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.

Phase diagram of supercooled water confined to hydrophilic nanopores

NASA Astrophysics Data System (ADS)

Limmer, David T.; Chandler, David

2012-07-01

We present a phase diagram for water confined to cylindrical silica nanopores in terms of pressure, temperature, and pore radius. The confining cylindrical wall is hydrophilic and disordered, which has a destabilizing effect on ordered water structure. The phase diagram for this class of systems is derived from general arguments, with parameters taken from experimental observations and computer simulations and with assumptions tested by computer simulation. Phase space divides into three regions: a single liquid, a crystal-like solid, and glass. For large pores, radii exceeding 1 nm, water exhibits liquid and crystal-like behaviors, with abrupt crossovers between these regimes. For small pore radii, crystal-like behavior is unstable and water remains amorphous for all non-zero temperatures. At low enough temperatures, these states are glasses. Several experimental results for supercooled water can be understood in terms of the phase diagram we present.

Physico-Chemical Properties and Phase Behaviour of Pyrrolidinium-Based Ionic Liquids

PubMed Central

Domańska, Urszula

2010-01-01

A review of the relevant literature on 1-alkyl-1-methylpyrrolidinium-based ionic liquids has been presented. The phase diagrams for the binary systems of {1-ethyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [EMPYR][CF3SO3] + water, or + 1-butanol} and for the binary systems of {1-propyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [PMPYR][CF3SO3] + water, or + an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol)} have been determined at atmospheric pressure using a dynamic method. The influence of alcohol chain length was discussed for the [PMPYR][CF3SO3]. A systematic decrease in the solubility was observed with an increase of the alkyl chain length of an alcohol. (Solid + liquid) phase equilibria with complete miscibility in the liquid phase region were observed for the systems involving water and alcohols. The solubility of the ionic liquid increases as the alkyl chain length on the pyrrolidinium cation increases. The correlation of the experimental data has been carried out using the Wilson, UNIQUAC and the NRTL equations. The phase diagrams reported here have been compared to the systems published earlier with the 1-alkyl-1-methylpyrrolidinium-based ionic liquids. The influence of the cation and anion on the phase behaviour has been discussed. The basic thermal properties of pure ILs, i.e., melting temperature and the enthalpy of fusion, the solid-solid phase transition temperature and enthalpy have been measured using a differential scanning microcalorimetry technique. PMID:20480044

Nanophase diagram of binary eutectic Au-Ge nanoalloys for vapor-liquid-solid semiconductor nanowires growth

NASA Astrophysics Data System (ADS)

Lu, Haiming; Meng, Xiangkang

2015-06-01

Although the vapor-liquid-solid growth of semiconductor nanowire is a non-equilibrium process, the equilibrium phase diagram of binary alloy provides important guidance on the growth conditions, such as the temperature and the equilibrium composition of the alloy. Given the small dimensions of the alloy seeds and the nanowires, the known phase diagram of bulk binary alloy cannot be expected to accurately predict the behavior of the nanowire growth. Here, we developed a unified model to describe the size- and dimensionality-dependent equilibrium phase diagram of Au-Ge binary eutectic nanoalloys based on the size-dependent cohesive energy model. It is found that the liquidus curves reduce and shift leftward with decreasing size and dimensionality. Moreover, the effects of size and dimensionality on the eutectic composition are small and negligible when both components in binary eutectic alloys have the same dimensionality. However, when two components have different dimensionality (e.g. Au nanoparticle-Ge nanowire usually used in the semiconductor nanowires growth), the eutectic composition reduces with decreasing size.

A quantitative study of factors influencing lamellar eutectic morphology during solidification

NASA Technical Reports Server (NTRS)

Kaukler, W. F. S.

1981-01-01

The factors that influence the shape of the solid-liquid interface of a lamellar binary eutectic alloy are evaluated. Alloys of carbon tetrabromide and hexachloroethane which serve as a transparent analogue of lamellar metallic eutectics are used. The observed interface shapes are analyzed by computer-aided methods. The solid-liquid interfacial free energies of each of the individual phases comprising the eutectic system are measured as a function of composition using a 'grain boundary groove' technique. The solid-liquid interfacial free energy of the two phases are evaluated directly from the eutectic interface. The phase diagram for the system, the heat of fusion as a function of composition, and the density as a function of composition are measured. The shape of the eutectic interface is controlled mainly by the solid-liquid and solid-solid interfacial free energy relationships at the interface and by the temperature gradient present, rather than by interlamellar diffusion in the liquid at the interface, over the range of growth rates studied.

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.

Lattice model theory of the equation of state covering the gas, liquid, and solid phases

NASA Technical Reports Server (NTRS)

Bonavito, N. L.; Tanaka, T.; Chan, E. M.; Horiguchi, T.; Foreman, J. C.

1975-01-01

The three stable states of matter and the corresponding phase transitions were obtained with a single model. Patterned after Lennard-Jones and Devonshires's theory, a simple cubic lattice model containing two fcc sublattices (alpha and beta) is adopted. The interatomic potential is taken to be the Lennard-Jones (6-12) potential. Employing the cluster variation method, the Weiss and the pair approximations on the lattice gas failed to give the correct phase diagrams. Hybrid approximations were devised to describe the lattice term in the free energy. A lattice vibration term corresponding to a free volume correction is included semi-phenomenologically. The combinations of the lattice part and the free volume part yield the three states and the proper phase diagrams. To determine the coexistence regions, the equalities of the pressure and Gibbs free energy per molecule of the coexisting phases were utilized. The ordered branch of the free energy gives rise to the solid phase while the disordered branch yields the gas and liquid phases. It is observed that the triple point and the critical point quantities, the phase diagrams and the coexistence regions plotted are in good agreement with the experimental values and graphs for argon.

Phase equilibrium modeling for high temperature metallization on GaAs solar cells

NASA Technical Reports Server (NTRS)

Chung, M. A.; Davison, J. E.; Smith, S. R.

1991-01-01

Recent trends in performance specifications and functional requirements have brought about the need for high temperature metallization technology to be developed for survivable DOD space systems and to enhance solar cell reliability. The temperature constitution phase diagrams of selected binary and ternary systems were reviewed to determine the temperature and type of phase transformation present in the alloy systems. Of paramount interest are the liquid-solid and solid-solid transformations. Data are being utilized to aid in the selection of electrical contact materials to gallium arsenide solar cells. Published data on the phase diagrams for binary systems is readily available. However, information for ternary systems is limited. A computer model is being developed which will enable the phase equilibrium predictions for ternary systems where experimental data is lacking.

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.

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

PubMed

Makov, G; Yahel, E

2011-05-28

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

Grain boundary premelting and activated sintering in binary refractory alloys

NASA Astrophysics Data System (ADS)

Shi, Xiaomeng

Quasi-liquid intergranular film (IGF) which has been widely observed in ceramic systems can persist into sub-solidus region whereby an analogy to Grain boundary (GB) premelting can be made. In this work, a grain boundary (GB) premelting/prewetting model in a metallic system was firstly built based on the Benedictus' model and computational thermodynamics, predicting that GB disordering can start at 60-85% of the bulk solidus temperatures in selected systems. This model quantitatively explains the long-standing mystery of subsolidus activated sintering in W-Pd, W-Ni, W-Co, W-Fe and W-Cu, and it has broad applications for understanding GB-controlled transport kinetics and physical properties. Furthermore, this study demonstrates the necessity of developing GB phase diagrams as a tool for materials design. Subsequently, Grain boundary (GB) wetting and prewetting in Ni-doped Mo are systematically evaluated via characterizing well-quenched specimens and thermodynamic modeling. In contrast to prior reports, the delta-NiMo phase does not wet Mo GBs in the solid state. In the solid-liquid two-phase region, the Ni-rich liquid wets Mo GBs completely. Furthermore, high-resolution transmission electron microscopy demonstrates that nanometer-thick quasi-liquid IGFs persist at GBs into the single-phase region where the bulk liquid phase is no longer stable; this is interpreted as a case of GB prewetting. An analytical thermodynamic model is developed and validated, and this model can be extended to other systems. Furthermore, the analytical model was refined based upon Beneditus' model with correction in determining interaction contribution of interfacial energy. A calculation-based GB phase diagram for Ni-Mo binary system was created and validated by comparing with GB diffusivities determined through a series of controlled sintering experiments. The dependence of GB diffusivity on doping level and temperature was examined and compared with model-predicted GB phase diagram. The consistency between GB phase diagram and GB diffusivity was evidently observed. This study revealed the existence of quasi-liquid IGF in Ni-Mo and re-confirmed our prior hypothesis proposed through work in Ni-W system. It also demonstrated further the necessity of a GB phase diagram as a new tool to guide the materials processing or design, such as selection of sintering aid and heat-treatment.

Phase diagram of Ag-Pd bimetallic nanoclusters by molecular dynamics simulations: solid-to-liquid transition and size-dependent behavior.

PubMed

Kim, Da Hye; Kim, Hyun You; Ryu, Ji Hoon; Lee, Hyuck Mo

2009-07-07

This report on the solid-to-liquid transition region of an Ag-Pd bimetallic nanocluster is based on a constant energy microcanonical ensemble molecular dynamics simulation combined with a collision method. By varying the size and composition of an Ag-Pd bimetallic cluster, we obtained a complete solid-solution type of binary phase diagram of the Ag-Pd system. Irrespective of the size and composition of the cluster, the melting temperature of Ag-Pd bimetallic clusters is lower than that of the bulk state and rises as the cluster size and the Pd composition increase. Additionally, the slope of the phase boundaries (even though not exactly linear) is lowered when the cluster size is reduced on account of the complex relations of the surface tension, the bulk melting temperature, and the heat of fusion. The melting of the cluster initially starts at the surface layer. The initiation and propagation of a five-fold icosahedron symmetry is related to the sequential melting of the cluster.

Tuning the phase diagram of colloid-polymer mixtures via Yukawa interactions

NASA Astrophysics Data System (ADS)

González García, Álvaro; Tuinier, Remco

2016-12-01

Theory that predicts the phase behavior of interacting Yukawa spheres in a solution containing nonadsorbing polymer is presented. Our approach accounts for multiple overlap of depletion zones. It is found that additional Yukawa interactions beyond hard core interactions strongly affect the location and presence of coexistence regions and phase states. The theoretical phase diagrams are compared with Monte Carlo simulations. The agreement between the two approaches supports the validity of the theoretical approximations made and confirms that, by choosing the parameters of the interaction potentials, tuning of the binodals is possible. The critical end point characterizes the phase diagram topology. It is demonstrated how an additional Yukawa interaction shifts this point with respect to the hard sphere case. Provided a certain depletant-to-colloid size ratio for which a stable colloidal gas-liquid phase coexistence takes place for hard spheres, added direct interactions turn this into a metastable gas-liquid equilibrium. The opposite case, the induction of a stable gas-liquid coexistence where only fluid-solid was present for hard spheres, is also reported.

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.

Numerical study of the effect of the shape of the phase diagram on the eutectic freezing temperature

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

Ode, M.; Shimono, M.; Sasajima, N.

2013-09-11

To evaluate the reliability of metal-carbon eutectic systems as fixed points for the next generation of high-temperature standards the effect of thermodynamic properties related to the shape of eutectic phase diagram on the freezing temperature is investigated within the context of the numerical multi-phase-field model. The partition coefficient and liquidus slopes of the two solids involved in the eutectic reaction are varied deliberately and independently. The difference between the eutectic temperature and the freezing temperature is determined in dependence of the solid/liquid (s/l) interface shape and concentration. Where appropriate reference is made to the Jackson-Hunt analytical theory. It is shownmore » that there are mainly two typical conditions to decrease the undercooling: 1) a small liquidus slope and 2) the associated difference between the eutectic composition and the liquid composition during solidification.« less

Building of Equations of State with Numerous Phase Transitions — Application to Bismuth

NASA Astrophysics Data System (ADS)

Heuzé, Olivier

2006-07-01

We propose an algorithm to build complete equation of state EOS including several solid/solid or solid/liquid phase transitions. Each phase has its own EOS and independent parameters. The phase diagram is deduced from the thermodynamic equilibrium assumption. Until now, such an approach was used in simple cases and limited to 2 or 3 phases. We have applied it in the general case to bismuth for which up to 13 phases have been identified. This study shows the great influence of binary mixtures and triple points properties in released isentropes after shock waves.

Critical Issues for Producing UHTC-Brazed Joints: Wetting and Reactivity

NASA Astrophysics Data System (ADS)

Passerone, A.; Muolo, M. L.; Valenza, F.

2016-08-01

A brief survey is presented of the most important interaction phenomena occurring at the solid-liquid interfaces in metal-ceramic systems at high temperatures, with special attention to the most recent developments concerning wetting and joining transition metals diborides. These phenomena are described and discussed from both the experimental and theoretical points of view in relation to joining ceramic and metal-ceramic systems by means of processes in the presence of a liquid phase (brazing, TLPB etc.). It is shown that wetting and the formation of interfacial dissolution regions are the results of the competition between different phenomena: dissolution of the ceramic in the liquid phase, reaction and formation of new phases at the solid-liquid interface, and drop spreading along the substrate surface. We emphasize the role of phase diagrams to support both the design of the experiments and the choice of active alloying elements, and to interpret the evolution of the system in relation to temperature and composition. In this respect, the sessile-drop technique has been shown to be helpful in assessing critical points of newly calculated phase diagrams. These studies are essential for the design of joining processes, for the creation of composite materials, and are of a particular relevance when applied to UHTC materials.

Thermodynamics of HMX Polymorphs and HMX/RDX Mixtures

DOE PAGES

Myint, Philip C.; Nichols, Albert L.

2016-12-09

In this paper, we present thermodynamic models for the five most commonly studied phases of the energetic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX): liquid HMX and four solid polymorphs (α-, β-, γ-, and δ-HMX). We show results for the density, heat capacity, bulk modulus, and sound speed, as well as a phase diagram that illustrates the temperature and pressure regions over which the various HMX phases are most thermodynamically stable. The models are based on the same equation of state presented in our recently published paper [Myint et al., Ind. Eng. Chem. Res., 2016, 55, 2252] on another energetic material, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Wemore » combine our HMX and RDX models together so that the equation of state can also be applied to liquid and solid mixtures of HMX/RDX. This allows us to generate an HMX/RDX phase diagram and calculate the enthalpy change associated with a few different kinds of phase transitions that these mixtures may undergo. Our paper is the first to present a single equation of state that is capable of modeling both pure HMX and HMX/RDX mixtures. A distinct feature of HMX is the strongly metastable nature of its polymorphs. This has caused some ambiguity in the literature regarding the thermodynamic stability of α-HMX. Finally, by examining possible arrangements for the relative order of the six different solid-solid transition (α–β, α–γ, α–δ, β–γ, β–δ, and γ–δ) temperatures, we conclude that α-HMX must be thermodynamically stable so that the HMX phase diagram must have an α phase region.« less

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

Myint, Philip C.; Nichols, Albert L.

In this paper, we present thermodynamic models for the five most commonly studied phases of the energetic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX): liquid HMX and four solid polymorphs (α-, β-, γ-, and δ-HMX). We show results for the density, heat capacity, bulk modulus, and sound speed, as well as a phase diagram that illustrates the temperature and pressure regions over which the various HMX phases are most thermodynamically stable. The models are based on the same equation of state presented in our recently published paper [Myint et al., Ind. Eng. Chem. Res., 2016, 55, 2252] on another energetic material, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Wemore » combine our HMX and RDX models together so that the equation of state can also be applied to liquid and solid mixtures of HMX/RDX. This allows us to generate an HMX/RDX phase diagram and calculate the enthalpy change associated with a few different kinds of phase transitions that these mixtures may undergo. Our paper is the first to present a single equation of state that is capable of modeling both pure HMX and HMX/RDX mixtures. A distinct feature of HMX is the strongly metastable nature of its polymorphs. This has caused some ambiguity in the literature regarding the thermodynamic stability of α-HMX. Finally, by examining possible arrangements for the relative order of the six different solid-solid transition (α–β, α–γ, α–δ, β–γ, β–δ, and γ–δ) temperatures, we conclude that α-HMX must be thermodynamically stable so that the HMX phase diagram must have an α phase region.« less

Buckling failure of square ice-nanotube arrays constrained in graphene nanocapillaries.

PubMed

Zhu, YinBo; Wang, FengChao; Wu, HengAn

2016-08-07

Graphene confinement provides a new physical and mechanical environment with ultrahigh van der Waals pressure, resulting in new quasi-two-dimensional phases of few-layer ice. Polymorphic transition can occur in bilayer constrained water/ice system. Here, we perform a comprehensive study of the phase transition of AA-stacked bilayer water constrained within a graphene nanocapillary. The compression-limit and superheating-limit (phase) diagrams are obtained, based on the extensive molecular-dynamics simulations at numerous thermodynamic states. Liquid-to-solid, solid-to-solid, and solid-to-liquid-to-solid phase transitions are observed in the compression and superheating of bilayer water. Interestingly, there is a temperature threshold (∼275 K) in the compression-limit diagram, which indicates that the first-order and continuous-like phase transitions of bilayer water depend on the temperature. Two obviously different physical processes, compression and superheating, display similar structural evolution; that is, square ice-nanotube arrays (BL-VHDI) will bend first and then transform into bilayer triangular AA stacking ice (BL-AAI). The superheating limit of BL-VHDI exhibits local maxima, while that of BL-AAI increases monotonically. More importantly, from a mechanics point of view, we propose a novel mechanism of the transformation from BL-VHDI to BL-AAI, both for the compression and superheating limits. This structural transformation can be regarded as the "buckling failure" of the square-ice-nanotube columns, which is dominated by the lateral pressure.

Segmented nanowires displaying locally controllable properties

DOEpatents

Sutter, Eli Anguelova; Sutter, Peter Werner

2013-03-05

Vapor-liquid-solid growth of nanowires is tailored to achieve complex one-dimensional material geometries using phase diagrams determined for nanoscale materials. Segmented one-dimensional nanowires having constant composition display locally variable electronic band structures that are determined by the diameter of the nanowires. The unique electrical and optical properties of the segmented nanowires are exploited to form electronic and optoelectronic devices. Using gold-germanium as a model system, in situ transmission electron microscopy establishes, for nanometer-sized Au--Ge alloy drops at the tips of Ge nanowires (NWs), the parts of the phase diagram that determine their temperature-dependent equilibrium composition. The nanoscale phase diagram is then used to determine the exchange of material between the NW and the drop. The phase diagram for the nanoscale drop deviates significantly from that of the bulk alloy.

