s, their synthesis and recovery at ambient conditions is problematic. Doping polynitrogens with other elements is a viable route to promote metastability while reducing synthesis pressure. In this work, rubidium poly-nitrides are being investigated as candidates for high energy density materials. Using first principles evolutionary structure search methods performed at varying stoichiometries and several pressures ranging from 0 to 100 GPa, several new polynitrogen compounds have been discovered. The phase diagrams containing thermodynamically stable and lowest metastable phases are calculated and the dynamical stability of the promising materials is investigated at various pressures. Raman spectra and XRD patterns are also calculated to provide experimentally relevant information useful for identification of these compounds during their synthesis.

Chemically stabilized epitaxial wurtzite-BN thin film

NASA Astrophysics Data System (ADS)

Vishal, Badri; Singh, Rajendra; Chaturvedi, Abhishek; Sharma, Ankit; Sreedhara, M. B.; Sahu, Rajib; Bhat, Usha; Ramamurty, Upadrasta; Datta, Ranjan

2018-03-01

We report on the chemically stabilized epitaxial w-BN thin film grown on c-plane sapphire by pulsed laser deposition under slow kinetic condition. Traces of no other allotropes such as cubic (c) or hexagonal (h) BN phases are present. Sapphire substrate plays a significant role in stabilizing the metastable w-BN from h-BN target under unusual PLD growth condition involving low temperature and pressure and is explained based on density functional theory calculation. The hardness and the elastic modulus of the w-BN film are 37 & 339 GPa, respectively measured by indentation along <0001> direction. The results are extremely promising in advancing the microelectronic and mechanical tooling industry.

Mechanisms of the Wurtzite to Rocksalt Transformation in CdSe Nanocrystals

NASA Astrophysics Data System (ADS)

Grünwald, Michael; Rabani, Eran; Dellago, Christoph

2006-06-01

We study the pressure-driven phase transition from the four-coordinate wurtzite to the six-coordinate rocksalt structure in CdSe nanocrystals with molecular dynamics computer simulations. With an ideal gas as the pressure medium, we apply hydrostatic pressure to spherical and faceted nanocrystals ranging in diameter from 25 to 62 Å. In spherical crystals, the main mechanism of the transformation involves the sliding of (100) planes, but depending on the specific surface structure we also observe a second mechanism proceeding through the flattening of (100) planes. In faceted crystals, the transition proceeds via a five-coordinated hexagonal structure, which is stabilized at intermediate pressures due to dominant surface energetics.

High pressure and Multiferroics materials. A happy marriage

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

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 andmore » the coupling to structural instabilities.« less

High-pressure Phase Relation In The MgAl2O4-Mg2SiO4 System

NASA Astrophysics Data System (ADS)

Kojitani, H.; Hisatomi, R.; Akaogi, M.

2005-12-01

High-pressure and high-temperature experiments indicate that high-pressure phases of oceanic basalts contain Al-rich phases. MgAl2O4 with calcium ferrite-type crystal structure is considered as a main component of such the Al-rich phases. Since the calcium ferrite-type MgAl2O4 can be synthesized at only the maximum pressure of a Kawai-type high-pressure apparatus with tungsten carbide (WC) anvils, the amount of a synthesized sample is very limited. Therefore, the crystal structure of the calcium ferrite-type MgAl2O4 has been hardly known in detail due to these difficulties in sample synthesis. In our high-pressure experiments in the MgO-Al2O3-SiO2 system, it was shown that Mg2SiO4 component could be dissolved in the MgAl2O4 calcium ferrite. In this study, we tried to synthesize a single phase MgAl2O4 calcium ferrite sample and to make the Rietveld refinement of the XRD pattern of the sample. The high-pressure phase relations in the MgAl2O4-Mg2SiO4 system were studied to know the stability field of the MgAl2O4-Mg2SiO4 calcium ferrite solid solutions. Lattice parameters-composition relation of the MgAl2O4-Mg2SiO4 calcium ferrite solid solutions was also determined. High-pressure and high-temperature experiments were performed by using a Kawai-type high-pressure apparatus at Gakushuin University. WC anvils with truncated edge length of 1.5 mm were used. Heating was made by a Re heater. Temperature was measured by a Pt/Pt-13%Rh thermocouple. Starting materials for the phase relation experiments were the mixture of MgO, Al2O3 and SiO2 with bulk compositions of MgAl2O4:Mg2SiO4 = 90:10, 78:22, 70:30 and 50:50. The starting materials were held at 21-27 GPa and 1600 °C for 3 hours and then were recovered by the quenching method. The MgAl2O4 calcium ferrite sample for the Rietveld analysis was prepared by heating MgAl2O4 spinel at 27 GPa and about 2200 °C for one hour. Powder X-ray diffraction (XRD) profiles of obtained samples were measured by using a X-ray diffractometer at Gakushuin University (RINT 2500V, Cr Kα, 45 kV, 250 mA). Composition analysis of the recovered samples was made using SEM-DES. The RIETAN-2000 program was used to perform the Rietveld refinement. The results of the high-pressure phase relation experiments show that stability field of single phase of MgAl2O4-Mg2SiO4 solid solutions spreads at lower pressure than that of pure MgAl2O4 calcium ferrite. The lowest pressure at which the calcium ferrite solid solution can be synthesized is about 23 GPa. The maximum solubility of Mg2SiO4 component is about 35%. Lattice parameters of pure MgAl2O4 calcium ferrite were determined as a = 9.9495(6) Å, b = 8.6466(5) Å, c = 2.7901(2) Å ( Pbnm space group) by the Rietveld refinement. Obtained atomic positions for calcium ferrite-type MgAl2O4 are very similar to those of CaFe2O4 calcium ferrite. Lattice parameters of MgAl2O4-Mg2SiO4 calcium ferrite solid solutions with various compositions indicate that c-axis does not change with the composition and that a- and b-axes have a linear increase and decrease trend with increasing Mg2SiO4 component, respectively.

Wavelet assessment of cerebrospinal compensatory reserve and cerebrovascular pressure reactivity

NASA Astrophysics Data System (ADS)

Latka, M.; Turalska, M.; Kolodziej, W.; Latka, D.; West, B.

2006-03-01

We employ complex continuous wavelet transforms to develop a consistent mathematical framework capable of quantifying both cerebrospinal compensatory reserve and cerebrovascular pressure--reactivity. The wavelet gain, defined as the frequency dependent ratio of time averaged wavelet coefficients of intracranial (ICP) and arterial blood pressure (ABP) fluctuations, characterizes the dampening of spontaneous arterial blood oscillations. This gain is introduced as a novel measure of cerebrospinal compensatory reserve. For a group of 10 patients who died as a result of head trauma (Glasgow Outcome Scale GOS =1) the average gain is 0.45 calculated at 0.05 Hz significantly exceeds that of 16 patients with favorable outcome (GOS=2): with gain of 0.24 with p=4x10-5. We also study the dynamics of instantaneous phase difference between the fluctuations of the ABP and ICP time series. The time-averaged synchronization index, which depends upon frequency, yields the information about the stability of the phase difference and is used as a cerebrovascular pressure--reactivity index. The average phase difference for GOS=1 is close to zero in sharp contrast to the mean value of 30^o for patients with GOS=2. We hypothesize that in patients who died the impairment of cerebral autoregulation is followed by the break down of residual pressure reactivity.

Phase Stability and Superconductivity of Compressed Argon-Hydrogen Compounds from First-Principles

NASA Astrophysics Data System (ADS)

Ishikawa, Takahiro; Nakanishi, Akitaka; Shimizu, Katsuya; Oda, Tatsuki

2017-12-01

We present the phase stability and superconductivity of Ar-H compounds under high pressure predicted by first-principles calculations and a genetic algorithm technique for crystal structure search. We found that insulating ArH4, earlier predicted to be metalized at 350 GPa, survives up to 700 GPa owing to the transition into a new phase Pnma at around 250 GPa and then decomposes into metallic ArH2 and pure solid hydrogen. At around 1500 GPa, the bonding form of ArH2 is changed by the dissociation of H2 molecules at the interstitial site of the argon lattice, and antibonding orbitals are partially filled, which causes an increase in the density of states at the Fermi level. Results showed that electron-phonon coupling is enhanced and the superconducting critical temperature is increased from 0.2 to 67 K.

Liquid-solid equilibria involving spinel, ilmenite, and ferropseudobrookite in the system 'FeO'-Al2O3-TiO2 in contact with metallic iron

NASA Technical Reports Server (NTRS)

Schreifels, W. A.; Muan, A.

1975-01-01

Phase relations in the liquidus temperature region of the system 'FeO'-Al2O3-TiO2 in contact with metallic iron, at a total pressure below 1 atm, have been determined by the quenching technique. Four invariant points have been located, with phase assemblages and temperatures as follows; wuestite, ulvoespinel, nercynite and liquid, 1306 C; ulvoespinel, ilmenite, ferropseudobrookite and liquid, 1340 C; ulvoespinel, hercynite, ferropseudobrookite and liquid, 1367 C; hercynite, ferropseudobrookite, corundum and liquid, 1465 C. The data obtained confirm the presence of a miscibility gap between titanate and aluminate spinels, and provide quantitative data for the effect of Al2O3 on mutual stability relations among spinel, ilmenite, and ferropseudobrookite phases in the presence of liquid at high temperatures and strongly reducing conditions. It is shown that Al2O3 has a strong stabilizing effect on the phase assemblage ferropseudobrookite and spinel relative to ilmenite.

Elastic Properties across the y→α Volume Collapse in Cerium versus Pressure and Temperature

DOE PAGES

Lipp, M. J.; Jenei, Zs.; Cynn, H.; ...

2017-10-31

Here, the longitudinal and transverse sound speeds, c L and c T, of polycrystalline cerium were measured isothermally vs pressure up to the critical temperature across the iso-structural γ-α volume collapse (VC) phase transition. We deduce values for the adiabatic bulk modulus BS, the shear modulus G = ρc T 2, the Poisson’s ratio ν and the Debye temperature, θ D(p). We find that the elastic constant C 12 is solely responsible for the decrease of B S with pressure towards the VC at RT. With increasing temperature, the lattice contribution ΔS vib(γ→α) to the total entropy change across themore » VC decreases more rapidly to zero than the total entropy itself suggesting that another mechanism, possibly disorder, assists in stabilizing the γ-phase entropically against the α-phase. Also, with increasing temperature, the Poisson’s ratio becomes negative near the VC transition, meaning that cerium metal takes on auxetic characteristics over a small pressure range. At the critical point the Poisson’s ratio ought to be -1, since the isothermal bulk modulus vanishes and the shear modulus remains nonzero.« less

Elastic Properties across the y→α Volume Collapse in Cerium versus Pressure and Temperature

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

Lipp, M. J.; Jenei, Zs.; Cynn, H.

Here, the longitudinal and transverse sound speeds, c L and c T, of polycrystalline cerium were measured isothermally vs pressure up to the critical temperature across the iso-structural γ-α volume collapse (VC) phase transition. We deduce values for the adiabatic bulk modulus BS, the shear modulus G = ρc T 2, the Poisson’s ratio ν and the Debye temperature, θ D(p). We find that the elastic constant C 12 is solely responsible for the decrease of B S with pressure towards the VC at RT. With increasing temperature, the lattice contribution ΔS vib(γ→α) to the total entropy change across themore » VC decreases more rapidly to zero than the total entropy itself suggesting that another mechanism, possibly disorder, assists in stabilizing the γ-phase entropically against the α-phase. Also, with increasing temperature, the Poisson’s ratio becomes negative near the VC transition, meaning that cerium metal takes on auxetic characteristics over a small pressure range. At the critical point the Poisson’s ratio ought to be -1, since the isothermal bulk modulus vanishes and the shear modulus remains nonzero.« less

Influence of slope steepness, foot position and turn phase on plantar pressure distribution during giant slalom alpine ski racing

PubMed Central

Falda-Buscaiot, Thomas; Hintzy, Frédérique; Rougier, Patrice; Lacouture, Patrick; Coulmy, Nicolas

2017-01-01

The purpose of this study was to investigate the evolution of ground reaction force during alpine skiing turns. Specifically, this study investigated how turn phases and slope steepness affected the whole foot normal GRF pattern while performing giant slalom turns in a race-like setting. Moreover, the outside foot was divided into different plantar regions to see whether those parameters affected the plantar pressure distribution. Eleven skiers performed one giant slalom course at race intensity. Runs were recorded synchronously using a video camera in the frontal plane and pressure insoles under both feet’s plantar surface. Turns were divided according to kinematic criteria into four consecutive phases: initiation, steering1, steering2 and completion; both steering phases being separated by the gate passage. Component of the averaged Ground Reaction Force normal to the ski’s surface(nGRF¯, /BW), and Pressure Time Integral relative to the entire foot surface (relPTI, %) parameters were calculated for each turn phases based on plantar pressure data. Results indicated that nGRF¯ under the total foot surface differed significantly depending on the slope (higher in steep sections vs. flat sections), and the turn phase (higher during steering2 vs. three other phases), although such modifications were observable only on the outside foot. Moreover, nGRF¯ under the outside foot was significantly greater than under the inside foot.RelPTI under different foot regions of the outside foot revealed a global shift from forefoot loading during initiation phase, toward heel loading during steering2 phase, but this was dependent on the slope studied. These results suggest a differentiated role played by each foot in alpine skiing turns: the outside foot has an active role in the turning process, while the inside foot may only play a role in stability. PMID:28472092

Synthesis and equation of state of post-perovskites in the (Mg,Fe)[subscript 3]Al[subscript 2]Si[subscript 3]O[subscript 12] system

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

Shieh, Sean R.; Dorfman, Susannah M.; Kubo, Atsushi

The formation and properties of the post-perovskite (CaIrO{sub 3}-type) phase were studied in Fe-rich compositions along the pyrope-almandine ((Mg,Fe){sub 3}Al{sub 2}Si{sub 3}O{sub 12}) join. Natural and synthetic garnet starting materials with almandine fractions from 38 to 90 mol% were studied using synchrotron X-ray diffraction in the laser-heated diamond anvil cell. Single-phase post-perovskite could be successfully synthesized from garnet compositions at pressures above 148 GPa and temperatures higher than 1600 K. In some cases, evidence for a minor amount of Al{sub 2}O{sub 3} post-perovskite was observed for Alm38 and Alm54 compositions in the perovskite + post-perovskite two-phase region. Pressure-volume data formore » the post-perovskite phases collected during decompression show that incorporation of Fe leads to a systematic increase of unit cell volume broadly similar to the variation observed in the (Mg,Fe)SiO{sub 3} system. The presence of Al{sub 2}O{sub 3} increases the stability of perovskite relative to post-perovskite, requiring higher pressures (> 148 GPa) for synthesis of pure post-perovskites. Our data together with those of Tateno et al. (2005) also suggest that in the Al-rich system the presence of Fe has no strong effect on the pressure required to synthesize the pure post-perovskite phase, but the two-phase perovskite and post-perovskite region may be broad and its width dependent on Fe content. Our results suggest that any regions highly enriched in Al{sub 2}O{sub 3} may consist of either the perovskite phase or a mixture of perovskite and post-perovskite phases throughout the entire thickness of the D* region. The observed synthesis pressures (> 148 GPa) for a pure post-perovskite phase are beyond that at the Earth's core-mantle boundary ({approx} 135 GPa).« less

Influence of slope steepness, foot position and turn phase on plantar pressure distribution during giant slalom alpine ski racing.

PubMed

Falda-Buscaiot, Thomas; Hintzy, Frédérique; Rougier, Patrice; Lacouture, Patrick; Coulmy, Nicolas

2017-01-01

The purpose of this study was to investigate the evolution of ground reaction force during alpine skiing turns. Specifically, this study investigated how turn phases and slope steepness affected the whole foot normal GRF pattern while performing giant slalom turns in a race-like setting. Moreover, the outside foot was divided into different plantar regions to see whether those parameters affected the plantar pressure distribution. Eleven skiers performed one giant slalom course at race intensity. Runs were recorded synchronously using a video camera in the frontal plane and pressure insoles under both feet's plantar surface. Turns were divided according to kinematic criteria into four consecutive phases: initiation, steering1, steering2 and completion; both steering phases being separated by the gate passage. Component of the averaged Ground Reaction Force normal to the ski's surface([Formula: see text], /BW), and Pressure Time Integral relative to the entire foot surface (relPTI, %) parameters were calculated for each turn phases based on plantar pressure data. Results indicated that [Formula: see text] under the total foot surface differed significantly depending on the slope (higher in steep sections vs. flat sections), and the turn phase (higher during steering2 vs. three other phases), although such modifications were observable only on the outside foot. Moreover, [Formula: see text] under the outside foot was significantly greater than under the inside foot.RelPTI under different foot regions of the outside foot revealed a global shift from forefoot loading during initiation phase, toward heel loading during steering2 phase, but this was dependent on the slope studied. These results suggest a differentiated role played by each foot in alpine skiing turns: the outside foot has an active role in the turning process, while the inside foot may only play a role in stability.

Metastable high-pressure transformations of orthoferrosilite Fs82

NASA Astrophysics Data System (ADS)

Dera, Przemyslaw; Finkelstein, Gregory J.; Duffy, Thomas S.; Downs, Robert T.; Meng, Yue; Prakapenka, Vitali; Tkachev, Sergey

2013-08-01

High-pressure single-crystal X-ray diffraction experiments with natural ferrosilite Fs82 (Fe2+0.82Mg0.16Al0.01Ca0.01)(Si0.99Al0.01)O3 orthopyroxene (opx) reveal that at ambient temperature the sample does not transform to the clinopyroxene (cpx) structure, as reported earlier for a synthetic Fs100 end-member (Hugh-Jones et al., 1996), but instead undergoes a series of two polymorphic transitions, first above 10.1(1) GPa, to the monoclinic P21/c phase β-opx (distinctly different from both P21/c and C2/c cpx), also observed in natural enstatite (Zhang et al., 2012), and then, above 12.3(1) GPa to a high-pressure orthorhombic Pbca phase γ-opx, predicted for MgSiO3 by atomistic simulations (Jahn, 2008). The structures of phases α, β and γ have been determined from the single-crystal data at pressures of 2.3(1), 11.1(1), and 14.6(1) GPa, respectively. The two new high-pressure transitions, very similar in their character to the P21/c-C2/c transformation of cpx, make opx approximately as dense as cpx above 12.3(1) GPa and significantly change the elastic anisotropy of the crystal, with the [1 0 0] direction becoming almost twice as stiff as in the ambient α-opx phase. Both transformations involve mainly tetrahedral rotation, are reversible and are not expected to leave microstructural evidence that could be used as a geobarometric proxy. The high Fe2+ content in Fs82 shifts the α-β transition to slightly lower pressure, compared to MgSiO3, and has a very dramatic effect on reducing the (meta) stability range of the β-phase.

[How can we improve symptomatic hypotension in hemodialysis patients: cold dialysis vs isothermic dialysis].

PubMed

Ramos, R; Soto, C; Mestres, R; Jara, J; Zequera, H; Merello, J I; Moreso, F

2007-01-01

Symptomatic hypotension is the most frequent acute complication affecting patients during chronic hemodialysis treatment sessions. Many reports have demonstrated that the use of cool dialysate has a protective effect on blood pressure during hemodialysis treatments. In the present study, we investigated whether preventing the hyperthermic response had favourable effects on hemodynamic stability during the hemodialysis procedure while affording good tolerance to patients. We investigated the effect of thermal control of dialysate on hemodynamic stability in hypotension-prone patients in our center. Patients were eligible for the study if they had symptomatic hypotensive episodes (> 3/12session/ month) during the screening phase. The study was designed with two phases for the same selected patients and two treatment arms, each phase lasting 4 weeks. In the first phase, we adjusted dialysate temperature on 36 masculineC for 12 sessions (cold dialysis) and in the second phase we used a device allowing the regulation of thermal balance (Blood Temperature Monitor; Fresenius Medical Care, Bad Homberg, Germany), that keep body temperature unchanged (isothermic dialysis). Nine HD patients were enrolled and completed the study. During the screening phase the mean ultrafiltration was 4 1% of dry weight, and blood pressure decreased from 9916 to 8016 mm Hg (p<0.001). In 5.01.7 sessions of 12 treatments were complicated by hypotension. In the first and second phase we observed a decrease of complicated treatments with symptomatic hypotension (5.01.7 versus 2.71.6 y 2.81.7; p<0.01). Both procedures: Cold dialysis and Isothermic dialysis was well tolerated by patients. Results show that active control of body temperature can significantly improve intradialytic tolerance in hypotension-prone patients.

Saving water in showers

NASA Astrophysics Data System (ADS)

Alkhaddar, R. A.; Phipps, D.; Morgan, R.; Karci, B.; Hordesseux, J.

2007-07-01

This project is part of a programme aimed at reducing water consumption. Power showers are water inefficient, but in order to persuade the user to accept a lower water use it will be necessary to sustain the "shower experience" to maintain user satisfaction. Previous work has indicated that users' requirements include temperature stability, adequate water volume and distribution, and skin pressure, all of which are substantially controlled by the showerhead. In the present phase of the project several commercially available domestic showerheads have been examined to determine pressure-volume characteristics, radial spray distributions at different flow rates, direct and indirect measures of "skin pressure" and measurements of vertical temperature profiles. Part of the practical work at LJMU has supported extensive theoretical studies by CFD carried out by staff at Arup (consulting engineers) for the Market Transformation Programme. A future phase will study user satisfaction in their own homes where user satisfaction will be surveyed and linked to the physical performance of the shower.

Evaluation of aero Commander propeller acoustic data: Static operations

NASA Technical Reports Server (NTRS)

Piersol, A. G.; Wilby, E. G.; Wilby, J. F.

1978-01-01

Acoustic data are analyzed from a series of ground tests performed on an Aero Commander propeller-driven aircraft with an array of microphones flush-mounted on one side of the fuselage. The analyses were concerned with the propeller blade passage noise during static operation at several different engine speeds and included calculations of the magnitude and phase of the blade passage tones, the amplitude stability of the tones, and the spatial phase and coherence of the tones. The results indicate that the pressure field impinging on the fuselage represents primarily aerodynamic (near field) effects in the plane of the propeller at all frequencies. Forward and aft of the propeller plane aerodynamic effects still dominate the pressure field at frequencies below 200 Hz; but at higher frequencies, the pressure field is due to acoustic propagation from an equivalent center located about 0.15 to 0.30 blade diameters inboard from the propeller hub.

Application of the lattice Boltzmann method for simulation of the mold filling process in the casting industry

NASA Astrophysics Data System (ADS)

Szucki, Michal; Suchy, J. S.; Lelito, J.; Malinowski, P.; Sobczyk, J.

2017-12-01

The aim of this work is the development of the lattice Boltzmann model for simulation of the mold filling process. The authors present a simplified approach to the modeling of liquid metal-gas flows with particular emphasis on the interactions between these phases. The boundary condition for momentum transfer of the moving free surface to the gaseous phase is shown. Simultaneously, the method for modeling influence of gas back pressure on a position and shape of the interfacial boundary is explained in details. The problem of the lattice Boltzmann method (LBM) stability is also analyzed. Since large differences in viscosity of both fluids are a source of the model instability, the so-called fractional step (FS) method allowing to improve the computation stability is applied. The presented solution is verified on the bases of the available reference data and the results of experiments. It is shown that the model describes properly such effects as: gas bubbles formation and air back pressure, accompanying liquid-gas flows in the casting mold. At the same time the proposed approach is easy to be implemented and characterized by a lower demand of operating memory as compared to typical LBM models of two-phase flows.

Carbon nanohorns under cold compression to 40 GPa: Raman scattering and X-ray diffraction experiments

NASA Astrophysics Data System (ADS)

Li, Bo; Nan, Yanli; Zhao, Xiang; Song, Xiaolong; Li, Haining; Wu, Jie; Su, Lei

2017-11-01

We report a high-pressure behavior of carbon nanohorns (CNHs) to 40 GPa at ambient temperature by in situ Raman spectroscopy and synchrotron radiation x-ray diffraction (XRD) in a diamond anvil cell. In Raman measurement, multiple structural transitions are observed. In particular, an additional band at ˜1540 cm-1 indicative of sp3 bonding is shown above 35 GPa, but it reverses upon releasing pressure, implying the formation of a metastable carbon phase having both sp2 and sp3 bonds. Raman frequencies of all bands (G, 2D, D + G, and 2D') are dependent upon pressure with respective pressure coefficients, among which the value for the G band is as small as ˜2.65 cm-1 GPa-1 above 10 GPa, showing a superior high-pressure structural stability. Analysis based on mode Grüneisen parameter demonstrates the similarity of high-pressure behavior between CNHs and single-walled carbon nanotubes. Furthermore, the bulk modulus and Grüneisen parameter for the G band of CNHs are calculated to be ˜33.3 GPa and 0.1, respectively. In addition, XRD data demonstrate that the structure of post-graphite phase derives from surface nanohorns. Based on topological defects within conical graphene lattice, a reasonable transformation route from nanohorns to the post-graphite phase is proposed.

Enhanced H-mode pedestals with lithium injection in DIII-D

DOE PAGES

Osborne, Thomas H.; Jackson, Gary L.; Yan, Zheng; ...

2015-05-08

Periods of edge localized mode (ELM)-free H-mode with increased pedestal pressure and width were observed in the DIII-D tokamak when density fluctuations localized to the region near the separatrix were present. Injection of a powder of 45 μm diameter lithium particles increased the duration of the enhanced pedestal phases to up to 350 ms, and also increased the likelihood of a transition to the enhanced phase. Lithium injection at a level sufficient for triggering the extended enhanced phases resulted in significant lithium in the plasma core, but carbon and other higher Z impurities as well as radiated power levels weremore » reduced. Recycling of the working deuterium gas appeared unaffected by this level of lithium injection. The ion scale, k θ ρ s ~ 0.1–0.2, density fluctuations propagated in the electron drift direction with f ~ 80 kHz and occurred in bursts every ~1 ms. The fluctuation bursts correlated with plasma loss resulting in a flattening of the pressure profile in a region near the separatrix. This localized flattening 2 allowed higher overall pedestal pressure at the peeling-ballooning stability limit and higher pressure than expected under the EPED model due to reduction of the pressure gradient below the “ballooning critical profile”. Furthermore, reduction of the ion pressure by lithium dilution may contribute to the long ELM-free periods.« less

Instability induced by orthopyroxene phase transformation and implications for deep earthquakes below 300 km depth

NASA Astrophysics Data System (ADS)

Shi, F.; Wang, Y.; Zhang, J.; Yu, T.; Zhu, L.

2017-12-01

Global earthquake occurrence rate falls exponentially from the surface to 300 km depth, and then peaks again near 500 km depth. Unassisted frictional sliding will not function at depth below the brittle-ductile transition depth (10-15 km) because increasing pressure trends to inhibit frictional sliding and increasing temperature promotes ductile flow. Two main hypotheses have been proposed and demonstrated in the laboratory for the generation of earthquakes at depth, including dehydration embrittlement (e.g., Rayleigh and Paterson, 1965) for intermediate-depth (70-300 km) earthquakes, metastable olivine phase transformation induced anticrack faulting (e.g., Green and Burnley, 1989) for deep-focus (410-660 km) earthquakes. However, the possibility of earthquake generation by pyroxene phase transformation, another important constituent mineral in the upper mantle and transition zone has never been explored in the laboratory. Here we report axial deformation experiments on hypersthene [(Mg,Fe)SiO3], which has the same structure as enstatite, with the phase transformation to high-pressure monoclinic phase (same structure as the high-pressure clinoenstatite) occurring at lower pressures, in a deformation-DIA (D-DIA) apparatus interfaced with an acoustic emission (AE) monitoring system. Our results show that hypersthene deformed within its stability field (<2GPa and 1000 oC) behaves in a ductile manner without any AE activity. In contrast, numerous AE events were observed during the deformation of metastable hyposthene in its high pressure monoclinic phase field (>5GPa, 1000-1300 oC). This finding provides an additional viable mechanism for earthquakes at depths >300km and moonquakes at 700 - 1200 km depths. Reference: Barcheck, C. Grace, et al. EPSL,349 (2012): 153-160;van Keken, Peter E., et al.JGR,116.B1 (2011);Green II, H. W., and P. C. Burnley. Nature 341.6244 (1989): 733-737.

Pressure-induced phase transitions in the CdC r2S e4 spinel

NASA Astrophysics Data System (ADS)

Efthimiopoulos, I.; Liu, Z. T. Y.; Kucway, M.; Khare, S. V.; Sarin, P.; Tsurkan, V.; Loidl, A.; Wang, Y.