Communication: Phase diagram of C36 by atomistic molecular dynamics and thermodynamic integration through coexistence regions

NASA Astrophysics Data System (ADS)

Abramo, M. C.; Caccamo, C.; Costa, D.; Munaò, G.

2014-09-01

We report an atomistic molecular dynamics determination of the phase diagram of a rigid-cage model of C36. We first show that free energies obtained via thermodynamic integrations along isotherms displaying "van der Waals loops," are fully reproduced by those obtained via isothermal-isochoric integration encompassing only stable states. We find that a similar result also holds for isochoric paths crossing van der Waals regions of the isotherms, and for integrations extending to rather high densities where liquid-solid coexistence can be expected to occur. On such a basis we are able to map the whole phase diagram of C36, with resulting triple point and critical temperatures about 1770 K and 2370 K, respectively. We thus predict a 600 K window of existence of a stable liquid phase. Also, at the triple point density, we find that the structural functions and the diffusion coefficient maintain a liquid-like character down to 1400-1300 K, this indicating a wide region of possible supercooling. We discuss why all these features might render possible the observation of the melting of C36 fullerite and of its liquid state, at variance with what previously experienced for C60.

Magnetic phase diagram of underdoped YBa 2 Cu 3 O y inferred from torque magnetization and thermal conductivity

DOE PAGES

Yu, Fan; Hirschberger, Max; Loew, Toshinao; ...

2016-10-24

We obtain the magnetic phase diagram in the underdoped cuprate YBa2Cu3Oy using torque magnetometry at temperatures 0.3–70 K and magnetic fields up to 45 T. At low fields, vortices (quantized flux tubes) form a vortex solid that is strongly pinned to the lattice. At large fields, melting of the solid to a vortex liquid produces nonzero dissipation. However, the vortex liquid persists to fields above 41 T. We have also mapped out the “transition” fields at which the charge-density–wave state (observed in X-ray diffraction experiments) becomes stable. Our results show that, in intense fields, superconductivity adjusts to coexist with themore » charge-density wave, but the Cooper pairs, which define the superconducting fluid, survive to fields well above 41 T.« less

Thermal fluids for CSP systems: Alkaline nitrates/nitrites thermodynamics modelling method

NASA Astrophysics Data System (ADS)

Tizzoni, A. C.; Sau, S.; Corsaro, N.; Giaconia, A.; D'Ottavi, C.; Licoccia, S.

2016-05-01

Molten salt (MS) mixtures are used for the transport (HTF-heat transfer fluid) and storage of heat (HSM-heat storage material) in Concentration Solar Plants (CSP). In general, alkaline and earth-alkaline nitrate/nitrite mixtures are employed. Along with its upper stability temperature, the melting point (liquidus point) of a MS mixture is one of the main parameters which defines its usefulness as a HTF and HSM medium. As a result, we would like to develop a predictive model which will allow us to forecast freezing points for different MS mixture compositions; thus circumventing the need to determine experimentally the phase diagram for each MS mixture. To model ternary/quaternary phase diagram, parameters for the binary subsystems are to be determined, which is the purpose of the concerned work. In a binary system with components A and B, in phase equilibrium conditions (e.g. liquid and solid) the chemical potentials (partial molar Gibbs energy) for each component in each phase are equal. For an ideal solution it is possible to calculate the mixing (A+B) Gibbs energy:ΔG = ΔH - TΔS = RT(xAlnxA + xBlnxB) In case of non-ideal solid/liquid mixtures, such as the nitrates/nitrites compositions investigated in this work, the actual value will differ from the ideal one by an amount defined as the "mixing" (mix) Gibbs free energy. If the resulting mixtures is assumed, as indicated in the previous literature, to follow a "regular solution" model, where all the non-ideality is considered included in the enthalpy of mixing value and considering, for instance, the A component:Δ G ≡0 =(Δ HA-T Δ SA)+(ΔH¯ m i x AL-T ΔS¯ m i x AL)-(ΔH¯ m i x AS-T ΔS¯ m i x AS)where the molar partial amounts can be calculated from the total value by the Gibbs Duhem equation: (ΔH¯m i x AL=ΔHm i x-XB Ld/Δ Hm i x d XB L ) L;(ΔH¯m i x AS=ΔHm i x-XB Sd/Δ Hm i x d XB S ) S and, in general, it is possible to express the mixing enthalpy for solids and liquids as a function of the mol fraction: Δ HL m i x=XA LXB L(a1+b1XA L+c1XA LXB L),Δ HS m i x=XA SXB S(a2+b2XA S+c2XA SXB S) From the latter expressions it can be possible to modelize the phase diagram of a binary mixtures by using the a,b and c couples of parameters. To calculate those coefficients a method commonly employed in literature is to measure the mixing enthalpies, or to use one reported of the enthalpy of mixing (for instance for the liquid state) and calculate the other one using the phase diagram points. A direct ΔHmix (in solid or liquid phase) measurement can be difficult to carry out using common DSC equipment generally present in research laboratories. In fact, such determinations can be, in principle, performed, but the obtained data will be affected by large experimental errors. On the other hand, it is possible to obtain values with great precision regarding the algebraic sum of mixing enthalpies and the phase diagram trend. For this reason, only the phase diagrams are proposed to be used to calculate a, b, c parameters, and, subsequently, the total (liquid-solid algebraic sum) enthalpy of mixing will be employed to verify their validity. At this aim, a C++ code was assessed and used. Three binary mixtures were considered by combining NaNO3, KNO3 and NaNO2.

Abnormal gas-liquid-solid phase transition behaviour of water observed with in situ environmental SEM.

PubMed

Chen, Xin; Shu, Jiapei; Chen, Qing

2017-04-24

Gas-liquid-solid phase transition behaviour of water is studied with environmental scanning electron microscopy for the first time. Abnormal phenomena are observed. At a fixed pressure of 450 Pa, with the temperature set to -7 °C, direct desublimation happens, and ice grows continuously along the substrate surface. At 550 Pa, although ice is the stable phase according to the phase diagram, metastable liquid droplets first nucleate and grow to ~100-200 μm sizes. Ice crystals nucleate within the large sized droplets, grow up and fill up the droplets. Later, the ice crystals grow continuously through desublimation. At 600 Pa, the metastable liquid grows quickly, with some ice nuclei floating in it, and the liquid-solid coexistence state exists for a long time. By lowering the vapour pressure and/or increasing the substrate temperature, ice sublimates into vapour phase, and especially, the remaining ice forms a porous structure due to preferential sublimation in the concave regions, which can be explained with surface tension effect. Interestingly, although it should be forbidden for ice to transform into liquid phase when the temperature is well below 0 °C, liquid like droplets form during the ice sublimation process, which is attributed to the surface tension effect and the quasiliquid layers.

Au-Ge MEAM potential fitted to the binary phase diagram

NASA Astrophysics Data System (ADS)

Wang, Yanming; Santana, Adriano; Cai, Wei

2017-02-01

We have developed a modified embedded atom method potential for the gold-germanium (Au-Ge) binary system that is fitted to the experimental binary phase diagram. The phase diagram is obtained from the common tangent construction of the free energy curves calculated by the adiabatic switching method. While maintaining the accuracy of the melting points of pure Au and Ge, this potential reproduces the eutectic temperature, eutectic composition and the solubility of Ge in solid Au, all in good agreement with the experimental values. To demonstrate the self-consistency of the potential, we performed benchmark molecular dynamics simulations of Ge crystal growth and etching in contact with a Au-Ge liquid alloy.

Stable and metastable nanowires displaying locally controllable properties

DOEpatents

Sutter, Eli Anguelova; Sutter, Peter Werner

2014-11-18

Vapor-liquid-solid growth of nanowires is tailored to achieve complex one-dimensional material geometries using phase diagrams determined for nanoscale materials. Segmented one-dimensional nanowires having constant composition display locally variable electronic band structures that are determined by the diameter of the nanowires. The unique electrical and optical properties of the segmented nanowires are exploited to form electronic and optoelectronic devices. Using gold-germanium as a model system, in situ transmission electron microscopy establishes, for nanometer-sized Au--Ge alloy drops at the tips of Ge nanowires (NWs), the parts of the phase diagram that determine their temperature-dependent equilibrium composition. The nanoscale phase diagram is then used to determine the exchange of material between the NW and the drop. The phase diagram for the nanoscale drop deviates significantly from that of the bulk alloy.

The Cu-Li-Sn Phase Diagram: Isopleths, Liquidus Projection and Reaction Scheme

PubMed Central

Flandorfer, Hans

2016-01-01

The Cu-Li-Sn phase diagram was constructed based on XRD and DTA data of 60 different alloy compositions. Eight ternary phases and 14 binary solid phases form 44 invariant ternary reactions, which are illustrated by a Scheil-Schulz reaction scheme and a liquidus projection. Phase equilibria as a function of concentration and temperature are shown along nine isopleths. This report together with an earlier publication of our group provides for the first time comprehensive investigations of phase equilibria and respective phase diagrams. Most of the phase equilibria could be established based on our experimental results. Only in the Li-rich part where many binary and ternary compounds are present estimations had to be done which are all indicated by dashed lines. A stable ternary miscibility gap could be found which was predicted by modelling the liquid ternary phase in a recent work. The phase diagrams are a crucial input for material databases and thermodynamic optimizations regarding new anode materials for high-power Li-ion batteries. PMID:27788175

Buckling failure of square ice-nanotube arrays constrained in graphene nanocapillaries

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

Zhu, YinBo; Wang, FengChao, E-mail: wangfc@ustc.edu.cn; Wu, HengAn

Graphene confinement provides a new physical and mechanical environment with ultrahigh van der Waals pressure, resulting in new quasi-two-dimensional phases of few-layer ice. Polymorphic transition can occur in bilayer constrained water/ice system. Here, we perform a comprehensive study of the phase transition of AA-stacked bilayer water constrained within a graphene nanocapillary. The compression-limit and superheating-limit (phase) diagrams are obtained, based on the extensive molecular-dynamics simulations at numerous thermodynamic states. Liquid-to-solid, solid-to-solid, and solid-to-liquid-to-solid phase transitions are observed in the compression and superheating of bilayer water. Interestingly, there is a temperature threshold (∼275 K) in the compression-limit diagram, which indicates thatmore » the first-order and continuous-like phase transitions of bilayer water depend on the temperature. Two obviously different physical processes, compression and superheating, display similar structural evolution; that is, square ice-nanotube arrays (BL-VHDI) will bend first and then transform into bilayer triangular AA stacking ice (BL-AAI). The superheating limit of BL-VHDI exhibits local maxima, while that of BL-AAI increases monotonically. More importantly, from a mechanics point of view, we propose a novel mechanism of the transformation from BL-VHDI to BL-AAI, both for the compression and superheating limits. This structural transformation can be regarded as the “buckling failure” of the square-ice-nanotube columns, which is dominated by the lateral pressure.« less

Thermodynamic assessment of the Sn-Co lead-free solder system

NASA Astrophysics Data System (ADS)

Liu, Libin; Andersson, Cristina; Liu, Johan

2004-09-01

The Sn-Co-Cu eutectic alloy can be a less expensive alternative for the Sn-Ag-Cu alloy. In order to find the eutectic solder composition of the Sn-Co-Cu system, the Sn-Co binary system has been thoroughly assessed with the calculation of phase diagram (CALPHAD) method. The liquid phase, the FCC and HCP Co-rich solid solution, and the BCT Sn-rich solid solution have been described by the Redlich-Kister model. The Hillert-Jarl-Inden model has been used to describe the magnetic contributions to Gibbs energy in FCC and HCP. The CoSn2, CoSn, Co3Sn2_β, and Co3Sn2_α phases have been treated as stoichiometric phases. A series of thermodynamic parameters have been obtained. The calculated phase diagram and thermodynamic properties are in good agreement with the experimental data. The obtained thermodynamic data was used to extrapolate the ternary Sn-Co-Cu phase diagram. The composition of the Sn-rich eutectic point of the Sn-Co-Cu system was found to be 224°C, 0.4% Co, and 0.7% Cu.

Glass and liquid phase diagram of a polyamorphic monatomic system

NASA Astrophysics Data System (ADS)

Reisman, Shaina; Giovambattista, Nicolas

2013-02-01

We perform out-of-equilibrium molecular dynamics (MD) simulations of a monatomic system with Fermi-Jagla (FJ) pair potential interactions. This model system exhibits polyamorphism both in the liquid and glass state. The two liquids, low-density (LDL) and high-density liquid (HDL), are accessible in equilibrium MD simulations and can form two glasses, low-density (LDA) and high-density amorphous (HDA) solid, upon isobaric cooling. The FJ model exhibits many of the anomalous properties observed in water and other polyamorphic liquids and thus, it is an excellent model system to explore qualitatively the thermodynamic properties of such substances. The liquid phase behavior of the FJ model system has been previously characterized. In this work, we focus on the glass behavior of the FJ system. Specifically, we perform systematic isothermal compression and decompression simulations of LDA and HDA at different temperatures and determine "phase diagrams" for the glass state; these phase diagrams varying with the compression/decompression rate used. We obtain the LDA-to-HDA and HDA-to-LDA transition pressure loci, PLDA-HDA(T) and PHDA-LDA(T), respectively. In addition, the compression-induced amorphization line, at which the low-pressure crystal (LPC) transforms to HDA, PLPC-HDA(T), is determined. As originally proposed by Poole et al. [Phys. Rev. E 48, 4605 (1993)], 10.1103/PhysRevE.48.4605 simulations suggest that the PLDA-HDA(T) and PHDA-LDA(T) loci are extensions of the LDL-to-HDL and HDL-to-LDL spinodal lines into the glass domain. Interestingly, our simulations indicate that the PLPC-HDA(T) locus is an extension, into the glass domain, of the LPC metastability limit relative to the liquid. We discuss the effects of compression/decompression rates on the behavior of the PLDA-HDA(T), PHDA-LDA(T), PLPC-HDA(T) loci. The competition between glass polyamorphism and crystallization is also addressed. At our "fast rate," crystallization can be partially suppressed and the glass phase diagram can be related directly with the liquid phase diagram. However, at our "slow rate," crystallization cannot be prevented at intermediate temperatures, within the glass region. In these cases, multiple crystal-crystal transformations are found upon compression/decompression (polymorphism).

Glass and liquid phase diagram of a polyamorphic monatomic system.

PubMed

Reisman, Shaina; Giovambattista, Nicolas

2013-02-14

We perform out-of-equilibrium molecular dynamics (MD) simulations of a monatomic system with Fermi-Jagla (FJ) pair potential interactions. This model system exhibits polyamorphism both in the liquid and glass state. The two liquids, low-density (LDL) and high-density liquid (HDL), are accessible in equilibrium MD simulations and can form two glasses, low-density (LDA) and high-density amorphous (HDA) solid, upon isobaric cooling. The FJ model exhibits many of the anomalous properties observed in water and other polyamorphic liquids and thus, it is an excellent model system to explore qualitatively the thermodynamic properties of such substances. The liquid phase behavior of the FJ model system has been previously characterized. In this work, we focus on the glass behavior of the FJ system. Specifically, we perform systematic isothermal compression and decompression simulations of LDA and HDA at different temperatures and determine "phase diagrams" for the glass state; these phase diagrams varying with the compression/decompression rate used. We obtain the LDA-to-HDA and HDA-to-LDA transition pressure loci, P(LDA-HDA)(T) and P(HDA-LDA)(T), respectively. In addition, the compression-induced amorphization line, at which the low-pressure crystal (LPC) transforms to HDA, P(LPC-HDA)(T), is determined. As originally proposed by Poole et al. [Phys. Rev. E 48, 4605 (1993)] simulations suggest that the P(LDA-HDA)(T) and P(HDA-LDA)(T) loci are extensions of the LDL-to-HDL and HDL-to-LDL spinodal lines into the glass domain. Interestingly, our simulations indicate that the P(LPC-HDA)(T) locus is an extension, into the glass domain, of the LPC metastability limit relative to the liquid. We discuss the effects of compression/decompression rates on the behavior of the P(LDA-HDA)(T), P(HDA-LDA)(T), P(LPC-HDA)(T) loci. The competition between glass polyamorphism and crystallization is also addressed. At our "fast rate," crystallization can be partially suppressed and the glass phase diagram can be related directly with the liquid phase diagram. However, at our "slow rate," crystallization cannot be prevented at intermediate temperatures, within the glass region. In these cases, multiple crystal-crystal transformations are found upon compression/decompression (polymorphism).

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.

Numerical formulation for the prediction of solid/liquid change of a binary alloy

NASA Technical Reports Server (NTRS)

Schneider, G. E.; Tiwari, S. N.

1990-01-01

A computational model is presented for the prediction of solid/liquid phase change energy transport including the influence of free convection fluid flow in the liquid phase region. The computational model considers the velocity components of all non-liquid phase change material control volumes to be zero but fully solves the coupled mass-momentum problem within the liquid region. The thermal energy model includes the entire domain and uses an enthalpy like model and a recently developed method for handling the phase change interface nonlinearity. Convergence studies are performed and comparisons made with experimental data for two different problem specifications. The convergence studies indicate that grid independence was achieved and the comparison with experimental data indicates excellent quantitative prediction of the melt fraction evolution. Qualitative data is also provided in the form of velocity vector diagrams and isotherm plots for selected times in the evolution of both problems. The computational costs incurred are quite low by comparison with previous efforts on solving these problems.

Thermodynamic assessment and binary nucleation modeling of Sn-seeded InGaAs nanowires

NASA Astrophysics Data System (ADS)

Ghasemi, Masoomeh; Selleby, Malin; Johansson, Jonas

2017-11-01

We have performed a thermodynamic assessment of the As-Ga-In-Sn system based on the CALculation of PHAse Diagram (CALPHAD) method. This system is part of a comprehensive thermodynamic database that we are developing for nanowire materials. Specifically, the As-Ga-In-Sn can be used in modeling the growth of GaAs, InAs, and InxGa1-xAs nanowires assisted by Sn liquid seeds. In this work, the As-Sn binary, the As-Ga-Sn, As-In-Sn, and Ga-In-Sn ternary systems have been thermodynamically assessed using the CALPHAD method. We show the relevant phase diagrams and property diagrams. They all show good agreement with experimental data. Using our optimized description we have modeled the nucleation of InxGa1-xAs in the zinc blende phase from a Sn-based quaternary liquid alloy using binary nucleation modeling. We have linked the composition of the solid nucleus to the composition of the liquid phase. Eventually, we have predicted the critical size of the nucleus that forms from InAs and GaAs pairs under various conditions. We believe that our modeling can guide future experimental realization of Sn-seeded InxGa1-xAs nanowires.

Melt-Vapor Phase Diagram of the Te-S System

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystals and Polytetrehedral-Phase-Forming Alloys

NASA Technical Reports Server (NTRS)

2003-01-01

By investigating the properties of quasicrystals and quasicrystal-forming liquid alloys, we may determine the role of ordering of the liquid phase in the formation of quasicrystals, leading to a better fundamental understanding of both the quasicrystal and the liquid. A quasicrystal is solid characterized by a symmetric but non-periodic arrangement of atoms, usually in the form of an icosahedron (12 atoms, 20 triangular faces). It is theorized that the short-range order in liquids takes this same form. The degree of ordering depends on the temperature of the liquid, and affects many of the liquid s properties, including specific heat, viscosity, and electrical resistivity. The MSFC role in this project includes solidification studies, phase diagram determination, and thermophysical property measurements on the liquid quasicrystal-forming alloys, all by electrostatic levitation (ESL). The viscosity of liquid quasicrystal-forming alloys is measured by the oscillating drop method, both in the stable and undercooled liquid state. The specific heat of solid, undercooled liquid, and stable liquid are measured by the radiative cooling rate of the droplets.

High-temperature phase relations and thermodynamics in the iron-lead-sulfur system

NASA Astrophysics Data System (ADS)

Eric, R. Hurman; Ozok, Hakan

1994-01-01

The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C at X Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.

A Binary Solid-Liquid Phase Diagram Experiment Including Determination of Purity, Enthalpy of Fusion and True Melting Point.

ERIC Educational Resources Information Center

Meyer, Edwin F.; Meyer, Joseph A.

1980-01-01

Describes an experiment as an alternative to undergraduate experiments limited to high temperature metal systems or lower temperature systems involving objectionable or unstable materials. Lists six advantages of the experiment. (Author/JN)

Optimized formulation of solid self-microemulsifying sirolimus delivery systems

PubMed Central

Cho, Wonkyung; Kim, Min-Soo; Kim, Jeong-Soo; Park, Junsung; Park, Hee Jun; Cha, Kwang-Ho; Park, Jeong-Sook; Hwang, Sung-Joo

2013-01-01

Background The aim of this study was to develop an optimized solid self-microemulsifying drug delivery system (SMEDDS) formulation for sirolimus to enhance its solubility, stability, and bioavailability. Methods Excipients used for enhancing the solubility and stability of sirolimus were screened. A phase-separation test, visual observation for emulsifying efficiency, and droplet size analysis were performed. Ternary phase diagrams were constructed to optimize the liquid SMEDDS formulation. The selected liquid SMEDDS formulations were prepared into solid form. The dissolution profiles and pharmacokinetic profiles in rats were analyzed. Results In the results of the oil and cosolvent screening studies, Capryol™ Propylene glycol monocapry late (PGMC) and glycofurol exhibited the highest solubility of all oils and cosolvents, respectively. In the surfactant screening test, D-α-tocopheryl polyethylene glycol 1000 succinate (vitamin E TPGS) was determined to be the most effective stabilizer of sirolimus in pH 1.2 simulated gastric fluids. The optimal formulation determined by the construction of ternary phase diagrams was the T32 (Capryol™ PGMC:glycofurol:vitamin E TPGS = 30:30:40 weight ratio) formulation with a mean droplet size of 108.2 ± 11.4 nm. The solid SMEDDS formulations were prepared with Sucroester 15 and mannitol. The droplet size of the reconstituted solid SMEDDS showed no significant difference compared with the liquid SMEDDS. In the dissolution study, the release amounts of sirolimus from the SMEDDS formulation were significantly higher than the raw sirolimus powder. In addition, the solid SMEDDS formulation was in a more stable state than liquid SMEDDS in pH 1.2 simulated gastric fluids. The results of the pharmacokinetic study indicate that the SMEDDS formulation shows significantly greater bioavailability than the raw sirolimus powder or commercial product (Rapamune® oral solution). Conclusion The results of this study suggest the potential use of a solid SMEDDS formulation for the delivery of poorly water-soluble drugs, such as sirolimus, through oral administration. PMID:23641156

Effects of a Cooperative Learning Strategy on Teaching and Learning Phases of Matter and One-Component Phase Diagrams

ERIC Educational Resources Information Center

Doymus, Kemal

2007-01-01

This study aims to determine the effects of cooperative learning (using the jigsaw method) on students' achievement in a general chemistry course. The Chemistry Achievement Test (CAT) and Phase Achievement Test (PAT) were used. The questions on the CAT relate to solids, liquids, gases, bonding, matter, and matter states. This test was given to…

Computer Series, 83. Bits and Pieces, 34.

ERIC Educational Resources Information Center

Moore, John W., Ed.

1987-01-01

Contains seven articles about computer applications to chemistry instruction. Includes descriptions of a three-dimensional animation of a potential energy surface, numerical solutions of kinetic equations, applications for spectroscopy courses, a computer-controlled experiment on the tin/lead solid/liquid phase diagram, an inexpensive thermistor…

The Iron-Iron Carbide Phase Diagram: A Practical Guide to Some Descriptive Solid State Chemistry.

ERIC Educational Resources Information Center

Long, Gary J.; Leighly, H. P., Jr.

1982-01-01

Discusses the solid state chemistry of iron and steel in terms of the iron-iron carbide phase diagram. Suggests that this is an excellent way of introducing the phase diagram (equilibrium diagram) to undergraduate students while at the same time introducing the descriptive solid state chemistry of iron and steel. (Author/JN)

The liquid⟷amorphous transition and the high pressure phase diagram of carbon

NASA Astrophysics Data System (ADS)

Robinson, David R.; Wilson, Mark

2013-04-01

The phase diagram of carbon is mapped to high pressure using a computationally-tractable potential model. The use of a relatively simple (Tersoff-II) potential model allows a large range of phase space to be explored. The coexistence (melting) curve for the diamond crystal/liquid dyad is mapped directly by modelling the solid/liquid interfaces. The melting curve is found to be re-entrant and belongs to a conformal class of diamond/liquid coexistence curves. On supercooling the liquid a phase transition to a tetrahedral amorphous form (ta-C) is observed. The liquid ⟷ amorphous coexistence curve is mapped onto the pT plane and is found to also be re-entrant. The entropy changes for both melting and the amorphous ⟶ liquid transitions are obtained from the respective coexistence curves and the associated changes in molar volume. The structural change on amorphization is analysed at different points on the coexistence curve including for transitions that are both isochoric and isocoordinate (no change in nearest-neighbour coordination number). The conformal nature of the melting curve is highlighted with respect to the known behaviour of Si. The relationship of the observed liquid/amorphous coexistence curve to the Si low- and high-density amorphous (LDA/HDA) transition is discussed.

Equilibrium p-T Phase Diagram of Boron: Experimental Study and Thermodynamic Analysis

PubMed Central

Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.

2013-01-01

Solid-state phase transformations and melting of high-purity crystalline boron have been in situ and ex situ studied at pressures to 20 GPa in the 1500–2500 K temperature range where diffusion processes become fast and lead to formation of thermodynamically stable phases. The equilibrium phase diagram of boron has been constructed based on thermodynamic analysis of experimental and literature data. The high-temperature part of the diagram contains p-T domains of thermodynamic stability of rhombohedral β-B106, orthorhombic γ-B28, pseudo-cubic (tetragonal) t'-B52, and liquid boron (L). The positions of two triple points have been experimentally estimated, i.e. β–t'–L at ~ 8.0 GPa and ~ 2490 K; and β–γ–t' at ~ 9.6 GPa and ~ 2230 K. Finally, the proposed phase diagram explains all thermodynamic aspects of boron allotropy and significantly improves our understanding of the fifth element. PMID:23912523

How Is the Freezing Point of a Binary Mixture of Liquids Related to the Composition? A Guided Inquiry Experiment

ERIC Educational Resources Information Center

Hunnicutt, Sally S.; Grushow, Alexander; Whitnell, Rob

2017-01-01

The principles of process-oriented guided inquiry learning (POGIL) are applied to a binary solid-liquid mixtures experiment. Over the course of two learning cycles, students predict, measure, and model the phase diagram of a mixture of fatty acids. The enthalpy of fusion of each fatty acid is determined from the results. This guided inquiry…

Crystallization of carbon-oxygen mixtures in white dwarf stars.

PubMed

Horowitz, C J; Schneider, A S; Berry, D K

2010-06-11

We determine the phase diagram for dense carbon-oxygen mixtures in white dwarf (WD) star interiors using molecular dynamics simulations involving liquid and solid phases. Our phase diagram agrees well with predictions from Ogata et al. and from Medin and Cumming and gives lower melting temperatures than Segretain et al. Observations of WD crystallization in the globular cluster NGC 6397 by Winget et al. suggest that the melting temperature of WD cores is close to that for pure carbon. If this is true, our phase diagram implies that the central oxygen abundance in these stars is less than about 60%. This constraint, along with assumptions about convection in stellar evolution models, limits the effective S factor for the 12C(α,γ)16O reaction to S(300)≤170  keV b.

Thermodynamics at the nanoscale: phase diagrams of nickel-carbon nanoclusters and equilibrium constants for phase transitions

NASA Astrophysics Data System (ADS)

Engelmann, Yannick; Bogaerts, Annemie; Neyts, Erik C.

2014-09-01

Using reactive molecular dynamics simulations, the melting behavior of nickel-carbon nanoclusters is examined. The phase diagrams of icosahedral and Wulff polyhedron clusters are determined using both the Lindemann index and the potential energy. Formulae are derived for calculating the equilibrium constants and the solid and liquid fractions during a phase transition, allowing more rational determination of the melting temperature with respect to the arbitrary Lindemann value. These results give more insight into the properties of nickel-carbon nanoclusters in general and can specifically be very useful for a better understanding of the synthesis of carbon nanotubes using the catalytic chemical vapor deposition method.

Parallel Grand Canonical Monte Carlo (ParaGrandMC) Simulation Code

NASA Technical Reports Server (NTRS)

Yamakov, Vesselin I.

2016-01-01

This report provides an overview of the Parallel Grand Canonical Monte Carlo (ParaGrandMC) simulation code. This is a highly scalable parallel FORTRAN code for simulating the thermodynamic evolution of metal alloy systems at the atomic level, and predicting the thermodynamic state, phase diagram, chemical composition and mechanical properties. The code is designed to simulate multi-component alloy systems, predict solid-state phase transformations such as austenite-martensite transformations, precipitate formation, recrystallization, capillary effects at interfaces, surface absorption, etc., which can aid the design of novel metallic alloys. While the software is mainly tailored for modeling metal alloys, it can also be used for other types of solid-state systems, and to some degree for liquid or gaseous systems, including multiphase systems forming solid-liquid-gas interfaces.

Control of ice chromatographic retention mechanism by changing temperature and dopant concentration.

PubMed

Tasaki, Yuiko; Okada, Tetsuo

2011-12-15

A liquid phase coexists with solid water ice in a typical binary system, such as NaCl-water, in the temperature range between the freezing point and the eutectic point (t(eu)) of the system. In ice chromatography with salt-doped ice as the stationary phase, both solid and liquid phase can contribute to solute retention in different fashions; that is, the solid ice surface acts as an adsorbent, while a solute can be partitioned into the liquid phase. Thus, both adsorption and partition mechanisms can be utilized for ice chromatographic separation. An important feature in this approach is that the liquid phase volume can be varied by changing the temperature and the concentration of a salt incorporated into the ice stationary phase. Thus, we can control the relative contribution from the partition mechanism in the entire retention because the liquid phase volume can be estimated from the freezing depression curve. Separation selectivity can thereby be modified. The applicability of this concept has been confirmed for the solutes of different adsorption and partition abilities. The predicted retention based on thermodynamics basically agrees well with the corresponding experimental retention. However, one important inconsistency has been found. The calculation predicts a step-like discontinuity of the solute retention at t(eu) because the phase diagram suggests that the liquid phase abruptly appears at t(eu) when the temperature increases. In contrast, the corresponding experimental plots are continuous over the wider range including the subeutectic temperatures. This discrepancy is explained by the existence of the liquid phase below t(eu). A difference between predicted and measured retention factors allows the estimation of the volume of the subeutectic liquid phase.

Solid-liquid phase equilibria in the ternary system (LiBO2 + Li2CO3 + H2O) at 288.15 and 298.15 K

NASA Astrophysics Data System (ADS)

Wang, Shi-qiang; Guo, Ya-fei; Yang, Jian-sen; Deng, Tian-long

2015-12-01

Experimental studies on the solubilities and physicochemical properties including density, refractive index and pH value in the ternary systems (LiBO2 + Li2CO3 + H2O) at 288.15 and 298.15 K were determined with the method of isothermal dissolution equilibrium. Based on the experimental results, the phase diagrams and their corresponding physicochemical properties versus composition diagram in the system were plotted. In the phase diagrams of the ternary system at 288.15 and 298.15 K, there are one eutectic point and two crystallization regions corresponding to lithium metaborate octahydrate (LiBO2 · 8H2O) and lithium carbonate (Li2CO3), respectively. This system at both temperatures belongs to hydrate type I, and neither double salt nor solid solution was found. A comparison of the phase diagrams for this ternary system at 288.15 and 298.15 K shows that the solid phase numbers and exist minerals are the same, and the area of crystallization region of Li2CO3 is increased obviously with the increasing temperature while that of LiBO2 · 8H2O is decreased. The physicochemical properties (density, pH value and refractive index) of the solutions of the ternary system at two temperatures changes regularly with the increasing lithium carbonate concentration. The calculated values of density and refractive index using empirical equations of the ternary system are in good agreement with the experimental values.

Optimising Drug Solubilisation in Amorphous Polymer Dispersions: Rational Selection of Hot-melt Extrusion Processing Parameters.

PubMed

Li, Shu; Tian, Yiwei; Jones, David S; Andrews, Gavin P

2016-02-01

The aim of this article was to construct a T-ϕ phase diagram for a model drug (FD) and amorphous polymer (Eudragit® EPO) and to use this information to understand the impact of how temperature-composition coordinates influenced the final properties of the extrudate. Defining process boundaries and understanding drug solubility in polymeric carriers is of utmost importance and will help in the successful manufacture of new delivery platforms for BCS class II drugs. Physically mixed felodipine (FD)-Eudragit(®) EPO (EPO) binary mixtures with pre-determined weight fractions were analysed using DSC to measure the endset of melting and glass transition temperature. Extrudates of 10 wt% FD-EPO were processed using temperatures (110°C, 126°C, 140°C and 150°C) selected from the temperature-composition (T-ϕ) phase diagrams and processing screw speed of 20, 100 and 200rpm. Extrudates were characterised using powder X-ray diffraction (PXRD), optical, polarised light and Raman microscopy. To ensure formation of a binary amorphous drug dispersion (ADD) at a specific composition, HME processing temperatures should at least be equal to, or exceed, the corresponding temperature value on the liquid-solid curve in a F-H T-ϕ phase diagram. If extruded between the spinodal and liquid-solid curve, the lack of thermodynamic forces to attain complete drug amorphisation may be compensated for through the use of an increased screw speed. Constructing F-H T-ϕ phase diagrams are valuable not only in the understanding drug-polymer miscibility behaviour but also in rationalising the selection of important processing parameters for HME to ensure miscibility of drug and polymer.

Possible quantum liquid crystal phases of helium monolayers

NASA Astrophysics Data System (ADS)

Nakamura, S.; Matsui, K.; Matsui, T.; Fukuyama, Hiroshi

2016-11-01

The second-layer phase diagrams of 4He and 3He adsorbed on graphite are investigated. Intrinsically rounded specific-heat anomalies are observed at 1.4 and 0.9 K, respectively, over extended density regions in between the liquid and incommensurate solid phases. They are identified to anomalies associated with the Kosterlitz-Thouless-Halperin-Nelson-Young type two-dimensional melting. The prospected low temperature phase (C2 phase) is a commensurate phase or a quantum hexatic phase with quasi-bond-orientational order, both containing zero-point defectons. In either case, this would be the first atomic realization of the quantum liquid crystal, a new state of matter. From the large enhancement of the melting temperature over 3He, we propose to assign the observed anomaly of 4He-C 2 phase at 1.4 K to the hypothetical supersolid or superhexatic transition.

Shear-induced criticality near a liquid-solid transition of colloidal suspensions

NASA Astrophysics Data System (ADS)

Miyama, Masamichi J.; Sasa, Shin-Ichi

2011-02-01

We investigate colloidal suspensions under shear flow through numerical experiments. By measuring the time-correlation function of a bond-orientational order parameter, we find a divergent time scale near a transition point from a disordered fluid phase to an ordered fluid phase, where the order is characterized by a nonzero value of the bond-orientational order parameter. We also present a phase diagram in the (ρ,γ˙ex) plane, where ρ is the density of the colloidal particles and γ˙ex is the shear rate of the solvent. The transition line in the phase diagram terminates at the equilibrium transition point, while a critical region near the transition line vanishes continuously as γ˙ex→0.

Studies on the phase diagram of Pb-Fe-O system and standard molar Gibbs energy of formation of 'PbFe5O8.5' and Pb2Fe2O5

NASA Astrophysics Data System (ADS)

Sahu, Sulata Kumari; Ganesan, Rajesh; Gnanasekaran, T.