2016-11-01

We have conducted high-pressure x-ray diffraction and Raman spectroscopic studies on the CdC r2S e4 spinel at room temperature up to 42 GPa. We have resolved three structural transitions up to 42 GPa, i.e., the starting F d 3 ¯m phase transforms at ˜11 GPa into a tetragonal I 41/a m d structure, an orthorhombic distortion was observed at ˜15 GPa , whereas structural disorder initiates beyond 25 GPa. Our ab initio density functional theory studies successfully reproduced the observed crystalline-to-crystalline structural transitions. In addition, our calculations propose an antiferromagnetic ordering as a potential magnetic ground state for the high-pressure tetragonal and orthorhombic modifications, compared with the starting ferromagnetic phase. Furthermore, the computational results indicate that all phases remain insulating in their stability pressure range, with a direct-to-indirect band gap transition for the F d 3 ¯m phase taking place at 5 GPa. We attempted also to offer an explanation behind the peculiar first-order character of the F d 3 ¯m (cubic ) →I 41/a m d (tetragonal) transition observed for several relevant Cr spinels, i.e., the sizeable volume change at the transition point, which is not expected from space group symmetry considerations. We detected a clear correlation between the cubic-tetragonal transition pressures and the next-nearest-neighbor magnetic exchange interactions for the Cr-bearing sulfide and selenide members, a strong indication that the cubic-tetragonal transitions in these systems are principally governed by magnetic effects.

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.

Volatiles in the deep Earth: An experimental study using the laser-heated diamond cell

NASA Technical Reports Server (NTRS)

Li, Xiaoyuan; Jeanloz, Raymond; Nguyen, Jeffrey H.

1994-01-01

Experiments with the laser-heated diamond cell show that H2O and CO2 can be stabilized within crystalline mineral structures of the lower-mantle, and hence can be present at relatively non-volatile components of the Earth's deep interior. Samples quenched from high pressures and temperatures document that the MgCO3-FeCO3 magnesite-siderite solid-solution is stable and coexists with (Mg,Fe)SiO3 perovskite at 30-40 GPa and approximately 1500-2000 K. In contrast, H2O combines with the silicate to form (Mg,Fe)SiH2O4 phase D, coexisting with (Mg,Fe)SiO3 perovskite at these conditions. If enough water is present, phase D can become the predominant phase in the MgSiO3-H2O system at lower-mantle conditions. Our work extends previous studies to Fe-bearing compositions and to the pressures of the mid-lower mantle. Thus, the results of high-pressure experiments suggest that both H2O and CO2 can be abundant in the Earth's lower mantle, being present in stable hydroxisilicate and carbonate phases.

Phase transitions of CaCO3 at high P and T determined by in-situ Vibrational Spectroscopy in Diamond-Anvil-Cells

NASA Astrophysics Data System (ADS)

Koch-Müller, Monika; Jahn, Sandro; Birkholz, Natalie; Schade, Ulrich

2014-05-01

Carbonates are the most abundant carbon-bearing minerals on Earth. They can be transported into the upper and lower mantle via subduction processes. Knowledge of the stability of solid carbonates adapting different structures with increasing pressure and temperature is therefore of great importance to understand the structure and dynamics of the Earth. Even for the very simple system CaCO3 the phase relations of at high pressure and temperature are still not fully understood. It has been known for many years that calcite (cc) can adopt different structures with increasing pressure (e.g. Bridgman, 1939: cc-I to III; Tyburczy and Ahrens, 1986: cc-VI). But only recently Merlini et al. (2012) were able to solve the crystal structures of some of these high-pressure polymorphs namely cc-III, cc-IIIb and cc-VI. They report that cc-VI has a higher density then aragonite under the same conditions. To study the stability of the CaCO3-polymorphs, experiments were performed in conventional diamond anvil cells (DAC) at ambient temperatures as a function of pressure up to 30 GPa as well as in internally heated diamond anvil cells (DAC-HT) in the pressure range 9 to 20 GPa and temperatures up to 800 K. As probe for the structural changes we used conventional mid-infrared-, synchrotron far-infrared- and Raman-spectroscopy. Within the cc-III stability field (3 to 15 GPa at room temperature, e.g. Catalli and Williams, 2005) we observed in all types of experiments consistently two different spectral patterns: one at lower P < 5 GPa and another at P > 5 < 15 GPa independent on the starting material and the pressure- and time-path of the experiments. Whether these P-induced structural changes may be linked to the above mentioned different structures of cc-III is not yet clear. Also, in all types of experiments we confirmed the transition of cc-III to cc-VI at about 15 GPa at room temperature. Merlini et al. (2012) speculated that temperature may stabilize the structures of cc-III to lower pressure and surprisingly we found the same for the cc-III to cc-VI transition. The reaction has a negative slope of about -0.007 GPa/K. However, our density-functional theory calculations indicate that cc-VI is still metastable in respect to aragonite at least at zero K. We will prove if temperature and the incorporation of smaller cations than Ca have an influence on the stability relations. References: Bridgman P.W. (1939) Am J Sci, 237, 7 - 18. Catalli K. and Williams Q. (2005) Am Mineral, 90, 1679 - 1682. Merlini M. et al. (2012) EPSL, 333-334, 265 - 271. Tyburczy J. A. and Ahrens T. J. (1986) J Geophysical Research, 91, 4730 - 4744.

Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases

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

Ren, Zhibo; Liu, Ning; Chen, Biaohua

Understanding the structural stability and dynamics at the interface between the solid metal oxide and aqueous phase is significant in a variety of industrial applications including heterogeneous catalysis and environmental remediation. In the present work, the stabilities of three low-index ceria (CeO2) surfaces, i.e., (111), (110) and (100) in vapor and aqueous phases were studied using ab initio molecular dynamics simulations and density functional theory (DFT) calculations. Gibbs surface free energies as a function of temperature, water partial pressure, and water coverages were calculated using DFT based atomistic thermodynamic approach. On the basis of surface free energies, the morphology andmore » exposed surface structures of the CeO2 nanoparticle were predicted using Wulff construction principle. It is found that the partially hydroxylated (111) and (100) are two major surface structures of CeO2 nanoparticles in vapor phase at ambient temperature (300 K). As the temperature increases, the fully dehydrated (111) surface gradually becomes the most dominant surface structure. While in aqueous phase, the exposed surface of the CeO2 nanoparticle is dominated by the hydroxylated (110) structure at 393 K. Finally, the morphology and stability of a cuboctahedron Pt13 nanocluster supported on CeO2 surfaces in both gas and aqueous phases were investigated. In gas phase, the supported Pt13 nanocluster has the tendency to wetting the CeO2 surface due to the strong metal-support interaction. The calculated interaction energies suggest the CeO2(110) surface provides the best stability for the Pt13 nanocluster. The CeO2 supported Pt13 nanoclusters are oxidized. Compared to the gas phase, the morphology of the CeO2 supported Pt13 nanocluster is less distorted due to the solvation effect provided by surrounding water molecules in aqueous phase. More electrons are transferred from the Pt13 nanocluster to the CeO2 support, implying the supported Pt13 nanocluster is further oxidized in aqueous phase.« less

Investigation of structural stability and elastic properties of CrH and MnH: A first principles study

NASA Astrophysics Data System (ADS)

Kanagaprabha, S.; Rajeswarapalanichamy, R.; Sudhapriyanga, G.; Murugan, A.; Santhosh, M.; Iyakutti, K.

2015-06-01

The structural and mechanical properties of CrH and MnH are investigated using first principles calculation based on density functional theory as implemented in VASP code with generalized gradient approximation. The calculated ground state properties are in good agreement with previous experimental and other theoretical results. A structural phase transition from NaCl to NiAs phase at a pressure of 76 GPa is predicted for both CrH and MnH.

Pressure Induced Phase Transition and Electronic Properties of 1d ZnO Nanocrystal: AN AB INITIO Study

NASA Astrophysics Data System (ADS)

Srivastava, Anurag; Tyagi, Neha

2012-10-01

We have analyzed the one-dimensional (1D) ZnO nanocrystals in its wurtzite (B4); zinc-blende (B3) and rocksalt (B1) type phases, by means of density functional theory (DFT) calculations. The energetic stability of nanocrystal has been analyzed using Revised Perdew-Burke-Ernzerhof (revPBE) type parameterized GGA potential. The B3 type phase is most stable amongst other phases of nanocrystals. The computation of ground state properties for all the phases of ZnO nanocrystals finds that the bulk modulus are smaller than their bulk counterpart, in turn softening the material at reduced dimensions. The electronic band structure analysis confirms the semiconducting nature of B4 type phase whereas other two are metallic.

Phase formation in the (1-y)BiFeO{sub 3}-yBiScO{sub 3} system under ambient and high pressure

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

Salak, A.N., E-mail: salak@ua.pt; Khalyavin, D.D., E-mail: dmitry.khalyavin@stfc.ac.uk; Pushkarev, A.V.

Formation and thermal stability of perovskite phases in the BiFe{sub 1-y}Sc{sub y}O{sub 3} 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, BiFeO{sub 3}) 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 BiFeO{sub 3}-like R3c phase and a cubic (I23) sillenite-type phase based on γ-Bi{sub 2}O{sub 3}. Single-phase perovskite ceramics of themore » BiFe{sub 1-y}Sc{sub y}O{sub 3} 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 √2a{sub p}×√2a{sub p}×2√3a{sub p} superstructure (a{sub p} ~ 4 Å is the pseudocubic perovskite unit-cell parameter). The orthorhombic Pnma phase (√2a{sub p}×4a{sub p}×2√2a{sub p}) was obtained in the range of 0.30≤y≤0.60, while the monoclinic C2/c phase (√6a{sub p}×√2a{sub p}×√6a{sub p}) 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 BiFe{sub 1-y}Sc{sub y}O{sub 3} 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. - Graphical abstract: Formation of perovskite phases in the BiFe{sub 1-y}Sc{sub y}O{sub 3} system when y≥0.15 requires application of pressure of several GPa. The phases formed under high pressure: R3c (0.20≤y≤0.25), Pnma (0.30≤y≤0.60) and C2/c (y≥0.70) are metastable. - Highlights: • Maximal Fe-to-Sc substitution rate in BiFeO{sub 3} at ambient pressure is about 15 at%. • R3c → Pnma → C2/c phase sequence in high-pressure prepared BiFe{sub 1-y}Sc{sub y}O{sub 3} ceramics. • The perovskite BiFe{sub 1-y}Sc{sub y}O{sub 3} phases formed under high pressure are metastable.« less

Phase behavior of a fluid with a double Gaussian potential displaying waterlike features

NASA Astrophysics Data System (ADS)

Speranza, Cristina; Prestipino, Santi; Malescio, Gianpietro; Giaquinta, Paolo V.

2014-07-01

Pair potentials that are bounded at the origin provide an accurate description of the effective interaction for many systems of dissolved soft macromolecules (e.g., flexible dendrimers). Using numerical free-energy calculations, we reconstruct the equilibrium phase diagram of a system of particles interacting through a potential that brings together a Gaussian repulsion with a much weaker Gaussian attraction, close to the thermodynamic stability threshold. Compared to the purely repulsive model, only the reentrant branch of the melting line survives, since for lower densities solidification is overridden by liquid-vapor separation. As a result, the phase diagram of the system recalls that of water up to moderate (i.e., a few tens of MPa) pressures. Upon superimposing a suitable hard core on the double-Gaussian potential, a further transition to a more compact solid phase is induced at high pressure, which might be regarded as the analog of the ice I-to-ice III transition in water.

Radiation-induced disorder in compressed lanthanide zirconates.

PubMed

Park, Sulgiye; Tracy, Cameron L; Zhang, Fuxiang; Park, Changyong; Trautmann, Christina; Tkachev, Sergey N; Lang, Maik; Mao, Wendy L; Ewing, Rodney C

2018-02-28

The effects of swift heavy ion irradiation-induced disordering on the behavior of lanthanide zirconate compounds (Ln 2 Zr 2 O 7 where Ln = Sm, Er, or Nd) at high pressures are investigated. After irradiation with 2.2 GeV 197 Au ions, the initial ordered pyrochlore structure (Fd3[combining macron]m) transformed to a defect-fluorite structure (Fm3[combining macron]m) in Sm 2 Zr 2 O 7 and Nd 2 Zr 2 O 7 . For irradiated Er 2 Zr 2 O 7 , which has a defect-fluorite structure, ion irradiation induces local disordering by introducing Frenkel defects despite retention of the initial structure. When subjected to high pressures (>29 GPa) in the absence of irradiation, all of these compounds transform to a cotunnite-like (Pnma) phase, followed by sluggish amorphization with further compression. However, if these compounds are irradiated prior to compression, the high pressure cotunnite-like phase is not formed. Rather, they transform directly from their post-irradiation defect-fluorite structure to an amorphous structure upon compression (>25 GPa). Defects and disordering induced by swift heavy ion irradiation alter the transformation pathways by raising the energetic barriers for the transformation to the high pressure cotunnite-like phase, rendering it inaccessible. As a result, the high pressure stability field of the amorphous phase is expanded to lower pressures when irradiation is coupled with compression. The responses of materials in the lanthanide zirconate system to irradiation and compression, both individually and in tandem, are strongly influenced by the specific lanthanide composition, which governs the defect energetics at extreme conditions.

Reversible stalling of transcription elongation complexes by high pressure.

PubMed

Erijman, L; Clegg, R M

1998-07-01

We have investigated the effect of high hydrostatic pressure on the stability of RNA polymerase molecules during transcription. RNA polymerase molecules participating in stalled or active ternary transcribing complexes do not dissociate from the template DNA and nascent RNA at pressures up to 180 MPa. A lower limit for the free energy of stabilization of an elongating ternary complex relative to the quaternary structure of the free RNAP molecules is estimated to be 20 kcal/mol. The rate of elongation decreases at high pressure; transcription completely halts at sufficiently high pressure. The overall rate of elongation has an apparent activation volume (DeltaVdouble dagger) of 55-65 ml . mol-1 (at 35 degrees C). The pressure-stalled transcripts are stable and resume elongation at the prepressure rate upon decompression. The efficiency of termination decreases at the rho-independent terminator tR2 after the transcription reaction has been exposed to high pressure. This suggests that high pressure modifies the ternary complex such that termination is affected in a manner different from that of elongation. The solvent and temperature dependence of the pressure-induced inhibition show evidence for major conformational changes in the core polymerase enzyme during RNA synthesis. It is proposed that the inhibition of the elongation phase of the transcription reaction at elevated pressures is related to a reduction of the partial specific volume of the RNA polymerase molecule; under high pressure, the RNA polymerase molecule does not have the necessary structural flexibility required for the protein to translocate.

X-ray Emission Spectroscopy in Magnetic 3d-Transition Metals

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

Iota, V; Park, J; Baer, B

2003-11-18

The application of high pressure affects the band structure and magnetic interactions in solids by modifying nearest-neighbor distances and interatomic potentials. While all materials experience electronic changes with increasing pressure, spin polarized, strongly electron correlated materials are expected to undergo the most dramatic transformations. In such materials, (d and f-electron metals and compounds), applied pressure reduces the strength of on-site correlations, leading to increased electron delocalization and, eventually, to loss of its magnetism. In this ongoing project, we study the electronic and magnetic properties of Group VIII, 3d (Fe, Co and Ni) magnetic transition metals and their compounds at highmore » pressures. The high-pressure properties of magnetic 3d-transition metals and compounds have been studied extensively over the years, because of iron being a major constituent of the Earth's core and its relevance to the planetary modeling to understand the chemical composition, internal structure, and geomagnetism. However, the fundamental scientific interest in the high-pressure properties of magnetic 3d-electron systems extends well beyond the geophysical applications to include the electron correlation-driven physics. The role of magnetic interactions in the stabilization of the ''non-standard'' ambient pressure structures of Fe, Co and Ni is still incompletely understood. Theoretical studies have predicted (and high pressure experiments are beginning to show) strong correlations between the electronic structure and phase stability in these materials. The phase diagrams of magnetic 3d systems reflect a delicate balance between spin interactions and structural configuration. At ambient conditions, the crystal structures of {alpha}-Fe(bcc) and {var_epsilon}-Co(hcp) phases depart from the standard sequence (hcp {yields} bcc{yields} hcp {yields} fcc), as observed in all other non-magnetic transition metals with increasing the d-band occupancy, and are different from those of their 4d- and 5d-counter parts. This anomalous behavior has been interpreted in terms of the spin-polarized d-band altering the d-band occupancy [1]. At high pressures, however, the d-valence band is expected to broaden resulting in a suppression or even a complete loss of magnetism. Experimentally, ferromagnetic {alpha}(bcc)-Fe has been confirmed to transform to non-magnetic {var_epsilon}-Fe (hcp) at 10 GPa [2,3]. Recently, we have also observed a similar transition in Co from ferromagnetic {alpha}(hcp)-Co to likely nonmagnetic {beta}(fcc)-Co at 105 GPa[4]. A similar structural phase transition is expected in Ni, probably in the second-order fcc-fcc transition. However, there has been no directly measured change in magnetism associated with the structural phase transition in Co, nor has yet been confirmed such an iso-structural phase transition in Ni. Similar electronic transitions have been proposed in these 3d-transition metal oxides (FeO, CoO and NiO) from high spin (magnetic) to low spin (nonmagnetic) states [5]. In each of these systems, the magnetic transition is accompanied by a first-order structural transition involving large volume collapse (10% in FeO, for example). So far, there have been no electronic measurements under pressure confirming these significant theoretical predictions, although the predicted pressures for the volume collapse transitions are within the experimental pressure range (80-200GPa).« less

Isostructural solid-solid phase transition in monolayers of soft core-shell particles at fluid interfaces: structure and mechanics.

PubMed

Rey, Marcel; Fernández-Rodríguez, Miguel Ángel; Steinacher, Mathias; Scheidegger, Laura; Geisel, Karen; Richtering, Walter; Squires, Todd M; Isa, Lucio

2016-04-21

We have studied the complete two-dimensional phase diagram of a core-shell microgel-laden fluid interface by synchronizing its compression with the deposition of the interfacial monolayer. Applying a new protocol, different positions on the substrate correspond to different values of the monolayer surface pressure and specific area. Analyzing the microstructure of the deposited monolayers, we discovered an isostructural solid-solid phase transition between two crystalline phases with the same hexagonal symmetry, but with two different lattice constants. The two phases corresponded to shell-shell and core-core inter-particle contacts, respectively; with increasing surface pressure the former mechanically failed enabling the particle cores to come into contact. In the phase-transition region, clusters of particles in core-core contacts nucleate, melting the surrounding shell-shell crystal, until the whole monolayer moves into the second phase. We furthermore measured the interfacial rheology of the monolayers as a function of the surface pressure using an interfacial microdisk rheometer. The interfaces always showed a strong elastic response, with a dip in the shear elastic modulus in correspondence with the melting of the shell-shell phase, followed by a steep increase upon the formation of a percolating network of the core-core contacts. These results demonstrate that the core-shell nature of the particles leads to a rich mechanical and structural behavior that can be externally tuned by compressing the interface, indicating new routes for applications, e.g. in surface patterning or emulsion stabilization.

Pressure-induced phase transformation, reversible amorphization, and anomalous visible light response in organolead bromide perovskite

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

Wang, Yonggang; Lu, Xujie; Yang, Wenge

Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH 3NH 3PbBr 3 (MAPbBr 3), under hydrostatic pressure up to 34 GPa at room temperature: Two phase transformations below 2 GPa (from Pm3¯m to Im3¯, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr 6 octahedra and destroying of long-rangemore » ordering of MA cations, respectively. The visible light response of MAPbBr 3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Lastly, our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.« less

Pressure-Induced Phase Transformation, Reversible Amorphization, and Anomalous Visible Light Response in Organolead Bromide Perovskite.

PubMed

Wang, Yonggang; Lü, Xujie; Yang, Wenge; Wen, Ting; Yang, Liuxiang; Ren, Xiangting; Wang, Lin; Lin, Zheshuai; Zhao, Yusheng

2015-09-02

Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH3NH3PbBr3 (MAPbBr3), under hydrostatic pressure up to 34 GPa at room temperature. Two phase transformations below 2 GPa (from Pm3̅m to Im3̅, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr6 octahedra and destroying of long-range ordering of MA cations, respectively. The visible light response of MAPbBr3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.

Pressure-induced phase transformation, reversible amorphization, and anomalous visible light response in organolead bromide perovskite

DOE PAGES

Wang, Yonggang; Lu, Xujie; Yang, Wenge; ...

2015-08-18

Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH 3NH 3PbBr 3 (MAPbBr 3), under hydrostatic pressure up to 34 GPa at room temperature: Two phase transformations below 2 GPa (from Pm3¯m to Im3¯, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr 6 octahedra and destroying of long-rangemore » ordering of MA cations, respectively. The visible light response of MAPbBr 3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Lastly, our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.« less

The stability of the epitaxially introduced metastable metallic structures of thin layers and multilayers

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

Cadeville, M.C.

Among the very large number of metallic thin films, sandwiches and multilayers which have been elaborated by epitaxy on various single crystalline substrates during the last decade, few new structures are reported. Limiting to the case of 3d metals, one finds with a great confidence bcc Cobalt, possibly bee Nickel and a non-compact hexagonal (hp) iron. Moreover structures existing at high temperature under ambient pressure are epitaxially stabilized at room temperature (RT) like fcc Cobalt, fcc Iron, fcc and bcc Manganese. The hcp iron which is stable under high pressure at RT would not be epitaxially stabilized at ambient pressuremore » conversely to first findings. The critical thickness of the metastable phase is generally limited to some monolayers in thin films, being slightly increased in sandwiches or multilayers, even if the phenomenological wetting criterion to build superlattices is not satisfied. No increased magnetic moment has been found up to now in the expanded lattices, contrary to band structure calculation predictions. 56 refs.« less

Nanoscale High Energetic Materials: A Polymeric Nitrogen Chain N8 Confined inside a Carbon Nanotube

NASA Astrophysics Data System (ADS)

Abou-Rachid, Hakima; Hu, Anguang; Timoshevskii, Vladimir; Song, Yanfeng; Lussier, Louis-Simon

2008-05-01

We present a theoretical study of a new hybrid material, nanostructured polymeric nitrogen, where a polymeric nitrogen chain is encapsulated in a carbon nanotube. The electronic and structural properties of the new system are studied by means of ab initio electronic structure and molecular dynamics calculations. Finite temperature simulations demonstrate the stability of this nitrogen phase at ambient pressure and room temperature using carbon nanotube confinement. This nanostructured confinement may open a new path towards stabilizing polynitrogen or polymeric nitrogen at ambient conditions.

In situ determination of crystal structure and chemistry of minerals at Earth's deep lower mantle conditions

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

Yuan, Hongsheng; Zhang, Li

Recent advances in experimental techniques and data processing allow in situ determination of mineral crystal structure and chemistry up to Mbar pressures in a laser-heated diamond anvil cell (DAC), providing the fundamental information of the mineralogical constitution of our Earth's interior. This work highlights several recent breakthroughs in the field of high-pressure mineral crystallography, including the stability of bridgmanite, the single-crystal structure studies of post-perovskite and H-phase as well as the identification of hydrous minerals and iron oxides in the deep lower mantle. The future development of high-pressure crystallography is also discussed.

Pressure-induced phase transition of KTa1/2Nb1/2O3 solid solutions: A first-principles study

NASA Astrophysics Data System (ADS)

Zhang, Huadi; Liu, Bing; Zhang, Cong; Qiu, Chengcheng; Wang, Xuping; Zhang, Yuanyuan; Lv, Xianshun; Wei, Lei; Li, Qinggang

2018-05-01

The structures and electronic properties of KTa1/2Nb1/2O3 under high pressures have been investigated using the first-principles calculations. Three candidates with B site cation ordered along the [1 0 0], [1 1 0] and [1 1 1] directions are found stable under different pressures by thermodynamics, mechanics and dynamics stability criteria. Further electronic analysis indicates that three structures are semiconductors with different band-gap characteristics. The peculiar chemical bonds of Nb-O and Ta-O are expected to be related to the different electronegativity of the corresponding cations.

First-principles theory of iron up to earth-core pressures: Structural, vibrational, and elastic properties

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

Soederlind, P.; Moriarty, J.A.; Wills, J.M.

1996-06-01

{ital Ab} {ital initio} electronic-structure calculations, based on density-functional theory and a full-potential linear-muffin-tin-orbital method, have been used to predict crystal-structure phase stabilities, elastic constants, and Brillouin-zone-boundary phonons for iron under compression. Total energies for five crystal structures, bcc, fcc, bct, hcp, and dhcp, have been calculated over a wide volume range. In agreement with experiment and previous theoretical calculations, a magnetic bcc ground state is obtained at ambient pressure and a nonmagnetic hcp ground state is found at high pressure, with a predicted bcc {r_arrow} hcp phase transition at about 10 GPa. Also in agreement with very recent diamond-anvil-cellmore » experiments, a metastable dhcp phase is found at high pressure, which remains magnetic and consequently accessible at high temperature up to about 50 GPa. In addition, the bcc structure becomes mechanically unstable at pressures above 2 Mbar (200 GPa) and a metastable, but still magnetic, bct phase ({ital c}/{ital a} {approx_equal} 0.875) develops. For high-pressure nonmagnetic iron, fcc and hcp elastic constants and fcc phonon frequencies have been calculated to above 4 Mbar. These quantities rise smoothly with pressure, but an increasing tendency towards elastic anisotropy as a function of compression is observed, and this has important implications for the solid inner-core of the earth. The fcc elastic-constant and phonon data have also been used in combination with generalized pseudopotential theory to develop many-body interatomic potentials, from which high-temperature thermodynamic properties and melting can be obtained. In this paper, these potentials have been used to calculate full fcc and hcp phonon spectra and corresponding Debye temperatures as a function of compression. {copyright} {ital 1996 The American Physical Society.}« less

Dolomite-II: A new high pressure polymorph of CaMg(CO3)2

NASA Astrophysics Data System (ADS)

Santillan, J.; Williams, Q.; Knittle, E.

2002-12-01

We have measured the infrared spectra and x-ray diffraction of CaMg(CO3)2-dolomite to pressures of 50 GPa at 300 K. We observe both splittings and disappearances of x-ray diffraction peaks between 15 and 20 GPa, as well as new bands in the infrared spectrum of dolomite. The onset of the changes in both the x-ray and infrared data appears to be gradual, and thus kinetically impeded: this is consistent with previous shock results. The infrared and x-ray data are consistent with dolomite adopting a calcite-III-like structure. The net volume change associated with the transition based on a calcite-III monoclinic unit cell is ~4 percent. We calculate that the high pressure phase of dolomite has a volume virtually indistinguishable from that of magnesite plus aragonite. Similarly, an assemblage of the high pressure phase of dolomite and magnesium silicate perovskite has an essentially volume to a magnesite plus calcium silicate perovskite assemblage. Our results thus indicate that high-pressure polymorphism in dolomite could stabilize CaMg(CO3)2 in the deep mantle, and thus that high-pressure polymorphs of dolomite could represent the main reservoir for carbon storage within Earth's lower mantle.

Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 1 of 2

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

Bryant, Steven; Juanes, Ruben

In this project we have sought to explain the co-existence of gas and hydrate phases in sediments within the gas hydrate stability zone. We have focused on the gas/brine interface at the scale of individual grains in the sediment. The capillary forces associated with a gas/brine interface play a dominant role in many processes that occur in the pores of sediments and sedimentary rocks. The mechanical forces associated with the same interface can lead to fracture initiation and propagation in hydrate-bearing sediments. Thus the unifying theme of the research reported here is that pore scale phenomena are key to understandingmore » large scale phenomena in hydrate-bearing sediments whenever a free gas phase is present. Our analysis of pore-scale phenomena in this project has delineated three regimes that govern processes in which the gas phase pressure is increasing: fracturing, capillary fingering and viscous fingering. These regimes are characterized by different morphology of the region invaded by the gas. On the other hand when the gas phase pressure is decreasing, the corresponding regimes are capillary fingering and compaction. In this project, we studied all these regimes except compaction. Many processes of interest in hydrate-bearing sediments can be better understood when placed in the context of the appropriate regime. For example, hydrate formation in sub-permafrost sediments falls in the capillary fingering regime, whereas gas invasion into ocean sediments is likely to fall into the fracturing regime. Our research provides insight into the mechanisms by which gas reservoirs are converted to hydrate as the base of the gas hydrate stability zone descends through the reservoir. If the reservoir was no longer being charged, then variation in grain size distribution within the reservoir explain hydrate saturation profiles such as that at Mt. Elbert, where sand-rich intervals containing little hydrate are interspersed between intervals containing large hydrate saturations. Large volumes (of order one pore volume) of gaseous and aqueous phases must be transported into the gas hydrate stability zone. The driver for this transport is the pressure sink induced by a reduction in occupied pore volume that accompanies the formation of hydrate from gas and water. Pore-scale imbibition models and bed-scale multiphase flow models indicate that the rate-limiting step in converting gas to hydrate is the supply of water to the hydrate stability zone. Moreover, the water supply rate is controlled by capillarity-driven flux for conditions typical of the Alaska North Slope. A meter-scale laboratory experiment confirms that significant volumes of fluid phases move into the hydrate stability zone and that capillarity is essential for the water flux. The model shows that without capillarity-driven flux, large saturations of hydrate cannot form. The observations of thick zones of large saturation at Mallik and Mt Elbert thus suggest that the primary control on these systems is the rate of transport of gaseous and aqueous phases, driven by the pressure sink at the base of the gas hydrate stability zone. A key finding of our project is the elucidation of ?capillary fracturing? as a dominant gas transport mechanism in low-permeability media. We initially investigate this phenomenon by means of grain-scale simulations in which we extended a discrete element mechanics code (PFC, by Itasca) to incorporate the dynamics of first single-phase and then multiphase flow. A reductionist model on a square lattice allows us to determine some of the fundamental dependencies of the mode of gas invasion (capillary fingering, viscous fingering, and fracturing) on the parameters of the system. We then show that the morphology of the gas-invaded region exerts a fundamental control on the fabric of methane hydrate formation, and on the overpressures caused by methane hydrate dissociation. We demonstrate the existence of the different invasion regimes by means of controlled laboratory experiments in a radial cell. We collapse the behavior in the form of a phase diagram fully characterized by two dimensionless groups: a modified capillary number and a ?fracturing number? that reflects the balance between the pressure forces that act to open conduits in the granular pack, and frictional forces that resist it. We use all this small-scale knowledge to propose simple mechanistic models of gas migration and hydrate formation at the geologic bed scale. We propose that methane transport in lake and oceanic sediments is controlled by dynamic conduits, which dilate and release gas as the falling hydrostatic pressure reduces the effective stress below the tensile strength of the sediments. We test our model against a four-month record of hydrostatic load and methane flux in Upper Mystic Lake, Mass., USA, and show that it captures the complex episodicity of methane ebullition. Our quantitative conceptualization opens the door to integrated modeling of methane transport to constrain global methane release from lakes and other methane-rich sediment systems, and to assess its climate feedbacks.« less

On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation

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

Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.

The mechanical properties and stability of studtite, (UO2)(O2)(H2O)2·2H2O, and metastudtite, (UO2)(O2)(H2O)2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO2)(O2)(H2O)2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO2)(O2)(H2O)2·2H2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh’s and Poisson’s ratios and the Cauchy pressure, both phases are considered ductile and shear modulus is the parameter limiting their mechanical stability. Debye temperatures of 294 and 271 K are predicted formore » polycrystalline (UO2)(O2)(H2O)2·2H2O and (UO2)(O2)(H2O)2, suggesting a lower micro-hardness of metastudtite.« less

Slip casting and extruding shapes of rhemium with metal oxide additives. Part 2: Development of grain stabilized rhenium parts for resistojets

NASA Technical Reports Server (NTRS)

Barr, Francis A.; Page, Russell J.

1987-01-01

The adaptation of the powdered particle process used for pure metal oxides to the coprocessing of rhenium oxides suitable to produce pure miniature resistojet hardware has been successful. Both slip casting and extrusion processes were used. The metal oxide ZrO2 was stabilized into the cubic phase with Y2O3, for use as a potentially grain stabilizing additive to rhenium. Straight meter long tubing in two sizes are reported. Tubing suitable for resistojet ohmic heater use of fully fired dimensions of nominally 3.8 mm o.d. x 2.2 mm i.d.. and 1.26 mm o.d. x .45 mm i.d. with 0, 0.5, 1.0 and 5.0% zirconia additives were produced for further study. Photomicrographs of these are discussed. The addition of the metal oxide zirconia to rhenium resulted in more dense and less porous parts. The additions of phase stabilized zirconia most likely act as a sintering aid. Tubes of varying diameter were slip cast which were representative of miniature pressure cases.

On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.

2015-09-11

The mechanical properties and stability of studtite, (UO 2)(O 2)(H 2O) 2·2H 2O, and metastudtite, (UO 2)(O 2)(H 2O) 2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO 2)(O 2)(H 2O) 2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO 2)(O 2)(H 2O) 2·2H 2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh's and Poisson's ratios and the Cauchy pressure, both phases are considered ductile and shearmore » modulus is the parameter limiting their mechanical stability. Furthermore, debye temperatures of 294 and 271 K are predicted for polycrystalline (UO 2)(O 2)(H 2O) 2·2H 2O and (UO 2)(O 2)(H 2O) 2, suggesting a lower micro-hardness of metastudtite.« less

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.

Carbonate stability in the earth's mantle - A vibrational spectroscopic study of aragonite and dolomite at high pressures and temperatures

NASA Technical Reports Server (NTRS)

Kraft, Susan; Knittle, Elise; Williams, Quentin

1991-01-01

The structural changes of aragonite and dolomite taking place at high pressures and temperatures were investigated by measuring the Raman spectra of these materials to pressures of 23 and 28 GPa (generated in a diamond anvil cell), respectively; in addition, the IR spectra of aragonite were measured to 40 GPa. The spectroscopic data demonstrated that, at 300 K, dolomite and aragonite samples were stable to pressures of 28 and 41 GPa, respectively. No phase transitions were observed following heating of aragonite and dolomite to temperatures of 2000 K and 800 K, respectively. The mode Grueneisen parameters indicate that the carbonate group in these two minerals is relatively insensitive to pressure, with the dominant compaction mechanism being the compression of the Ca and Mg polyhedra.

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

Zhang, Fei; Wu, Yuan; Lou, Hongbo

Polymorphism, which describes the occurrence of different lattice structures in a crystalline material, is a critical phenomenon in materials science and condensed matter physics. Recently, configuration disorder was compositionally engineered into single lattices, leading to the discovery of high-entropy alloys and high-entropy oxides. For these novel entropy-stabilized forms of crystalline matter with extremely high structural stability, is polymorphism still possible? Here by employing in situ high-pressure synchrotron radiation X-ray diffraction, we reveal a polymorphic transition from face-centred-cubic (fcc) structure to hexagonal-close-packing (hcp) structure in the prototype CoCrFeMnNi high-entropy alloy. The transition is irreversible, and our in situ high-temperature synchrotron radiationmore » X-ray diffraction experiments at different pressures of the retained hcp high-entropy alloy reveal that the fcc phase is a stable polymorph at high temperatures, while the hcp structure is more thermodynamically favourable at lower temperatures. Lastly, as pressure is increased, the critical temperature for the hcp-to-fcc transformation also rises.« less

Ab initio simulations of iron-nickel alloys at Earth's core conditions

NASA Astrophysics Data System (ADS)

Côté, Alexander S.; Vočadlo, Lidunka; Brodholt, John P.

2012-09-01

We report ab initio density functional theory calculations on iron-nickel (FeNi) alloys at conditions representative of the Earth's inner core. We test different concentrations of Ni, up to ∼39 wt% using ab initio lattice dynamics, and investigate the thermodynamic and vibrational stability of the three candidate crystal structures (bcc, hcp and fcc). First of all, at inner core pressures, we find that pure Fe transforms from the hcp to the fcc phase at around 6000 K. Secondly, in agreement with low pressure experiments on Fe-Ni alloys, we find the fcc structure is stabilised by the incorporation of Ni under core pressures and temperatures. Our results show that the fcc structure may, therefore, be stable under core conditions depending on the temperature in the inner core and the Ni content. Lastly, we find that within the quasi-harmonic approximation, there is no stability field for FeNi alloys in the bcc structure under core conditions.

Polymorphism in a high-entropy alloy

DOE PAGES

Zhang, Fei; Wu, Yuan; Lou, Hongbo; ...

2017-06-01

Polymorphism, which describes the occurrence of different lattice structures in a crystalline material, is a critical phenomenon in materials science and condensed matter physics. Recently, configuration disorder was compositionally engineered into single lattices, leading to the discovery of high-entropy alloys and high-entropy oxides. For these novel entropy-stabilized forms of crystalline matter with extremely high structural stability, is polymorphism still possible? Here by employing in situ high-pressure synchrotron radiation X-ray diffraction, we reveal a polymorphic transition from face-centred-cubic (fcc) structure to hexagonal-close-packing (hcp) structure in the prototype CoCrFeMnNi high-entropy alloy. The transition is irreversible, and our in situ high-temperature synchrotron radiationmore » X-ray diffraction experiments at different pressures of the retained hcp high-entropy alloy reveal that the fcc phase is a stable polymorph at high temperatures, while the hcp structure is more thermodynamically favourable at lower temperatures. Lastly, as pressure is increased, the critical temperature for the hcp-to-fcc transformation also rises.« less

Effects of Iron and Aluminum on Phase Boundaries at 600-800 km Depths

NASA Astrophysics Data System (ADS)

Shim, Sang-Heon; Ye, Yu; Prakapenka, Vitali; Meng, Yue

2014-05-01

High-resolution seismic studies have reported complex discontinuity structures at 600-800 km depths. However, the origin of the structures have not been well understood. In order to understand compositional effects, we have measured the post-spinel, post-garnet, and post-ilmenite phase boundaries in MgO-Al2O3-SiO2 (iron free) and CaO-MgO-Al2O3-SiO2-FeO (iron bearing) systems with pyrolitic oxide ratios. In-situ X-ray diffraction measurements were performed at 20-30 GPa and 1500-2300 K in the laser-heated diamond-anvil cell at the GSECARS and HPCAT sectors of the Advanced Photon Source. We use the Pt and Au pressure scales for the iron-free and iron-bearing compositions, respectively. The Pt and Au scales were calibrated with respect to each other in separate experiments. In most experiments, Ar was cryogenically loaded in the sample chamber as a thermal insulation and pressure transmitting medium, except for a few experiments where a KCl medium was used. At temperatures above 1900 K, the post-garnet transition occurs at higher pressures than the post-spinel transition in both the iron-free and iron-bearing systems. At lower temperatures, while the post-ilmenite transition occurs at nearly same pressures as the post-spinel transition in the iron-bearing system, the post-ilmenite transition occurs at slightly higher pressure (1 GPa) than the post-spinel transitions in the iron-free system. In the iron-free system, akimotoite is stable to much higher temperature (2300 K) than previously thought. In the iron-bearing system, the stability of akimotoite is limited to 2050 K. Our data indicate that Al partitions more into akimotoite than garnet in the iron-free system, which is the opposite to what has been found in iron-bearing systems. The high Al content in akimotoite seems to be responsible for the high-temperature stability of akimotoite in the iron-free system. The Clapeyron slope of the post-garnet boundary is greater by a factor of 2.5 in the iron-bearing system than the iron-free system, while the Clapeyron slopes of the other phase boundaries do not change. Our results suggest that lateral variations in Fe and Al may significantly change the mineralogy in the mantle transition zone. For example, a decrease in iron content will stabilize Al-rich akimotoite even at average mantle temperatures. An increase in iron content will limit the stability of akimotoite and make garnet more important in the mantle transition zone. The large positive Clapeyron slope (5 MPa/K) of the post-garnet boundary in iron-rich regions may allow more vigorous mantle flow across the boundary between the upper and the lower mantle.

Dynamics and stability of relativistic gamma-ray-bursts blast waves

NASA Astrophysics Data System (ADS)

Meliani, Z.; Keppens, R.

2010-09-01

Aims: In gamma-ray-bursts (GRBs), ultra-relativistic blast waves are ejected into the circumburst medium. We analyse in unprecedented detail the deceleration of a self-similar Blandford-McKee blast wave from a Lorentz factor 25 to the nonrelativistic Sedov phase. Our goal is to determine the stability properties of its frontal shock. Methods: We carried out a grid-adaptive relativistic 2D hydro-simulation at extreme resolving power, following the GRB jet during the entire afterglow phase. We investigate the effect of the finite initial jet opening angle on the deceleration of the blast wave, and identify the growth of various instabilities throughout the coasting shock front. Results: We find that during the relativistic phase, the blast wave is subject to pressure-ram pressure instabilities that ripple and fragment the frontal shock. These instabilities manifest themselves in the ultra-relativistic phase alone, remain in full agreement with causality arguments, and decay slowly to finally disappear in the near-Newtonian phase as the shell Lorentz factor drops below 3. From then on, the compression rate decreases to levels predicted to be stable by a linear analysis of the Sedov phase. Our simulations confirm previous findings that the shell also spreads laterally because a rarefaction wave slowly propagates to the jet axis, inducing a clear shell deformation from its initial spherical shape. The blast front becomes meridionally stratified, with decreasing speed from axis to jet edge. In the wings of the jetted flow, Kelvin-Helmholtz instabilities occur, which are of negligible importance from the energetic viewpoint. Conclusions: Relativistic blast waves are subject to hydrodynamical instabilities that can significantly affect their deceleration properties. Future work will quantify their effect on the afterglow light curves.

Raman spectroscopy analysis of air grown oxide scale developed on pure zirconium substrate

NASA Astrophysics Data System (ADS)

Kurpaska, L.; Favergeon, J.; Lahoche, L.; El-Marssi, M.; Grosseau Poussard, J.-L.; Moulin, G.; Roelandt, J.-M.

2015-11-01

Using Raman spectroscopy technique, external and internal parts of zirconia oxide films developed at 500 °C and 600 °C on pure zirconium substrate under air at normal atmospheric pressure have been examined. Comparison of Raman peak positions of tetragonal and monoclinic zirconia phases, recorded during the oxide growth at elevated temperature, and after cooling at room temperature have been presented. Subsequently, Raman peak positions (or shifts) were interpreted in relation with the stress evolution in the growing zirconia scale, especially closed to the metal/oxide interface, where the influence of compressive stress in the oxide is the biggest. Reported results, for the first time show the presence of a continuous layer of tetragonal zirconia phase developed in the proximity of pure zirconium substrate. Based on the Raman peak positions we prove that this tetragonal layer is stabilized by the high compressive stress and sub-stoichiometry level. Presence of the tetragonal phase located in the outer part of the scale have been confirmed, yet its Raman characteristics suggest a stress-free tetragonal phase, therefore different type of stabilization mechanism. Presented study suggest that its stabilization could be related to the lattice defects introduced by highstoichiometry of zirconia or presence of heterovalent cations.

First-principles predictions of structural, mechanical and electronic properties of βTiNb under high pressure

NASA Astrophysics Data System (ADS)

Wang, Z. P.; Fang, Q. H.; Li, J.; Liu, B.

2018-04-01

Structural, mechanical and electronic properties of βTiNb alloy under high pressure have been investigated based on the density functional theory (DFT). The dependences of dimensionless volume ratio, elastic constants, bulk modulus, Young's modulus, shear modulus, ductile/brittle, anisotropy and Poisson's ratio on applied pressure are all calculated successfully. The results reveal that βTiNb alloy is mechanically stable under pressure below 23.45 GPa, and the pressure-induced phase transformation could occur beyond this critical value. Meanwhile, the applied pressure can effectively promote the mechanical properties of βTiNb alloy, including the resistances to volume change, elastic deformation and shear deformation, as well as the material ductility and metallicity. Furthermore, the calculated electronic structures testify that βTiNb alloy performs the metallicity and the higher pressure reduces the structural stability of unit cell.

High-pressure Infrared Spectra of Tal and Lawsonite

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

Scott,H.; Liu, Z.; Hemley, R.

2007-01-01

We present high-pressure infrared spectra of two geologically important hydrous minerals: talc, Mg3Si4O10(OH)2 and lawsonite, CaAl2Si2O7(OH)2{center_dot}H2O,{center_dot}at room temperature. For lawsonite, our data span the far infrared region from 150 to 550 cm-1 and extend to 25 GPa. We combine our new spectroscopic data with previously published high-pressure mid-infrared and Raman data to constrain the Gr{umlt u}neisen parameter and vibrational density of states under pressure. In the case of talc, we present high-pressure infrared data that span both the mid and far infrared from 150 to 3800 cm-1 covering lattice, silicate, and hydroxyl stretching vibrations to a maximum pressure of 30more » GPa. Both phases show remarkable metastability well beyond their nominal maximum thermodynamic stability at simultaneous high-pressure and high-temperature conditions.« less

Interface-induced superconductivity at ∼25 K at ambient pressure in undoped CaFe2As2 single crystals

PubMed Central

Zhao, Kui; Lv, Bing; Deng, Liangzi; Huyan, Shu-Yuan; Xue, Yu-Yi; Chu, Ching-Wu

2016-01-01

Superconductivity has been reversibly induced/suppressed in undoped CaFe2As2 (Ca122) single crystals through proper thermal treatments, with Tc at ∼25 K at ambient pressure and up to 30 K at 1.7 GPa. We found that Ca122 can be stabilized in two distinct tetragonal (T) phases at room temperature and ambient pressure: PI with a nonmagnetic collapsed tetragonal (cT) phase at low temperature and PII with an antiferromagnetic orthorhombic (O) phase at low temperature, depending on the low-temperature annealing condition. Neither phase at ambient pressure is superconducting down to 2 K. However, systematic annealing for different time periods at 350 °C on the as-synthesized crystals, which were obtained by quenching the crystal ingot from 850 °C, reveals the emergence of superconductivity over a narrow time window. Whereas the onset Tc is insensitive to the anneal time, the superconductive volume fraction evolves with the time in a dome-shaped fashion. Detailed X-ray diffraction profile analyses further reveal mesoscopically stacked layers of the PI and the PII phases. The deduced interface density correlates well with the superconducting volume measured. The transport anomalies of the T–cT transition, which is sensitive to lattice strain, and the T–O transition, which is associated with the spin-density-wave (SDW) transition, are gradually suppressed over the superconductive region, presumably due to the interface interactions between the nonmagnetic metallic cT phase and the antiferromagnetic O phase. The results provide the most direct evidence to date for interface-enhanced superconductivity in undoped Ca122, consistent with the recent theoretical prediction. PMID:27799564

A theoretical study of the stability of anionic defects in cubic ZrO 2 at extreme conditions

DOE PAGES

Samanta, Amit

2016-02-19

Using first principles density functional theory calculations, we present a study of the structure, mobility, and the thermodynamic stability of anionic defects in the high-temperature cubic phase of ZrO 2. Our results suggest that the local structure of an oxygen interstitial depends on the charge state and the cubic symmetry of the anionic sublattice is unstable at 0 K. In addition, the oxygen interstitials and the vacancies exhibit symmetry breaking transitions to low-energy structures with tetragonal distortion of the oxygen sublattice at 0 K. However, the vibrational entropy stabilizes the defect structures with cubic symmetry at 2600–2980 K. The formationmore » free energies of the anionic defects and Gibbs free energy changes associated with different defect reactions are calculated by including the vibrational free energy contributions and the effect of pressure on these defect structures. By analyzing the defect chemistry, we obtain the defect concentrations at finite temperature and pressure conditions using the zero temperature ab initio results as input and find that at low oxygen partial pressures, neutral oxygen vacancies are most dominant and at high oxygen partial pressures, doubly charged anionic defects are dominant. As a result, the relevance of the results to the thermal protective coating capabilities of zirconium-based ceramic composites is elucidated.« less

β -B i2O3 under compression: Optical and elastic properties and electron density topology analysis

NASA Astrophysics Data System (ADS)

Pereira, A. L. J.; Gomis, O.; Sans, J. A.; Contreras-García, J.; Manjón, F. J.; Rodríguez-Hernández, P.; Muñoz, A.; Beltrán, A.

2016-06-01

We report a joint experimental and theoretical study of the optical properties of tetragonal bismuth oxide (β -B i2O3 ) at high pressure by means of optical absorption measurements combined with ab initio electronic band structure calculations. Our results are consistent with previous results that show the presence of a second-order isostructural phase transition in B i2O3 (from β to β') around 2 GPa and a phase transition above 15 GPa combined with a pressure-induced amorphization above 17-20 GPa. In order to further understand the pressure-induced phase transitions and amorphization occurring in β -B i2O3 , we theoretically studied the mechanical and dynamical stability of the tetragonal structures of β - and β'-B i2O3 at high pressure through calculations of their elastic constants, elastic stiffness coefficients, and phonon dispersion curves. The pressure dependence of the elastic stiffness coefficients and phonon dispersion curves confirms that the isostructural phase transition near 2 GPa is of ferroelastic nature. Furthermore, a topological study of the electron density shows that the ferroelastic transition is not caused by a change in number of critical points (cusp catastrophe), but by the equalization of the electron densities of both independent O atoms in the unit cell due to a local rise in symmetry. Finally, from theoretical simulations, β'-B i2O3 is found to be mechanically and dynamically stable at least up to 26.7 GPa under hydrostatic conditions; thus, the pressure-induced amorphization reported above 17-20 GPa in powder β'-B i2O3 using methanol-ethanol-water as pressure-transmitting medium could be related to the frustration of a reconstructive phase transition at room temperature and the presence of mechanical or dynamical instabilities under nonhydrostatic conditions.

Phase transitions and Al partitioning in a pyrolitic MgO-Al2O3-SiO2 composition at 16-31 GPa and 1500-2300 K

NASA Astrophysics Data System (ADS)

Ye, Y.; Gu, C.; Shim, S.; Prakapenka, V.; MacDowell, A.

2013-12-01

In order to understand strong seismic heterogeneities found in the base of the mantle transition zone, it is important to explore the effects of temperature and composition on the phase boundaries in the region. We have determined the phase boundaries near the 660-km discontinuity in an iron-free pyrolitic MgO-Al2O3-SiO2 (MAS) composition by combining in-situ synchrotron X-ray diffraction and laser-heated diamond-anvil cell at 16-31 GPa and 1500-2300 K. The pyrolitic MAS composition glass starting materials were mixed with platinum (laser coupler and internal pressure scale) and loaded into the diamond-anvil cells together with argon (pressure transmitting medium and thermal insulator). The in-situ measurements were conducted at the GSECARS sector of Advanced Photon Source and beamline 12.2.2 of Advanced Light Source. We found that the post-spinel transition (ringwoodite to perovskite+periclase) occurs at the pressure and temperature conditions expected for the 660-km discontinuity at 1800 K if the shockwave platinum pressure scale by Holmes et al. (1989) is used. At temperatures above 1900 K, ringwoodite breaks down to garnet+periclase, instead of perovskite+periclase, followed by the post-garnet transition (garnet to perovskite) at the pressure-temperature conditions expected for warm heterogeneities at 650-680 km depths (23-24 GPa and 1900-2300 K). The Clapeyron slopes of the post-spinel and post-garnet boundaries are constrained to be -2.8×0.2 and +2.4×0.3 MPa/K, respectively, indicating similar magnitude of thermal effects (with opposite signs) on the topography of the 660-km discontinuity by these phase boundaries. The dominance of the post-garnet transition above normal mantle temperatures will facilitate material exchange across the 660 discontinuity in warm mantle heterogeneities due to its positive Clapeyron slope. In our pyrolitic MAS composition, akimotoite was observed up to 2000-2300 K between 20 and 22 GPa in both fresh sample heating and reversal measurements, and the post-ilmenite transition (akimotoite to perovskite) occurs at 1-2 GPa higher pressures than the post-spinel transition below 1800 K, significantly different from phase behaviors found in iron-bearing systems. Molar volumes of the temperature quenched samples indicate that Al strongly partitions into akimotoite (akimotoite can contain even greater amount of Al2O3 than coexisting garnet and perovskite). The strong partitioning of Al into akimotoite in iron-free system may be responsible for the observed stability of akimotoite to higher pressures and temperatures, suggesting variations in iron content can produce mineralogical heterogeneities through control of relative stability of akimotoite and garnet.

Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped and lead-free Bi-2212 systems

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Maroni, V. A.

1996-02-01

Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made on lead-doped and lead-free Bi 2- zPb zSr 2Ca 1Cu 2O x superconducting ceramics in the temperature range ≈ 700-815°C by means of an oxygen-titration techique that employs an yttria-stabilized zirconia electrolyte. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Thermodynamic assessments of the partial molar quantities Δ overlineH(O 2) and Δ overlineS(O 2) for lead-doped Bi-2212 and lead-free Bi-2212 indicate that the solid-state decomposition of these bismuth cuprates at low oxygen partial pressure can be represented by the diphasic CuOCu 2O system.

Sintering, thermal stability and mechanical properties of ZrO2-WC composites obtained by pulsed electric current sintering

NASA Astrophysics Data System (ADS)

Huang, Shuigen; Vanmeensel, Kim; van der Biest, Omer; Vleugels, Jozef

2011-03-01

ZrO2-WC composites exhibit comparable mechanical properties as traditional WC-Co materials, which provides an opportunity to partially replace WC-Co for some applications. In this study, 2 mol.% Y2O3 stabilized ZrO2 composites with 40 vol.% WC were consolidated in the 1150°C-1850°C range under a pressure of 60 MPa by pulsed electric current sintering (PECS). The densification behavior, microstructure and phase constitution of the composites were investigated to clarify the role of the sintering temperature on the grain growth, mechanical properties and thermal stability of ZrO2 and WC components. Analysis results indicated that the composites sintered at 1350°C and 1450°C exhibited the highest tetragonal ZrO2 phase transformability, maximum toughness, and hardness and an optimal flexural strength. Chemical reaction of ZrO2 and C, originating from the graphite die, was detected in the composite PECS for 20 min at 1850°C in vacuum.

Phase transition and chemical decomposition of hydrogen peroxide and its water mixtures under high pressures.

PubMed

Chen, Jing-Yin; Kim, Minseob; Yoo, Choong-Shik; Dattelbaum, Dana M; Sheffield, Stephen

2010-06-07

We have studied the pressure-induced phase transition and chemical decomposition of hydrogen peroxide and its mixtures with water to 50 GPa, using confocal micro-Raman and synchrotron x-ray diffractions. The x-ray results indicate that pure hydrogen peroxide crystallizes into a tetragonal structure (P4(1)2(1)2), the same structure previously found in 82.7% H(2)O(2) at high pressures and in pure H(2)O(2) at low temperatures. The tetragonal phase (H(2)O(2)-I) is stable to 15 GPa, above which transforms into an orthorhombic structure (H(2)O(2)-II) over a relatively large pressure range between 13 and 18 GPa. Inferring from the splitting of the nu(s)(O-O) stretching mode, the phase I-to-II transition pressure decreases in diluted H(2)O(2) to around 7 GPa for the 41.7% H(2)O(2) and 3 GPa for the 9.5%. Above 18 GPa H(2)O(2)-II gradually decomposes to a mixture of H(2)O and O(2), which completes at around 40 GPa for pure and 45 GPa for the 9.5% H(2)O(2). Upon pressure unloading, H(2)O(2) also decomposes to H(2)O and O(2) mixtures across the melts, occurring at 2.5 GPa for pure and 1.5 GPa for the 9.5% mixture. At H(2)O(2) concentrations below 20%, decomposed mixtures form oxygen hydrate clathrates at around 0.8 GPa--just after H(2)O melts. The compression data of pure H(2)O(2) and the stability data of the mixtures seem to indicate that the high-pressure decomposition is likely due to the pressure-induced densification, whereas the low-pressure decomposition is related to the heterogeneous nucleation process associated with H(2)O(2) melting.

Structures of dolomite at ultrahigh pressure and their influence on the deep carbon cycle

PubMed Central

Merlini, Marco; Crichton, Wilson A.; Hanfland, Michael; Gemmi, Mauro; Müller, Harald; Kupenko, Ilya; Dubrovinsky, Leonid

2012-01-01

Carbon-bearing solids, fluids, and melts in the Earth's deep interior may play an important role in the long-term carbon cycle. Here we apply synchrotron X-ray single crystal micro-diffraction techniques to identify and characterize the high-pressure polymorphs of dolomite. Dolomite-II, observed above 17 GPa, is triclinic, and its structure is topologically related to CaCO3-II. It transforms above 35 GPa to dolomite-III, also triclinic, which features carbon in [3 + 1] coordination at the highest pressures investigated (60 GPa). The structure is therefore representative of an intermediate between the low-pressure carbonates and the predicted ultra-high pressure carbonates, with carbon in tetrahedral coordination. Dolomite-III does not decompose up to the melting point (2,600 K at 43 GPa) and its thermodynamic stability demonstrates that this complex phase can transport carbon to depths of at least up to 1,700 km. Dolomite-III, therefore, is a likely occurring phase in areas containing recycled crustal slabs, which are more oxidized and Ca-enriched than the primitive lower mantle. Indeed, these phases may play an important role as carbon carriers in the whole mantle carbon cycling. As such, they are expected to participate in the fundamental petrological processes which, through carbon-bearing fluids and carbonate melts, will return carbon back to the Earth’s surface. PMID:22869705

Collapsed tetragonal phase as a strongly covalent and fully nonmagnetic state: Persistent magnetism with interlayer As-As bond formation in Rh-doped Ca0 .8Sr0 .2Fe2As2

NASA Astrophysics Data System (ADS)

Zhao, K.; Glasbrenner, J. K.; Gretarsson, H.; Schmitz, D.; Bednarcik, J.; Etter, M.; Sun, J. P.; Manna, R. S.; Al-Zein, A.; Lafuerza, S.; Scherer, W.; Cheng, J. G.; Gegenwart, P.

2018-02-01

A well-known feature of the CaFe2As2 -based superconductors is the pressure-induced collapsed tetragonal phase that is commonly ascribed to the formation of an interlayer As-As bond. Using detailed x-ray scattering and spectroscopy, we find that Rh-doped Ca0.8Sr0.2Fe2As2 does not undergo a first-order phase transition and that local Fe moments persist despite the formation of interlayer As-As bonds. Our density functional theory calculations reveal that the Fe-As bond geometry is critical for stabilizing magnetism and the pressure-induced drop in the c lattice parameter observed in pure CaFe2As2 is mostly due to a constriction within the FeAs planes. The collapsed tetragonal phase emerges when covalent bonding of strongly hybridized Fe 3 d and As 4 p states completely wins out over their exchange splitting. Thus the collapsed tetragonal phase is properly understood as a strong covalent phase that is fully nonmagnetic with the As-As bond forming as a by-product.

Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 2 of 2

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

Bryant, Steven; Juanes, Ruben

In this project we have sought to explain the co-existence of gas and hydrate phases in sediments within the gas hydrate stability zone. We have focused on the gas/brine interface at the scale of individual grains in the sediment. The capillary forces associated with a gas/brine interface play a dominant role in many processes that occur in the pores of sediments and sedimentary rocks. The mechanical forces associated with the same interface can lead to fracture initiation and propagation in hydrate-bearing sediments. Thus the unifying theme of the research reported here is that pore scale phenomena are key to understandingmore » large scale phenomena in hydrate-bearing sediments whenever a free gas phase is present. Our analysis of pore-scale phenomena in this project has delineated three regimes that govern processes in which the gas phase pressure is increasing: fracturing, capillary fingering and viscous fingering. These regimes are characterized by different morphology of the region invaded by the gas. On the other hand when the gas phase pressure is decreasing, the corresponding regimes are capillary fingering and compaction. In this project, we studied all these regimes except compaction. Many processes of interest in hydrate-bearing sediments can be better understood when placed in the context of the appropriate regime. For example, hydrate formation in sub-permafrost sediments falls in the capillary fingering regime, whereas gas invasion into ocean sediments is likely to fall into the fracturing regime. Our research provides insight into the mechanisms by which gas reservoirs are converted to hydrate as the base of the gas hydrate stability zone descends through the reservoir. If the reservoir was no longer being charged, then variation in grain size distribution within the reservoir explain hydrate saturation profiles such as that at Mt. Elbert, where sand-rich intervals containing little hydrate are interspersed between intervals containing large hydrate saturations. Large volumes (of order one pore volume) of gaseous and aqueous phases must be transported into the gas hydrate stability zone. The driver for this transport is the pressure sink induced by a reduction in occupied pore volume that accompanies the formation of hydrate from gas and water. Pore-scale imbibition models and bed-scale multiphase flow models indicate that the rate-limiting step in converting gas to hydrate is the supply of water to the hydrate stability zone. Moreover, the water supply rate is controlled by capillarity-driven flux for conditions typical of the Alaska North Slope. A meter-scale laboratory experiment confirms that significant volumes of fluid phases move into the hydrate stability zone and that capillarity is essential for the water flux. The model shows that without capillarity-driven flux, large saturations of hydrate cannot form. The observations of thick zones of large saturation at Mallik and Mt Elbert thus suggest that the primary control on these systems is the rate of transport of gaseous and aqueous phases, driven by the pressure sink at the base of the gas hydrate stability zone. A key finding of our project is the elucidation of ?capillary fracturing? as a dominant gas transport mechanism in low-permeability media. We initially investigate this phenomenon by means of grain-scale simulations in which we extended a discrete element mechanics code (PFC, by Itasca) to incorporate the dynamics of first singlephase and then multiphase flow. A reductionist model on a square lattice allows us to determine some of the fundamental dependencies of the mode of gas invasion (capillary fingering, viscous fingering, and fracturing) on the parameters of the system. We then show that the morphology of the gas-invaded region exerts a fundamental control on the fabric of methane hydrate formation, and on the overpressures caused by methane hydrate dissociation. We demonstrate the existence of the different invasion regimes by means of controlled laboratory experiments in a radial cell. We collapse the behavior in the form of a phase diagram fully characterized by two dimensionless groups: a modified capillary number and a ?fracturing number? that reflects the balance between the pressure forces that act to open conduits in the granular pack, and frictional forces that resist it. We use all this small-scale knowledge to propose simple mechanistic models of gas migration and hydrate formation at the geologic bed scale. We propose that methane transport in lake and oceanic sediments is controlled by dynamic conduits, which dilate and release gas as the falling hydrostatic pressure reduces the effective stress below the tensile strength of the sediments. We test our model against a four-month record of hydrostatic load and methane flux in Upper Mystic Lake, Mass., USA, and show that it captures the complex episodicity of methane ebullition. Our quantitative conceptualization opens the door to integrated modeling of methane transport to constrain global methane release from lakes and other methane-rich sediment systems, and to assess its climate feedbacks.« less

On the room-temperature phase diagram of high pressure hydrogen: an ab initio molecular dynamics perspective and a diffusion Monte Carlo study.

PubMed

Chen, Ji; Ren, Xinguo; Li, Xin-Zheng; Alfè, Dario; Wang, Enge

2014-07-14

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.

Phase stability of transition metals and alloys

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

Hixson, R.S.; Schiferl, D.; Wills, J.M.

1997-06-01

This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project was focused on resolving unexplained differences in calculated and measured phase transition pressures in transition metals. Part of the approach was to do new, higher accuracy calculations of transmission pressures for group 4B and group 6B metals. Theory indicates that the transition pressures for these baseline metals should change if alloyed with a d-electron donor metal, and calculations done using the Local Density Approximation (LDA) and the Virtual Crystal Approximation (VCA) indicate that this is true. Alloymore » systems were calculated for Ti, Zr and Hf based alloys with various solute concentrations. The second part of the program was to do new Diamond Anvil Cell (DAC) measurements to experimentally verify calculational results. Alloys were prepared for these systems with grain size suitable for Diamond Anvil Cell experiments. Experiments were done on pure Ti as well as Ti-V and Ti-Ta alloys. Measuring unambiguous transition pressures for these systems proved difficult, but a new technique developed yielded good results.« less

Ab initio and shell model studies of structural, thermoelastic and vibrational properties of SnO2 under pressure

NASA Astrophysics Data System (ADS)

Casali, R. A.; Lasave, J.; Caravaca, M. A.; Koval, S.; Ponce, C. A.; Migoni, R. L.

2013-04-01

The pressure dependences of the structural, thermoelastic and vibrational properties of SnO2 in its rutile phase are studied, as well as the pressure-induced transition to a CaCl2-type phase. These studies have been performed by means of ab initio (AI) density functional theory calculations using the localized basis code SIESTA. The results are employed to develop a shell model (SM) for application in future studies of nanostructured SnO2. A good agreement of the SM results for the pressure dependences of the above properties with the ones obtained from present and previous AI calculations as well as from experiments is achieved. The transition is characterized by a rotation of the Sn-centered oxygen octahedra around the tetragonal axis through the Sn. This rotation breaks the tetragonal symmetry of the lattice and an orthorhombic distortion appears above the critical pressure Pc. A zone-center phonon of B1g symmetry in the rutile phase involves such rotation and softens on approaching Pc. It becomes an Ag mode which stabilizes with increasing pressure in the CaCl2 phase. This behavior, together with the softening of the shear modulus (C11-C12)/2 related to the orthorhombic distortion, allows a precise determination of a value for Pc. An additional determination is provided by the splitting of the basal plane lattice parameters. Both the AI and the experimentally observed softening of the B1g mode are incomplete, indicating a small discontinuity at the transition. However, all results show continuous changes in volume and lattice parameters, indicating a second-order transition. All these results indicate that there should be sufficient confidence for the future employment of the shell model.

Stabilizing detached Bridgman melt crystal growth: Proportional-integral feedback control

NASA Astrophysics Data System (ADS)

Yeckel, Andrew; Daoutidis, Prodromos; Derby, Jeffrey J.

2012-10-01

The dynamics, operability limits, and tuning of a proportional-integral feedback controller to stabilize detached vertical Bridgman crystal growth are analyzed using a capillary model of shape stability. The manipulated variable is the pressure difference between upper and lower vapor spaces, and the controlled variable is the gap width at the triple-phase line. Open and closed loop dynamics of step changes in these state variables are analyzed under both shape stable and shape unstable growth conditions. Effects of step changes in static contact angle and growth angle are also studied. Proportional and proportional-integral control can stabilize unstable growth, but only within tight operability limits imposed by the narrow range of allowed meniscus shapes. These limits are used to establish safe operating ranges of controller gain. Strong nonlinearity of the capillary model restricts the range of perturbations that can be stabilized, and under some circumstances, stabilizes a spurious operating state far from the set point. Stabilizing detachment at low growth angle proves difficult and becomes impossible at zero growth angle.

First principles investigation of Fe and Al bearing phase H

NASA Astrophysics Data System (ADS)

Tsuchiya, J.; Tsuchiya, T.

2015-12-01

The global circulation of water in the earth is important to investigate the evolution history and dynamics of the earth, since the physical properties (e.g. atomic diffusivity, melting temperature, electrical conductivity and seismic velocities) of the constituent minerals are considerably changed by the presence of water. 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) which are also known as alphabet phases (phase A, superhydrous phase B, and phase D etc.) in the descending cold plate. It has been thought that the relay of these hydrous phases was terminated at ~1200 km depth by the dehydration of phase D which was the highest pressure phase of DHMSs. Recently, we have theoretically predicted the high pressure phase of phase D and experimentally confirmed the existence of this new DHMS in lower mantle pressure conditions above ~45 GPa. This phase has MgSiO4H2chemical 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 relevant hydrous phases in the subducting slabs. Interestingly, the crystal structure of these hydrous phases are almost same and have CaCl2type structure. This suggests that these hydrous phases may potentially 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 (e.g. Kawai et al. 2009). 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 further extends our exploration of these hydrous phases, such as the spin transition of Fe in phase H and the possibility of further phase transition 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.

Anticipatory Postural Control of Stability during Gait Initiation Over Obstacles of Different Height and Distance Made Under Reaction-Time and Self-Initiated Instructions.

PubMed

Yiou, Eric; Artico, Romain; Teyssedre, Claudine A; Labaune, Ombeline; Fourcade, Paul

2016-01-01

Despite the abundant literature on obstacle crossing in humans, the question of how the central nervous system (CNS) controls postural stability during gait initiation with the goal to clear an obstacle remains unclear. Stabilizing features of gait initiation include anticipatory postural adjustments (APAs) and lateral swing foot placement. To answer the above question, 14 participants initiated gait as fast as possible in three conditions of obstacle height, three conditions of obstacle distance and one obstacle-free (control) condition. Each of these conditions was performed with two levels of temporal pressure: reaction-time (high-pressure) and self-initiated (low-pressure) movements. A mechanical model of the body falling laterally under the influence of gravity and submitted to an elastic restoring force is proposed to assess the effect of initial (foot-off) center-of-mass position and velocity (or "initial center-of-mass set") on the stability at foot-contact. Results showed that the anticipatory peak of mediolateral (ML) center-of-pressure shift, the initial ML center-of-mass velocity and the duration of the swing phase, of gait initiation increased with obstacle height, but not with obstacle distance. These results suggest that ML APAs are scaled with swing duration in order to maintain an equivalent stability across experimental conditions. This statement is strengthened by the results obtained with the mechanical model, which showed how stability would be degraded if there was no adaptation of the initial center-of-mass set to swing duration. The anteroposterior (AP) component of APAs varied also according to obstacle height and distance, but in an opposite way to the ML component. Indeed, results showed that the anticipatory peak of backward center-of-pressure shift and the initial forward center-of-mass set decreased with obstacle height, probably in order to limit the risk to trip over the obstacle, while the forward center-of-mass velocity at foot-off increased with obstacle distance, allowing a further step to be taken. These effects of obstacle height and distance were globally similar under low and high-temporal pressure. Collectively, these findings imply that the CNS is able to predict the potential instability elicited by the obstacle clearance and that it scales the spatiotemporal parameters of APAs accordingly.

Anticipatory Postural Control of Stability during Gait Initiation Over Obstacles of Different Height and Distance Made Under Reaction-Time and Self-Initiated Instructions

PubMed Central

Yiou, Eric; Artico, Romain; Teyssedre, Claudine A.; Labaune, Ombeline; Fourcade, Paul

2016-01-01

Despite the abundant literature on obstacle crossing in humans, the question of how the central nervous system (CNS) controls postural stability during gait initiation with the goal to clear an obstacle remains unclear. Stabilizing features of gait initiation include anticipatory postural adjustments (APAs) and lateral swing foot placement. To answer the above question, 14 participants initiated gait as fast as possible in three conditions of obstacle height, three conditions of obstacle distance and one obstacle-free (control) condition. Each of these conditions was performed with two levels of temporal pressure: reaction-time (high-pressure) and self-initiated (low-pressure) movements. A mechanical model of the body falling laterally under the influence of gravity and submitted to an elastic restoring force is proposed to assess the effect of initial (foot-off) center-of-mass position and velocity (or “initial center-of-mass set”) on the stability at foot-contact. Results showed that the anticipatory peak of mediolateral (ML) center-of-pressure shift, the initial ML center-of-mass velocity and the duration of the swing phase, of gait initiation increased with obstacle height, but not with obstacle distance. These results suggest that ML APAs are scaled with swing duration in order to maintain an equivalent stability across experimental conditions. This statement is strengthened by the results obtained with the mechanical model, which showed how stability would be degraded if there was no adaptation of the initial center-of-mass set to swing duration. The anteroposterior (AP) component of APAs varied also according to obstacle height and distance, but in an opposite way to the ML component. Indeed, results showed that the anticipatory peak of backward center-of-pressure shift and the initial forward center-of-mass set decreased with obstacle height, probably in order to limit the risk to trip over the obstacle, while the forward center-of-mass velocity at foot-off increased with obstacle distance, allowing a further step to be taken. These effects of obstacle height and distance were globally similar under low and high-temporal pressure. Collectively, these findings imply that the CNS is able to predict the potential instability elicited by the obstacle clearance and that it scales the spatiotemporal parameters of APAs accordingly. PMID:27656138

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

Du Frane, W. L.; Cervantes, O.; Ellsworth, G. F.

When we Consolidate cubic boron nitride (cBN) it typically requires either a matrix of metal bearing materials that are undesirable for certain applications, or very high pressures within the cBN phase stability field that are prohibitive to manufacturing size and cost. We present new methodology for consolidating high stiffness cBN composites within a hexagonal boron nitride (hBN) matrix (15–25 vol%) with the aid of a binder phase (0–6 vol%) at moderate pressures (0.5–1.0 GPa) and temperatures (900–1300 °C). The composites are demonstrated to be highly tailorable with a range of compositions and resulting physical/mechanical properties. Ultrasonic measurements indicate that inmore » some cases these composites have elastic mechanical properties that exceed those of the highest strength steel alloys. Moreover, two methods were identified to prevent phase transformation of the metastable cBN phase into hBN during consolidation: 1. removal of hydrocarbons, and 2. increased cBN particle size. Lithium tetraborate worked better as a binder than boron oxide, aiding consolidation without enhancing cBN to hBN phase transformation kinetics. These powder mixtures consolidated within error of their full theoretical mass densities at 1 GPa, and had only slightly lower densities at 0.5 GPa. This shows potential for consolidation of these composites into larger parts, in a variety of shapes, at even lower pressures using more conventional manufacturing methods, such as hot-pressing.« less

High-pressure compressibility and vibrational properties of (Ca,Mn)CO 3

DOE PAGES

Liu, Jin; Caracas, Razvan; Fan, Dawei; ...

2016-12-01

Knowledge of potential carbon carriers such as carbonates is critical for our understanding of the deep-carbon cycle and related geological processes within the planet. Here we investigated the high-pressure behavior of (Ca,Mn)CO 3 up to 75 GPa by synchrotron single-crystal X-ray diffraction, laser Raman spectroscopy, and theoretical calculations. MnCO 3-rich carbonate underwent a structural phase transition from the CaCO 3-I structure into the CaCO 3-VI structure at 45–48 GPa, while CaCO 3-rich carbonate transformed into CaCO 3-III and CaCO 3-VI at approximately 2 and 15 GPa, respectively. The equation of state and vibrational properties of MnCO 3-rich and CaCO 3-richmore » carbonates changed dramatically across the phase transition. The CaCO 3-VI-structured CaCO 3-rich and MnCO 3-rich carbonates were stable at room temperature up to at least 53 and 75 GPa, respectively. In conclusion, the addition of smaller cations (e.g., Mn 2+, Mg 2+, and Fe 2+) can enlarge the stability field of the CaCO 3-I phase as well as increase the pressure of the structural transition into the CaCO 3-VI phase.« less

Theoretical investigation of the structural stabilities, optoelectronic properties and thermodynamic characteristics of GaPxSb1-x ternary alloys

NASA Astrophysics Data System (ADS)

Oumelaz, F.; Nemiri, O.; Boumaza, A.; Ghemid, S.; Meradji, H.; Bin Omran, S.; El Haj Hassan, F.; Rai, D. P.; Khenata, R.

2018-06-01

In this theoretical study, we have investigated the structural, phase transition, electronic, thermodynamic and optical properties of GaPxSb1-x ternary alloys. Our calculations are performed with the WIEN2k code based on density functional theory using the full-potential linearized augmented plane wave method. For the electron exchange-correlation potential, a generalized gradient approximation within Wu-Cohen scheme is considered. The recently developed Tran-Blaha modified Becke-Johnson potential has also been used to improve the underestimated band gap. The structural properties, including the lattice constants, the bulk moduli and their pressure derivatives are in very good agreement with the available experimental data and theoretical results. Several structural phase transitions were studied here to establish the stable structure and to predict the phase transition under hydrostatic pressure. The computed transition pressure (Pt) of the material of our interest from the zinc blende (B3) to the rock salt (B1) phase has been determined and found to agree well with the experimental and theoretical data. The calculated band structure shows that GaSb binary compound and the ternary alloys are direct band gap semiconductors. Optical parameters such as the dielectric constants and the refractive indices are calculated and analyzed. The thermodynamic results are also interpreted and analyzed.

Phase equilibria in the KFeS2-Fe-S system at 300-600 °C and bartonite stability

NASA Astrophysics Data System (ADS)

Osadchii, Valentin O.; Voronin, Mikhail V.; Baranov, Alexander V.

2018-05-01

The article deals with phase relations in the KFeS2-Fe-S system studied by the dry synthesis method in the range of 300-600 °C and at a pressure of 1 bar. At the temperature below 513 ± 3 °C, pyrite coexists with rasvumite and there are pyrite-rasvumite-KFeS2 and pyrite-rasvumite-pyrrhotite equilibria established. Above 513 ± 3 °C pyrite and rasvumite react to form KFeS2 and pyrrhotite, limiting the pyrite-rasvumite association to temperatures below this in nature. The experiments also outline the compositional stability range of the copper-free analog of murunskite (K x Fe2- y S2) and suggest that mineral called bartonite is not stable in the Cl-free system, at least at atmospheric pressure and the temperature in the experiments. Chlorbartonite could be easily produced after adding KCl in the experiment. Possible parageneses in the quaternary K-Fe-S-Cl system were described based on the data obtained in this research and found in the previous studies. The factors affecting the formation of potassium-iron sulfides in nature were discussed.

Equation of state of an ideal gas with nonergodic behavior in two connected vessels.

PubMed

Naplekov, D M; Semynozhenko, V P; Yanovsky, V V

2014-01-01

We consider a two-dimensional collisionless ideal gas in the two vessels connected through a small hole. One of them is a well-behaved chaotic billiard, another one is known to be nonergodic. A significant part of the second vessel's phase space is occupied by an island of stability. In the works of Zaslavsky and coauthors, distribution of Poincaré recurrence times in similar systems was considered. We study the gas pressure in the vessels; it is uniform in the first vessel and not uniform in second one. An equation of the gas state in the first vessel is obtained. Despite the very different phase-space structure, behavior of the second vessel is found to be very close to the behavior of a good ergodic billiard but of different volume. The equation of state differs from the ordinary equation of ideal gas state by an amendment to the vessel's volume. Correlation of this amendment with a share of the phase space under remaining intact islands of stability is shown.

Development of lycopene-loaded lipid-core nanocapsules: physicochemical characterization and stability study

NASA Astrophysics Data System (ADS)

dos Santos, Priscilla Pereira; Paese, Karina; Guterres, Silvia Stanisçuaski; Pohlmann, Adriana Raffin; Costa, Tania Hass; Jablonski, André; Flôres, Simone Hickmann; Rios, Alessandro de Oliveira

2015-02-01

The objective of this study was to develop lycopene-loaded lipid-core nanocapsules (Lyc-LNCs) by the interfacial deposition of preformed poly(ɛ-caprolactone) (PCL). Lyc extract (93.9 %) was obtained from tomatoes, and the organic phase was prepared with polymer (PCL), caprylic/capric triglycerides, sorbitan monostearate, and Lyc in a mixture of acetone and ethanol under magnetic stirring at 40 °C. The organic phase was injected into an aqueous phase containing polysorbate 80, and the suspension was concentrated under reduced pressure. The formulation with a Lyc concentration of 85 µg/mL was characterized in terms of size distribution, zeta potential, encapsulation efficiency, pH, viscosity, and color. The Lyc-LNC formulation presented stable values for the z-average (193 ± 4.7 nm) and zeta potential (-11.5 ± 0.40 mV). Despite the lower pH, Lyc content, and color change of the suspension, the nanocapsules showed satisfactory stability, presenting around 50 % Lyc content after 14 days of storage at room temperature (25 °C).

SmNiO3/NdNiO3 thin film multilayers

NASA Astrophysics Data System (ADS)

Girardot, C.; Pignard, S.; Weiss, F.; Kreisel, J.

2011-06-01

Rare earth nickelates RENiO3 (RE =rare earth), which attract interest due to their sharp metal-insulator phase transition, are instable in bulk form due to the necessity of an important oxygen pressure to stabilize Ni in its 3+ state of oxidation. Here, we report the stabilization of RE nickelates in [(SmNiO3)t/(NdNiO3)t]n thin film multilayers, t being the thickness of layers alternated n times. Both bilayers and multilayers have been deposited by metal-organic chemical vapor deposition. The multilayer structure and the presence of the metastable phases SmNiO3 and NdNiO3 are evidenced from by x-ray and Raman scattering. Electric measurements of a bilayer structure further support the structural quality of the embedded RE nickelate layers.

Topological superfluids confined in a nanoscale slab geometry

NASA Astrophysics Data System (ADS)

Saunders, John

2013-03-01

Nanofluidic samples of superfluid 3He provide a route to explore odd-parity topological superfluids and their surface, edge and defect-bound excitations under well controlled conditions. We have cooled superfluid 3He confined in a precisely defined nano-fabricated cavity to well below 1 mK for the first time. We fingerprint the order parameter by nuclear magnetic resonance, exploiting a SQUID NMR spectrometer of exquisite sensitivity. We demonstrate that dimensional confinement, at length scales comparable to the superfluid Cooper-pair diameter, has a profound influence on the superfluid order of 3He. The chiral A-phase is stabilized at low pressures, in a cavity of height 650 nm. At higher pressures we observe 3He-B with a surface induced planar distortion. 3He-B is a time-reversal invariant topological superfluid, supporting gapless Majorana surface states. In the presence of the small symmetry breaking NMR static magnetic field we observe two possible B-phase states of the order parameter manifold, which can coexist as domains. Non-linear NMR on these states enables a measurement of the surface induced planar distortion, which determines the spectral weight of the surface excitations. The expected structure of the domain walls is such that, at the cavity surface, the line separating the two domains is predicted to host fermion zero modes, protected by symmetry and topology. Increasing confinement should stabilize new p-wave superfluid states of matter, such as the quasi-2D gapped A phase, which breaks time reversal symmetry, has a protected chiral edge mode, and may host half-quantum vortices with a Majorana zero-mode at the core. We discuss experimental progress toward this phase, through measurements on a 100 nm cavity. On the other hand, a cavity height of 1000 nm may stabilize a novel ``striped'' superfluid with spatially modulated order parameter. Supported by EPSRC (UK) GR/J022004/1 and European Microkelvin Consortium, FP7 grant 228464

Freezing Transition Studies Through Constrained Cell Model Simulation

NASA Astrophysics Data System (ADS)

Nayhouse, Michael; Kwon, Joseph Sang-Il; Heng, Vincent R.; Amlani, Ankur M.; Orkoulas, G.

2014-10-01

In the present work, a simulation method based on cell models is used to deduce the fluid-solid transition of a system of particles that interact via a pair potential, , which is of the form with . The simulations are implemented under constant-pressure conditions on a generalized version of the constrained cell model. The constrained cell model is constructed by dividing the volume into Wigner-Seitz cells and confining each particle in a single cell. This model is a special case of a more general cell model which is formed by introducing an additional field variable that controls the number of particles per cell and, thus, the relative stability of the solid against the fluid phase. High field values force configurations with one particle per cell and thus favor the solid phase. Fluid-solid coexistence on the isotherm that corresponds to a reduced temperature of 2 is determined from constant-pressure simulations of the generalized cell model using tempering and histogram reweighting techniques. The entire fluid-solid phase boundary is determined through a thermodynamic integration technique based on histogram reweighting, using the previous coexistence point as a reference point. The vapor-liquid phase diagram is obtained from constant-pressure simulations of the unconstrained system using tempering and histogram reweighting. The phase diagram of the system is found to contain a stable critical point and a triple point. The phase diagram of the corresponding constrained cell model is also found to contain both a stable critical point and a triple point.

Metastable tantalum oxide formation during the devitrification of amorphous tantalum thin films

DOE PAGES

Donaldson, Olivia K.; Hattar, Khalid; Trelewicz, Jason R.

2016-07-04

Microstructural evolution during the devitrification of amorphous tantalum thin films synthesized via pulsed laser deposition was investigated using in situ transmission electron microscopy (TEM) combined with ex situ isothermal annealing, bright-field imaging, and electron-diffraction analysis. The phases formed during crystallization and their stability were characterized as a function of the chamber pressure during deposition, devitrification temperature, and annealing time. A range of metastable nanocrystalline tantalum oxides were identified following devitrification including multiple orthorhombic oxide phases, which often were present with, or evolved to, the tetragonal TaO 2 phase. While the appearance of these phases indicated the films were evolving tomore » the stable form of tantalum oxide—monoclinic tantalum pentoxide—it was likely not achieved for the conditions considered due to an insufficient amount of oxygen present in the films following deposition. Nevertheless, the collective in situ and ex situ TEM analysis applied to thin film samples enabled the isolation of a number of metastable tantalum oxides. As a result, new insights were gained into the transformation sequence and stability of these nanocrystalline phases, which presents opportunities for the development of advanced tantalum oxide-based dielectric materials for novel memristor designs.« less

Research study of pressure instrumentation

NASA Technical Reports Server (NTRS)

Hoogenboom, L.; Hull-Allen, G.

1984-01-01

To obtain a more vibration resistant pressure sensor for use on the Space Shuttle Main Engine, a proximity probe based, diaphragm type pressure sensor breadboard was developed. A fiber optic proximity probe was selected as the sensor. In combination with existing electronics, a thermal stability evaluation of the entire probe system was made. Based upon the results, a breadboard design of the pressure sensor and electronics was made and fabricated. A brief series of functional experiments was made with the breadboard to calibrate, thermally compensate, and linearize its response. In these experiments, the performance obtained in the temperature range of -320 F (liquid N2) to +200 F was comparable to that of the strain gage based sensor presently in use on the engine. In tests at NASA-Marshall Space Flight Center (MSFC), after some time at or near liquid nitrogen temperatures, the sensor output varied over the entire output range. These large spurious signals were attributed to condensation of air in the sensing gap. In the next phase of development of this sensor, an evaluation of fabrication techniques toward greater thermal and mechanical stability of the fiber probe assembly must be made. In addition to this, a positive optics to metal seal must be developed to withstand the pressure that would result from a diaphragm failure.

Kinetic effects on the morphology and stability of the pressure-induced extended-solid of carbon monoxide

NASA Astrophysics Data System (ADS)

Dang, Nhan C.; Ciezak-Jenkins, Jennifer A.

2018-04-01

In this work, the dependence of the morphology and stability of the extended solid of carbon monoxide (CO) is correlated to the rate of transformation from the molecular CO to extended solid of CO using optical imaging, photoluminescence, Raman spectroscopy, and X-ray diffraction. The analyses show the rate and pressure of the transformation to be strongly controlled by catalytic effects, both chemical and optical. In a larger volume per reaction area, the transformation was found to require either a longer time at an elevated pressure or a higher pressure compared to a sample synthesized in a smaller volume per reaction area, leading to the conclusion that the transformation rate is slower for a sample in a larger volume per reaction area. A faster rate of transformation was also noted when the reaction area of a CO sample was catalyzed with H2SO4. Through variation of the volume per reaction area, pressure or the addition of catalysts, it was possible to control the rate of the phase transition and therefore the morphology. In general, the extended solid of CO synthesized with a faster rate showed a more ordered structure and increased metastability relative to the material formed with a slower compression rate.