2012-07-01

Partial phase diagram of Pb-Fe-O system has been established by phase equilibration studies over a wide temperature range coupled with high temperature solid electrolyte based emf cells. Ternary oxides are found to coexist with liquid lead only at temperatures above 900 K. At temperatures below 900 K, iron oxides coexist with liquid lead. Standard molar Gibbs energy of formation of ternary oxides 'PbFe5O8.5' and Pb2Fe2O5 were determined by measuring equilibrium oxygen partial pressures over relevant phase fields using emf cells and are given by the following expressions: ΔfGmo 'PbFeO'±1.0(kJ mol)=-2208.1+0.6677(T/K) (917⩽T/K⩽1117) ΔfGmo PbFeO±0.8(kJ mol)=-1178.4+0.3724(T/K) (1050⩽T/K⩽1131) .

The phase diagram of high-pressure superionic ice

DOE PAGES

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

2015-08-28

Superionic ice is a special group of ice phases at high temperature and pressure, which may exist in ice-rich planets and exoplanets. In superionic ice liquid hydrogen coexists with a crystalline oxygen sublattice. At high pressures, the properties of superionic ice are largely unknown. Here we report evidence that from 280 GPa to 1.3 TPa, there are several competing phases within the close-packed oxygen sublattice. At even higher pressure, the close-packed structure of the oxygen sublattice becomes unstable to a new unusual superionic phase in which the oxygen sublattice takes the P2 1/c symmetry. We also discover that higher pressuremore » phases have lower transition temperatures. The diffusive hydrogen in the P2 1/c superionic phase shows strong anisotropic behaviour and forms a quasi-two-dimensional liquid. The ionic conductivity changes abruptly in the solid to close-packed superionic phase transition, but continuously in the solid to P2 1/c superionic phase transition.« less

Binary Phase Diagrams and Thermodynamic Properties of Silicon and Essential Doping Elements (Al, As, B, Bi, Ga, In, N, P, Sb and Tl)

PubMed Central

Mostafa, Ahmad; Medraj, Mamoun

2017-01-01

Fabrication of solar and electronic silicon wafers involves direct contact between solid, liquid and gas phases at near equilibrium conditions. Understanding of the phase diagrams and thermochemical properties of the Si-dopant binary systems is essential for providing processing conditions and for understanding the phase formation and transformation. In this work, ten Si-based binary phase diagrams, including Si with group IIIA elements (Al, B, Ga, In and Tl) and with group VA elements (As, Bi, N, P and Sb), have been reviewed. Each of these systems has been critically discussed on both aspects of phase diagram and thermodynamic properties. The available experimental data and thermodynamic parameters in the literature have been summarized and assessed thoroughly to provide consistent understanding of each system. Some systems were re-calculated to obtain a combination of the best evaluated phase diagram and a set of optimized thermodynamic parameters. As doping levels of solar and electronic silicon are of high technological importance, diffusion data has been presented to serve as a useful reference on the properties, behavior and quantities of metal impurities in silicon. This paper is meant to bridge the theoretical understanding of phase diagrams with the research and development of solar-grade silicon production, relying on the available information in the literature and our own analysis. PMID:28773034

Phase Diagram of Kob-Andersen-Type Binary Lennard-Jones Mixtures

NASA Astrophysics Data System (ADS)

Pedersen, Ulf R.; Schrøder, Thomas B.; Dyre, Jeppe C.

2018-04-01

The binary Kob-Andersen (KA) Lennard-Jones mixture is the standard model for computational studies of viscous liquids and the glass transition. For very long simulations, the viscous KA system crystallizes, however, by phase separating into a pure A particle phase forming a fcc crystal. We present the thermodynamic phase diagram for KA-type mixtures consisting of up to 50% small (B ) particles showing, in particular, that the melting temperature of the standard KA system at liquid density 1.2 is 1.028(3) in A particle Lennard-Jones units. At large B particle concentrations, the system crystallizes into the CsCl crystal structure. The eutectic corresponding to the fcc and CsCl structures is cutoff in a narrow interval of B particle concentrations around 26% at which the bipyramidal orthorhombic PuBr3 structure is the thermodynamically stable phase. The melting temperature's variation with B particle concentration at two constant pressures, as well as at the constant density 1.2, is estimated from simulations at pressure 10.19 using isomorph theory. Our data demonstrate approximate identity between the melting temperature and the onset temperature below which viscous dynamics appears. Finally, the nature of the solid-liquid interface is briefly discussed.

Stability of dense liquid carbon dioxide.

PubMed

Boates, Brian; Teweldeberhan, Amanuel M; Bonev, Stanimir A

2012-09-11

We present ab initio calculations of the phase diagram of liquid CO(2) and its melting curve over a wide range of pressure and temperature conditions, including those relevant to the Earth. Several distinct liquid phases are predicted up to 200 GPa and 10,000 K based on their structural and electronic characteristics. We provide evidence for a first-order liquid-liquid phase transition with a critical point near 48 GPa and 3,200 K that intersects the mantle geotherm; a liquid-liquid-solid triple point is predicted near 45 GPa and 1,850 K. Unlike known first-order transitions between thermodynamically stable liquids, the coexistence of molecular and polymeric CO(2) phases predicted here is not accompanied by metallization. The absence of an electrical anomaly would be unique among known liquid-liquid transitions. Furthermore, the previously suggested phase separation of CO(2) into its constituent elements at lower mantle conditions is examined by evaluating their Gibbs free energies. We find that liquid CO(2) does not decompose into carbon and oxygen up to at least 200 GPa and 10,000 K.

Beamline Electrostatic Levitator (BESL) for in-situ High Energy K-Ray Diffraction Studies of Levitated Solids and Liquids at High Temperature

NASA Technical Reports Server (NTRS)

Gangopadhyay, A. K.; Lee, G. W.; Kelton, K. F.; Rogers, J. R.; Goldman, A. I.; Robinson, D. S.; Rathz, T. J.; Hyers, R. W.

2005-01-01

Determinations of the phase formation sequence, the crystal structures and the thermodynamic properties of materials at high temperatures are difficult because of contamination from the sample container and environment. Containerless processing techniques, such as electrostatic (ESL), electromagnetic (EML), aerodynamic, and acoustic levitation, are most suitable these studies. An adaptation of ESL for in-situ structural studies of a wide range of materials, including metals, semiconductors, insulators using high energy (125 keV) synchrotron x-rays is described here. This beamline ESL (BESL) allows the in-situ determination of the atomic structures of equilibrium solid and liquid phases, including undercooled liquids, as well as real-time studies of solid-solid and liquid-solid phase transformations. The use of image plate (MAR345) or GE-Angio detectors enables fast (30 ms - 1s) acquisition of complete diffraction patterns over a wide q-range (4 - 140/mm). The wide temperature range (300 - 2500 K), containerless processing under high vacuum (10(exp -7) - 10(exp -8) torr), and fast data acquisition, make BESL particularly suitable for phase diagram studies of high temperature materials. An additional, critically important, feature of BESL is the ability to also make simultaneous measurement of a host of thermo-physical properties, including the specific heat, enthalpy of transformation, solidus and liquidus temperatures, density, viscosity, and surface tension; all on the same sample and simultaneous with the structural measurements.

Scheil-Gulliver Constituent Diagrams

NASA Astrophysics Data System (ADS)

Pelton, Arthur D.; Eriksson, Gunnar; Bale, Christopher W.

2017-06-01

During solidification of alloys, conditions often approach those of Scheil-Gulliver cooling in which it is assumed that solid phases, once precipitated, remain unchanged. That is, they no longer react with the liquid or with each other. In the case of equilibrium solidification, equilibrium phase diagrams provide a valuable means of visualizing the effects of composition changes upon the final microstructure. In the present study, we propose for the first time the concept of Scheil-Gulliver constituent diagrams which play the same role as that in the case of Scheil-Gulliver cooling. It is shown how these diagrams can be calculated and plotted by the currently available thermodynamic database computing systems that combine Gibbs energy minimization software with large databases of optimized thermodynamic properties of solutions and compounds. Examples calculated using the FactSage system are presented for the Al-Li and Al-Mg-Zn systems, and for the Au-Bi-Sb-Pb system and its binary and ternary subsystems.

Drowning-out crystallisation of sodium sulphate using aqueous two-phase systems.

PubMed

Taboada, M E; Graber, T A; Asenjo, J A; Andrews, B A

2000-06-23

A novel method to obtain crystals of pure, anhydrous salt, using aqueous two-phase systems was studied. A concentrated salt solution is mixed with polyethylene glycol (PEG), upon which three phases are formed: salt crystals, a PEG-rich liquid and a salt-rich liquid. After removal of the solid salt, a two-phase system is obtained. Both liquid phases are recycled, allowing the design of a continuous process, which could be exploited industrially. The phase diagram of the system water-Na2SO4-PEG 3350 at 28 degrees C was used. Several process alternatives are proposed and their economic potential is discussed. The process steps needed to produce sodium sulphate crystals include mixing, crystallisation, settling and, optionally, evaporation of water. The yield of sodium sulphate increases dramatically if an evaporation step is used.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Properties of iron alloys under the Earth's core conditions

NASA Astrophysics Data System (ADS)

Morard, Guillaume; Andrault, Denis; Antonangeli, Daniele; Bouchet, Johann

2014-05-01

The Earth's core is constituted of iron and nickel alloyed with lighter elements. In view of their affinity with the metallic phase, their relative high abundance in the solar system and their moderate volatility, a list of potential light elements have been established, including sulfur, silicon and oxygen. We will review the effects of these elements on different aspects of Fe-X high pressure phase diagrams under Earth's core conditions, such as melting temperature depression, solid-liquid partitioning during crystallization, and crystalline structure of the solid phases. Once extrapolated to the inner-outer core boundary, these petrological properties can be used to constrain the Earth's core properties.

Studies in Three Phase Gas-Liquid Fluidised Systems

NASA Astrophysics Data System (ADS)

Awofisayo, Joyce Ololade

1992-01-01

Available from UMI in association with The British Library. The work is a logical continuation of research started at Aston some years ago when studies were conducted on fermentations in bubble columns. The present work highlights typical design and operating problems that could arise in such systems as waste water, chemical, biochemical and petroleum operations involving three-phase, gas-liquid -solid fluidisation; such systems are in increasing use. It is believed that this is one of few studies concerned with "true" three-phase, gas-liquid-solid fluidised systems, and that this work will contribute significantly to closing some of the gaps in knowledge in this area. The research work was experimentally based and involved studies of the hydrodynamic parameters, phase holdups (gas and solid), particle mixing and segregation, and phase flow dynamics (flow regime and circulation patterns). The studies have focused particularly on the solid behaviour and the influence of properties of solids present on the above parameters in three-phase, gas-liquid-solid fluidised systems containing single particle components and those containing binary and ternary mixtures of particles. All particles were near spherical in shape and two particle sizes and total concentration levels were used. Experiments were carried out in two- and three-dimensional bubble columns. Quantitative results are presented in graphical form and are supported by qualitative results from visual studies which are also shown as schematic diagrams and in photographic form. Gas and solid holdup results are compared for air-water containing single, binary and ternary component particle mixtures. It should be noted that the criteria for selection of the materials used are very important if true three-phase fluidisation is to be achieved: this is very evident when comparing the results with those in the literature. The fluid flow and circulation patterns observed were assessed for validation of the generally accepted patterns, and the author believes that the present work provides more accurate insight into the modelling of liquid circulation in bubble columns. The characteristic bubbly flow at low gas velocity in a two-phase system is suppressed in the three-phase system. The degree of mixing within the system is found to be dependent on flow regime, liquid circulation and the ratio of solid phase physical properties.

Generation of 1:1 Carbamazepine:Nicotinamide cocrystals by spray drying.

PubMed

Patil, Shashank P; Modi, Sameer R; Bansal, Arvind K

2014-10-01

The present study investigates the potential of spray drying as a technique for generation of pharmaceutical cocrystals. Carbamazepine-Nicotinamide cocrystal (CNC) was chosen as model cocrystal system for this study. Firstly, CNC was generated using liquid assisted grinding and used for generation of phase solubility diagram (PSD) and ternary phase diagram (TPD). Both PSD and TPD were carefully evaluated for phase behavior of CNC when equilibrated with solvent. The undersaturated region with respect to CNC, as depicted by TPD, was selected as target region to initiate cocrystallization experiments. Various points in this region, representative of different compositions of Carbamazepine, Nicotinamide and CNC, were selected and spray drying was carried out. The spray dried product was characterized for solid state properties and was compared with CNC generated by liquid assisted grinding. Spray drying successfully generated CNC of similar quality as those generated by liquid assisted grinding. Moreover, there was no significant impact of process variables on formation of CNC. Spray drying, owing to its simplicity and industrial scalability, can be a promising method for large scale cocrystal generation. Copyright © 2014 Elsevier B.V. All rights reserved.

Amorphous ices explained in terms of nonequilibrium phase transitions in supercooled water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2013-03-01

We analyze the phase diagram of supercooled water out-of-equilibrium using concepts from space-time thermodynamics and the dynamic facilitation theory of the glass transition, together with molecular dynamics simulations. We find that when water is driven out-of-equilibrium, it can exist in multiple amorphous states. In contrast, we find that when water is at equilibrium, it can exist in only one liquid state. The amorphous non-equilibrium states are solids, distinguished from the liquid by their lack of mobility, and distinguished from each other by their different densities and local structure. This finding explains the experimentally observed polyamorphism of water as a class of nonequilibrium phenomena involving glasses of different densities. While the amorphous solids can be long lived, they are thermodynamically unstable. When allowed to relax to equilibrium, they crystallize with pathways that pass first through liquid state configurations and then to ordered ice.

Advanced methods for preparation and characterization of infrared detector materials. [mercury cadmium telluride alloys

NASA Technical Reports Server (NTRS)

Lehoczky, S. L.; Szofran, F. R.

1981-01-01

Differential thermal analysis data were obtained on mercury cadmium telluride alloys in order to establish the liquidus temperatures for the various alloy compositions. Preliminary theoretical analyses was performed to establish the ternary phase equilibrium parameters for the metal rich region of the phase diagram. Liquid-solid equilibrium parameters were determined for the pseudobinary alloy system. Phase equilibrium was calculated and Hg(l-x) Cd(x) Te alloys were directionally solidified from pseudobinary melts. Electrical resistivity and Hall coefficient measurements were obtained.

Phase diagram and high-pressure boundary of hydrate formation in the ethane-water system.

PubMed

Kurnosov, Alexander V; Ogienko, Andrey G; Goryainov, Sergei V; Larionov, Eduard G; Manakov, Andrey Y; Lihacheva, Anna Y; Aladko, Eugeny Y; Zhurko, Fridrikh V; Voronin, Vladimir I; Berger, Ivan F; Ancharov, Aleksei I

2006-11-02

Dissociation temperatures of gas hydrate formed in the ethane-water system were studied at pressures up to 1500 MPa. In situ neutron diffraction analysis and X-ray diffraction analysis in a diamond anvil cell showed that the gas hydrate formed in the ethane-water system at 340, 700, and 1840 MPa and room temperature belongs to the cubic structure I (CS-I). Raman spectra of C-C vibrations of ethane molecules in the hydrate phase, as well as the spectra of solid and liquid ethane under high-pressure conditions were studied at pressures up to 6900 MPa. Within 170-3600 MPa Raman shift of the C-C vibration mode of ethane in the hydrate phase did not show any discontinuities, which could be evidence of possible phase transformations. The upper pressure boundary of high-pressure hydrate existence was discovered at the pressure of 3600 MPa. This boundary corresponds to decomposition of the hydrate to solid ethane and ice VII. The type of phase diagram of ethane-water system was proposed in the pressure range of hydrate formation (0-3600 MPa).

Bulk and surface properties of liquid Al-Cr and Cr-Ni alloys.

PubMed

Novakovic, R

2011-06-15

The energetics of mixing and structural arrangement in liquid Al-Cr and Cr-Ni alloys has been analysed through the study of surface properties (surface tension and surface segregation), dynamic properties (chemical diffusion) and microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the framework of statistical mechanical theory in conjunction with quasi-lattice theory. The Al-Cr phase diagram exhibits the existence of different intermetallic compounds in the solid state, while that of Cr-Ni is a simple eutectic-type phase diagram at high temperatures and includes the low-temperature peritectoid reaction in the range near a CrNi(2) composition. Accordingly, the mixing behaviour in Al-Cr and Cr-Ni alloy melts was studied using the complex formation model in the weak interaction approximation and by postulating Al(8)Cr(5) and CrNi(2) chemical complexes, respectively, as energetically favoured.

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.

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.

Gel phase in hydrated calcium dipicolinate

NASA Astrophysics Data System (ADS)

Rajak, Pankaj; Mishra, Ankit; Sheng, Chunyang; Tiwari, Subodh; Krishnamoorthy, Aravind; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya

2017-11-01

The mineralization of dipicolinic acid (DPA) molecules in bacterial spore cores with Ca2+ ions to form Ca-DPA is critical to the wet-heat resistance of spores. This resistance to "wet-heat" also depends on the physical properties of water and DPA in the hydrated Ca-DPA-rich protoplasm. Using reactive molecular dynamics simulations, we have determined the phase diagram of hydrated Ca-DPA as a function of temperature and water concentration, which shows the existence of a gel phase along with distinct solid-gel and gel-liquid phase transitions. Simulations reveal monotonically decreasing solid-gel-liquid transition temperatures with increasing hydration, which explains the experimental trend of wet-heat resistance of bacterial spores. Our observation of different phases of water also reconciles previous conflicting experimental findings on the state of water in bacterial spores. Further comparison with an unmineralized hydrated DPA system allows us to quantify the importance of Ca mineralization in decreasing diffusivity and increasing the heat resistance of the spore.

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

Study of the high-pressure helium phase diagram using molecular dynamics

NASA Astrophysics Data System (ADS)

Koci, L.; Ahuja, R.; Belonoshko, A. B.; Johansson, B.

2007-01-01

The rich occurrence of helium and hydrogen in space makes their properties highly interesting. By means of molecular dynamics (MD), we have examined two interatomic potentials for 4He. Both potentials are demonstrated to reproduce high-pressure solid and liquid equation of state (EOS) data. The EOS, solid-solid transitions and melting at high pressures (P) were studied using a two-phase method. The Buckingham potential shows a good agreement with theoretical and experimental EOS, but does not reproduce experimental melting data. The Aziz potential shows a perfect match with theoretical melting data. We conclude that there is a stable body-centred-cubic (bcc) phase for 4He at temperatures (T) above 340 K and pressures above 22 GPa for the Buckingham potential, whereas no bcc phase is found for the Aziz potential in the applied PT range.

Cellular solidification of transparent monotectics

NASA Technical Reports Server (NTRS)

Kaulker, W. F.

1986-01-01

Understanding how liquid phase particles are engulfed or pushed during freezing of a monotectic is addressed. The additional complication is that the solid-liquid interface is nonplanar due to constitutional undercooling. Some evidence of particle pushing where the particles are the liquid phase of the montectic was already observed. Cellular freezing of the succinonitrile-glycerol system also occurred. Only a few compositions were tested at that time. The starting materials were not especially pure so that cellular interface observed was likely due to the presence of unkown impurities, the major portion of which was water. Topics addressed include: the effort of modeling the particle pushing process using the computer, establishing an apparatus for the determination of phase diagrams, and the measurement of the temperature gradients with a specimen which will solidify on the temperature gradient microscope stage.

Phase diagrams for understanding gold-seeded growth of GaAs and InAs nanowires

NASA Astrophysics Data System (ADS)

Ghasemi, Masoomeh; Johansson, Jonas

2017-04-01

Phase diagrams are useful tools to study the phase equilibria of nanowire materials systems because the growth of nanowires is accompanied by phase formation and phase transition. We have modeled the phase equilibria of the As-Au-Ga ternary system by means of the CALPHAD method. This method is a well-established semi-empirical technique for thermodynamic modeling in which Gibbs energy functions with free parameters are defined for all phases in a system followed by adjusting these parameters to the experimental data. Using the resulting As-Au-Ga thermodynamic database, four vertical cuts of this ternary system are calculated and all show good agreement with experiments. This ternary system is particularly useful for predicting the state of the Au seed alloys when growing GaAs nanowires and we discuss such predictions. Similar calculations are performed for Au-seeded InAs nanowires. We show that the vapor-liquid-solid (VLS) growth fails for InAs nanowires, while GaAs nanowires can grow from a liquid particle. Our calculations are in agreement with experimental data on the growth of Au-seeded GaAs and InAs nanowires.

Magnetic Phase Diagram of α-RuCl3

NASA Astrophysics Data System (ADS)

Sears, Jennifer; Kim, Young-June; Zhao, Yang; Lynn, Jeffrey

The layered honeycomb material α-RuCl3 is thought to possess unusual magnetic interactions including a strong bond-dependent Kitaev term, offering a potential opportunity to study a material near a well understood spin liquid phase. Although this material orders magnetically at low temperatures and is thus not a realization of a Kitaev spin liquid, it does show a broad continuum of magnetic excitations reminiscent of that expected for the spin liquid phase. It has also been proposed that a magnetic field could destabilize the magnetic order in this material and induce a transition into a spin liquid phase. Low temperature magnetization and specific heat measurements in this material have suggested a complex magnetic phase diagram with multiple unidentified magnetic phases present at low temperature. This has provided motivation for our work characterizing the magnetic transitions and phase diagram in α-RuCl3. I will present detailed bulk measurements combined with magnetic neutron diffraction measurements to map out the phase diagram and identify the various phases present.

Identification of polymer stabilized blue-phase liquid crystal display by chromaticity diagram

NASA Astrophysics Data System (ADS)

Lan, Yi-Fen; Tsai, Cheng-Yeh; Wang, Ling-Yung; Ku, Po-Jen; Huang, Tai-Hsiang; Liu, Chu-Yu; Sugiura, Norio

2012-04-01

We reported an identification method of blue phase liquid crystal (BPLC) display status by using Commission International de l'Éclairage (CIE) chromaticity diagram. The BPLC was injected into in-plane-switch (IPS) cell, polymer stabilized (PS) by ultraviolet cured process and analyzed by luminance colorimeter. The results of CIE chromaticity diagram showed a remarkable turning point when polymer stabilized blue phase liquid crystal II (PSBPLC-II) formed in the IPS cell. A mechanism of CIE chromaticity diagram identify PSBPLC display status was proposed, and we believe this finding will be useful to application and production of PSBPLC display.

Monolayer adsorption of noble gases on graphene

NASA Astrophysics Data System (ADS)

Maiga, Sidi M.; Gatica, Silvina M.

2018-02-01

We report our results of simulations of the adsorption of noble gases (Kr, Ar, Xe) on graphene. For Kr, we consider two configurations: supported and free-standing graphene, where atoms are adsorbed only on one or two sides of the graphene. For Ar and Xe, we studied only the case of supported graphene. For the single-side adsorption, we calculated the two-dimensional gas-liquid critical temperature for each adsorbate. We determined the different phases of the monolayers and constructed the phase diagrams. We found two-dimensional incommensurate solid phases for krypton, argon and xenon, and a two-dimensional commensurate solid phase for krypton. For double side adsorption of Kr, we do not see evidence of an ordering transition driven by the interlayer forces.

Using reweighting and free energy surface interpolation to predict solid-solid phase diagrams

NASA Astrophysics Data System (ADS)

Schieber, Natalie P.; Dybeck, Eric C.; Shirts, Michael R.

2018-04-01

Many physical properties of small organic molecules are dependent on the current crystal packing, or polymorph, of the material, including bioavailability of pharmaceuticals, optical properties of dyes, and charge transport properties of semiconductors. Predicting the most stable crystalline form at a given temperature and pressure requires determining the crystalline form with the lowest relative Gibbs free energy. Effective computational prediction of the most stable polymorph could save significant time and effort in the design of novel molecular crystalline solids or predict their behavior under new conditions. In this study, we introduce a new approach using multistate reweighting to address the problem of determining solid-solid phase diagrams and apply this approach to the phase diagram of solid benzene. For this approach, we perform sampling at a selection of temperature and pressure states in the region of interest. We use multistate reweighting methods to determine the reduced free energy differences between T and P states within a given polymorph and validate this phase diagram using several measures. The relative stability of the polymorphs at the sampled states can be successively interpolated from these points to create the phase diagram by combining these reduced free energy differences with a reference Gibbs free energy difference between polymorphs. The method also allows for straightforward estimation of uncertainties in the phase boundary. We also find that when properly implemented, multistate reweighting for phase diagram determination scales better with the size of the system than previously estimated.

A reversible transition in liquid Bi under pressure.

PubMed

Emuna, M; Matityahu, S; Yahel, E; Makov, G; Greenberg, Y

2018-01-21

The electrical resistance of solid and liquid Bi has been measured at high pressures and temperatures using a novel experimental design for high sensitivity measurements utilizing a "Paris-Edinburgh" toroid large volume press. An anomalous sharp decrease in resistivity with increasing temperature at constant pressures was observed in the region beyond melting which implies a possible novel transition in the melt. The proposed transition was observed across a range of pressures both in heating and cooling cycles of the sample demonstrating its reversibility. From the measurements it was possible to determine a "phase-line" of this transition on the Bi pressure-temperature phase diagram terminating at the melting curve.

The 3-5 semiconductor solid solution single crystal growth. [low gravity float zone growth experiments using gallium indium antimonides and cadmium tellurides

NASA Technical Reports Server (NTRS)

Gertner, E. R.

1980-01-01

Techniques used for liquid and vapor phase epitaxy of gallium indium arsenide are described and the difficulties encountered are examined. Results show that the growth of bulk III-V solid solution single crystals in a low gravity environment will not have a major technological impact. The float zone technique in a low gravity environment is demonstrated using cadmium telluride. It is shown that this approach can result in the synthesis of a class of semiconductors that can not be grown in normal gravity because of growth problems rooted in the nature of their phase diagrams.

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

Miller, D.J.; Pask, J.A.

The sintering of TiC-Ni particle compacts was studied with specific attention to effects of processing conditions. Densification was progressively inhibited with the increasing additions of free carbon to the system. These results are explained on the basis of changes in the eutectic reactions in the system, reduced solubility of TiC in the Ni-rich liquid, and decreased wetting of the solid by the liquid. Presintering hydrogen heat treatment reduced the carbon content of the TiC-Ni compacts and led to reduction in sintering rates and elevated temperatures of liquid-phase formation. Wetting experiments with hydrogen-treated materials showed a time-dependent wetting angle. These resultsmore » are discussed based on wetting theory and reactions predicted by the equilibrium ternary-phase diagram.« less

Growth and analysis of gallium arsenide-gallium antimonide single and two-phase nanoparticles

NASA Astrophysics Data System (ADS)

Schamp, Crispin T.

When evaluating the path of phase transformations in systems with nanoscopic dimensions one often relies on bulk phase diagrams for guidance because of the lack of phase diagrams that show the effect of particle size. The GaAs-GaSb pseudo-binary alloy is chosen for study to gain insight into the size dependence of solid-solubility in a two-phase system. To this end, a study is performed using independent laser ablation of high purity targets of GaAs and GaSb. The resultant samples are analyzed by transmission electron microscopy. Experimental results indicate that GaAs-GaSb nanoparticles have been formed with compositions that lie within the miscibility gap of bulk GaAs-GaSb. An unusual nanoparticle morpohology resembling the appearance of ice cream cones has been observed in single component experiments. These particles are composed of a spherical cap of Ga in contact with a crystalline cone of either GaAs or GaSb. The cones take the projected 2-D shape of a triangle or a faceted gem. The liquid Ga is found to consistently be of spherical shape and wets to the widest corners of the cone, suggesting an energy minimum exists at that wetting condition. To explore this observation a liquid sphere is modeled as being penetrated by a solid gem. The surface energies of the solid and liquid, and interfacial energy are summed as a function of penetration depth, with the sum showing a cusped minimum at the penetration depth corresponding to the waist of the gem. The angle of contact of the liquid wetting the cone is also calculated, and Young's contact angle is found to occur when the derivative of the total energy with respect to penetration depth is zero, which can be a maximum or a minimum depending on the geometrical details. The spill-over of the meniscus across the gem corners is found to be energetically favorable when the contact angle achieves the value of the equilibrium angle; otherwise the meniscus is pinned at the corners.

Phase diagram of two-dimensional hard ellipses.

PubMed

Bautista-Carbajal, Gustavo; Odriozola, Gerardo

2014-05-28

We report the phase diagram of two-dimensional hard ellipses as obtained from replica exchange Monte Carlo simulations. The replica exchange is implemented by expanding the isobaric ensemble in pressure. The phase diagram shows four regions: isotropic, nematic, plastic, and solid (letting aside the hexatic phase at the isotropic-plastic two-step transition [E. P. Bernard and W. Krauth, Phys. Rev. Lett. 107, 155704 (2011)]). At low anisotropies, the isotropic fluid turns into a plastic phase which in turn yields a solid for increasing pressure (area fraction). Intermediate anisotropies lead to a single first order transition (isotropic-solid). Finally, large anisotropies yield an isotropic-nematic transition at low pressures and a high-pressure nematic-solid transition. We obtain continuous isotropic-nematic transitions. For the transitions involving quasi-long-range positional ordering, i.e., isotropic-plastic, isotropic-solid, and nematic-solid, we observe bimodal probability density functions. This supports first order transition scenarios.

A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach

USGS Publications Warehouse

Mehta, A.P.; Makogon, T.Y.; Burruss, R.C.; Wendlandt, R.F.; Sloan, E.D.

1996-01-01

A composite phase diagram is presented for Structure H (sH) clathrate hydrates. In this work, we derived the reactions occurring among the various phases along each four-phase (Ice/Liquid water, liquid hydrocarbon, vapor, and hydrate) equilibrium line. A powerful method (though seldom used in chemical engineering) for multicomponent equilibria developed by Schreinemakers is applied to determine the relative location of all quadruple (four-phase) lines emanating from three quintuple (five-phase) points. Experimental evidence validating the approximate phase diagram is also provided. The use of Schreinemakers' rules for the development of the phase diagram is novel for hydrates, but these rules may be extended to resolve the phase space of other more complex systems commonly encountered in chemical engineering.

Hydration of dimethyldodecylamine-N-oxide: enthalpy and entropy driven processes.

PubMed

Kocherbitov, Vitaly; Söderman, Olle

2006-07-13

Dimethyldodecylamine-N-oxide (DDAO) has only one polar atom that is able to interact with water. Still, this surfactant shows very hydrophilic properties: in mixtures with water, it forms normal liquid crystalline phases and micelles. Moreover, there is data in the literature indicating that the hydration of this surfactant is driven by enthalpy while other studies show that hydration of surfactants and lipids typically is driven by entropy. Sorption calorimetry allows resolving enthalpic and entropic contributions to the free energy of hydration at constant temperature and thus directly determines the driving forces of hydration. The results of the present sorption calorimetric study show that the hydration of liquid crystalline phases of DDAO is driven by entropy, except for the hydration of the liquid crystalline lamellar phase which is co-driven by enthalpy. The exothermic heat effect of the hydration of the lamellar phase arises from formation of strong hydrogen bonds between DDAO and water. Another issue is the driving forces of the phase transitions caused by the hydration. The sorption calorimetric results show that the transitions from the lamellar to cubic and from the cubic to the hexagonal phase are driven by enthalpy. Transitions from solid phases to the liquid crystalline lamellar phase are entropically driven, while the formation of the monohydrate from the dry surfactant is driven by enthalpy. The driving forces of the transition from the hexagonal phase to the isotropic solution are close to zero. These sorption calorimetric results are in good agreement with the analysis of the binary phase diagram based on the van der Waals differential equation. The phase diagram of the DDAO-water system determined using DSC and sorption calorimetry is presented.

Predicted reentrant melting of dense hydrogen at ultra-high pressures

PubMed Central

Geng, Hua Y.; Wu, Q.

2016-01-01

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

The topological pressure-temperature phase diagram of ritonavir, an extraordinary case of crystalline dimorphism.

PubMed

Céolin, R; Rietveld, I B

2015-01-01

A topological pressure-temperature phase diagram involving the phase relationships of ritonavir forms I and II has been constructed using experimental calorimetric and volumetric data available from the literature. The triple point I-II-liquid is located at a temperature of about 407 K and a pressure as extraordinarily small as 17.5 MPa (175 bar). Thus, the less soluble solid phase (form II) will become metastable on increasing pressure. At room temperature, form I becomes stable around 100 MPa indicating that form II may turn into form I at a relatively low pressure of 1000 bar, which may occur under processing conditions such as mixing or grinding. This case is a good example for which a proper thermodynamic evaluation trumps "rules of thumb" such as the density rule. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Thermodynamic Optimization of the Ag-Bi-Cu-Ni Quaternary System: Part I, Binary Subsystems

NASA Astrophysics Data System (ADS)

Wang, Jian; Cui, Senlin; Rao, Weifeng

2018-07-01

A comprehensive literature review and thermodynamic optimization of the phase diagrams and thermodynamic properties of the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary systems are presented. CALculation of PHAse Diagrams (CALPHAD)-type thermodynamic optimization was carried out to reproduce all available and reliable experimental phase equilibrium and thermodynamic data. The modified quasichemical model was used to model the liquid solution. The compound energy formalism was utilized to describe the Gibbs energies of all terminal solid solutions and intermetallic compounds. A self-consistent thermodynamic database for the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary subsystems of the Ag-Bi-Cu-Ni quaternary system was developed. This database can be used as a guide for research and development of lead-free solders.

Thermodynamic Optimization of the Ag-Bi-Cu-Ni Quaternary System: Part I, Binary Subsystems

NASA Astrophysics Data System (ADS)

Wang, Jian; Cui, Senlin; Rao, Weifeng

2018-05-01

A comprehensive literature review and thermodynamic optimization of the phase diagrams and thermodynamic properties of the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary systems are presented. CALculation of PHAse Diagrams (CALPHAD)-type thermodynamic optimization was carried out to reproduce all available and reliable experimental phase equilibrium and thermodynamic data. The modified quasichemical model was used to model the liquid solution. The compound energy formalism was utilized to describe the Gibbs energies of all terminal solid solutions and intermetallic compounds. A self-consistent thermodynamic database for the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary subsystems of the Ag-Bi-Cu-Ni quaternary system was developed. This database can be used as a guide for research and development of lead-free solders.

Thermodynamic study of (anthracene + benzo[a]pyrene) solid mixtures

PubMed Central

Rice, James W.; Suuberg, Eric M.

2010-01-01

To characterize better the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the {anthracene (1) + benzo[a]pyrene (2)} system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at x1 = 0.26. The eutectic mixture is an amorphous solid that lacks organized crystal structure and melts between T = (414 and 420) K. For mixtures that contain 0.10 < x1 < 0.90, the enthalpy of fusion is dominated by that of the eutectic. Solid-vapor equilibrium studies show that mixtures of anthracene and benzo[a]pyrene at x1 < 0.10 sublime at the vapor pressure of pure benzo[a]pyrene. These results suggest that the solid-vapor equilibrium of benzo[a]pyrene is not significantly influenced by moderate levels of anthracene in the crystal structure. PMID:20814451

The high-pressure phase diagram of Fe(0.94)O - A possible constituent of the earth's core

NASA Technical Reports Server (NTRS)

Knittle, Elise; Jeanloz, Raymond

1991-01-01

Electrical resistivity measurements to pressures of 83 GPa and temperatures ranging from 300 K to 4300 K confirm the presence of both crystalline and liquid metallic phases of FeO at pressures above 60-70 GPa and temperatures above 1000 K. By experimentally determinig the melting temperature of FeO to 100 GPa and of a model-core composition at 83 GPa, it is found that the solid-melt equilibria can be described by complete solid solution across the Fe-FeO system at pressures above 70 GPa. The results indicate that oxygen is a viable and likely candidate for the major light alloying element of the earth's liquid outer core. The data suggest that the temperature at the core-mantle boundary is close to 4800 K and that heat lost out of the core accounts for more than 20 percent of the heat flux observed at the surface.