Modeling normal shock velocity curvature relations for heterogeneous explosives

NASA Astrophysics Data System (ADS)

Yoo, Choong-Shik; Tomasino, Dane; Smith, Jesse; Kim, Minseob

2017-01-01

Many simple molecules such as N2 and CO2 have the potential to form extended "polymeric" solids under extreme conditions, which can store a large sum of chemical energy in its three-dimensional network structures made of strong covalent bonds. Diatomic nitrogen is particularly of interest because of the uniquely large energy difference between the single (160 kJ/mol) and triple (950 kJ/mol) bonds. As such, the transformation of singly bonded polymeric nitrogen back to triply bonded diatomic nitrogen molecules can release large energy ( 33 kJ/cm3 - three times that of HMX) without any negative environmental impact. Therefore, the goal of the present study has been to investigate the transformation of nitrogen and nitrogen-rich compounds to new singly bonded nitrogen-rich solids at high pressures and temperatures, using heated diamond anvil cells, Raman spectroscopy, and third-generation synchrotron x-ray diffraction. Recently, we have found a new form of singly bonded layered polymeric nitrogen (LP-N), synthesized in the stability pressure-temperature field higher than that of cg-N. This new phase is characterized by a 2D layered structure similar to the predicted Pba2 and two colossal Raman bands, arising from two groups of highly polarized nitrogen atoms. This result also provides a new constraint for the nitrogen phase diagram, highlighting an unusual symmetry lowering 3D cg- to 2D LP-N transition and thereby the enhanced electrostatic contribution to the stabilization of this densely packed LP-N. In this paper, we will review this finding of LP-N, update the phase diagram of nitrogen, and offer a chemistry view of pressure-induced transformations in dense molecular solids.

Nonlinear stability of oscillatory core-annular flow: A generalized Kuramoto-Sivashinsky equation with time periodic coefficients

NASA Technical Reports Server (NTRS)

Coward, Adrian V.; Papageorgiou, Demetrios T.; Smyrlis, Yiorgos S.

1994-01-01

In this paper the nonlinear stability of two-phase core-annular flow in a pipe is examined when the acting pressure gradient is modulated by time harmonic oscillations and viscosity stratification and interfacial tension is present. An exact solution of the Navier-Stokes equations is used as the background state to develop an asymptotic theory valid for thin annular layers, which leads to a novel nonlinear evolution describing the spatio-temporal evolution of the interface. The evolution equation is an extension of the equation found for constant pressure gradients and generalizes the Kuramoto-Sivashinsky equation with dispersive effects found by Papageorgiou, Maldarelli & Rumschitzki, Phys. Fluids A 2(3), 1990, pp. 340-352, to a similar system with time periodic coefficients. The distinct regimes of slow and moderate flow are considered and the corresponding evolution is derived. Certain solutions are described analytically in the neighborhood of the first bifurcation point by use of multiple scales asymptotics. Extensive numerical experiments, using dynamical systems ideas, are carried out in order to evaluate the effect of the oscillatory pressure gradient on the solutions in the presence of a constant pressure gradient.

Pressure-induced kinetics of the α to ω transition in zirconium

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

Jacobsen, M. K.; Velisavljevic, N., E-mail: nenad@lanl.gov; Sinogeikin, S. V.

Diamond anvil cells (DAC) coupled with x-ray diffraction (XRD) measurements are one of the primary techniques for investigating structural stability of materials at high pressure-temperature (P-T) conditions. DAC-XRD has been predominantly used to resolve structural information at set P-T conditions and, consequently, provides P-T phase diagram information on a broad range of materials. With advances in large scale synchrotron x-ray facilities and corresponding x-ray diagnostic capabilities, it is now becoming possible to perform sub-second time resolved measurements on micron sized DAC samples. As a result, there is an opportunity to gain valuable information about the kinetics of structural phase transformationsmore » and extend our understanding of material behavior at high P-T conditions. Using DAC-XRD time resolved measurements, we have investigated the kinetics of the α to ω transformation in zirconium. We observe a clear time and pressure dependence in the martensitic α-ω transition as a function of pressure-jump, i.e., drive pressure. The resulting data are fit using available kinetics models, which can provide further insight into transformation mechanism that influence transformation kinetics. Our results help shed light on the discrepancies observed in previous measurements of the α-ω transition pressure in zirconium.« less

Pressure-induced kinetics of the α to ω transition in zirconium

DOE PAGES

Jacobsen, M. K.; Velisavljevic, N.; Sinogeikin, S. V.

2015-07-13

Diamond anvil cells (DAC) coupled with x-ray diffraction (XRD) measurements are one of the primary techniques for investigating structural stability of materials at high pressure-temperature (P-T) conditions. DAC-XRD has been predominantly used to resolve structural information at set P-T conditions and, consequently, provides P-T phase diagram information on a broad range of materials. With advances in large scale synchrotron x-ray facilities and corresponding x-ray diagnostic capabilities, it is now becoming possible to perform sub-second time resolved measurements on micron sized DAC samples. As a result, there is an opportunity to gain valuable information about the kinetics of structural phase transformationsmore » and extend our understanding of material behavior at high P-T conditions. Using DAC-XRD time resolved measurements, we have investigated the kinetics of the α to ω transformation in zirconium. We observe a clear time and pressure dependence in the martensitic α-ω transition as a function of pressure-jump, i.e., drive pressure. The resulting data are fit using available kinetics models, which can provide further insight into transformation mechanism that influence transformation kinetics. Our results help shed light on the discrepancies observed in previous measurements of the α-ω transition pressure in zirconium.« less

Two-dimensional lattice-fluid model with waterlike anomalies.

PubMed

Buzano, C; De Stefanis, E; Pelizzola, A; Pretti, M

2004-06-01

We investigate a lattice-fluid model defined on a two-dimensional triangular lattice, with the aim of reproducing qualitatively some anomalous properties of water. Model molecules are of the "Mercedes Benz" type, i.e., they possess a D3 (equilateral triangle) symmetry, with three bonding arms. Bond formation depends both on orientation and local density. We work out phase diagrams, response functions, and stability limits for the liquid phase, making use of a generalized first order approximation on a triangle cluster, whose accuracy is verified, in some cases, by Monte Carlo simulations. The phase diagram displays one ordered (solid) phase which is less dense than the liquid one. At fixed pressure the liquid phase response functions show the typical anomalous behavior observed in liquid water, while, in the supercooled region, a reentrant spinodal is observed.

Free Energy Minimization by Simulated Annealing with Applications to Lithospheric Slabs and Mantle Plumes

NASA Astrophysics Data System (ADS)

Bina, C. R.

An optimization algorithm based upon the method of simulated annealing is of utility in calculating equilibrium phase assemblages as functions of pressure, temperature, and chemical composi tion. Operating by analogy to the statistical mechanics of the chemical system, it is applicable both to problems of strict chemical equilibrium and to problems involving metastability. The method reproduces known phase diagrams and illustrates the expected thermal deflection of phase transitions in thermal models of subducting lithospheric slabs and buoyant mantle plumes. It reveals temperature-induced changes in phase transition sharpness and the stability of Fe-rich γ phase within an α+γ field in cold slab thermal models, and it suggests that transitions such as the possible breakdown of silicate perovskite to mixed oxides can amplify velocity anomalies.

Lithium silicide nanocrystals: synthesis, chemical stability, thermal stability, and carbon encapsulation.

PubMed

Cloud, Jacqueline E; Wang, Yonglong; Li, Xuemin; Yoder, Tara S; Yang, Yuan; Yang, Yongan

2014-10-20

Lithium silicide (LixSi) is the lithiated form of silicon, one of the most promising anode materials for the next generation of lithium-ion batteries (LIBs). In contrast to silicon, LixSi has not been well studied. Herein we report a facile high-energy ball-milling-based synthesis of four phase-pure LixSi (x = 4.4, 3.75, 3.25, and 2.33), using hexane as the lubricant. Surprisingly, the obtained Li3.75Si phase shows significant downward shifts in all X-ray diffraction peak positions, compared with the standard. Our interpretation is that the high-energy ball-mill-synthesized Li3.75Si presents smaller internal pressures and larger lattice constants. The chemical-stability study reveals that only surface reactions occur after Li4.4Si and Li3.75Si are immersed in several battery-assembly-related chemicals. The thermal-stability study shows that Li4.4Si is stable up to 350 °C and Li3.75Si is stable up to 200 °C. This remarkable thermal stability of Li3.75Si is in stark contrast to the long-observed metastability for electrochemically synthesized Li3.75Si. The carbon encapsulation of Li4.4Si has also been studied for its potential applications in LIBs.

The stability and Raman spectra of ikaite, CaCO3·6H2O, at high pressure and temperature

USGS Publications Warehouse

Shahar, Anat; Bassett, William A.; Mao, Ho-kwang; Chou, I-Ming; Mao, Wendy

2005-01-01

Raman analyses of single crystals of ikaite, CaCO3·6H2O, synthesized in a diamond-anvil cell at ambient temperature yield spectra from 0.14 to 4.08 GPa; the most intense peaks are at 228 and 1081 cm−1 corresponding to Eg(external) and A1g (internal) modes of vibrations in CO2− 3 ions, respectively. These are in good agreement with Raman spectra previously published for ikaite in powder form at ambient temperature and pressure. Visual observations of a sample consisting initially of a mixture of calcite + water in a hydrothermal diamond-anvil cell yielded a P-T phase diagram up to 2 GPa and 120 °C; the boundary for the reaction ikaite ↔ aragonite + water has a positive slope and is curved convexly toward the aragonite + water field similar to typical melt curves. This curvature can be explained in terms of the Clapeyron equation for a boundary between a solid phase and a more compressible liquid phase or largely liquid phase assemblage.

Phase Stability and Transformations in Vanadium Oxide Nanocrystals

NASA Astrophysics Data System (ADS)

Bergerud, Amy Jo

Vanadium oxides are both fascinating and complex, due in part to the many compounds and phases that can be stabilized as well as the phase transformations which occur between them. The metal to insulator transitions (MITs) that take place in vanadium oxides are particularly interesting for both fundamental and applied study as they can be induced by a variety of stimuli ( i.e., temperature, pressure, doping) and utilized in many applications (i.e., smart windows, sensors, phase change memory). Nanocrystals also tend to demonstrate interesting phase behavior, due in part to the enhanced influence of surface energy on material thermodynamics. Vanadium oxide nanocrystals are thus expected to demonstrate very interesting properties in regard to phase stability and phase transformations, although synthesizing vanadium oxides in nanocrystal form remains a challenge. Vanadium sesquioxide (V2O3) is an example of a material that undergoes a MIT. For decades, the low temperature monoclinic phase and high temperature corundum phase were the only known crystal structures of V2O3. However, in 2011, a new metastable polymorph of V2O3 was reported with a cubic, bixbyite crystal structure. In Chapter 2, a colloidal route to bixbyite V2O 3 nanocrystals is presented. In addition to being one of the first reported observations of the bixbyite phase in V2O3, it is also one of the first successful colloidal syntheses of any of the vanadium oxides. The nanocrystals possess a flower-like morphology, the size and shape of which are dependent on synthesis time and temperature, respectively. An aminolysis reaction mechanism is determined from Fourier transform infrared spectroscopy data and the bixbyite crystal structure is confirmed by Rietveld refinement of X-ray diffraction (XRD) data. Phase stability is assessed in both air and inert environments, confirming the metastable nature of the material. Upon heating in an inert atmosphere above 700°C, the nanocrystals irreversibly transform to the bulk stable corundum phase of V2O3 with concurrent particle coarsening. This, in combination with the enhanced stability of the nanocrystals over bulk, suggests that the bixbyite phase may be stabilized due to surface energy effects, a well-known phenomenon in nanocrystal research. In Chapter 3, the reversible incorporation of oxygen in bixbyite V 2O3 is reported, which can be controlled by varying temperature and oxygen partial pressure. Based on XRD and thermogravimetric analysis, it is found that oxygen occupies interstitial sites in the bixbyite lattice. Two oxygen atoms per unit cell can be incorporated rapidly and with minimal changes to the structure while the addition of three or more oxygen atoms destabilizes the structure, resulting in a phase change that can be reversed upon oxygen removal. Density functional theory (DFT) supports the reversible occupation of interstitial sites in bixbyite by oxygen and the 1.1 eV barrier to oxygen diffusion predicted by DFT matches the activation energy of the oxidation process derived from observations by in situ XRD. The observed rapid oxidation kinetics are thus facilitated by short diffusion paths through the bixbyite nanocrystals. Due to the exceptionally low temperatures of oxidation and reduction, this material, made from earth-abundant atoms, is proposed for use in oxygen storage applications, where oxygen is reversibly stored and released. Further oxidation of bixbyite V2O3 under controlled oxygen partial pressure can lead to the formation of nanocrystalline vanadium dioxide (VO2), a material that is studied for its MIT that occurs at 68 C in the bulk. This transformation is accompanied by a change in crystal structure, from monoclinic to rutile phase, and a change in optical properties, from infrared transparent to infrared blocking. Because of this, VO2 is promising for thermochromic smart window applications, where optical properties vary with temperature. Recently, alternative stimuli have been utilized to trigger MITs in VO2, including electrochemical gating. Rather than inducing the expected monoclinic to rutile phase transition as originally proposed, electrochemical gating of the insulating phase was recently shown to induce oxygen vacancy formation in VO2, thereby inducing metallization, while the characteristic V-V dimerization of the monoclinic phase was retained. In Chapter 4, the preparation and electrochemical reduction of VO2 nanocrystal films is presented. The nanocrystalline morphology allows for the study of transformations under conditions that enhance the gating effect by creating a large VO2-electrolyte interfacial area and by reducing the path length for diffusion. The resulting transitions are observed optically, from insulator to metal to insulator and back, with in situ visible-near infrared spectroelectrochemistry and correlated with structural changes monitored by Raman and X-ray absorption spectroscopies. The never-before-seen transition to an insulating phase under progressive electrochemical reduction is attributed to an oxygen defect induced phase transition to a new phase. This is likely enabled by the nanocrystalline nature of the sample, which may enhance the kinetics of oxygen diffusion, support a higher degree of lattice expansion-induced strain, or simply alter the thermodynamics of the system.

Flow of High Internal Phase Ratio Emulsions through Pipes

NASA Astrophysics Data System (ADS)

Kostak, K.; Özsaygı, R.; Gündüz, I.; Yorgancıoǧlu, E.; Tekden, E.; Güzel, O.; Sadıklar, D.; Peker, S.; Helvacı, Ş. Ş.

2015-04-01

The flow behavior of W/O type of HIPRE stabilized by hydrogen bonds with a sugar (sorbitol) in the aqueous phase, was studied. Two groups of experiments were done in this work: The effect of wall shear stresses were investigated in flow through pipes of different diameters. For this end, HIPREs prestirred at constant rate for the same duration were used to obtain similar drop size distributions. Existence and extent of elongational viscosity were used as a probe to elucidate the effect of drop size distribution on the flow behavior: HIPREs prestirred for the same duration at different rates were subjected to flow through converging pipes. The experimental flow curves for flow through small cylindrical pipes indicated four different stages: 1) initial increase in the flow rate at low pressure difference, 2) subsequent decrease in the flow rate due to capillary flow, 3) pressure increase after reaching the minimum flow rate and 4) slip flow after a critical pressure difference. HIPREs with sufficient external liquid phase in the plateau borders can elongate during passage through converging pipes. In the absence of liquid stored in the plateau borders, the drops rupture during extension and slip flow takes place without elongation.

Development of Nanoparticle-Stabilized Foams to Improve Performance of Water-less Hydraulic Fracturing

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

Prodanovic, Masa; Johnston, Keith P.

We have successfully created ultra dry carbon-dioxide-in-water and nitrogen-in-water foams (with water content down to 2-5% range), that are remarkably stable at high temperatures (up to 120 deg, C) and pressures (up to 3000psi) and viscous enough (100-200 cP tunable range) to carry proppant. Two generations of these ultra-dry foams have been developed; they are stabilized either with a synergy of surfactants and nanoparticle, or just with viscoelastic surfactants that viscosify the aqueous phase. Not only does this reduce water utilization and disposal, but it minimizes fluid blocking of hydrocarbon production. Further, the most recent development shows successful use ofmore » environmentally friendly surfactants at high temperature and pressure. We pay special attention to the role of nanoparticles in stabilization of the foams, specifically for high salinity brines. The preliminary numerical simulation for which shows they open wider fractures with shorter half-length and require less clean-up due to minimal water use. We also tested the stability and sand carrying properties of these foams at high pressure, room temperature conditions in sapphire cell. We performed on a preliminary numerical investigation of applicability for improved oil recovery applications. The applicability was evaluated by running multiphase flow injection simulations in a case-study oil reservoir. The results of this research thus expand the options available to operators for hydraulic fracturing and can simplify the design and field implementation of foamed fracturing fluids.« less

Conducting linear chains of sulphur inside carbon nanotubes

PubMed Central

Fujimori, Toshihiko; Morelos-Gómez, Aarón; Zhu, Zhen; Muramatsu, Hiroyuki; Futamura, Ryusuke; Urita, Koki; Terrones, Mauricio; Hayashi, Takuya; Endo, Morinobu; Young Hong, Sang; Chul Choi, Young; Tománek, David; Kaneko, Katsumi

2013-01-01

Despite extensive research for more than 200 years, the experimental isolation of monatomic sulphur chains, which are believed to exhibit a conducting character, has eluded scientists. Here we report the synthesis of a previously unobserved composite material of elemental sulphur, consisting of monatomic chains stabilized in the constraining volume of a carbon nanotube. This one-dimensional phase is confirmed by high-resolution transmission electron microscopy and synchrotron X-ray diffraction. Interestingly, these one-dimensional sulphur chains exhibit long domain sizes of up to 160 nm and high thermal stability (~800 K). Synchrotron X-ray diffraction shows a sharp structural transition of the one-dimensional sulphur occurring at ~450–650 K. Our observations, and corresponding electronic structure and quantum transport calculations, indicate the conducting character of the one-dimensional sulphur chains under ambient pressure. This is in stark contrast to bulk sulphur that needs ultrahigh pressures exceeding ~90 GPa to become metallic. PMID:23851903

Unique Pressure Dependence of the Order-Disorder Transition Temperature of a Series of PEP-PDMS Diblock Copolymers

NASA Astrophysics Data System (ADS)

Mortensen, K.; Almdal, K.; Schwahn, D.; Frielinghaus, H.

1997-03-01

Studies of the phase behavior of polymer systems has proven that the sensitivity to fluctuations is much more distinct than originally anticipated based on theoretical arguments. In blends of homo-polymers, studies have revealed that fluctuations give rise to significant re-normalized critical behavior. It has been argued that the free volume causes an entropic contribution to the Flory-Huggins interaction parameter, \\chi, and is thereby responsible for the re-normalized behavior. In block copolymers fluctuations have even more pronounced effects, as it changes the second order critical point at f=0.5 to first order and additional complex phases are stabilized. Measurements of the structure factor S(q) of PEP-PDMS diblock copolymers have revealed unique character in the phase-diagram with re-entrant ordered structure. Moreover, an unexpected singularity in the conformational compressibility, as identified from the peak-position, q, is observed. In contrary to binary polymer blends, pressure does not affect the Ginzburg number.

Hydrothermal stability of SAPO-34 for refrigeration and air conditioning applications

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

Chen, Haijun; Cui, Qun, E-mail: cuiqun@njtech.edu.cn; Wu, Juan

Graphical abstract: The SAPO-34 was synthesized by a hydrothermal method using diethylamine as a template. Water adsorption strength on SAPO-34 is between that on 13X and A type silica gel. During 100–400 Pa, the water uptake on SAPO-34 increases sensitively to pressure, and equilibrium water uptake reaches 0.35 kg/kg, 25% higher than 13X. SAPO-34 shows no significant reduced cyclic water uptake over 60 cycles. Most of the initial SAPO-34 phase is restored, while the regular cubic-like morphology is well maintained, and the specific surface area only decreases by 8.6%. - Highlights: • Water adsorption strength on SAPO-34 is between thatmore » on 13X and A type silica gel. During 100–400 Pa, the water uptake on SAPO-34 increases sensitively to pressure, and equilibrium water uptake reaches 0.35 kg/kg, 25% higher than 13X. • SAPO-34 with diethylamine as the template shows no significant reduced cyclic water uptake over 60 cycles, and most of the initial SAPO-34 phase is well maintained. • SAPO-34 has an excellent adsorption performance and a good hydrothermal stability, thus is promising for application in adsorption refrigeration. - Abstract: Hydrothermal stability is one of the crucial factors in applying SAPO-34 molecular sieve to adsorption refrigration. The SAPO-34 was synthesized by a hydrothermal method using diethylamine as a template. Both a vacuum gravimetric method and an intelligent gravimetric analyzer were applied to analyze the water adsorption performance of SAPO-34. Cyclic hydrothermal performance was determined on the modified simulation adsorption refrigeration test rig. Crystal phase, morphology, and porosity of SAPO-34 were characterized by X-ray diffraction, scanning electron microscopy, and N{sub 2} sorption, respectively. The results show that, water adsorption strength on SAPO-34 is between that on 13X and A type silica gel. During 100–400 Pa, the water uptake on SAPO-34 increases sensitively to pressure, and equilibrium water uptake reaches 0.35 kg/kg, 25% higher than 13X. SAPO-34 shows no significant reduced cyclic water uptake over 60 cycles. Most of the initial SAPO-34 phase is restored, while the regular cubic-like morphology is well maintained, and the specific surface area only decreases by 8.6%.« less

Exotic magnetic structures in high-pressure synthesized perovskites

NASA Astrophysics Data System (ADS)

Manuel, Pascal; Khalyavin, Dmitry; Ding, Lei; Yi, Wei; Kumagai, Yu; Oba, Fumiyasu; Orlandi, Fabio; Belik, Alexei

We present a neutron powder diffraction study of the crystal and magnetic structures of the high-pressure stabilized perovskite phases of TlMnO3, ScCrO3, InCrO3 and TlCrO3. These compounds exhibit original magnetic structures compared to other members of their respective manganite and orthochromite families with TlMnO3 also displaying unusual orbital ordering pattern. For both systems, we rationalise the structures through a combination of group theory and first principle calculations. We also highlight the dominant mechanism controlling the spin direction as being the single ion anisotropy.

Calculations of combustion response profiles and oscillations

NASA Technical Reports Server (NTRS)

Priem, Richard J.; Breisacher, Kevin J.

1993-01-01

The theory and procedures for determining the characteristics of pressure oscillations in rocket engines with prescribed burning rate oscillations are presented. Pressure and velocity oscillations calculated using this procedure are presented for the Space Shuttle Main Engine (SSME) to show the influence of baffles and absorbers on the burning rate oscillations required to achieve neutral stability. Results of calculations to determine local combustion responses using detailed physical models for injection, atomization, and vaporization with gas phase oscillations in baffled and unbaffled SSME combustors are presented. The contributions of the various physical phenomena occurring in a combustor to oscillations in combustion response were determined.

Interfacial nonequilibrium and Bénard-Marangoni instability of a liquid-vapor system

NASA Astrophysics Data System (ADS)

Margerit, J.; Colinet, P.; Lebon, G.; Iorio, C. S.; Legros, J. C.

2003-10-01

We study Bénard-Marangoni instability in a system formed by a horizontal liquid layer and its overlying vapor. The liquid is lying on a hot rigid plate and the vapor is bounded by a cold parallel plate. A pump maintains a reduced pressure in the vapor layer and evacuates the vapor. This investigation is undertaken within the classical quasisteady approximation for both the vapor and the liquid phases. The two layers are separated by a deformable interface. Temporarily frozen temperature and velocity distributions are employed at each instant for the stability analysis, limited to infinitesimal disturbances (linear regime). We use irreversible thermodynamics to model the phase change under interfacial nonequilibrium. Within this description, the interface appears as a barrier for transport of both heat and mass. Hence, in contrast with previous studies, we consider the possibility of a temperature jump across the interface, as recently measured experimentally. The stability analysis shows that the interfacial resistances to heat and mass transfer have a destabilizing influence compared to an interface that is in thermodynamic equilibrium. The role of the fluctuations in the vapor phase on the onset of instability is discussed. The conditions to reduce the system to a one phase model are also established. Finally, the influence of the evaporation parameters and of the presence of an inert gas on the marginal stability curves is discussed.

Cristobalite X-I: A bridge between low and high density silica polymorphs

NASA Astrophysics Data System (ADS)

Shelton, H.; Tiange, B.; Zurek, E.; Smith, J.; Dera, P.

2017-12-01

SiO2 is one of the most common compounds found on Earth. Despite its chemical simplicity, and because of its crystal chemical characteristics, SiO2 exhibits a complex phase diagram. SiO2 has a wide variety of thermodynamically stable crystalline phases, as well as numerous metastable crystalline and amorphous polymorphs. Many of the phase transition sequences that produce metastable phases of SiO2 are strongly path-dependent, where the rate of change controls the transition just as much as the final conditions. The elusive metastable polymorphs of SiO2 may provide a better understanding of the factors controlling its densification. On compression of α-cristobalite (the high temperature tetrahedral phase of SiO2) to pressures above 12 GPa, a new polymorph known as cristobalite X-I forms. Existence of cristobalite X-I has been known for several decades, however, consensus regarding the exact atomic arrangement has not yet been reached. The X-I phase constitutes an important step in the silica densification process, separating low-density tetrahedral framework structures from high-density octahedral polymorphs. It is unique in being the only non-quenchable high-density SiO2 phase, which reverts back to the tetrahedral low-density form on decompression at ambient temperature. Our new single crystal synchrotron X-ray diffraction experiments, with quasihydrostatic neon as the pressure medium, revealed the structure of this enigmatic phase to consist of octahedral silicate chains with 4-60°-2 zigzag chain geometry. This geometry has not been considered before, but is closely related to post-quartz, stishovite and seifertite. Density functional theory calculations support this observation, confirming the dynamic stability of the X-I arrangement and reasonably reproducing the pressure at which the transformation takes place. The enthalpy of cristobalite X-I is higher than stishovite and seifertite, but it is favored as a high-pressure successor of cristobalite due to a unique transformation pathway.

Influence of thickness and camber on the aeroelastic stability of supersonic throughflow fans: An engineering approach

NASA Technical Reports Server (NTRS)

Ramsey, John K.

1989-01-01

An engineering approach was used to include the nonlinear effects of thickness and camber in an analytical aeroelastic analysis of cascades in supersonic acial flow (supersonic leading-edge locus). A hybrid code using Lighthill's nonlinear piston theory and Lanes's linear potential theory was developed to include these nonlinear effects. Lighthill's theory was used to calculate the unsteady pressures on the noninterference surface regions of the airfoils in cascade. Lane's theory was used to calculate the unsteady pressures on the remaining interference surface regions. Two airfoil profiles was investigated (a supersonic throughflow fan design and a NACA 66-206 airfoil with a sharp leading edge). Results show that compared with predictions of Lane's potential theory for flat plates, the inclusion of thickness (with or without camber) may increase or decrease the aeroelastic stability, depending on the airfoil geometry and operating conditions. When thickness effects are included in the aeroelastic analysis, inclusion of camber will influence the predicted stability in proportion to the magnitude of the added camber. The critical interblade phase angle, depending on the airfoil profile and operating conditions, may also be influenced by thickness and camber. Compared with predictions of Lane's linear potential theory, the inclusion of thickness and camber decreased the aerodynamic stifness and increased the aerodynamic damping at Mach 2 and 2.95 for a cascade of supersonic throughflow fan airfoils oscillating 180 degrees out of phase at a reduced frequency of 0.1.

Edge Stability and Performance of the ELM-Free Quiescent H-Mode and the Quiescent Double Barrier Mode on DIII-D

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

West, W P; Burrell, K H; Casper, T A

2004-12-03

The quiescent H (QH) mode, an edge localized mode (ELM)-free, high-confinement mode, combines well with an internal transport barrier to form quiescent double barrier (QDB) stationary state, high performance plasmas. The QH-mode edge pedestal pressure is similar to that seen in ELMing phases of the same discharge, with similar global energy confinement. The pedestal density in early ELMing phases of strongly pumped counter injection discharges drops and a transition to QH-mode occurs, leading to lower calculated edge bootstrap current. Plasmas current ramp experiment and ELITE code modeling of edge stability suggest that QH-modes lie near an edge current stability boundary.more » At high triangularity, QH-mode discharges operate at higher pedestal density and pressure, and have achieved ITER level values of {beta}{sub PED} and {nu}*. The QDB achieves performance of {alpha}{sub N}H{sub 89} {approx} 7 in quasi-stationary conditions for a duration of 10 tE, limited by hardware. Recently we demonstrated stationary state QDB discharges with little change in kinetic and q profiles (q{sub 0} > 1) for 2 s, comparable to ELMing ''hybrid scenarios'', yet without the debilitating effects of ELMs. Plasma profile control tools, including electron cyclotron heating and current drive and neutral beam heating, have been demonstrated to control simultaneously the q profile development, the density peaking, impurity accumulation and plasma beta.« less

Ground state structure of high-energy-density polymeric carbon monoxide

NASA Astrophysics Data System (ADS)

Xia, Kang; Sun, Jian; Pickard, Chris J.; Klug, Dennis D.; Needs, Richard J.

2017-04-01

Crystal structure prediction methods and first-principles calculations have been used to explore low-energy structures of carbon monoxide (CO). Contrary to the standard wisdom, the most stable structure of CO at ambient pressure was found to be a polymeric structure of P n a 21 symmetry rather than a molecular solid. This phase is formed from six-membered (four carbon + two oxygen) rings connected by C=C double bonds with two double-bonded oxygen atoms attached to each ring. Interestingly, the polymeric P n a 21 phase of CO has a much higher energy density than trinitrotoluene (TNT). On compression to about 7 GPa, P n a 21 is found to transform into another chainlike phase of C c symmetry which has similar ring units to P n a 21 . On compression to 12 GPa, it is energetically favorable for CO to polymerize into a purely single bonded C m c a phase, which is stable over a wide pressure range and transforms into the previously known C m c m phase at around 100 GPa. Thermodynamic stability of these structures was verified using calculations with different density functionals, including hybrid and van der Waals corrected functionals.