Metastability Gap in the Phase Diagram of Monoclonal IgG Antibody.

PubMed

Rowe, Jacob B; Cancel, Rachel A; Evangelous, Tyler D; Flynn, Rhiannon P; Pechenov, Sergei; Subramony, J Anand; Zhang, Jifeng; Wang, Ying

2017-10-17

Crystallization of IgG antibodies has important applications in the fields of structural biology, biotechnology, and biopharmaceutics. However, a rational approach to crystallize antibodies is still lacking. In this work, we report a method to estimate the solubility of antibodies at various temperatures. We experimentally determined the full phase diagram of an IgG antibody. Using the full diagram, we examined the metastability gaps, i.e., the distance between the crystal solubility line and the liquid-liquid coexistence curve, of IgG antibodies. By comparing our results to the partial phase diagrams of other IgGs reported in literature, we found that IgG antibodies have similar metastability gaps. Thereby, we present an equation with two phenomenological parameters to predict the approximate location of the solubility line of IgG antibodies with respect to their liquid-liquid coexistence curves. We have previously shown that the coexistence curve of an antibody solution can be readily determined by the polyethylene glycol-induced liquid-liquid phase separation method. Combining the polyethylene glycol-induced liquid-liquid phase separation measurements and the phenomenological equation in this article, we provide a general and practical means to predict the thermodynamic conditions for crystallizing IgG antibodies in the solution environments of interest. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Predicting the Fluid-Phase Behavior of Aqueous Solutions of ELP (VPGVG) Sequences Using SAFT-VR.

PubMed

Zhao, Binwu; Lindeboom, Tom; Benner, Steven; Jackson, George; Galindo, Amparo; Hall, Carol K

2017-10-24

The statistical associating fluid theory for potentials of variable range (SAFT-VR) is used to predict the fluid phase behavior of elastin-like polypeptide (ELP) sequences in aqueous solution with special focus on the loci of lower critical solution temperatures (LCSTs). A SAFT-VR model for these solutions is developed following a coarse-graining approach combining information from atomistic simulations and from previous SAFT models for previously reported relevant systems. Constant-pressure temperature-composition phase diagrams are determined for solutions of (VPGVG) n sequences + water with n = 1 to 300. The SAFT-VR equation of state lends itself to the straightforward calculation of phase boundaries so that complete fluid-phase equilibria can be calculated efficiently. A broad range of thermodynamic conditions of temperature and pressure are considered, and regions of vapor-liquid and liquid-liquid coexistence, including LCSTs, are found. The calculated phase boundaries at low concentrations match those measured experimentally. The temperature-composition phase diagrams of the aqueous ELP solutions at low pressure (0.1 MPa) are similar to those of types V and VI phase behavior in the classification of Scott and van Konynenburg. An analysis of the high-pressure phase behavior confirms, however, that a closed-loop liquid-liquid immiscibility region, separate from the gas-liquid envelope, is present for aqueous solutions of (VPGVG) 30 ; such a phase diagram is typical of type VI phase behavior. ELPs with shorter lengths exhibit both liquid-liquid and gas-liquid regions, both of which become less extensive as the chain length of the ELP is decreased. The strength of the hydrogen-bonding interaction is also found to affect the phase diagram of the (VPGVG) 30 system in that the liquid-liquid and gas-liquid regions expand as the hydrogen-bonding strength is decreased and shrink as it is increased. The LCSTs of the mixtures are seen to decrease as the ELP chain length is increased.

Renormalization group study of the melting of a two-dimensional system of collapsing hard disks

NASA Astrophysics Data System (ADS)

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

2017-06-01

We consider the melting of a two-dimensional system of collapsing hard disks (a system with a hard-disk potential to which a repulsive step is added) for different values of the repulsive-step width. We calculate the system phase diagram by the method of the density functional in crystallization theory using equations of the Berezinskii-Kosterlitz-Thouless-Halperin-Nelson-Young theory to determine the lines of stability with respect to the dissociation of dislocation pairs, which corresponds to the continuous transition from the solid to the hexatic phase. We show that the crystal phase can melt via a continuous transition at low densities (the transition to the hexatic phase) with a subsequent transition from the hexatic phase to the isotropic liquid and via a first-order transition. Using the solution of renormalization group equations with the presence of singular defects (dislocations) in the system taken into account, we consider the influence of the renormalization of the elastic moduli on the form of the phase diagram.

Water in Inhomogeneous Nanoconfinement: Coexistence of Multilayered Liquid and Transition to Ice Nanoribbons.

PubMed

Qiu, Hu; Zeng, Xiao Cheng; Guo, Wanlin

2015-10-27

Phase behavior and the associated phase transition of water within inhomogeneous nanoconfinement are investigated using molecular dynamics simulations. The nanoconfinement is constructed by a flat bottom plate and a convex top plate. At 300 K, the confined water can be viewed as a coexistence of monolayer, bilayer, and trilayer liquid domains to accommodate the inhomogeneous confinement. With increasing liquid density, the confined water with uneven layers transforms separately into two-dimensional ice crystals with unchanged layer number and rhombic in-plane symmetry for oxygen atoms. The monolayer water undergoes the transition first into a puckered ice nanoribbon, and the bilayer water transforms into a rhombic ice nanoribbon next, followed by the transition of trilayer water into a trilayer ice nanoribbon. The sequential localized liquid-to-solid transition within the inhomogeneous confinement can also be achieved by gradually decreasing the temperature at low liquid densities. These findings of phase behaviors of water under the inhomogeneous nanoconfinement not only extend the phase diagram of confined water but also have implications for realistic nanofluidic systems and microporous materials.

Organic alloy systems suitable for the investigation of regular binary and ternary eutectic growth

NASA Astrophysics Data System (ADS)

Sturz, L.; Witusiewicz, V. T.; Hecht, U.; Rex, S.

2004-09-01

Transparent organic alloys showing a plastic crystal phase were investigated experimentally using differential scanning calorimetry and directional solidification with respect to find a suitable model system for regular ternary eutectic growth. The temperature, enthalpy and entropy of phase transitions have been determined for a number of pure substances. A distinction of substances with and without plastic crystal phases was made from their entropy of melting. Binary phase diagrams were determined for selected plastic crystal alloys with the aim to identify eutectic reactions. Examples for lamellar and rod-like eutectic solidification microstructures in binary systems are given. The system (D)Camphor-Neopentylglycol-Succinonitrile is identified as a system that exhibits, among others, univariant and a nonvariant eutectic reaction. The ternary eutectic alloy close to the nonvariant eutectic composition solidifies with a partially faceted solid-liquid interface. However, by adding a small amount of Amino-Methyl-Propanediol (AMPD), the temperature of the nonvariant eutectic reaction and of the solid state transformation from plastic to crystalline state are shifted such, that regular eutectic growth with three distinct nonfaceted phases is observed in univariant eutectic reaction for the first time. The ternary phase diagram and examples for eutectic microstructures in the ternary and the quaternary eutectic alloy are given.

Lead sulfate nano- and microparticles in the acid plant blow-down generated at the sulfuric acid plant of the El Teniente mine, Chile.

PubMed

Barassi, Giancarlo M; Klimsa, Martin; Borrmann, Thomas; Cairns, Mathew J; Kinkel, Joachim; Valenzuela, Fernando

2014-12-01

The acid plant 'blow-down' (also called weak acid) produced at El Teniente mine in Chile was characterized. This liquid waste (tailing) is generated during the cooling and cleaning of the smelter gas prior to the production of sulfuric acid. The weak acid was composed of a liquid and a solid phase (suspended solids). The liquid phase of the sample analyzed in this study mainly contained Cu (562 mg L(-1)), SO4(2-) (32 800 mg L(-1)), Ca (1449 mg L(-1)), Fe (185 mg L(-1)), As (6 mg L(-1)), K (467 mg L(-1)) and Al (113 mg L(-1)). Additionally, the sample had a pH-value and total acidity of 0.45 and 2970 mg L(-1) as CaCO3, respectively. Hence, this waste was classified as extremely acidic and with a high metal content following the Ficklin diagram classification. Elemental analysis using atomic absorption, inductively coupled plasma, X-ray diffraction and electron microscopy showed that the suspended solids were anglesite (PbSO4) nano- and microparticles ranging from 50 nm to 500 nm in diameter.

Thermophysical Properties of Fluid Latent Heat Storage Material using Urea-Water Mixture

NASA Astrophysics Data System (ADS)

Hokamura, Taku; Ohkubo, Hidetoshi; Ashizawa, Kiyonori

This study is concerned with the measurement of thermophysical properties of a urea-water mixture with the aim of adopting the mixture as a latent heat storage material for air-conditioning systems. The urea-water mixture is made of natural substances and has a good fluidity. The urea concentration in the mixture was controlled by measuring the refractive index of the mixture. Being a multi-component substance, a urea-water solution has a liquid-solid co-existent phase on a phase-diagram. Therefore, the liquidus temperature was measured to establish a relationship between the fraction of the solid-phase and temperature. Furthermore, apparent values of specific heat and coefficient of viscosity were measured in the two-phase region where the solid phase is ice. The apparent specific heat and coefficient of viscosity were measure by using an adiabatic calorimeter and a stirring torque meter respectively. The results revealed that the urea-water mixture can probably be used as a latent heat storage material of good fluidity.

Phase diagram and high-pressure boundary of hydrate formation in the carbon dioxide-water system.

PubMed

Manakov, Andrej Yu; Dyadin, Yuriy A; Ogienko, Andrey G; Kurnosov, Alexander V; Aladko, Eugeny Ya; Larionov, Eduard G; Zhurko, Fridrih V; Voronin, Vladimir I; Berger, Ivan F; Goryainov, Sergei V; Lihacheva, Anna Yu; Ancharov, Aleksei I

2009-05-21

Experimental investigation of the phase diagram of the system carbon dioxide-water at pressures up to 2.7 GPa has been carried out in order to explain earlier controversial results on the decomposition curves of the hydrates formed in this system. According to X-ray diffraction data, solid and/or liquid phases of water and CO2 coexist in the system at room temperature within the pressure range from 0.8 to 2.6 GPa; no clathrate hydrates are observed. The results of neutron diffraction experiments involving the samples with different CO2/H2O molar ratios, and the data on the phase diagram of the system carbon dioxide-water show that CO2 hydrate of cubic structure I is the only clathrate phase present in this system under studied P-T conditions. We suppose that in the cubic structure I hydrate of CO2 multiple occupation of the large hydrate cavities with CO2 molecules takes place. At pressure of about 0.8 GPa this hydrate decomposes into components indicating the presence of the upper pressure boundary of the existence of clathrate hydrates in the system.

Equation of state of solid, liquid and gaseous tantalum from first principles

DOE PAGES

Miljacic, Ljubomir; Demers, Steven; Hong, Qi-Jun; ...

2015-09-18

Here, we present ab initio calculations of the phase diagram and the equation of state of Ta in a wide range of volumes and temperatures, with volumes from 9 to 180 Å 3/atom, temperature as high as 20000 K, and pressure up to 7 Mbars. The calculations are based on first principles, in combination with techniques of molecular dynamics, thermodynamic integration, and statistical modeling. Multiple phases are studied, including the solid, fluid, and gas single phases, as well as two-phase coexistences. We calculate the critical point by direct molecular dynamics sampling, and extend the equation of state to very lowmore » density through virial series fitting. The accuracy of the equation of state is assessed by comparing both the predicted melting curve and the critical point with previous experimental and theoretical investigations.« less

Effects of the interaction range on structural phases of flexible polymers.

PubMed

Gross, J; Neuhaus, T; Vogel, T; Bachmann, M

2013-02-21

We systematically investigate how the range of interaction between non-bonded monomers influences the formation of structural phases of elastic, flexible polymers. Massively parallel replica-exchange simulations of a generic, coarse-grained model, performed partly on graphics processing units and in multiple-gaussian modified ensembles, pave the way for the construction of the structural phase diagram, parametrized by interaction range and temperature. Conformational transitions between gas-like, liquid, and diverse solid (pseudo) phases are identified by microcanonical statistical inflection-point analysis. We find evidence for finite-size effects that cause the crossover of "collapse" and "freezing" transitions for very short interaction ranges.

Complex Fluids at Interfaces and Interfaces of Complex Fluids

NASA Astrophysics Data System (ADS)

Nouri, Mariam

The present thesis deals with two independent projects and is consequently divided into two parts. The first part details a computational study of the fluid structure of ring-shaped molecules and their positional and orientational molecular organizations in different degrees of confinement, while the second part concerns an experimental study of phase behavior and interfacial phenomena in confined colloid-polymer systems. In the first part, ring-shaped molecules are studied using Monte Carlo simulation techniques in one, two and three dimensions. The model used to describe ring-shaped molecules is composed of hard-spheres linked together to form planar rigid rings. For rings of various sizes and for a wide range of densities, positional and orientational orderings are reported in forms of pair distribution functions of the ring centers and correlation functions of the ring normal orientations. Special emphasis is given to understand structural formation at interfaces, i.e., the structure and orderings of these molecules when they are confined to two dimensions. In a plane but the rings themselves are free to rotate around all axes, nematic ordering is observed at sufficiently high densities. In the second part, phase equilibria of confined aqueous colloid-polymer systems are studied experimentally using fluorescence microscopy. Aqueous mixtures of fluorescent polystyrene spheres and polyacrylamide are confined between a glass slide and a coverslip. The phase diagram is determined as a function of the colloidal and polymer concentrations. Liquid-liquid phase coexistence between a colloid-rich phase and a polymer-rich phase occurs at intermediate polymer concentrations, while liquid-solid phase coexistence between a polymer-rich liquid and a colloid-rich solid is observed at high polymer concentrations. Interfacial thickness and tension of the interface between these coexisting phases are measured using image analysis techniques. It is also observed that the colloid-rich solid and liquid domains coarsen mainly by Ostwald ripening.

Phase Relations in Ternary Systems in the Subsolidus Region: Methods to Formulate Solid Solution Equations and to Find Particular Compositions

ERIC Educational Resources Information Center

Alvarez-Montan~o, Victor E.; Farías, Mario H.; Brown, Francisco; Mun~oz-Palma, Iliana C.; Cubillas, Fernando; Castillon-Barraza, Felipe F.

2017-01-01

A good understanding of ternary phase diagrams is required to advance and/or to reproduce experimental research in solid-state and materials chemistry. The aim of this paper is to describe the solutions to problems that appear when studying or determining ternary phase diagrams. A brief description of the principal features shown in phase diagrams…

Water, Water Everywhere: Phase Diagrams of Ordinary Water Substance

ERIC Educational Resources Information Center

Glasser, L.

2004-01-01

The full phase diagram of water in the form of a graphical representation of the three-dimensional (3D) PVT diagram using authentic data is presented. An interesting controversy regarding the phase behavior of water was the much-touted proposal of a solid phase of water, polywater, supposedly stable under atmospheric conditions.

The Binary Temperature-Composition Phase Diagram

ERIC Educational Resources Information Center

Sanders, Philip C.; Reeves, James H.; Messina, Michael

2006-01-01

The equations for the liquid and gas lines in the binary temperature-composition phase diagram are derived by approximating that delta(H)[subscript vap] of the two liquids are equal. It is shown that within this approximation, the resulting equations are not too difficult to present in an undergraduate physical chemistry lecture.

Equilibrium properties and phase diagram of two-dimensional Yukawa systems

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

Hartmann, P.; Donko, Z.; Kutasi, K.

Properties of two-dimensional strongly coupled Yukawa systems are explored through molecular dynamics simulations. An effective coupling coefficient {gamma}{sup *} for the liquid phase is introduced on the basis of the constancy of the first peak amplitude of the pair-correlation functions. Thermodynamic quantities are calculated from the pair-correlation function. The solid-liquid transition of the system is investigated through the analysis of the bond-angular order parameter. The static structure function satisfies consistency relation, attesting to the reliability of the computational method. The response is shown to be governed by the correlational part of the inverse compressibility. An analysis of the velocity autocorrelationmore » demonstrates that this latter also exhibits a universal behavior.« less

Spin crossover in solid and liquid (Mg,Fe)O at extreme conditions

NASA Astrophysics Data System (ADS)

Stixrude, Lars; Holmstrom, Eero

Ferropericlase, (Mg,Fe)O, is a major constituent of the Earth's lower mantle (24-136 GPa). Understanding the properties of this component is important not only in the solid state, but also in the molten state, as the planet almost certainly hosted an extensive magma ocean initially. With increasing pressure, the Fe ions in the material begin to collapse from a magnetic to a nonmagnetic spin state. This crossover affects thermodynamic, transport, and electrical properties. Using first-principles molecular dynamics simulations, thermodynamic integration, and adiabatic switching, we present a phase diagram of the spin crossover. In both solid and liquid, we find a broad pressure range of coexisting magnetic and non-magnetic ions due to the favorable enthalpy of mixing of the two. In the solid increasing temperature favors the high spin state, while in the liquid the opposite occurs, due to the higher electronic entropy of the low spin state. Because the physics of the crossover differ in solid and liquid, melting produces a large change in spin state that may affect the buoyancy of crystals freezing from the magma ocean in the earliest Earth. This research was supported by the European Research Council under Advanced Grant No. 291432 ``MoltenEarth'' (FP7/2007-2013).

Phase separations in mixtures of a liquid crystal and a nanocolloidal particle.

PubMed

Matsuyama, Akihiko

2009-11-28

We present a mean field theory to describe phase separations in mixtures of a liquid crystal and a nanocolloidal particle. By taking into account a nematic, a smectic A ordering of the liquid crystal, and a crystalline ordering of the nanoparticle, we calculate the phase diagrams on the temperature-concentration plane. We predict various phase separations, such as a smectic A-crystal phase separation and a smectic A-isotropic-crystal triple point, etc., depending on the interactions between the liquid crystal and the colloidal surface. Inside binodal curves, we find new unstable and metastable regions, which are important in the phase ordering dynamics. We also find a crystalline ordering of the nanoparticles dispersed in a smectic A phase and a nematic phase. The cooperative phenomena between liquid-crystalline ordering and crystalline ordering induce a variety of phase diagrams.

Thermodynamic integration based on classical atomistic simulations to determine the Gibbs energy of condensed phases: Calculation of the aluminum-zirconium system

NASA Astrophysics Data System (ADS)

Harvey, J.-P.; Gheribi, A. E.; Chartrand, P.

2012-12-01

In this work, an in silico procedure to generate a fully coherent set of thermodynamic properties obtained from classical molecular dynamics (MD) and Monte Carlo (MC) simulations is proposed. The procedure is applied to the Al-Zr system because of its importance in the development of high strength Al-Li alloys and of bulk metallic glasses. Cohesive energies of the studied condensed phases of the Al-Zr system (the liquid phase, the fcc solid solution, and various orthorhombic stoichiometric compounds) are calculated using the modified embedded atom model (MEAM) in the second-nearest-neighbor formalism (2NN). The Al-Zr MEAM-2NN potential is parameterized in this work using ab initio and experimental data found in the literature for the AlZr3-L12 structure, while its predictive ability is confirmed for several other solid structures and for the liquid phase. The thermodynamic integration (TI) method is implemented in a general MC algorithm in order to evaluate the absolute Gibbs energy of the liquid and the fcc solutions. The entropy of mixing calculated from the TI method, combined to the enthalpy of mixing and the heat capacity data generated from MD/MC simulations performed in the isobaric-isothermal/canonical (NPT/NVT) ensembles are used to parameterize the Gibbs energy function of all the condensed phases in the Al-rich side of the Al-Zr system in a CALculation of PHAse Diagrams (CALPHAD) approach. The modified quasichemical model in the pair approximation (MQMPA) and the cluster variation method (CVM) in the tetrahedron approximation are used to define the Gibbs energy of the liquid and the fcc solid solution respectively for their entire range of composition. Thermodynamic and structural data generated from our MD/MC simulations are used as input data to parameterize these thermodynamic models. A detailed analysis of the validity and transferability of the Al-Zr MEAM-2NN potential is presented throughout our work by comparing the predicted properties obtained from this formalism with available ab initio and experimental data for both liquid and solid phases.

Atomic density functional and diagram of structures in the phase field crystal model

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

Ankudinov, V. E., E-mail: vladimir@ankudinov.org; Galenko, P. K.; Kropotin, N. V.

2016-02-15

The phase field crystal model provides a continual description of the atomic density over the diffusion time of reactions. We consider a homogeneous structure (liquid) and a perfect periodic crystal, which are constructed from the one-mode approximation of the phase field crystal model. A diagram of 2D structures is constructed from the analytic solutions of the model using atomic density functionals. The diagram predicts equilibrium atomic configurations for transitions from the metastable state and includes the domains of existence of homogeneous, triangular, and striped structures corresponding to a liquid, a body-centered cubic crystal, and a longitudinal cross section of cylindricalmore » tubes. The method developed here is employed for constructing the diagram for the homogeneous liquid phase and the body-centered iron lattice. The expression for the free energy is derived analytically from density functional theory. The specific features of approximating the phase field crystal model are compared with the approximations and conclusions of the weak crystallization and 2D melting theories.« less

Separation of non-racemic mixtures of enantiomers: an essential part of optical resolution.

PubMed

Faigl, Ferenc; Fogassy, Elemér; Nógrádi, Mihály; Pálovics, Emese; Schindler, József

2010-03-07

Non-racemic enantiomeric mixtures form homochiral and heterochiral aggregates in melt or suspension, during adsorption or recrystallization, and these diastereomeric associations determine the distribution of the enantiomers between the solid and other (liquid or vapour) phases. That distribution depends on the stability order of the homo- and heterochiral aggregates (conglomerate or racemate formation). Therefore, there is a correlation between the binary melting point phase diagrams and the experimental ee(I)vs. ee(0) curves (ee(I) refers to the crystallized enantiomeric mixtures, ee(0) is the composition of the starting ones). Accordingly, distribution of the enantiomeric mixtures between two phases is characteristic and usually significant enrichment can be achieved. There are two exceptions: no enrichment could be observed under thermodynamically controlled conditions when the starting enantiomer composition corresponded to the eutectic composition, or when the method used was unsuitable for separation. In several cases, when kinetic control governed the crystallization, the character of the ee(0)-ee(I) curve did not correlate with the melting point binary phase diagram.

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.

Stabilizing the hexagonal close packed structure of hard spheres with polymers: Phase diagram, structure, and dynamics

NASA Astrophysics Data System (ADS)

Edison, John R.; Dasgupta, Tonnishtha; Dijkstra, Marjolein

2016-08-01

We study the phase behaviour of a binary mixture of colloidal hard spheres and freely jointed chains of beads using Monte Carlo simulations. Recently Panagiotopoulos and co-workers predicted [Nat. Commun. 5, 4472 (2014)] that the hexagonal close packed (HCP) structure of hard spheres can be stabilized in such a mixture due to the interplay between polymer and the void structure in the crystal phase. Their predictions were based on estimates of the free-energy penalty for adding a single hard polymer chain in the HCP and the competing face centered cubic (FCC) phase. Here we calculate the phase diagram using free-energy calculations of the full binary mixture and find a broad fluid-solid coexistence region and a metastable gas-liquid coexistence region. For the colloid-monomer size ratio considered in this work, we find that the HCP phase is only stable in a small window at relatively high polymer reservoir packing fractions, where the coexisting HCP phase is nearly close packed. Additionally we investigate the structure and dynamic behaviour of these mixtures.

The Effect of Molecular Orientation to Solid-Solid and Melting Transitions

NASA Astrophysics Data System (ADS)

Yazici, Mustafa; Özgan, Şükrü

The thermodynamics of solid-solid and solid-liquid transitions are investigated with an account of the number of molecular orientation. The variations of the positional and orientational orders with the reduced temperature are studied. It is found out that orientational order parameter is very sensitive to the number of allowed orientation. The reduced transition temperatures, volume changes and entropy changes of the phase transitions and theoretical phase diagrams are obtained. The entropy changes of melting transitions for different numbers of allowed orientation of the present model are compared with the theoretical results and some experimental data. The quantitative predictions of the model are compared with experimental results for plastic crystals and agreement between predictions of the model and the experimental results are approximately good. Also, different numbers of allowed orientation D correspond to different experimental results HI, HBr, H2S for D = 2; HBr, CCl4, HI for D = 4; C2H12 for D = 6; CH4, PH3 for D = 20.

Lyotropic liquid crystalline phase behaviour in amphiphile-protic ionic liquid systems.

PubMed

Chen, Zhengfei; Greaves, Tamar L; Fong, Celesta; Caruso, Rachel A; Drummond, Calum J

2012-03-21

Approximate partial phase diagrams for nine amphiphile-protic ionic liquid (PIL) systems have been determined by synchrotron source small angle X-ray scattering, differential scanning calorimetry and cross polarised optical microscopy. The binary phase diagrams of some common cationic (hexadecyltrimethyl ammonium chloride, CTAC, and hexadecylpyridinium bromide, HDPB) and nonionic (polyoxyethylene (10) oleyl ether, Brij 97, and Pluronic block copolymer, P123) amphiphiles with the PILs, ethylammonium nitrate (EAN), ethanolammonium nitrate (EOAN) and diethanolammonium formate (DEOAF), have been studied. The phase diagrams were constructed for concentrations from 10 wt% to 80 wt% amphiphile, in the temperature range 25 °C to >100 °C. Lyotropic liquid crystalline phases (hexagonal, cubic and lamellar) were formed at high surfactant concentrations (typically >50 wt%), whereas at <40 wt%, only micelles or polydisperse crystals were present. With the exception of Brij 97, the thermal stability of the phases formed by these surfactants persisted to temperatures above 100 °C. The phase behaviour of amphiphile-PIL systems was interpreted by considering the PIL cohesive energy, liquid nanoscale order, polarity and ionicity. For comparison the phase behaviour of the four amphiphiles was also studied in water.

Impact of Metal Droplets: A Numerical Approach to Solidification

NASA Astrophysics Data System (ADS)

Koldeweij, Robin; Mandamparambil, Rajesh; Lohse, Detlef

2016-11-01

Layer-wise deposition of material to produce complex products is a subject of increasing technological relevance. Subsequent deposition of droplets is one of the possible 3d printing technologies to accomplish this. The shape of the solidified droplet is crucial for product quality. We employ the volume-of-fluid method (in the form of the open-source code Gerris) to study liquid metal (in particular tin) droplet impact. Heat transfer has been implemented based on the enthalpy approach for the liquid-solid phase. Solidification is modeled by adding a sink term to the momentum equations, reducing Navier-Stokes to Darcy's law for high solid fraction. Good agreement is found when validating the results against experimental data. We then map out a phase diagram in which we distinguish between solidification behavior based on Weber and Stefan number. In an intermediate impact regime impact, solidification due to a retracting phase occurs. In this regime the maximum spreading diameter almost exclusively depends on Weber number. Droplet shape oscillations lead to a broad variation of the morphology of the solidified droplet and determine the final droplet height. TNO.

Practical physics behind growing crystals of biological macromolecules.

PubMed

Candoni, Nadine; Grossier, Romain; Hammadi, Zoubida; Morin, Roger; Veesler, Stéphane

2012-07-01

The aim of this review is to provide biocrystallographers who intend to tackle protein-crystallization with theory and practical examples. Crystallization involves two separate processes, nucleation and growth, which are rarely completely unconnected. Here we give theoretical background and concrete examples illustrating protein crystallization. We describe the nucleation of a new phase, solid or liquid, and the growth and transformation of existing crystals obtained by primary or secondary nucleation or by seeding. Above all, we believe that a thorough knowledge of the phase diagram is vital to the selection of starting position and path for any crystallization experiment.

Thermodynamic Modeling of the YO(l.5)-ZrO2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

2003-01-01

The YO1.5-ZrO2 system consists of five solid solutions, one liquid solution, and one intermediate compound. A thermodynamic description of this system is developed, which allows calculation of the phase diagram and thermodynamic properties. Two different solution models are used-a neutral species model with YO1.5 and ZrO2 as the components and a charged species model with Y(+3), Zr(+4), O(-2), and vacancies as components. For each model, regular and sub-regular solution parameters are derived fiom selected equilibrium phase and thermodynamic data.

Nature of the first-order liquid-liquid phase transition in supercooled silicon

NASA Astrophysics Data System (ADS)

Zhao, G.; Yu, Y. J.; Tan, X. M.

2015-08-01

The first-order liquid-liquid phase transition in supercooled Si is revisited by long-time first-principle molecular dynamics simulations. As the focus of the present paper, its nature is revealed by analyzing the inherent structures of low-density liquid (LDL) and high-density liquid (HDL). Our results show that it is a transition between a sp3-hybridization LDL and a white-tin-like HDL. This uncovers the origin of the semimetal-metal transition accompanying it and also proves that HDL is the metastable extension of high temperature equilibrium liquid into the supercooled regime. The pressure-temperature diagram of supercooled Si thus can be regarded in some respects as shifted reflection of its crystalline phase diagram.

Silicon Nitride Equation of State

NASA Astrophysics Data System (ADS)

Swaminathan, Pazhayannur; Brown, Robert

2015-06-01

This report presents the development a global, multi-phase equation of state (EOS) for the ceramic silicon nitride (Si3N4) . Structural forms include amorphous silicon nitride normally used as a thin film and three crystalline polymorphs. Crystalline phases include hexagonal α-Si3N4, hexagonalβ-Si3N4, and the cubic spinel c-Si3N4. Decomposition at about 1900 °C results in a liquid silicon phase and gas phase products such as molecular nitrogen, atomic nitrogen, and atomic silicon. The silicon nitride EOS was developed using EOSPro which is a new and extended version of the PANDA II code. Both codes are valuable tools and have been used successfully for a variety of material classes. Both PANDA II and EOSPro can generate a tabular EOS that can be used in conjunction with hydrocodes. The paper describes the development efforts for the component solid phases and presents results obtained using the EOSPro phase transition model to investigate the solid-solid phase transitions in relation to the available shock data. Furthermore, the EOSPro mixture model is used to develop a model for the decomposition products and then combined with the single component solid models to study the global phase diagram. Sponsored by the NASA Goddard Space Flight Center Living With a Star program office.

Mixed Stationary Liquid Phases for Gas-Liquid Chromatography.

ERIC Educational Resources Information Center

Koury, Albert M.; Parcher, Jon F.

1979-01-01

Describes a laboratory technique for use in an undergraduate instrumental analysis course that, using the interpretation of window diagrams, prepares a mixed liquid phase column for gas-liquid chromatography. A detailed procedure is provided. (BT)

Determination of protein phase diagrams by microbatch experiments: exploring the influence of precipitants and pH.

PubMed

Baumgartner, Kai; Galm, Lara; Nötzold, Juliane; Sigloch, Heike; Morgenstern, Josefine; Schleining, Kristina; Suhm, Susanna; Oelmeier, Stefan A; Hubbuch, Jürgen

2015-02-01

Knowledge of protein phase behavior is essential for downstream process design in the biopharmaceutical industry. Proteins can either be soluble, crystalline or precipitated. Additionally liquid-liquid phase separation, gelation and skin formation can occur. A method to generate phase diagrams in high throughput on an automated liquid handling station in microbatch scale was developed. For lysozyme from chicken egg white, human lysozyme, glucose oxidase and glucose isomerase phase diagrams were generated at four different pH values – pH 3, 5, 7 and 9. Sodium chloride, ammonium sulfate, polyethylene glycol 300 and polyethylene glycol 1000 were used as precipitants. Crystallizing conditions could be found for lysozyme from chicken egg white using sodium chloride, for human lysozyme using sodium chloride or ammonium sulfate and glucose isomerase using ammonium sulfate. PEG caused destabilization of human lysozyme and glucose oxidase solutions or a balance of stabilizing and destabilizing effects for glucose isomerase near the isoelectric point. This work presents a systematic generation and extensive study of phase diagrams of proteins. Thus, it adds to the general understanding of protein behavior in liquid formulation and presents a convenient methodology applicable to any protein solution. Copyright © 2014 Elsevier B.V. All rights reserved.

On the existence of vapor-liquid phase transition in dusty plasmas

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

Kundu, M.; Sen, A.; Ganesh, R.

2014-10-15

The phenomenon of phase transition in a dusty-plasma system (DPS) has attracted some attention in the past. Earlier Farouki and Hamaguchi [J. Chem. Phys. 101, 9876 (1994)] have demonstrated the existence of a liquid to solid transition in DPS where the dust particles interact through a Yukawa potential. However, the question of the existence of a vapor-liquid (VL) transition in such a system remains unanswered and relatively unexplored so far. We have investigated this problem by performing extensive molecular dynamics simulations which show that the VL transition does not have a critical curve in the pressure versus volume diagram formore » a large range of the Yukawa screening parameter κ and the Coulomb coupling parameter Γ. Thus, the VL phase transition is found to be super-critical, meaning that this transition is continuous in the dusty plasma model given by Farouki and Hamaguchi. We provide an approximate analytic explanation of this finding by means of a simple model calculation.« less

Experimental Determination of the Phase Diagram of the CaO-SiO2-5 pctMgO-10 pctAl2O3-TiO2 System

NASA Astrophysics Data System (ADS)

Shi, Junjie; Sun, Lifeng; Zhang, Bo; Liu, Xuqiang; Qiu, Jiyu; Wang, Zhaoyun; Jiang, Maofa

2016-02-01

Ti-bearing CaO-SiO2-MgO-Al2O3-TiO2 slags are important for the smelting of vanadium-titanium bearing magnetite. In the current study, the pseudo-melting temperatures were determined by the single-hot thermocouple technique for the specified content of 5 to 25 pct TiO2 in the CaO-SiO2-5 pctMgO-10 pctAl2O3-TiO2 phase diagram system. The 1573 K to 1773 K (1300 °C to 1500 °C) liquidus lines were first calculated based on the pseudo-melting temperatures according to thermodynamic equations in the specific primary crystal field. The phase equilibria at 1573 K (1300 °C) were determined experimentally using the high-temperature equilibrium and quench method followed by X-ray fluorescence, X-ray diffraction, scanning electron microscope, and energy dispersive X-ray spectroscope analysis; the liquid phase, melilite solid solution phase (C2MS2,C2AS)ss, and perovskite phase of CaO·TiO2 were found. Therefore, the phase diagram was constructed for the specified region of the CaO-SiO2-5 pctMgO-10 pctAl2O3-TiO2 system.

An epistemology on the nature of polymers.

PubMed

Laridjani, Mortéza; Leboucher, Pierre

2014-01-01

Liquids have neither a periodic structure nor the completely random character of gases therefore the detailed study of their x-ray scattering diagram encounters many difficulties. The idea of periodic regularity in molecules of liquid polymers has been an attractive proposition for the simple interpretation of liquid polymer x-ray diagrams. The categorisation of polymer substances as being between a crystal phase with a perfect order and an amorphous disordered state is an over simplification of the complex reality. For obtaining structural information, during the early stages of the application of x-ray diffraction, a near crystalline model of the molecular arrangements in liquids was utilised. However, the results from these investigations led to just an approximation of the crystalline state. Our studies have analysed the real image of Fourier space of liquid polymers, for the first time, using anomalous diffractometry. The findings show the precise atomic structure of liquid polymers when transformed, by cooling, to solid polymers. We demonstrate that there is an intermediate ordered structure, characterised by the real full image of Fourier space. This prominent state of matter, an intermediate ordered structure, is defined by a regular unit cell with a five-fold symmetry. These structural atomic studies contribute to a more detailed understanding of the properties of polymers than the traditional studies of the degree of crystallinity.