Dynamic stability analysis for capillary channel flow: One-dimensional and three-dimensional computations and the equivalent steady state technique

NASA Astrophysics Data System (ADS)

Grah, Aleksander; Dreyer, Michael E.

2010-01-01

Spacecraft technology provides a series of applications for capillary channel flow. It can serve as a reliable means for positioning and transport of liquids under low gravity conditions. Basically, capillary channels provide liquid paths with one or more free surfaces. A problem may be flow instabilities leading to a collapse of the liquid surfaces. A result is undesired gas ingestion and a two phase flow which can in consequence cause several technical problems. The presented capillary channel consists of parallel plates with two free liquid surfaces. The flow rate is established by a pump at the channel outlet, creating a lower pressure within the channel. Owing to the pressure difference between the liquid phase and the ambient gas phase the free surfaces bend inwards and remain stable as long as they are able to resist the steady and unsteady pressure effects. For the numerical prediction of the flow stability two very different models are used. The one-dimensional unsteady model is mainly based on the Bernoulli equation, the continuity equation, and the Gauss-Laplace equation. For three-dimensional evaluations an open source computational fluid dynamics (CFD) tool is applied. For verifications the numerical results are compared with quasisteady and unsteady data of a sounding rocket experiment. Contrary to previous experiments this one results in a significantly longer observation sequence. Furthermore, the critical point of the steady flow instability could be approached by a quasisteady technique. As in previous experiments the comparison to the numerical model evaluation shows a very good agreement for the movement of the liquid surfaces and for the predicted flow instability. The theoretical prediction of the flow instability is related to the speed index, based on characteristic velocities of the capillary channel flow. Stable flow regimes are defined by stability criteria for steady and unsteady flow. The one-dimensional computation of the speed index is based on the technique of the equivalent steady system, which is published for the first time in the present paper. This approach assumes that for every unsteady state an equivalent steady state with a special boundary condition can be formulated. The equivalent steady state technique enables a reformulation of the equation system and an efficient and reliable speed index computation. Furthermore, the existence of the numerical singularity at the critical point of the steady flow instability, postulated in previous publication, is demonstrated in detail. The numerical singularity is related to the stability criterion for steady flow and represents the numerical consequence of the liquid surface collapse. The evaluation and generation of the pressure diagram is demonstrated in detail with a series of numerical dynamic flow studies. The stability diagram, based on one-dimensional computation, gives a detailed overview of the stable and instable flow regimes. This prediction is in good agreement with the experimentally observed critical flow conditions and results of three-dimensional CFD computations.

Hydrogen-bond symmetrization breakdown and dehydrogenation mechanism in FeO2H at high pressure

NASA Astrophysics Data System (ADS)

Hu, Q.; Zhu, S.; Mao, H. K.; Mao, W. L.; Sheng, H.

2017-12-01

The cycling of hydrogen plays an important role in the geochemical evolution of our planet. In Earth's interiors, hydrogen cycling is mainly carried out by hydrous minerals. Under high-pressure conditions, asymmetric hydroxyl bonds in hydrous minerals tend to form a symmetric O-H-O configuration that improves their thermal stability. Therefore it is possible to transport water into the deeper part of the Earth's lower mantle. Here, we employ first-principles free-energy landscape sampling methods based on a recently developed stochastic surface walking algorithm to reveal the transition mechanism of a water-bearing mineral, FeO2H, at deep mantle conditions. By resolving the lowest-energy transition pathway from ɛ-FeO2H to the high-pressure Py-phase, we demonstrate that half of the O-H bonds in the mineral rupture during the structural transition, leading toward the breakdown of symmetrized hydrogen bonds and eventual dehydrogenation. Our study sheds new light on the stability of symmetric hydrogen bonds in hydrous minerals during structural transitions and suggests a dehydrogenation mechanism from water in the deep mantle.

Thermal Decomposition of RP-2 with Stabilizing Additives

DTIC Science & Technology

2010-04-01

was analyzed by gas chromatography . The increase in a suite of light decomposition products was used to monitor the extent of decomposition. The...approximate initial pressure of 34.5 MPa (5000 psi). After each reaction, the thermally stressed liquid phase was analyzed by gas chromatography . The...and operational specifications for these fluids and facilitate new applications. 14,15 The thermophysical properties that are being measured include

Surface pressure affects B-hordein network formation at the air-water interface in relation to gastric digestibility.

PubMed

Yang, Jingqi; Huang, Jun; Zeng, Hongbo; Chen, Lingyun

2015-11-01

Protein interfacial network formation under mechanical pressure and its influence on degradation was investigated at molecular level using Langmuir-Blodgett B-hordein monolayer as a 2D model. Surface properties, such as surface pressure, dilatational and shear rheology and the surface pressure--area (π-A) isotherm, of B-hordein at air-water interface were analyzed by tensiometer, rheometer and a Langmuir-Blodgett trough respectively. B-Hordein conformation and orientation under different surface pressures were determined by polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS). The interfacial network morphology was observed by atomic force microscopy (AFM). B-Hordein could reduce the air-water surface tension rapidly to ∼ 45 mN/m and form a solid-like network with high rheological elasticity and compressibility at interface, which could be a result of interactions developed by intermolecular β-sheets. The results also revealed that B-hordein interfacial network switched from an expanded liquid phase to a solid-like film with increasing compression pressure. The orientation of B-hordein was parallel to the surface when in expended liquid phase, whereas upon compression, the hydrophobic repetitive region tilted away from water phase. When compressed to 30 mN/m, a strong elastic network was formed at the interface, and it was resistant to a harsh gastric-like environment of low pH and pepsin. This work generated fundamental knowledge, which suggested the potential to design B-hordein stabilized emulsions and encapsulations with controllable digestibility for small intestine targeted delivery of bioactive compounds. Copyright © 2015 Elsevier B.V. All rights reserved.

Sebum/Meibum Surface Film Interactions and Phase Transitional Differences.

PubMed

Mudgil, Poonam; Borchman, Douglas; Gerlach, Dylan; Yappert, Marta C

2016-05-01

Sebum may contribute to the composition of the tear film lipid layer naturally or as a contaminant artifact from collection. The aims of this study were to determine: if sebum changes the rheology of meibum surface films; if the resonance near 5.2 ppm in the 1H-NMR spectra of sebum is due to squalene (SQ); and if sebum or SQ, a major component of sebum, interacts with human meibum. Human meibum was collected from the lid margin with a platinum spatula. Human sebum was collected using lipid absorbent tape. Langmuir trough technology was used to measure the rheology of surface films. Infrared spectroscopy was used to measure lipid conformation and phase transitions. We used 1H-NMR to measure composition and confirm the primary structure of SQ. The NMR resonance near 5.2 ppm in the spectra of human sebum was from SQ which composed 28 mole percent of sebum. Both sebum and SQ lowered the lipid order of meibum. Sebum expanded meibum films at lower concentrations and condensed meibum films at higher concentrations. Sebum caused meibum to be more stable at higher pressures (greater maximum surface pressure). Physiological levels of sebum would be expected to expand or fluidize meibum making it spread better and be more surface active (qualities beneficial for tear film stability). Sebum would also be expected to stabilize the tear film lipid layer, which may allow it to withstand the high shear pressure of a blink.

Sebum/Meibum Surface Film Interactions and Phase Transitional Differences

PubMed Central

Mudgil, Poonam; Borchman, Douglas; Gerlach, Dylan; Yappert, Marta C.

2016-01-01

Purpose Sebum may contribute to the composition of the tear film lipid layer naturally or as a contaminant artifact from collection. The aims of this study were to determine: if sebum changes the rheology of meibum surface films; if the resonance near 5.2 ppm in the 1H-NMR spectra of sebum is due to squalene (SQ); and if sebum or SQ, a major component of sebum, interacts with human meibum. Methods Human meibum was collected from the lid margin with a platinum spatula. Human sebum was collected using lipid absorbent tape. Langmuir trough technology was used to measure the rheology of surface films. Infrared spectroscopy was used to measure lipid conformation and phase transitions. We used 1H-NMR to measure composition and confirm the primary structure of SQ. Results The NMR resonance near 5.2 ppm in the spectra of human sebum was from SQ which composed 28 mole percent of sebum. Both sebum and SQ lowered the lipid order of meibum. Sebum expanded meibum films at lower concentrations and condensed meibum films at higher concentrations. Sebum caused meibum to be more stable at higher pressures (greater maximum surface pressure). Conclusions Physiological levels of sebum would be expected to expand or fluidize meibum making it spread better and be more surface active (qualities beneficial for tear film stability). Sebum would also be expected to stabilize the tear film lipid layer, which may allow it to withstand the high shear pressure of a blink. PMID:27145473

Path-integral simulation of ice Ih: The effect of pressure

NASA Astrophysics Data System (ADS)

Herrero, Carlos P.; Ramírez, Rafael

2011-12-01

The effect of pressure on structural and thermodynamic properties of ice Ih has been studied by means of path-integral molecular dynamics simulations at temperatures between 50 and 300 K. Interatomic interactions were modeled by using the effective q-TIP4P/F potential for flexible water. Positive (compression) and negative (tension) pressures have been considered, which allowed us to approach the limits for the mechanical stability of this solid water phase. We have studied the pressure dependence of the crystal volume, bulk modulus, interatomic distances, atomic delocalization, and kinetic energy. The spinodal point at both negative and positive pressures is derived from the vanishing of the bulk modulus. For P<0, the spinodal pressure changes from -1.38 to - 0.73 GPa in the range from 50 to 300 K. At positive pressure the spinodal is associated with ice amorphization, and at low temperatures it is found to be between 1.1 and 1.3 GPa. Quantum nuclear effects cause a reduction of the metastability region of ice Ih.

Effect of organic matters on CO2 hydrate phase equilibrium conditions in Na-montmorillonite clay

NASA Astrophysics Data System (ADS)

Park, T.; Kyung, D.; Lee, W.

2013-12-01

Formation of gas hydrates provides an attractive idea for storing greenhouse gases in a long-term stable geological formation. Since the phase equilibrium conditions of gas hydrates indicate the stability of hydrates, estimation of the phase equilibrium conditions of gas hydrates in marine geological conditions is necessary. In this study, we have identified the effects of organic matters (glycine, glucose, and urea) and solid surface (montmorillonite (MMT)) on the three-phase (liquid-hydrate-vapor) equilibrium conditions of CO2 hydrate. CO2 phase equilibrium experiments were conducted using 0.5mol% organic matter solutions with and without 10g soil mineral were experimentally conducted. Addition of organic matters shifted the phase equilibrium conditions of CO2 hydrate to the higher pressure or lower pressure region because of higher competition of water molecules due to the dissolved organic matters. Presence of MMT also leaded to the higher equilibrium pressure due to the interaction of cations with water molecules. By addition of organic matters to the clay suspension, the hydrate phase equilibrium conditions were less inhibited compared to those of MMT and organic matters independently. The diminished magnitudes by addition of organic matters to the clay suspension (MMT > MMT+urea > MMT+glycine > MMT+glucose > DIW) were different to the order of inhibition degree without MMT (Glucose > glycine > urea > DIW). X-ray diffraction (XRD), scanning electron microscope (SEM), and ion chromatography (IC) analysis were conducted to support the hypothesis that the organic matters interact with cations in MMT interlayer space, and leads to the less inhibition of phase equilibrium conditions. The present study provides basic information for the formation and dissociation of CO2 hydrates in the geological formation when sequestering CO2 as a form of CO2 hydrate.

CO2 packing polymorphism under pressure: Mechanism and thermodynamics of the I-III polymorphic transition

NASA Astrophysics Data System (ADS)

Gimondi, Ilaria; Salvalaglio, Matteo

2017-09-01

In this work, we describe the thermodynamics and mechanism of CO2 polymorphic transitions under pressure from form I to form III combining standard molecular dynamics, well-tempered metadynamics, and committor analysis. We find that the phase transformation takes place through a concerted rearrangement of CO2 molecules, which unfolds via an anisotropic expansion of the CO2 supercell. Furthermore, at high pressures, we find that defected form I configurations are thermodynamically more stable with respect to form I without structural defects. Our computational approach shows the capability of simultaneously providing an extensive sampling of the configurational space, estimates of the thermodynamic stability, and a suitable description of a complex, collective polymorphic transition mechanism.

CO2 packing polymorphism under pressure: Mechanism and thermodynamics of the I-III polymorphic transition.

PubMed

Gimondi, Ilaria; Salvalaglio, Matteo

2017-09-21

In this work, we describe the thermodynamics and mechanism of CO 2 polymorphic transitions under pressure from form I to form III combining standard molecular dynamics, well-tempered metadynamics, and committor analysis. We find that the phase transformation takes place through a concerted rearrangement of CO 2 molecules, which unfolds via an anisotropic expansion of the CO 2 supercell. Furthermore, at high pressures, we find that defected form I configurations are thermodynamically more stable with respect to form I without structural defects. Our computational approach shows the capability of simultaneously providing an extensive sampling of the configurational space, estimates of the thermodynamic stability, and a suitable description of a complex, collective polymorphic transition mechanism.

High pressure behavior of complex phosphate K2Ce[PO4]2: Grüneisen parameter and anharmonicity properties

NASA Astrophysics Data System (ADS)

Mishra, Karuna Kara; Bevara, Samatha; Ravindran, T. R.; Patwe, S. J.; Gupta, Mayanak K.; Mittal, Ranjan; Krishnan, R. Venkata; Achary, S. N.; Tyagi, A. K.

2018-02-01

Herein we reported structural stability, vibrational and thermal properties of K2Ce[PO4]2, a relatively underexplored complex phosphate of tetravalent Ce4+ from in situ high-pressure Raman spectroscopic investigations up to 28 GPa using a diamond anvil cell. The studies identified the soft phonons that lead to a reversible phase transformation above 8 GPa, and a phase coexistence of ambient (PI) and high pressure (PII) phases in a wider pressure region 6-11 GPa. From a visual representation of the computed eigen vector displacements, the Ag soft mode at 82 cm-1 is assigned as a lattice mode of K+ cation. Pressure-induced positional disorder is apparent from the substantial broadening of internal modes and the disappearance of low frequency lattice and external modes in phase PII above 18 GPa. Isothermal mode Grüneisen parameters γi of the various phonon modes are calculated and compared for several modes. Using these values, thermal properties such as average Grüneisen parameter, and thermal expansion coefficient are estimated as 0.47, and 2.5 × 10-6 K-1, respectively. The specific heat value was estimated from all optical modes obtained from DFT calculations as 314 J-mol-1 K-1. Our earlier reported temperature dependence of phonon frequencies is used to decouple the "true anharmonic" (explicit contribution at constant volume) and "quasi harmonic" (implicit contribution brought out by volume change) contributions from the total anharmonicity. In addition to the 81 cm-1 Ag lattice mode, several other lattice and external modes of PO43- ions are found to be strongly anharmonic.

Fluorescence, polarized fluorescence, and Brewster angle microscopy of palmitic acid and lung surfactant protein B monolayers.

PubMed Central

Lipp, M M; Lee, K Y; Waring, A; Zasadzinski, J A

1997-01-01

Fluorescence, polarized fluorescence, and Brewster angle microscopy reveal that human lung surfactant protein SP-B and its amino terminus (SP-B[1-25]) alter the phase behavior of palmitic acid monolayers by inhibiting the formation of condensed phases and creating a new fluid protein-rich phase. This fluid phase forms a network that separates condensed phase domains at coexistence and persists to high surface pressures. The network changes the monolayer collapse mechanism from heterogeneous nucleation/growth and fracturing processes to a more homogeneous process through isolating individual condensed phase domains. This results in higher surface pressures at collapse, and monolayers easier to respread on expansion, factors essential to the in vivo function of lung surfactant. The network is stabilized by a low-line tension between the coexisting phases, as confirmed by the observation of extended linear domains, or "stripe" phases, and a Gouy-Chapman analysis of protein-containing monolayers. Comparison of isotherm data and observed morphologies of monolayers containing SP-B(1-25) with those containing the full SP-B sequence show that the shortened peptide retains most of the native activity of the full-length protein, which may lead to cheaper and more effective synthetic replacement formulations. Images FIGURE 1 FIGURE 3 FIGURE 4 FIGURE 6 FIGURE 7 FIGURE 8 FIGURE 9 FIGURE 10 PMID:9168053

Some experiments related to L-star instability in rocket motors

NASA Technical Reports Server (NTRS)

Kumar, R. N.; Mcnamara, R. P.

1973-01-01

The influence of condensed phase heterogeneity on the L-star instability of nonmetallized AP/PBAN propellants is explored using four propellants (with monomodal AP particle distributions having 50 per cent weight average points at 11, 39.5, 175, and 350 microns). An economical firing program is used. One-dimensional nature of the Helmholtz mode and the complex nature of the chuff mode are revealed through color movies. The stability boundary on the L-star pressure plot is found to be parabolic. Frequency correlations and many other features reveal the important role of condensed phase details in propellant combustion.

High pressure study of water-salt systems, phase equilibria, partitioning, thermodynic properties and implication for large icy worlds hydrospheres.

NASA Astrophysics Data System (ADS)

Journaux, B.; Brown, J. M.; Abramson, E.; Petitgirard, S.; Pakhomova, A.; Boffa Ballaran, T.; Collings, I.

2017-12-01

Water salt systems are predicted to be present in deep hydrosphere inside water-rich planetary bodies, following water/rock chemical interaction during early differentiation stages or later hydrothermal activity. Unfortunately the current knowledge of the thermodynamic and physical properties of aqueous salt mixtures at high pressure and high temperature is still insufficient to allow realistic modeling of the chemical or dynamic of thick planetary hydrospheres. Recent experimental results have shown that the presence of solutes, and more particularly salts, in equilibrium with high pressure ices have large effects on the stability fields, buoyancy and chemistry of all the phases present at these extreme conditions. Effects currently being investigated by our research group also covers ice melting curve depressions that depend on the salt species and incorporation of solutes inside the crystallographic lattice of high pressure ices. Both of these could have very important implication at the planetary scale, enabling thicker/deeper liquid oceans, and allowing chemical transportation through the high pressure ice layer in large icy worlds. We will present the latest results obtained in-situ using diamond anvil cell, coupled with Synchrotron X-Ray diffraction, Raman Spectroscopy and optical observations, allowing to probe the crystallographic structure, equations of state, partitioning and phase boundary of high pressure ice VI and VII in equilibrium with Na-Mg-SO4-Cl ionic species at high pressures (1-10 GPa). The difference in melting behavior depending on the dissolved salt species was characterized, suggesting differences in ionic speciation at liquidus conditions. The solidus P-T conditions were also measured as well as an increase of lattice volumes interpreted as an outcome of ionic incorporation in HP ice during incongruent crystallization. The measured phase diagrams, lattice volumes and important salt incorporations suggest a more complex picture of the structure, dynamic and evolution of icy worlds hydrospheres that could allow, among others, deep liquid reservoirs, chemical transport at the solid state through HP ices layers and/or complex dynamic due to salt exsolutions at HP ices solid-solid phase boundaries.

Chemical beam epitaxy of GaAs1-xNx using MMHy and DMHy precursors, modeled by ab initio study of GaAs(100) surfaces stability over As2, H2 and N2

NASA Astrophysics Data System (ADS)

Valencia, Hubert; Kangawa, Yoshihiro; Kakimoto, Koichi

2017-06-01

Using ab initio calculations, a simple model for GaAs1-xNx vapor-phase epitaxy on (100) surface of GaAs was created. By studying As2 and H2 molecules adsorptions and As/N atom substitutions on (100) GaAs surfaces, we obtain a relative stability diagram of all stable surfaces under varying As2, H2, and N2 conditions. We previously proved that this model could describe the vapor-phase epitaxy of GaAs1-x Nx with simple, fully decomposed, precursors. In this paper, we show that in more complex reaction conditions using monomethylhydrazine (MMHy), and dimethylhydrazine (DMHy), it is still possible to use our model to obtain an accurate description of the temperature and pressure stability domains for each surfaces, linked to chemical beam epitaxy (CBE) growth conditions. Moreover, the different N-incorporation regimes observed experimentally at different temperature can be explain and predict by our model. The use of MMHy and DMHy precursors can also be rationalized. Our model should then help to better understand the conditions needed to obtain an high quality GaAs1-xNx using vapor-phase epitaxy.

Consolidation of cubic and hexagonal boron nitride composites

DOE PAGES

Du Frane, W. L.; Cervantes, O.; Ellsworth, G. F.; ...

2015-12-08

When we Consolidate cubic boron nitride (cBN) it typically requires either a matrix of metal bearing materials that are undesirable for certain applications, or very high pressures within the cBN phase stability field that are prohibitive to manufacturing size and cost. We present new methodology for consolidating high stiffness cBN composites within a hexagonal boron nitride (hBN) matrix (15–25 vol%) with the aid of a binder phase (0–6 vol%) at moderate pressures (0.5–1.0 GPa) and temperatures (900–1300 °C). The composites are demonstrated to be highly tailorable with a range of compositions and resulting physical/mechanical properties. Ultrasonic measurements indicate that inmore » some cases these composites have elastic mechanical properties that exceed those of the highest strength steel alloys. Moreover, two methods were identified to prevent phase transformation of the metastable cBN phase into hBN during consolidation: 1. removal of hydrocarbons, and 2. increased cBN particle size. Lithium tetraborate worked better as a binder than boron oxide, aiding consolidation without enhancing cBN to hBN phase transformation kinetics. These powder mixtures consolidated within error of their full theoretical mass densities at 1 GPa, and had only slightly lower densities at 0.5 GPa. This shows potential for consolidation of these composites into larger parts, in a variety of shapes, at even lower pressures using more conventional manufacturing methods, such as hot-pressing.« less

Evidence for the antiferromagnetic ground state of Zr2TiAl: a first-principles study

NASA Astrophysics Data System (ADS)

Sreenivasa Reddy, P. V.; Kanchana, V.; Vaitheeswaran, G.; Ruban, Andrei V.; Christensen, N. E.

2017-07-01

A detailed study on the ternary Zr-based intermetallic compound Zr2TiAl has been carried out using first-principles electronic structure calculations. From the total energy calculations, we find an antiferromagnetic L11-like (AFM) phase with alternating (1 1 1) spin-up and spin-down layers to be a stable phase among some others with magnetic moment on Ti being 1.22 {μ\\text{B}} . The calculated magnetic exchange interaction parameters of the Heisenberg Hamiltonian and subsequent Heisenberg Monte Carlo simulations confirm that this phase is the magnetic ground structure with Néel temperature between 30 and 100 K. The phonon dispersion relations further confirm the stability of the magnetic phase while the non-magnetic phase is found to have imaginary phonon modes and the same is also found from the calculated elastic constants. The magnetic moment of Ti is found to decrease under pressure eventually driving the system to the non-magnetic phase at around 46 GPa, where the phonon modes are found to be positive indicating stability of the non-magnetic phase. A continuous change in the band structure under compression leads to the corresponding change of the Fermi surface topology and electronic topological transitions (ETT) in both majority and minority spin cases, which are also evident from the calculated elastic constants and density of state calculations for the material under compression.

Two-dimensional lattice-fluid model with waterlike anomalies

NASA Astrophysics Data System (ADS)

Buzano, C.; de Stefanis, E.; Pelizzola, A.; Pretti, M.

2004-06-01

We investigate a lattice-fluid model defined on a two-dimensional triangular lattice, with the aim of reproducing qualitatively some anomalous properties of water. Model molecules are of the “Mercedes Benz” type, i.e., they possess a D3 (equilateral triangle) symmetry, with three bonding arms. Bond formation depends both on orientation and local density. We work out phase diagrams, response functions, and stability limits for the liquid phase, making use of a generalized first order approximation on a triangle cluster, whose accuracy is verified, in some cases, by Monte Carlo simulations. The phase diagram displays one ordered (solid) phase which is less dense than the liquid one. At fixed pressure the liquid phase response functions show the typical anomalous behavior observed in liquid water, while, in the supercooled region, a reentrant spinodal is observed.

Stability limits of unsteady open capillary channel flow

NASA Astrophysics Data System (ADS)

Grah, Aleksander; Haake, Dennis; Rosendahl, Uwe; Klatte, J.?Rg; Dreyer, Michael E.

This paper is concerned with steady and unsteady flow rate limitations in open capillary channels under low-gravity conditions. Capillary channels are widely used in Space technology for liquid transportation and positioning, e.g. in fuel tanks and life support systems. The channel observed in this work consists of two parallel plates bounded by free liquid surfaces along the open sides. The capillary forces of the free surfaces prevent leaking of the liquid and gas ingestion into the flow.In the case of steady stable flow the capillary pressure balances the differential pressure between the liquid and the surrounding constant-pressure gas phase. Increasing the flow rate in small steps causes a decrease of the liquid pressure. A maximum steady flow rate is achieved when the flow rate exceeds a certain limit leading to a collapse of the free surfaces due to the choking effect. In the case of unsteady flow additional dynamic effects take place due to flow rate transition and liquid acceleration. The maximum flow rate is smaller than in the case of steady flow. On the other hand, the choking effect does not necessarily cause surface collapse and stable temporarily choked flow is possible under certain circumstances.To determine the limiting volumetric flow rate and stable flow dynamic properties, a new stability theory for both steady and unsteady flow is introduced. Subcritical and supercritical (choked) flow regimes are defined. Stability criteria are formulated for each flow type. The steady (subcritical) criterion corresponds to the speed index defined by the limiting longitudinal small-amplitude wave speed, similar to the Mach number. The unsteady (supercritical) criterion for choked flow is defined by a new characteristic number, the dynamic index. It is based on pressure balances and reaches unity at the stability limit.The unsteady model based on the Bernoulli equation and the mass balance equation is solved numerically for perfectly wetting incompressible liquids. The unsteady model and the stability theory are verified by comparison to results of a sounding rocket experiment (TEXUS 41) on capillary channel flows launched in December 2005 from ESRANGE in north Sweden. For a clear overview of subcritical, supercritical, and unstable flow, parametric studies and stability diagrams are shown and compared to experimental observations.

Computational phase diagrams of noble gas hydrates under pressure

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

Teeratchanan, Pattanasak, E-mail: s1270872@sms.ed.ac.uk; Hermann, Andreas, E-mail: a.hermann@ed.ac.uk

2015-10-21

We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogenmore » hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.« less

High-pressure and high-temperature phase diagram for Fe0.9Ni0.1-H alloy

NASA Astrophysics Data System (ADS)

Shibazaki, Yuki; Terasaki, Hidenori; Ohtani, Eiji; Tateyama, Ryuji; Nishida, Keisuke; Funakoshi, Ken-ichi; Higo, Yuji

2014-03-01

Planetary cores are considered to consist of an iron-nickel (Fe-Ni) alloy and light elements and hydrogen is one of plausible light elements in the core. Here we have performed in situ X-ray diffraction experiments on an Fe0.9Ni0.1-H system up to 15.1 GPa and 1673 K, and investigated the effect of Ni on phase relations of FeHx under high pressure and high temperature. The experimental system in the present work was oversaturated with hydrogen. We found a face-center-cubic (fcc) phase (with hydrogen concentration up to x∼1) and a body-center-cubic (bcc) phase (x < 0.1) as stable phases. The partial melting was observed below 6 GPa. We could not observe a double-hexagonal-close-packed (dhcp) phase because of limitations in pressure and temperature conditions. The stability field of each phase of Fe0.9Ni0.1Hx was almost same as that of FeHx. The solidus of Fe0.9Ni0.1Hx was 500-700 K lower than the melting curve of Fe and its liquidus was 400-600 K lower than that of Fe in the pressure range of this study. Both the solidus and liquidus of Fe0.9Ni0.1Hx were depressed at around 3.5 GPa, as was the solidus of FeHx. The hydrogen contents in fcc-Fe0.9Ni0.1Hx just below solidus were slightly lower than those of fcc-FeHx, which suggests that nickel is likely to prevent dissolution of hydrogen into iron. Due to the lower hydrogen solubilities in Fe0.9Ni0.1 compared to Fe, the solidus of Fe0.9Ni0.1Hx is about 100-150 K higher than that of FeHx.

Phase Relations of Iron and Iron-Nickel Alloys up to 3 Mbars

NASA Astrophysics Data System (ADS)

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

2007-12-01

Iron is believed to be the major component of the Earth's core because it is the most abundant element that satisfies the observed seismic densities. Based on cosmochemical models and the studies of iron meteorites, it is generally accepted that the Earth's core also contains substantial amounts of nickel. Therefore, the high pressure behaviour of iron-nickel alloys is crucially important for interpreting and constraining geophysical and geochemical models of the Earth's core. The phase relation of iron at relatively low pressure has been well established. α-Fe with bcc structure at ambient condition transforms to γ-Fe at high temperature and to ɛ-Fe with hcp structure at above ~ 10 GPa. In contrast, the phase relation and the crystal structure at high pressure and temperature are still highly controversial. The phase relations of iron-nickel alloys were also studied in an externally-heated diamond-anvil cell (Huang et al. 1988, 1992) and in a laser-heated diamond-anvil cell (Lin et al. 2002, Mao et al. 2005, Dubrovinsky et al. 2007), but these experiments were limited to the pressure of 225 GPa. Applications of the previous results to the Earth's inner core conditions required significant extrapolations. In this study, we have investigated the phase relations of iron and a number of iron-nickel alloys in a wide range of pressures (>300 GPa), temperatures (>2000 K) and compositions (0-80 wt% Ni) using a laser-heated diamond-anvil cell with synchrotron x-ray diffraction. For iron, in-situ x-ray diffraction studies showed a wide range of stability of ɛ-Fe with an hcp structure up to 300 GPa and 2000 K and up to 343 GPa at room temperature. No evidence for the existence of phases other than ɛ-Fe, such as β-Fe with a dhcp structure (suggested by Dubrovinsky et al. 2000) or orthorhombic structure (suggested by Andrault et al. 1997), was observed. For iron-nickel alloys, high pressure and temperature experiments were conducted on Fe-18.4 wt% Ni, Fe-24.9 wt% Ni, Fe-35.7 wt% Ni, Fe-50.0 wt% Ni and Fe-80.0 wt% Ni up to 300 GPa. The experimental results indicate that the iron-nickel alloys strongly favour an fcc structure under multimegabar pressures. Our results can directly apply to the Earth's inner core pressures and the phase relations of iron- nickel alloys may interpret seismically observed anisotropy and discontinuity in the Earth's inner core.

Conventional freezing plus high pressure-low temperature treatment: Physical properties, microbial quality and storage stability of beef meat.

PubMed

Fernández, Pedro P; Sanz, Pedro D; Molina-García, Antonio D; Otero, Laura; Guignon, Bérengère; Vaudagna, Sergio R

2007-12-01

Meat high-hydrostatic pressure treatment causes severe decolouration, preventing its commercialisation due to consumer rejection. Novel procedures involving product freezing plus low-temperature pressure processing are here investigated. Room temperature (20°C) pressurisation (650MPa/10min) and air blast freezing (-30°C) are compared to air blast freezing plus high pressure at subzero temperature (-35°C) in terms of drip loss, expressible moisture, shear force, colour, microbial quality and storage stability of fresh and salt-added beef samples (Longissimus dorsi muscle). The latter treatment induced solid water transitions among ice phases. Fresh beef high pressure treatment (650MPa/20°C/10min) increased significantly expressible moisture while it decreased in pressurised (650MPa/-35°C/10min) frozen beef. Salt addition reduced high pressure-induced water loss. Treatments studied did not change fresh or salt-added samples shear force. Frozen beef pressurised at low temperature showed L, a and b values after thawing close to fresh samples. However, these samples in frozen state, presented chromatic parameters similar to unfrozen beef pressurised at room temperature. Apparently, freezing protects meat against pressure colour deterioration, fresh colour being recovered after thawing. High pressure processing (20°C or -35°C) was very effective reducing aerobic total (2-log(10) cycles) and lactic acid bacteria counts (2.4-log(10) cycles), in fresh and salt-added samples. Frozen+pressurised beef stored at -18°C during 45 days recovered its original colour after thawing, similarly to just-treated samples while their counts remain below detection limits during storage.

Distinct magnetic spectra in the hidden order and antiferromagnetic phases in URu 2 - x Fe x Si 2

DOE PAGES

Butch, Nicholas P.; Ran, Sheng; Jeon, Inho; ...

2016-11-07

We use neutron scattering to compare the magnetic excitations in the hidden order (HO) and antiferromagnetic (AFM) phases in URu 2-xFe xSi 2 as a function of Fe concentration. The magnetic excitation spectra change significantly between x = 0.05 and x = 0.10, following the enhancement of the AFM ordered moment, in good analogy to the behavior of the parent compound under applied pressure. Prominent lattice-commensurate low-energy excitations characteristic of the HO phase vanish in the AFM phase. The magnetic scattering is dominated by strong excitations along the Brillouin zone edges, underscoring the important role of electron hybridization to bothmore » HO and AFM phases, and the similarity of the underlying electronic structure. The stability of the AFM phase is correlated with enhanced local-itinerant electron hybridization.« less

The properties of clusters in the gas phase. IV - Complexes of H2O and HNOx clustering on NOx/-/

NASA Technical Reports Server (NTRS)

Lee, N.; Castleman, A. W., Jr.; Keesee, R. G.

1980-01-01

Thermodynamic quantities for the gas-phase clustering equilibria of NO2(-) and NO3(-) were determined with high-pressure mass spectrometry. A comparison of values of the free energy of hydration derived from the data shows good agreement with formerly reported values at 296 K. New data for larger NO2(-) and NO3(-) hydrates as well as NO2(-)(HNO2)n were obtained in this study. To aid in understanding the bonding and stability of the hydrates of nitrite and nitrate ions, CNDO/2 calculations were performed, and the results are discussed. A correlation between the aqueous-phase total hydration enthalpy of a single ion and its gas-phase hydration enthalpy was obtained. Atmospheric implications of the data are also briefly discussed.

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

NASA Astrophysics Data System (ADS)

Johannes, Wilhelm

1980-09-01

Beginning of melting and subsolidus relationships in the system K2O-CaO-Al2O3-SiO2-H2O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt. The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K2O-CaO-Al2O3-SiO2-H2O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al2O3-SiO2-H2O. The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al2O3-SiO2-H2O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper. The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al2SiO5 polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.

Multiphase Flow Technology Impacts on Thermal Control Systems for Exploration

NASA Technical Reports Server (NTRS)

McQuillen, John; Sankovic, John; Lekan, Jack

2006-01-01

The Two-Phase Flow Facility (TPHIFFy) Project focused on bridging the critical knowledge gap by developing and demonstrating critical multiphase fluid products for advanced life support, thermal management and power conversion systems that are required to enable the Vision for Space Exploration. Safety and reliability of future systems will be enhanced by addressing critical microgravity fluid physics issues associated with flow boiling, condensation, phase separation, and system stability. The project included concept development, normal gravity testing, and reduced gravity aircraft flight campaigns, in preparation for the development of a space flight experiment implementation. Data will be utilized to develop predictive models that could be used for system design and operation. A single fluid, two-phase closed thermodynamic loop test bed was designed, assembled and tested. The major components in this test bed include: a boiler, a condenser, a phase separator and a circulating pump. The test loop was instrumented with flow meters, thermocouples, pressure transducers and both high speed and normal speed video cameras. A low boiling point surrogate fluid, FC-72, was selected based on scaling analyses using preliminary designs for operational systems. Preliminary results are presented which include flow regime transitions and some observations regarding system stability.

A Local Condensation Analysis Representing Two-phase Annular Flow in Condenser/radiator Capillary Tubes

NASA Technical Reports Server (NTRS)

Karimi, Amir

1991-01-01

NASA's effort for the thermal environmental control of the Space Station Freedom is directed towards the design, analysis, and development of an Active Thermal Control System (ATCS). A two phase, flow through condenser/radiator concept was baselined, as a part of the ATCS, for the radiation of space station thermal load into space. The proposed condenser rejects heat through direct condensation of ATCS working fluid (ammonia) in the small diameter radiator tubes. Analysis of the condensation process and design of condenser tubes are based on the available two phase flow models for the prediction of flow regimes, heat transfer, and pressure drops. The prediction formulas use the existing empirical relationships of friction factor at gas-liquid interface. An attempt is made to study the stability of interfacial waves in two phase annular flow. The formulation is presented of a stability problem in cylindrical coordinates. The contribution of fluid viscosity, surface tension, and transverse radius of curvature to the interfacial surface is included. A solution is obtained for Kelvin-Helmholtz instability problem which can be used to determine the critical and most dangerous wavelengths for interfacial waves.

Gas chromatography on wall-coated open-tubular columns with ionic liquid stationary phases.

PubMed

Poole, Colin F; Lenca, Nicole

2014-08-29

Ionic liquids have moved from novel to practical stationary phases for gas chromatography with an increasing portfolio of applications. Ionic liquids complement conventional stationary phases because of a combination of thermophysical and solvation properties that only exist for ionic solvents. Their high thermal stability and low vapor pressure makes them suitable as polar stationary phases for separations requiring high temperatures. Ionic liquids are good solvents and can be used to expand the chemical space for separations. They are the only stationary phases with significant hydrogen-bond acidity in common use; they extend the hydrogen-bond basicity of conventional stationary phases; they are as dipolar/polarizable as the most polar conventional stationary phases; and some ionic liquids are significantly less cohesive than conventional polar stationary phases. Problems in column coating techniques and related low column performance, column activity, and stationary phase reactivity require further exploration as the reasons for these features are poorly understood at present. Copyright © 2014 Elsevier B.V. All rights reserved.

Parabolized Stability Equations analysis of nonlinear interactions with forced eigenmodes to control subsonic jet instabilities

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

Itasse, Maxime, E-mail: Maxime.Itasse@onera.fr; Brazier, Jean-Philippe, E-mail: Jean-Philippe.Brazier@onera.fr; Léon, Olivier, E-mail: Olivier.Leon@onera.fr

2015-08-15

Nonlinear evolution of disturbances in an axisymmetric, high subsonic, high Reynolds number hot jet with forced eigenmodes is studied using the Parabolized Stability Equations (PSE) approach to understand how modes interact with one another. Both frequency and azimuthal harmonic interactions are analyzed by setting up one or two modes at higher initial amplitudes and various phases. While single mode excitation leads to harmonic growth and jet noise amplification, controlling the evolution of a specific mode has been made possible by forcing two modes (m{sub 1}, n{sub 1}), (m{sub 2}, n{sub 2}), such that the difference in azimuth and in frequencymore » matches the desired “target” mode (m{sub 1} − m{sub 2}, n{sub 1} − n{sub 2}). A careful setup of the initial amplitudes and phases of the forced modes, defined as the “killer” modes, has allowed the minimizing of the initially dominant instability in the near pressure field, as well as its estimated radiated noise with a 15 dB loss. Although an increase of the overall sound pressure has been found in the range of azimuth and frequency analyzed, the present paper reveals the possibility to make the initially dominant instability ineffective acoustically using nonlinear interactions with forced eigenmodes.« less

Formation of H2-He substellar bodies in cold conditions. Gravitational stability of binary mixtures in a phase transition

NASA Astrophysics Data System (ADS)

Füglistaler, A.; Pfenniger, D.

2016-06-01

Context. Molecular clouds typically consist of 3/4 H2, 1/4 He and traces of heavier elements. In an earlier work we showed that at very low temperatures and high densities, H2 can be in a phase transition leading to the formation of ice clumps as large as comets or even planets. However, He has very different chemical properties and no phase transition is expected before H2 in dense interstellar medium conditions. The gravitational stability of fluid mixtures has been studied before, but these studies did not include a phase transition. Aims: We study the gravitational stability of binary fluid mixtures with special emphasis on when one component is in a phase transition. The numerical results are aimed at applications in molecular cloud conditions, but the theoretical results are more general. Methods: First, we study the gravitational stability of van der Waals fluid mixtures using linearized analysis and examine virial equilibrium conditions using the Lennard-Jones intermolecular potential. Then, combining the Lennard-Jones and gravitational potentials, the non-linear dynamics of fluid mixtures are studied via computer simulations using the molecular dynamics code LAMMPS. Results: Along with the classical, ideal-gas Jeans instability criterion, a fluid mixture is always gravitationally unstable if it is in a phase transition because compression does not increase pressure. However, the condensed phase fraction increases. In unstable situations the species can separate: in some conditions He precipitates faster than H2, while in other conditions the converse occurs. Also, for an initial gas phase collapse the geometry is essential. Contrary to spherical or filamentary collapses, sheet-like collapses starting below 15 K easily reach H2 condensation conditions because then they are fastest and both the increase of heating and opacity are limited. Conclusions: Depending on density, temperature and mass, either rocky H2 planetoids, or gaseous He planetoids form. H2 planetoids are favoured by high density, low temperature and low mass, while He planetoids need more mass and can form at temperature well above the critical value.

Unsteady viscous effects in the flow over an oscillating surface. [mathematical model

NASA Technical Reports Server (NTRS)

Lerner, J. I.

1972-01-01

A theoretical model for the interaction of a turbulent boundary layer with an oscillating wavy surface over which a fluid is flowing is developed, with an application to wind-driven water waves and to panel flutter in low supersonic flow. A systematic methodology is developed to obtain the surface pressure distribution by considering separately the effects on the perturbed flow of a mean shear velocity profile, viscous stresses, the turbulent Reynolds stresses, compressibility, and three-dimensionality. The inviscid theory is applied to the wind-water wave problem by specializing to traveling-wave disturbances, and the pressure magnitude and phase shift as a function of the wave phase speed are computed for a logarithmic mean velocity profile and compared with inviscid theory and experiment. The results agree with experimental evidence for the stabilization of the panel motion due to the influence of the unsteady boundary layer.

Rotordynamic stability problems and solutions in high pressure turbocompressors

NASA Technical Reports Server (NTRS)

Schmied, J.

1989-01-01

The stability of a high pressure compressor is investigated with special regard to the self-exciting effects in oil seals and labyrinths. It is shown how to stabilize a rotor in spite of these effects and even increase its stability with increasing pressure.

Role of organic matter on aggregate stability and related mechanisms through organic amendments

NASA Astrophysics Data System (ADS)

Zaher, Hafida

2010-05-01

To date, only a few studies have tried to simultaneously compare the role of neutral and uronic sugars and lipids on soil structural stability. Moreover, evidence for the mechanisms involved has often been established following wetting of moist aggregates after various pre-treatments thus altering aggregate structure and resulting in manipulations on altered aggregates on which the rapid wetting process may not be involved anymore. To the best of our knowledge, the objective of this work was to study the role of neutral and uronic sugars and lipids in affecting key mechanisms (swelling rate, pressure evolution) involved in the stabilization of soil structure. A long-term incubation study (48-wk) was performed on a clay loam and a silty-clay loam amended with de-inking-secondary sludge mix at three rates (8, 16 and 24 Mg dry matter ha-1), primary-secondary sludge mix at one rate (18 Mg oven-dry ha-1) and composted de-inking sludge at one rate (24 Mg ha-1). Different structural stability indices (stability of moist and dry aggregates, the amount of dispersible clay and loss of soil material following sudden wetting) were measured on a regular basis during the incubation, along with CO2 evolved, neutral and uronic sugar, and lipid contents. During the course of the incubations, significant increases in all stability indices were measured for both soil types. In general, the improvements in stability were proportional to the amount of C added as organic amendments. These improvements were linked to a very intense phase of C mineralization and associated with increases in neutral and uronic sugars as well as lipid contents. The statistical relationships found between the different carbonaceous fractions and stability indices were all highly significant and indicated no clear superiority of one fraction over another. Paper sludge amendments also resulted in significant decreases in maximum internal pressure of aggregate and aggregate swelling following immersion in water, two mechanisms affecting structural stability. Overall, the results suggest that reduction in maximum internal pressure induced by organic amendments most likely resulted from increases in pore surface roughness and pore occlusion rather than by increase in surface wetting angles. This study also supports the view of a non specific action of the lipids, neutral and uronic sugars on aggregate stability to rapid wetting. Key words: soil aggregate stability, polysaccharides, lipids, mechanisms, organic matter

Formation of the –N(NO)N(NO)– polymer at high pressure and stabilization at ambient conditions

PubMed Central

Xiao, Hai; An, Qi; Goddard, William A.; Liu, Wei-Guang; Zybin, Sergey V.

2013-01-01

A number of exotic structures have been formed through high-pressure chemistry, but applications have been hindered by difficulties in recovering the high-pressure phase to ambient conditions (i.e., one atmosphere and 300 K). Here we use dispersion-corrected density functional theory [PBE-ulg (Perdew-Burke-Ernzerhof flavor of DFT with the universal low gradient correction for long range London dispersion)] to predict that above 60 gigapascal (GPa) the most stable form of N2O (the laughing gas in its molecular form) is a one-dimensional polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03∼0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions, both polymers relax below 14 GPa to the same stable nonplanar trans-polymer. The predicted phonon spectrum and dissociation kinetics validates the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a type of conducting nonlinear optical polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions (very high pressure or temperature). PMID:23503849

Investigation of Natural Circulation Instability and Transients in Passively Safe Small Modular Reactors

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

Ishii, Mamoru

The NEUP funded project, NEUP-3496, aims to experimentally investigate two-phase natural circulation flow instability that could occur in Small Modular Reactors (SMRs), especially for natural circulation SMRs. The objective has been achieved by systematically performing tests to study the general natural circulation instability characteristics and the natural circulation behavior under start-up or design basis accident conditions. Experimental data sets highlighting the effect of void reactivity feedback as well as the effect of power ramp-up rate and system pressure have been used to develop a comprehensive stability map. The safety analysis code, RELAP5, has been used to evaluate experimental results andmore » models. Improvements to the constitutive relations for flashing have been made in order to develop a reliable analysis tool. This research has been focusing on two generic SMR designs, i.e. a small modular Simplified Boiling Water Reactor (SBWR) like design and a small integral Pressurized Water Reactor (PWR) like design. A BWR-type natural circulation test facility was firstly built based on the three-level scaling analysis of the Purdue Novel Modular Reactor (NMR) with an electric output of 50 MWe, namely NMR-50, which represents a BWR-type SMR with a significantly reduced reactor pressure vessel (RPV) height. The experimental facility was installed with various equipment to measure thermalhydraulic parameters such as pressure, temperature, mass flow rate and void fraction. Characterization tests were performed before the startup transient tests and quasi-steady tests to determine the loop flow resistance. The control system and data acquisition system were programmed with LabVIEW to realize the realtime control and data storage. The thermal-hydraulic and nuclear coupled startup transients were performed to investigate the flow instabilities at low pressure and low power conditions for NMR-50. Two different power ramps were chosen to study the effect of startup power density on the flow instability. The experimental startup transient results showed the existence of three different flow instability mechanisms, i.e., flashing instability, condensation induced flow instability, and density wave oscillations. In addition, the void-reactivity feedback did not have significant effects on the flow instability during the startup transients for NMR-50. ii Several initial startup procedures with different power ramp rates were experimentally investigated to eliminate the flow instabilities observed from the startup transients. Particularly, the very slow startup transient and pressurized startup transient tests were performed and compared. It was found that the very slow startup transients by applying very small power density can eliminate the flashing oscillations in the single-phase natural circulation and stabilize the flow oscillations in the phase of net vapor generation. The initially pressurized startup procedure was tested to eliminate the flashing instability during the startup transients as well. The pressurized startup procedure included the initial pressurization, heat-up, and venting process. The startup transient tests showed that the pressurized startup procedure could eliminate the flow instability during the transition from single-phase flow to two-phase flow at low pressure conditions. The experimental results indicated that both startup procedures were applicable to the initial startup of NMR. However, the pressurized startup procedures might be preferred due to short operating hours required. In order to have a deeper understanding of natural circulation flow instability, the quasi-steady tests were performed using the test facility installed with preheater and subcooler. The effect of system pressure, core inlet subcooling, core power density, inlet flow resistance coefficient, and void reactivity feedback were investigated in the quasi-steady state tests. The experimental stability boundaries were determined between unstable and stable flow conditions in the dimensionless stability plane of inlet subcooling number and Zuber number. To predict the stability boundary theoretically, linear stability analysis in the frequency domain was performed at four sections of the natural circulation test loop. The flashing phenomena in the chimney section was considered as an axially uniform heat source. And the dimensionless characteristic equation of the pressure drop perturbation was obtained by considering the void fraction effect and outlet flow resistance in the core section. The theoretical flashing boundary showed some discrepancies with previous experimental data from the quasi-steady state tests. In the future, thermal non-equilibrium was recommended to improve the accuracy of flashing instability boundary. As another part of the funded research, flow instabilities of a PWR-type SMR under low pressure and low power conditions were investigated experimentally as well. The NuScale reactor design was selected as the prototype for the PWR-type SMR. In order to experimentally study the natural circulation behavior of NuScale iii reactor during accidental scenarios, detailed scaling analyses are necessary to ensure that the scaled phenomena could be obtained in a laboratory test facility. The three-level scaling method is used as well to obtain the scaling ratios derived from various non-dimensional numbers. The design of the ideally scaled facility (ISF) was initially accomplished based on these scaling ratios. Then the engineering scaled facility (ESF) was designed and constructed based on the ISF by considering engineering limitations including laboratory space, pipe size, and pipe connections etc. PWR-type SMR experiments were performed in this well-scaled test facility to investigate the potential thermal hydraulic flow instability during the blowdown events, which might occur during the loss of coolant accident (LOCA) and loss of heat sink accident (LOHS) of the prototype PWR-type SMR. Two kinds of experiments, normal blowdown event and cold blowdown event, were experimentally investigated and compared with code predictions. The normal blowdown event was experimentally simulated since an initial condition where the pressure was lower than the designed pressure of the experiment facility, while the code prediction of blowdown started from the normal operation condition. Important thermal hydraulic parameters including reactor pressure vessel (RPV) pressure, containment pressure, local void fraction and temperature, pressure drop and natural circulation flow rate were measured and analyzed during the blowdown event. The pressure and water level transients are similar to the experimental results published by NuScale [51], which proves the capability of current loop in simulating the thermal hydraulic transient of real PWR-type SMR. During the 20000s blowdown experiment, water level in the core was always above the active fuel assemble during the experiment and proved the safety of natural circulation cooling and water recycling design of PWR-type SMR. Besides, pressure, temperature, and water level transient can be accurately predicted by RELAP5 code. However, the oscillations of natural circulation flow rate, water level and pressure drops were observed during the blowdown transients. This kind of flow oscillations are related to the water level and the location upper plenum, which is a path for coolant flow from chimney to steam generator and down comer. In order to investigate the transients start from the opening of ADS valve in both experimental and numerical way, the cold blow-down experiment is conducted. For the cold blowdown event, different from setting both reactor iv pressure vessel (RPV) and containment at high temperature and pressure, only RPV was heated close to the highest designed pressure and then open the ADS valve, same process was predicted using RELAP5 code. By doing cold blowdown experiment, the entire transients from the opening of ADS can be investigated by code and benchmarked with experimental data. Similar flow instability observed in the cold blowdown experiment. The comparison between code prediction and experiment data showed that the RELAP5 code can successfully predict the pressure void fraction and temperature transient during the cold blowdown event with limited error, but numerical instability exists in predicting natural circulation flow rate. Besides, the code is lack of capability in predicting the water level related flow instability observed in experiments.« less

Thermostable ferroelectric capacitors based on graded films of barium strontium titanate

NASA Astrophysics Data System (ADS)

Tumarkin, A. V.; Razumov, S. V.; Volpyas, V. A.; Gagarin, A. G.; Odinets, A. A.; Zlygostov, M. V.; Sapego, E. N.

2017-10-01

The influence of the pressure of working gas during the ion-plasma sputtering on properties of deposited ferroelectric barium strontium titanate coatings has been experimentally studied. Variations in the of pressure of the working gas during deposition allows the component composition of the deposited layer to be changed, which leads to the diffusion of the phase transition and the improvement of temperature stability of properties of ferroelectric film. The gradation of layers has an impact on the temperature of the dielectric permittivity maximum, the shape of the dependence of the capacity on temperature, and the capacitance-voltage characteristics of the capacitor structures.

Synthesis and surface engineering of nanomaterials by atmospheric-pressure microplasmas

NASA Astrophysics Data System (ADS)

McKenna, J.; Patel, J.; Mitra, S.; Soin, N.; Švrček, V.; Maguire, P.; Mariotti, D.

2011-11-01

Two different atmospheric pressure microplasma systems are discussed and used for the synthesis and surface engineering of a range of nanomaterials. Specifically a gas-phase approach from vaporized tetramethylsilane has been used to synthesize silicon carbide nanoparticles with diameters below 10 nm. A different microplasma system that interfaces with a liquid solution has then been used for the synthesis of surfactant-free electrically stabilized gold nanoparticles with varying size. A similar microplasma-liquid system has been finally successfully used to tailor surface properties of silicon nanoparticles and to reduce graphene oxide into graphene. The synthesis and surface engineering mechanisms are also discussed.

Increasing dissolution of trospium chloride by co-crystallization with urea

NASA Astrophysics Data System (ADS)

Skořepová, Eliška; Hušák, Michal; Čejka, Jan; Zámostný, Petr; Kratochvíl, Bohumil

2014-08-01

The search for various solid forms of an active pharmaceutical ingredient (API) is an important step in drug development. Our aim was to prepare co-crystals of trospium chloride, an anticholinergic drug used for the treatment of incontinence, and to investigate if they have advantageous properties for drug formulation. Phase identification was done by powder X-ray diffraction and single-crystal X-ray diffraction. The chemical composition was verified by solution NMR and the dissolution rate of the prepared phases was studied by IDR (intrinsic dissolution rate). For further analysis of phase stability and transitions, combined thermal analysis and temperature-resolved X-ray powder diffraction were used. Urea was selected as a co-crystallization partner. Trospium chloride urea (1:1) co-crystal was prepared by a solvent evaporation. From single-crystal data, the co-crystal structure was solved in a space group P21/c and compared to previously published structures of trospium chloride. Intrinsic dissolution rate revealed that the co-crystal dissolves 32% faster than pure API. However, its low thermal and pressure stability makes it a challenging choice for the final drug formulation.

Thermodynamic investigation of the phase equilibrium boundary between TiO2 rutile and its α-PbO2-type high-pressure polymorph

NASA Astrophysics Data System (ADS)

Kojitani, Hiroshi; Yamazaki, Monami; Kojima, Meiko; Inaguma, Yoshiyuki; Mori, Daisuke; Akaogi, Masaki

2018-06-01

Heat capacity (C P) of rutile and α-PbO2 type TiO2 (TiO2-II) were measured by the differential scanning calorimetry and thermal relaxation method. Using the results, standard entropies at 1 atm and 298.15 K of rutile and TiO2-II were determined to be 50.04(4) and 46.54(2) J/mol K, respectively. Furthermore, thermal expansivity (α) determined by high-temperature X-ray diffraction measurement and mode Grüneisen parameters obtained by high-pressure Raman spectroscopy suggested the thermal Grüneisen parameter (γ th) for TiO2-II of 1.7(1). By applying the obtained low-temperature C P and γ th, the measured C P and α data of TiO2-II were extrapolated to higher temperature region using a lattice vibrational model calculation, as well as rutile. Internally consistent thermodynamic data sets of both rutile and TiO2-II assessed in this study were used to thermodynamically calculate the rutile‒TiO2-II phase equilibrium boundary. The most plausible boundary was obtained to be P (GPa) = 0.0074T (K) - 1.7. Our boundary suggests that the crystal growth of TiO2-II observed below 5.5 GPa and 900 K in previous studies advanced in its stability field. The phase boundary calculation also suggested small, exothermic phase transition enthalpy from rutile to TiO2-II at 1 atm and 298.15 K of - 0.5 to - 1.1 kJ/mol. This implies that the thermodynamic stability of rutile at 1 atm above room temperature is due to larger contribution of entropy term.

Stability of laser-propelled wafer satellites

NASA Astrophysics Data System (ADS)

Srinivasan, Prashant; Hughes, Gary B.; Lubin, Philip; Zhang, Qicheng; Madajian, Jonathan; Brashears, Travis; Kulkarni, Neeraj; Cohen, Alexander; Griswold, Janelle

2016-09-01

For interstellar missions, directed energy is envisioned to drive wafer-scale spacecraft to relativistic speeds. Spacecraft propulsion is provided by a large array of phase-locked lasers, either in Earth orbit or stationed on the ground. The directed-energy beam is focused on the spacecraft, which includes a reflective sail that propels the craft by reflecting the beam. Fluctuations and asymmetry in the beam will create rotational forces on the sail, so the sail geometry must possess an inherent, passive stabilizing effect. A hyperboloid shape is proposed, since changes in the incident beam angle due to yaw will passively counteract rotational forces. This paper explores passive stability properties of a hyperboloid reflector being bombarded by directed-energy beam. A 2D cross-section is analyzed for stability under simulated asymmetric loads. Passive stabilization is confirmed over a range of asymmetries. Realistic values of radiation pressure magnitude are drawn from the physics of light-mirror interaction. Estimates of beam asymmetry are drawn from optical modeling of a laser array far-field intensity using fixed and stochastic phase perturbations. A 3D multi-physics model is presented, using boundary conditions and forcing terms derived from beam simulations and lightmirror interaction models. The question of optimal sail geometry can be pursued, using concepts developed for the baseline hyperboloid. For example, higher curvature of the hyperboloid increases stability, but reduces effective thrust. A hyperboloid sail could be optimized by seeking the minimum curvature that is stable over the expected range of beam asymmetries.

Effect of Pressure on the Stability and Electronic Structure of ZnO0.5S0.5 and ZnO0.5Se0.5

NASA Astrophysics Data System (ADS)

Manotum, R.; Klinkla, R.; Phaisangittisakul, N.; Pinsook, U.; Bovornratanaraks, T.

2017-12-01

Structures and high-pressure phase transitions in ZnO0.5S0.5 and ZnO0.5Se0.5 have been investigated using density functional theory calculations. The previously proposed structures of ZnO0.5S0.5 and ZnO0.5Se0.5 which are chalcopyrite ( I\\bar{4}2d ), rocksalt ( Fm3m ), wurtzite ( P63 mc ) and CuAu-I ( P\\bar{4}m2 ) have been fully investigated. Stabilities of these materials have been systematically studied up to 40 GPa using various approaches. We have confirmed the stability of the chalcopyrite structure up to 30 GPa for which the CuAu-I structure has been previously proposed. However, our calculation revealed that CuAu-I is not a stable structure under 32 GPa and 33 GPa for both ZnO0.5S0.5 and ZnO0.5Se0.5, respectively, which could explain the failure in several attempts to fabricate these materials under such conditions. We have also examined the pressure-dependence of the bandgap and electronic structure up to 30 GPa. We can conclude from our PDOS analysis that the applied pressure does not change the atomic state characters of electronic states near the top of valence and the bottom of conduction bands, but mainly modifies the dominant Zn-3d atomic state of the deep Bloch state at -1 eV below Fermi level.

A High-Pressure Study of Manganese Metal and its Reactions with CO2 at 6, 23, and 44 GPa

NASA Astrophysics Data System (ADS)

Sawchuk, K. L. S.; McGuire, C. P.; Greenburg, A.; Makhluf, A.; Kavner, A.

2017-12-01

The free energies of formation of oxides and carbonates at the extreme pressures and temperatures of Earth's interior provides some of the thermodynamic constrains for models of mantle/core formation and subsequent chemical evolution. The broad goal of our research program is to measure the pressure- and temperature-dependence of free energies of formation of transition metal oxides and carbonates. This requires measurements of the phase stability, density, and thermoelastic properties of metals, oxides, and carbonates at deep-Earth and planetary conditions. Manganese is of interest because it is one of the most abundant transition metal geochemical tracers, it readily forms a carbonate at ambient pressure, and its high-pressure carbonate and oxide densities and equation of state parameters are relatively unknown. Here we report new data on the pressure/volume equation of state and structure of manganese metal as well as its reactions with CO2. These measurements were made using a laser heated diamond anvil cell in conjunction with synchrotron-based X-ray diffraction at beamline 12.2.2 at the Advanced Light Source. Three samples of manganese metal were gas-loaded in a CO2 pressure medium and pressurized to 6, 23, and 44 GPa. Upon laser heating, the CO2 reacted with the Mn metal generating new phases. To analyze the diffraction patterns, we we use a python-based program developed in-house for extracting high resolution 2-dimensional diffraction peak position and intensity information from two-dimensional X-ray diffraction patterns. At each pressure step, the structure and density of the quenched Mn metal phase was determined. At 6 GPa, Mn metal adopts a BCC structure, and at 23 GPa a tetragonal distortion is observed in the lattice. The measured equation of state is in good agreement with an existing meaurement by Fujihisa and Takemura (1995). MnCO3 rhodochrosite is observed in the sample quenched after heating at 6 GPa. Additional high pressure phases are evident in the diffraction patterns from the samples at 23 GPa and 44 GPa. The density and equation of state parameters for our observed oxide, carbonate, and metal manganese structures are used in conjunction with existing thermodynamic information to predict how the free energies of formation of Mn- oxide and Mn-carbonate change as a function of pressure.

Investigation of exotic stable calcium carbides using theory and experiment

DOE PAGES

Li, Yan-Ling; Wang, Sheng-Nan; Oganov, Artem R.; ...

2015-05-11

It is well known that pressure causes profound changes in the properties of atoms and chemical bonding, leading to the formation of many unusual materials. Here we systematically explore all stable calcium carbides at pressures from ambient to 100 GPa using variable-composition evolutionary structure predictions. We find that Ca 5C 2, Ca 2C, Ca 3C 2, CaC, Ca 2C 3, and CaC 2 have stability fields on the phase diagram. Among these, Ca2C and Ca2C3 are successfully synthesized for the first time via high-pressure experiments with excellent structural correspondence to theoretical predictions. Of particular significance are the base-centered monoclinic phasemore » (space group C 2/m) of Ca 2C, a quasi-two-dimensional metal with layers of negatively charged calcium atoms, and the primitive monoclinic phase (space group P21/c) of CaC with zigzag C 4 groups. Interestingly, strong interstitial charge localization is found in the structure of R-3m-Ca 5C 2 with semimetallic behaviour.« less

Unusual Electronic Structures of CO2 at Deep Mantle Pressures

NASA Astrophysics Data System (ADS)

Shieh, S. R.; Jarrige, I.; Hiraoka, N.; Wu, M.; Tse, J.; MI, Z.; Kaci, L.; Cai, Y.

2011-12-01

Carbon dioxide (CO2) is an important planetary gas phase found in the Venus, Earth and Mars. The high-pressure behavior of CO2 will have important implications for understanding the evolution and dynamics of planetary interiors. CO2 shows six solid phases and one amorphous phase at various pressure and temperature conditions. However, knowledge of its electronic structure remains unclear and may provide clues for the stability fields. Here we report the electronic structures of CO2 at high pressure and room temperature. The high-pressure inelastic x-ray scattering measurements of CO2 were conducted at beamline BL12XU, SPring-8. A monochromatic beam with incident energy about 10 KeV was focused to a size of 20 by 30 um2. The inelastic x-ray scattering photons were collected at about 35 degrees and a solid state Si detector with resolution of about 1.4 eV was used. Each spectrum was collected for 8-20 hours. Our oxygen K-edge results show that a strong pi resonance peak and some weak sigma peaks were observed in CO2-I. For the carbon K-edge of CO2-I, only a single strong pi resonance peak and a weak broad sigma peak at 313 eV was observed. This unique feature of carbon K-edge spectrum differs from those of graphite and diamond. Furthermore, we found that feature of oxygen K-edge spectra showed change at above 7.4 GPa, indicating the phase transition to CO2-III at pressure lower than those of x-ray diffraction reports. Moreover, at about 50 GPa, both oxygen and carbon K-edge of CO2 exhibit dramatic feature change and could be attributed to polymerization phenomena. It is found that only theoretical calculations including excitonic effects reproduced the experimental trend and indicate polymerization has occurred at 50 GPa and 300 K.

Hybrid simulation of fishbone instabilities in the EAST tokamak

DOE PAGES

Shen, Wei; Wang, Feng; Fu, G. Y.; ...

2017-08-11

Hybrid simulations with the global kinetic-magnetohydrodynamic (MHD) code M3D-K have been carried out to investigate the linear stability and nonlinear dynamics of beam-driven fishbone in the experimental advanced superconducting tokamak (EAST) experiment. Linear simulations show that a low frequency fishbone instability is excited at experimental value of beam ion pressure. The mode is mainly driven by low energy beam ions via precessional resonance. Our results are consistent with the experimental measurement with respect to mode frequency and mode structure. When the beam ion pressure is increased to exceed a critical value, the low frequency mode transits to a beta-induced Alfvenmore » eigenmode (BAE) with much higher frequency. This BAE is driven by higher energy beam ions. Nonlinear simulations show that the frequency of the low frequency fishbone chirps up and down with corresponding hole-clump structures in phase space, consistent with the Berk-Breizman theory. In addition to the low frequency mode, the high frequency BAE is excited during the nonlinear evolution. Furthermore, for the transient case of beam pressure fraction where the low and high frequency modes are simultaneously excited in the linear phase, only one dominant mode appears in the nonlinear phase with frequency jumps up and down during nonlinear evolution.« less

[The association between blood pressure variability and sleep stability in essential hypertensive patients with sleep disorder].

PubMed

Zhu, Y Q; Long, Q; Xiao, Q F; Zhang, M; Wei, Y L; Jiang, H; Tang, B

2018-03-13

Objective: To investigate the association of blood pressure variability and sleep stability in essential hypertensive patients with sleep disorder by cardiopulmonary coupling. Methods: Performed according to strict inclusion and exclusion criteria, 88 new cases of essential hypertension who came from the international department and the cardiology department of china-japan friendship hospital were enrolled. Sleep stability and 24 h ambulatory blood pressure data were collected by the portable sleep monitor based on cardiopulmonary coupling technique and 24 h ambulatory blood pressure monitor. Analysis the correlation of blood pressure variability and sleep stability. Results: In the nighttime, systolic blood pressure standard deviation, systolic blood pressure variation coefficient, the ratio of the systolic blood pressure minimum to the maximum, diastolic blood pressure standard deviation, diastolic blood pressure variation coefficient were positively correlated with unstable sleep duration ( r =0.185, 0.24, 0.237, 0.43, 0.276, P <0.05). Conclusions: Blood pressure variability is associated with sleep stability, especially at night, the longer the unstable sleep duration, the greater the variability in night blood pressure.

High-pressure Raman scattering studies of magnon-phonon interactions and ferroelastic phase transitions

NASA Astrophysics Data System (ADS)

Rosenblum, Steven S.

1997-11-01

Using high-pressure Raman spectroscopy, this dissertation investigates several areas of condensed matter physics. With metal thiophosphates (MnPSsb3, NiPSsb3) as our reference systems, we investigate coupling between phonons and two-magnon continua. We find that MnPSsb3's two-magnon excitation can be tuned into resonance with the 155 cmsp{-1} phonon at a temperature near 60 K. In NiPSsb3, we find that the two-magnon excitation has a linewidth broader than that predicted by standard two-magnon theory, reminiscent of the similar linewidth observed in the undoped cuprate superconductors. This observation calls into question the role quantum fluctuations associated with spin 1/2 play in the cuprates' two-magnon spectrum. Additionally, high-pressure Raman measurements of NiPSsb3 yielded evidence of resonant enhancement of the two-magnon excitation-previously only observed in the cuprate superconductors. Additionally, we investigated the rutile-to-CaClsb2 ferroelastic phase transition occurring in RuOsb2. We observed the splitting of the (rutile) Esb{g} mode, and used this to find a transition pressure of 11.8 GPa. Based on the lower transition pressure found in previous work and on other results in the literature, we speculate that stoichiometry plays a critical role in determining the stability of the rutile or CaClsb2 phase of the metal dioxides. These experiments were performed with a variety of single-, double-, and triple-grating spectrometers (Renishaw, SPEX, and Dilor, respectively). The excitation sources used were primarily ion lasers (either argon or helium-neon). Pressures up to 35 GPa were achieved via a Mao-Bell style Diamond Anvil Cell.

Role of 5f electrons in the structural stability of light actinide (Th-U) mononitrides under pressure.

PubMed

Modak, P; Verma, Ashok K

2016-03-28

Pressure induced structural sequences and their mechanism for light actinide (Th-U) mononitrides were studied as a function of 5f-electron number using first-principles total energy and electronic structure calculations. Zero pressure lattice constants, bulk module and C11 elastic module vary systematically with 5f-electron number implying its direct role on crystal binding. There is a critical 5f-electron number below which the system makes B1-B2 and above it B1-R3̄m-B2 structural sequence under pressure. Also, the B1-B2 transition pressure increases with increasing 5f-electron number whereas an opposite trend is obtained for the B1-R3̄m transition pressure. The ascending of N p anti-bonding states through the Fermi level at high pressure is responsible for the structural instability of the system. Above the critical 5f-electron number in the system a narrow 5f-band occurs very close to the Fermi level which allows the system to lower its symmetry via band Jahn-Teller type lattice distortion and the system undergoes a B1-R3̄m phase transition. However, below the critical 5f-electron number this mechanism is not favorable due to a lack of sufficient 5f-state occupancy and thus the system undergoes a B1-B2 phase transition like other ionic solids.

The phase diagram and hardness of carbon nitrides

DOE PAGES

Dong, Huafeng; Oganov, Artem R.; Zhu, Qiang; ...

2015-05-06

Novel superhard materials, especially those with superior thermal and chemical stability, are needed to replace diamond. Carbon nitrides (C-N), which are likely to possess these characteristics and have even been expected to be harder than diamond, are excellent candidates. Here we report three new superhard and thermodynamically stable carbon nitride phases. Based on a systematic evolutionary structure searches, we report a complete phase diagram of the C-N system at 0–300 GPa and analyze the hardest metastable structures. Surprisingly, we find that at zero pressure, the earlier proposed graphitic-C 3N 4 structure (P6-bar m2) is dynamically unstable, and we find themore » lowest-energy structure based on s-triazine unit and s-heptazine unit.« less

Elastic properties and phase transitions of Fe7C3 and new constraints on the light element budget of the Earth's inner core

NASA Astrophysics Data System (ADS)

Prescher, C.; Bykova, E.; Kupenko, I.; Glazyrin, K.; Kantor, A.; McCammon, C. A.; Mookherjee, M.; Miyajima, N.; Cerantola, V.; Nakajima, Y.; Prakapenka, V.; Rüffer, R.; Chumakov, A.; Dubrovinsky, L. S.

2013-12-01

The Earth's inner core consists mainly of iron (or iron-nickel alloy) with some amount of light element(s) whereby their nature remains controversial. Seismological data suggest that the material forming Earth's inner core (pressures over 330 GPa and temperatures above 5000 K) has an enigmatically high Poisson's ratio ~0.44, while iron or it alloys with Si, S, O, or H expected to have at appropriate thermodynamic conditions Poisson's ratio well below 0.39. We will present an experimental study on a new high pressure variant in the iron carbide system. We have synthesized and solved structure of high-pressure orthorhombic phase of o-Fe7C3, and investigated its stability and behavior at pressures over 180 GPa and temperatures above 3500 K by means of different methods including single crystal X-ray diffraction, Mössbauer spectroscopy, and nuclear resonance scattering. O-Fe7C3 is structurally stable to at least outer core conditions and demonstrates magnetic or electronic transitions at ~18 GPa and ~70 GPa. The high pressure phase of o-Fe7C3 above 70 GPa exhibits anomalous elastic properties. When extrapolated to the conditions of the Earth's inner core it shows shear wave velocities and Poisson's ratios close to the values inferred by seismological models. Our results not only support earlier works suggesting that carbon may be an important component of Earth's core, but shows that it may drastically change iron's elastic properties, thus explaining anomalous Earth's inner core elastic properties.

Influence of temporal pressure constraint on the biomechanical organization of gait initiation made with or without an obstacle to clear.

PubMed

Yiou, Eric; Fourcade, Paul; Artico, Romain; Caderby, Teddy

2016-06-01

Many daily motor tasks have to be performed under a temporal pressure constraint. This study aimed to explore the influence of such constraint on motor performance and postural stability during gait initiation. Young healthy participants initiated gait at maximal velocity under two conditions of temporal pressure: in the low-pressure condition, gait was self-initiated (self-initiated condition, SI); in the high-pressure condition, it was initiated as soon as possible after an acoustic signal (reaction-time condition, RT). Gait was initiated with and without an environmental constraint in the form of an obstacle to be cleared placed in front of participants. Results showed that the duration of postural adjustments preceding swing heel-off ("anticipatory postural adjustments", APAs) was shorter, while their amplitude was larger in RT compared to SI. These larger APAs allowed the participants to reach equivalent postural stability and motor performance in both RT and SI. In addition, the duration of the execution phase of gait initiation increased greatly in the condition with an obstacle to be cleared (OBST) compared to the condition without an obstacle (NO OBST), thereby increasing lateral instability and thus involving larger mediolateral APA. Similar effects of temporal pressure were obtained in NO OBST and OBST. This study shows the adaptability of the postural system to temporal pressure in healthy young adults initiating gait. The outcome of this study may provide a basis for better understanding the aetiology of balance impairments with the risk of falling in frail populations while performing daily complex tasks involving a whole-body progression.

Investigating the anticipatory postural adjustment phase of gait initiation in different directions in chronic ankle instability patients.

PubMed

Ebrahimabadi, Zahra; Naimi, Sedigheh Sadat; Rahimi, Abbas; Sadeghi, Heydar; Hosseini, Seyed Majid; Baghban, Alireza Akbarzadeh; Arslan, Syed Asadullah

2018-01-01

The main objective of the present study was to analyze how supra spinal motor control mechanisms are altered in different directions during anticipatory postural phase of gait initiation in chronic ankle instability patients. It seems that supra spinal pathways modulate anticipatory postural adjustment phase of gait initiation. Yet, there is a dearth of research on the effect of chronic ankle instability on the anticipatory postural adjustment phase of gait initiation in different directions. A total of 20 chronic ankle instability participants and 20 healthy individuals initiated gait on a force plate in forward, 30° lateral, and 30° medial directions. According to the results of the present study, the peak lateral center of pressure shift decreased in forward direction compared to that in other directions in both groups. Also, it was found that the peak lateral center of pressure shift and the vertical center of mass velocity decreased significantly in chronic ankle instability patients, as compared with those of the healthy individuals. According to the results of the present study, it seems that chronic ankle instability patients modulate the anticipatory postural adjustment phase of gait initiation, compared with healthy control group, in order to maintain postural stability. These changes were observed in different directions, too. Copyright © 2017 Elsevier Ltd. All rights reserved.

Storage and recycling of water and carbon dioxide in the earth

NASA Technical Reports Server (NTRS)

Wood, Bernard J.

1994-01-01

The stabilities and properties of water- and carbon-bearing phases in the earth have been determined from phase equilibrium measurements, combined with new data on the equations of state of water, carbon dioxide, carbonates and hydrates. The data have then been used to predict the fate of calcite and hydrous phases in subducting oceanic lithosphere. From the compositions of MORB's one can estimate concentrations of water and carbon of around 200 ppm and 80 ppm respectively in the upper mantle. Lower mantle estimates are very uncertain, but 1900 ppm water and 2000 ppm C are plausible concentrations. Measurements of the density of supercritical water to 3 GPa demonstrate that this phase is less compressible than anticipated from the equations of state of Haar et al. or Saul and Wagner and is closer to predictions based on molecular dynamics simulations. Conversely, fugacity measurements on carbon dioxide to 7 GPa show that this fluid is more compressible than predicted from the MRK equation of state. The results imply that hydrates are relatively more stable and carbonates less stable at pressures greater than 5 GPa than would be predicted from simple extrapolation of the low pressure data. Nevertheless, carbonates remain extremely refractory phases within both the upper and lower mantle.

Formation of natural gas hydrates in marine sediments. Gas hydrate growth and stability conditioned by host sediment properties

USGS Publications Warehouse

Clennell, M.B.; Henry, P.; Hovland, M.; Booth, J.S.; Winters, W.J.; Thomas, M.

2000-01-01

The stability conditions of submarine gas hydrates (methane clathrates) are largely dictated by pressure, temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of the host sediments also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our model presumes that gas hydrate behaves in a way analogous to ice in the pores of a freezing soil, where capillary forces influence the energy balance. Hydrate growth is inhibited within fine-grained sediments because of the excess internal phase pressure of small crystals with high surface curvature that coexist with liquid water in small pores. Therefore, the base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature, and so nearer to the seabed than would be calculated from bulk thermodynamic equilibrium. The growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, sheets, and lenses in muds; cements in sand and ash layers) can be explained by a requirement to minimize the excess of mechanical and surface energy in the system.

Sustainable steric stabilization of colloidal titania nanoparticles

NASA Astrophysics Data System (ADS)

Elbasuney, Sherif

2017-07-01

A route to produce a stable colloidal suspension is essential if mono-dispersed particles are to be successfully synthesized, isolated, and used in subsequent nanocomposite manufacture. Dispersing nanoparticles in fluids was found to be an important approach for avoiding poor dispersion characteristics. However, there is still a great tendency for colloidal nanoparticles to flocculate over time. Steric stabilization can prevent coagulation by introducing a thick adsorbed organic layer which constitutes a significant steric barrier that can prevent the particle surfaces from coming into direct contact. One of the main features of hydrothermal synthesis technique is that it offers novel approaches for sustainable nanoparticle surface modification. This manuscript reports on the sustainable steric stabilization of titanium dioxide nanoparticles. Nanoparticle surface modification was performed via two main approaches including post-synthesis and in situ surface modification. The tuneable hydrothermal conditions (i.e. temperature, pressure, flow rates, and surfactant addition) were optimized to enable controlled steric stabilization in a continuous fashion. Effective post synthesis surface modification with organic ligand (dodecenyl succinic anhydride (DDSA)) was achieved; the optimum surface coating temperature was reported to be 180-240 °C to ensure DDSA ring opening and binding to titania nanoparticles. Organic-modified titania demonstrated complete change in surface properties from hydrophilic to hydrophobic and exhibited phase transfer from the aqueous phase to the organic phase. Exclusive surface modification in the reactor was found to be an effective approach; it demonstrated surfactant loading level 2.2 times that of post synthesis surface modification. Titania was also stabilized in aqueous media using poly acrylic acid (PAA) as polar polymeric dispersant. PAA-titania nanoparticles demonstrated a durable amorphous polymeric layer of 2 nm thickness. This manuscript revealed the state of the art for the real development of stable colloidal mono-dispersed particles with controlled surface properties.

Physical stability, microstructure and micro-rheological properties of water-in-oil-in-water (W/O/W) emulsions stabilized by porcine gelatin.

PubMed

Zhu, Qiaomei; Qiu, Shuang; Zhang, Hongwei; Cheng, Yongqiang; Yin, Lijun

2018-07-01

Water-in-oil-in-water (W/O/W) emulsions could be utilized for fat-reduced food formulation and delivery of bioactive nutrients. However, due to thermodynamic instability, it is difficult to prepare stable double emulsions. The purpose of this study was to improve the stability of W/O/W double emulsions containing 2.0 M MgCl 2 by adding porcine gelatin in the inner water phase. The impact of gelatin on the physical stability, microstructure and micro-rheological properties of W/O/W emulsions was investigated. It was found that, when the concentration of porcine gelatin exceeded 4.0 wt%, the stability of emulsions was improved, due to increased viscoelasticity of emulsion droplets. When MgCl 2 concentration increased to 2.0 M, the particle size of emulsions increased, due to the osmotic pressure gradient, and the presence of gelatin further increased the droplet size. Confocal microscopy results showed that the presence of gelatin could improve the stability of W/O/W emulsions against coalescence。. Copyright © 2018. Published by Elsevier Ltd.

Effect of Internal Pressure and Temperature on Phase Transitions in Perovskite Oxides: The Case of the Solid Oxide Fuel Cell Cathode Materials of the La2-xSrxCoTiO6 Series.

PubMed

Gómez-Pérez, Alejandro; Hoelzel, Markus; Muñoz-Noval, Álvaro; García-Alvarado, Flaviano; Amador, Ulises

2016-12-19

The symmetry of the room-temperature (RT) structure of title compounds La 2-x Sr x CoTiO 6-δ changes with x, from P2 1 /n (0 ≤ x ≤ 0.2) to Pnma (0.3 ≤ x ≤ 0.5) and to R3̅c (0.6 ≤ x ≤ 1). For x = 1 the three pseudocubic cell parameters become very close suggesting a transition to a cubic structure for higher Sr contents. Similar phase transitions were expected to occur on heating, paralleling the effect of internal pressure induced by substitution of La 3+ by Sr 2+ . However, only some of these aforementioned transitions have been thermally induced. The symmetry-adapted modes formalism is used in the structural refinements and fitting of neutron diffraction data recorded from RT to 1273 K. Thus, for x = 1, the out-of-phase tilting of the BO 6 octahedra vanishes progressively on heating, and a cubic structure with Pm3̅m symmetry is found at 1073 K. For lower Sr contents this transition is predicted to occur far above the temperature limit of common experimental setups. The analysis of the evolution of the perovskite tolerance factor, t-factor, with both Sr content and temperature indicates that temperature has a limited ability to release structural stress and thus to enable transitions to more symmetric phases. This is particularly true when compared to the effect of internal pressure induced by substitution of La by Sr. The existence of phase transitions in materials for solid oxide fuel cells that are usually exposed to heating-cooling cycles may have a detrimental effect. This work suggests strategies to stabilize the high-symmetry high-temperature phase of perovskite oxides through internal-pressure chemically induced.

An equilibrium ab initio atomistic thermodynamics study of chlorine adsorption on the Cu(001) surface.

PubMed

Suleiman, Ibrahim A; Radny, Marian W; Gladys, Michael J; Smith, Phillip V; Mackie, John C; Kennedy, Eric M; Dlugogorski, Bogdan Z

2011-06-07

The effect of chlorine (Cl) chemisorption on the energetics and atomic structure of the Cu(001) surface over a wide range of chlorine pressures and temperatures has been studied using equilibrium ab initio atomistic thermodynamics to elucidate the formation of cuprous chloride (CuCl) as part of the Deacon reaction on copper metal. The calculated surface free energies show that the 1/2 monolayer (ML) c(2 × 2)-Cl phase with chlorine atoms adsorbed at the hollow sites is the most stable structure for a wide range of Cl chemical potential, in agreement with experimental observations. It is also found that at very low pressure and exposure, but elevated temperature, the 1/9 ML and 1/4 ML phases become the most stable. By contrast, a high coverage of Cl does not lead to thermodynamically stable geometries. The subsurface adsorption of Cl atoms, however, dramatically increases the stability of the 1 ML and 2 ML adsorption configurations providing a possible pathway for the formation of the bulk-chloride surface phases in the kinetic regime.

Stability Improvement of High-Pressure-Ratio Turbocharger Centrifugal Compressor by Asymmetrical Flow Control-Part II: Nonaxisymmetrical Self-Recirculation Casing Treatment.

PubMed

Zheng, Xinqian; Zhang, Yangjun; Yang, Mingyang; Bamba, Takahiro; Tamaki, Hideaki

2013-03-01

This is part II of a two-part paper involving the development of an asymmetrical flow control method to widen the operating range of a turbocharger centrifugal compressor with high-pressure ratio. A nonaxisymmetrical self-recirculation casing treatment (SRCT) as an instance of asymmetrical flow control method is presented. Experimental and numerical methods were used to investigate the impact of nonaxisymmetrical SRCT on the surge point of the centrifugal compressor. First, the influence of the geometry of a symmetric SRCT on the compressor performance was studied by means of numerical simulation. The key parameter of the SRCT was found to be the distance from the main blade leading edge to the rear groove (S r ). Next, several arrangements of a nonaxisymmetrical SRCT were designed, based on flow analysis presented in part I. Then, a series of experiments were carried out to analyze the influence of nonaxisymmetrical SRCT on the compressor performance. Results show that the nonaxisymmetrical SRCT has a certain influence on the performance and has a larger potential for stability improvement than the traditional symmetric SRCT. For the investigated SRCT, the surge flow rate of the compressor with the nonaxisymmetrical SRCTs is about 10% lower than that of the compressor with symmetric SRCT. The largest surge margin (smallest surge flow rate) can be obtained when the phase of the largest S r is coincident with the phase of the minimum static pressure in the vicinity of the leading edge of the splitter blades.

Ti(Ni,Cu) pseudobinary compounds as efficient negative electrodes for Ni-MH batteries

NASA Astrophysics Data System (ADS)

Emami, Hoda; Cuevas, Fermin; Latroche, Michel

2014-11-01

The effect of Ni by Cu substitution on the structural, solid-gas and electrochemical hydrogenation properties of TiNi has been investigated. Pseudo-binary TiNi1-xCux (x ≤ 0.5) compounds have been synthesized by induction melting. They crystallize in B2 structure above 350 K and either in B19‧ (x < 0.1) or B19 (0.2 ≤ x ≤ 0.5) at room temperature (RT). For all compounds, Pressure-Composition Isotherms at 423 K exhibit a single slopping plateau pressure within the range 10-3-1 MPa of hydrogen pressure revealing a metal to hydride transformation. Both the hydrogenation capacity and the hydride stability decrease with Cu-content. The hydrided pseudobinary compounds crystallize in the tetragonal S.G. I4/mmm structure as for TiNi hydride. The electrochemical discharge capacity increases with Cu content from 150 mAh g-1 for TiNi up to 300 mAh g-1 for TiNi0.8Cu0.2 and then decreases again for larger Cu amounts. Electrochemical isotherms and in-situ neutron diffraction measurements at RT demonstrate that such a capacity increase results from a metal to hydride phase transformation in which the hydride phase is destabilized by Cu substitution. The TiNi0.8Cu0.2 compound exhibits interesting cycling stability for 30 cycles and good high-rate capability at D/2 rate. This compound has promising electrochemical properties as compared to commercial LaNi5-type alloys with the advantage of being rare-earth metal free.

REFINING FLUORINATED COMPOUNDS

DOEpatents

Linch, A.L.

1963-01-01

This invention relates to the method of refining a liquid perfluorinated hydrocarbon oil containing fluorocarbons from 12 to 28 carbon atoms per molecule by distilling between 150 deg C and 300 deg C at 10 mm Hg absolute pressure. The perfluorinated oil is washed with a chlorinated lower aliphatic hydrocarbon, which mairtains a separate liquid phase when mixed with the oil. Impurities detrimental to the stability of the oil are extracted by the chlorinated lower aliphatic hydrocarbon. (AEC)