An Epistemology on the Nature of Polymers

PubMed Central

Laridjani, Mortéza; Leboucher, Pierre

2014-01-01

Liquids have neither a periodic structure nor the completely random character of gases therefore the detailed study of their x-ray scattering diagram encounters many difficulties. The idea of periodic regularity in molecules of liquid polymers has been an attractive proposition for the simple interpretation of liquid polymer x-ray diagrams. The categorisation of polymer substances as being between a crystal phase with a perfect order and an amorphous disordered state is an over simplification of the complex reality. For obtaining structural information, during the early stages of the application of x-ray diffraction, a near crystalline model of the molecular arrangements in liquids was utilised. However, the results from these investigations led to just an approximation of the crystalline state. Our studies have analysed the real image of Fourier space of liquid polymers, for the first time, using anomalous diffractometry. The findings show the precise atomic structure of liquid polymers when transformed, by cooling, to solid polymers. We demonstrate that there is an intermediate ordered structure, characterised by the real full image of Fourier space. This prominent state of matter, an intermediate ordered structure, is defined by a regular unit cell with a five-fold symmetry. These structural atomic studies contribute to a more detailed understanding of the properties of polymers than the traditional studies of the degree of crystallinity. PMID:25329440

Enhancement of superconductivity under pressure and the magnetic phase diagram of tantalum disulfide single crystals

PubMed Central

Abdel-Hafiez, M.; Zhao, X.-M.; Kordyuk, A. A.; Fang, Y.-W.; Pan, B.; He, Z.; Duan, C.-G.; Zhao, J.; Chen, X.-J.

2016-01-01

In low-dimensional electron systems, charge density waves (CDW) and superconductivity are two of the most fundamental collective quantum phenomena. For all known quasi-two-dimensional superconductors, the origin and exact boundary of the electronic orderings and superconductivity are still attractive problems. Through transport and thermodynamic measurements, we report on the field-temperature phase diagram in 2H-TaS2 single crystals. We show that the superconducting transition temperature (Tc) increases by one order of magnitude from temperatures at 0.98 K up to 9.15 K at 8.7 GPa when the Tc becomes very sharp. Additionally, the effects of 8.7 GPa illustrate a suppression of the CDW ground state, with critically small Fermi surfaces. Below the Tc the lattice of magnetic flux lines melts from a solid-like state to a broad vortex liquid phase region. Our measurements indicate an unconventional s-wave-like picture with two energy gaps evidencing its multi-band nature. PMID:27534898

Coupling geodynamic with thermodynamic modelling for reconstructions of magmatic systems

NASA Astrophysics Data System (ADS)

Rummel, Lisa; Kaus, Boris J. P.; White, Richard

2016-04-01

Coupling geodynamic with petrological models is fundamental for understanding magmatic systems from the melting source in the mantle to the point of magma crystallisation in the upper crust. Most geodynamic codes use very simplified petrological models consisting of a single, fixed, chemistry. Here, we develop a method to better track the petrological evolution of the source rock and corresponding volcanic and plutonic rocks by combining a geodynamic code with a thermodynamic model for magma generation and evolution. For the geodynamic modelling a finite element code (MVEP2) solves the conservation of mass, momentum and energy equations. The thermodynamic modelling of phase equilibria in magmatic systems is performed with pMELTS for mantle-like bulk compositions. The thermodynamic dependent properties calculated by pMELTS are density, melt fraction and the composition of the liquid and solid phase in the chemical system: SiO2-TiO2-Al2O3-Fe2O3-Cr2O3-FeO-MgO-CaO-Na2O-K2O-P2O5-H2O. In order to take into account the chemical depletion of the source rock with increasing melt extraction events, calculation of phase diagrams is performed in two steps: 1) With an initial rock composition density, melt fraction as well as liquid and solid composition are computed over the full upper mantle P-T range. 2) Once the residual rock composition (equivalent to the solid composition after melt extraction) is significantly different from the initial rock composition and the melt fraction is lower than a critical value, the residual composition is used for next calculations with pMELTS. The implementation of several melt extraction events take the change in chemistry into account until the solidus is shifted to such high temperatures that the rock cannot be molten anymore under upper mantle conditions. An advantage of this approach is that we can track the change of melt chemistry with time, which can be compared with natural constraints. In the thermo-mechanical code the thermodynamic dependent properties from pre-computed phase diagrams are carried by each particle using marker-in-cell method . Thus the physical and chemical properties can change locally as a function of previous melt extraction events, pressure and temperature conditions. After each melt extraction event, the residual rock composition is compared with the bulk composition of previous computed phase diagrams, so that the used phase diagram is replaced by the phase diagram with the closest bulk chemistry. In the thermo-mechanical code, the melt is extracted directly to the surface as volcanites and within the crust as plutonites. The density of the crust and new generated crust is calculated with the thermodynamic modelling tool Perple_X. We have investigated the influence of several input parameters on the magma composition to compare it with real rock samples from Eifel (West-Germany). In order to take the very inhomogeneous chemistry of European mantle into account, we include not only primitive mantle but also metasomatised mantle fragments in the melting source of a plume (Eifel plume).

Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystal and Polytetrahedral-Phase Forming Alloys

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Gangopadhyay, Anup K.; Lee, G. W.; Hyers, Robert W.; Rathz, T. J.; Robinson, Michael B.; Rogers, Jan R.

2003-01-01

From extensive ground based work on the phase diagram and undercooling studies of Ti-Zr-Ni alloys, have clearly identified the composition of three different phases with progressively increasing polytetrahedral order such as, (Ti/Zr), the C14 Laves phase, and the i-phase, that nucleate directly from the undercooled liquid. The reduced undercooling decreases progressively with increasing polytetrahedral order in the solid, supporting Frank s hypothesis. A new facility for direct measurements of the structures and phase transitions in undercooled liquids (BESL) was developed and has provided direct proof of the primary nucleation of a metastable icosahedral phase in some Ti-Zr-Ni alloys. The first measurements of specific heat and viscosity in the undercooled liquid of this alloy system have been completed. Other than the importance of thermo-physical properties for modeling nucleation and growth processes in these materials, these studies have also revealed some interesting new results (such as a maximum of C(sup q, sub p) in the undercooled state). These ground-based results have clearly established the necessary background and the need for conducting benchmark nucleation experiments at the ISS on this alloy system.

Equation of state and phase diagram of carbon

NASA Astrophysics Data System (ADS)

Averin, A. B.; Dremov, V. V.; Samarin, S. I.; Sapozhnikov, A. T.

1996-05-01

Thermodynamically consistent equation of state (EOS) for graphite and diamond is proposed. The EOS satisfactorily describes experimental data on shock compression, heat capacity, thermal expansion and phase equilibrium and can be used in mathematical models and computer codes for calculation of graphite-diamond phase transition under dynamic loading. Monte-Carlo calculations of diamond thermodynamic properties have been carried out to check correctness of the EOS in the regions of phase diagram where experimental data are absent. On the basis of the EOS and Grover's model of liquid state the EOS of liquid carbon have been constructed and carbon phase diagram (graphite and diamond melting curves and triple point) have been calculated. Comparison of calculated and experimental Hugoniots has stated a question about diamond melting curve.

Phase separation and the formation of the pyrenoid, a carbon-fixing organelle

NASA Astrophysics Data System (ADS)

Xu, Bin; Freeman Rosenzweig, Elizabeth; Mackinder, Luke; Jonikas, Martin; Wingreen, Ned S.

In the chloroplasts of most algae, the carbon-fixing enzyme Rubisco is concentrated in a non-membrane-bound structure called the pyrenoid, which enables more efficient carbon capture than that of most land plants. In contrast to the long-held assumptions of the field, the pyrenoid matrix is not a solid crystal, but behaves as a phase-separated, liquid-like organelle. In this system, the linker protein EPYC1 is thought to form multivalent specific bonds with Rubisco, and the formation of the pyrenoid occurs via the phase separation of these two associating proteins. Through analytical and numerical studies, we determine a phase diagram for this system. We also show how the length of the linker protein can affect the formation and dissolution of the pyrenoid in an unexpected manner. This new view of the pyrenoid matrix provides important insights into the structure, regulation, and inheritance of pyrenoid. More broadly, our findings give insights into fundamental principles of the architecture and inheritance of liquid-phase organelles.

Phenomenological model and phase behavior of saturated and unsaturated lipids and cholesterol.

PubMed

Putzel, G Garbès; Schick, M

2008-11-15

We present a phenomenological theory for the phase behavior of ternary mixtures of cholesterol and saturated and unsaturated lipids, one that describes both liquid and gel phases. It leads to the following description of the mechanism of the phase behavior: In a binary system of the lipids, phase separation occurs when the saturated chains are well ordered, as in the gel phase, simply due to packing effects. In the liquid phase, the saturated ones are not sufficiently well ordered for separation to occur. The addition of cholesterol, however, increases the saturated lipid order to the point that phase separation is once again favorable. Our theory addresses this last mechanism-the means by which cholesterol-mediated ordering of membrane lipids leads to liquid-liquid immiscibility. It produces, for the system above the main chain transition of the saturated lipid, phase diagrams in which there can be liquid-liquid phase separation in the ternary system but not in any of the binary ones, while below that temperature it yields the more common phase diagram in which a gel phase, rich in saturated lipid, appears in addition to the two liquid phases.

Phase Behavior of Binary Mixture of Heptaethylene Glycol Decyl Ether and Water: Formation of Phase Compound in Solid Phase

PubMed

Nibu; Suemori; Inoue

1997-07-01

Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR) were used to construct and characterize the phase diagram for a binary mixture of heptaethylene glycol decyl ether (C10 E7 ) and water in the temperature range from -60 to 80°C. Plots of the endothermic peak temperatures obtained by DSC measurements against compositions provided eutectic solid-liquid phase boundaries with a eutectic composition of 34 wt% of H2 O. On the other hand, heat of fusion per unit weight of the mixture changed discretely at the composition corresponding to the "eutectic" composition. Furthermore, the IR spectra obtained for the mixture in the solid phase were well reproduced as a superposition of those for the mixture of 34 wt% H2 O and pure components but were not reproduced by superimposing the spectra obtained for the solid surfactant and ice. These observations indicate that a solid phase compound is formed between C10 E7 and water with a stoichiometry of 1:14 and that the compound and pure components exist as separate phases, rather than the phases separating into surfactant and ice, which would be expected if the C10 E7 /water mixture formed a true eutectic mixture system. It is estimated from the composition corresponding to the phase compounds that two molecules of water per oxyethylene unit are bound to hydrophilic polyoxyethylene chain of C10 E7 to form a hydrated compound.

Pressure-induced transformations in computer simulations of glassy water.

PubMed

Chiu, Janet; Starr, Francis W; Giovambattista, Nicolas

2013-11-14

Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water.

Pressure-induced transformations in computer simulations of glassy water

NASA Astrophysics Data System (ADS)

Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

2013-11-01

Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water.

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.

Machine learning Z2 quantum spin liquids with quasiparticle statistics

NASA Astrophysics Data System (ADS)

Zhang, Yi; Melko, Roger G.; Kim, Eun-Ah

2017-12-01

After decades of progress and effort, obtaining a phase diagram for a strongly correlated topological system still remains a challenge. Although in principle one could turn to Wilson loops and long-range entanglement, evaluating these nonlocal observables at many points in phase space can be prohibitively costly. With growing excitement over topological quantum computation comes the need for an efficient approach for obtaining topological phase diagrams. Here we turn to machine learning using quantum loop topography (QLT), a notion we have recently introduced. Specifically, we propose a construction of QLT that is sensitive to quasiparticle statistics. We then use mutual statistics between the spinons and visons to detect a Z2 quantum spin liquid in a multiparameter phase space. We successfully obtain the quantum phase boundary between the topological and trivial phases using a simple feed-forward neural network. Furthermore, we demonstrate advantages of our approach for the evaluation of phase diagrams relating to speed and storage. Such statistics-based machine learning of topological phases opens new efficient routes to studying topological phase diagrams in strongly correlated systems.

Evaluating the Liquid Liquid Phase Transition Hypothesis of Supercoooled Water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2011-03-01

To explain the anomalous behavior of supercooled water it has been conjectured that buried within an experimentally inaccessible region of liquid water's phase diagram there exists a second critical point, which is the terminus of a first order transition line between two distinct liquid phases. The so-called liquid-liquid phase transition (LLPT) has since generated much study, though to date there is no consensus on its existence. In this talk, we will discuss our efforts to systematically study the metastable phase diagram of supercooled water through computer simulation. By employing importance-sampling techniques, we have calculated free energies as a function of the density and long-range order to determine unambiguously if two distinct liquid phases exist. We will argue that, contrary to the LLPT hypothesis, the observed phenomenology can be understood as a consequence of the limit of stability of the liquid far away from coexistence. Our results suggest that homogeneous nucleation is the cause of the increased fluctuations present upon supercooling. Further we will show how this understanding can be extended to explain experimental observations of hysteresis in confined supercooled water systems.

Thermodynamic Study of Solid-Liquid Equilibrium in NaCl-NaBr-H2O System at 288.15 K

NASA Astrophysics Data System (ADS)

Li, Dan; Meng, Ling-zong; Deng, Tian-long; Guo, Ya-fei; Fu, Qing-Tao

2018-06-01

The solubility data, composition of the solid solution and refractive indices of the NaCl-NaBr-H2O system at 288.15 K were studied with the isothermal equilibrium dissolution method. The solubility diagram and refractive index diagram of this system were plotted at 288.15 K. The solubility diagram consists of two crystallization zones for solid solution Na(Cl,Br) · 2H2O and Na(Cl,Br), one invariant points cosaturated with two solid solution and two univariant solubility isothermal curves. On the basis of Pitzer and Harvie-Weare (HW) chemical models, the composition equations and solubility equilibrium constant equations of the solid solutions at 288.15 K were acquired using the solubility data, the composition of solid solutions, and binary Pitzer parameters. The solubilities calculated using the new method combining the equations are in good agreement with the experimental data.

Solid-like features in dense vapors near the fluid critical point

NASA Astrophysics Data System (ADS)

Ruppeiner, George; Dyjack, Nathan; McAloon, Abigail; Stoops, Jerry

2017-06-01

The phase diagram (pressure versus temperature) of the pure fluid is typically envisioned as being featureless apart from the presence of the liquid-vapor coexistence curve terminating at the critical point. However, a number of recent authors have proposed that this simple picture misses important features, such as the Widom line, the Fisher-Widom line, and the Frenkel line. In our paper, we discuss another way of augmenting the pure fluid phase diagram, lines of zero thermodynamic curvature R = 0 separating regimes of fluid solid-like behavior (R > 0) from gas-like or liquid-like behavior (R < 0). We systematically evaluate R for the 121 pure fluids in the NIST/REFPROP (version 9.1) fluid database near the saturated vapor line from the triple point to the critical point. Our specific goal was to identify regions of positive R abutting the saturated vapor line ("feature D"). We found the following: (i) 97/121 of the NIST/REFPROP fluids have feature D. (ii) The presence and character of feature D correlates with molecular complexity, taken to be the number of atoms Q per molecule. (iii) The solid-like properties of feature D might be attributable to a mesoscopic model based on correlations among coordinated spinning molecules, a model that might be testable with computer simulations. (iv) There are a number of correlations between thermodynamic quantities, including the acentric factor ω , but we found little explicit correlation between ω and the shape of a molecule. (v) Feature D seriously constrains the size of the asymptotic fluid critical point regime, possibly resolving a long-standing mystery about why these are so small. (vi) Feature D correlates roughly with regimes of anomalous sound propagation.

Density-functional theory for fluid-solid and solid-solid phase transitions.

PubMed

Bharadwaj, Atul S; Singh, Yashwant

2017-03-01

We develop a theory to describe solid-solid phase transitions. The density functional formalism of classical statistical mechanics is used to find an exact expression for the difference in the grand thermodynamic potentials of the two coexisting phases. The expression involves both the symmetry conserving and the symmetry broken parts of the direct pair correlation function. The theory is used to calculate phase diagram of systems of soft spheres interacting via inverse power potentials u(r)=ε(σ/r)^{n}, where parameter n measures softness of the potential. We find that for 1/n<0.154 systems freeze into the face centered cubic (fcc) structure while for 1/n≥0.154 the body-centred-cubic (bcc) structure is preferred. The bcc structure transforms into the fcc structure upon increasing the density. The calculated phase diagram is in good agreement with the one found from molecular simulations.

Nanostructure Formation by controlled dewetting on patterned substrates: A combined theoretical, modeling and experimental study.

PubMed

Lu, Liang-Xing; Wang, Ying-Min; Srinivasan, Bharathi Madurai; Asbahi, Mohamed; Yang, Joel K W; Zhang, Yong-Wei

2016-09-01

We perform systematic two-dimensional energetic analysis to study the stability of various nanostructures formed by dewetting solid films deposited on patterned substrates. Our analytical results show that by controlling system parameters such as the substrate surface pattern, film thickness and wetting angle, a variety of equilibrium nanostructures can be obtained. Phase diagrams are presented to show the complex relations between these system parameters and various nanostructure morphologies. We further carry out both phase field simulations and dewetting experiments to validate the analytically derived phase diagrams. Good agreements between the results from our energetic analyses and those from our phase field simulations and experiments verify our analysis. Hence, the phase diagrams presented here provide guidelines for using solid-state dewetting as a tool to achieve various nanostructures.

MBSSAS: A code for the computation of margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.

1991-01-01

The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henry's law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system. ?? 1991.

Highly Accurate Calculations of the Phase Diagram of Cold Lithium

NASA Astrophysics Data System (ADS)

Shulenburger, Luke; Baczewski, Andrew

The phase diagram of lithium is particularly complicated, exhibiting many different solid phases under the modest application of pressure. Experimental efforts to identify these phases using diamond anvil cells have been complemented by ab initio theory, primarily using density functional theory (DFT). Due to the multiplicity of crystal structures whose enthalpy is nearly degenerate and the uncertainty introduced by density functional approximations, we apply the highly accurate many-body diffusion Monte Carlo (DMC) method to the study of the solid phases at low temperature. These calculations span many different phases, including several with low symmetry, demonstrating the viability of DMC as a method for calculating phase diagrams for complex solids. Our results can be used as a benchmark to test the accuracy of various density functionals. This can strengthen confidence in DFT based predictions of more complex phenomena such as the anomalous melting behavior predicted for lithium at high pressures. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under contract DE-AC04-94AL85000.

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

NASA Astrophysics Data System (ADS)

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

2012-01-01

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

Core-softened potentials, multiple liquid-liquid critical points, and density anomaly regions: An exact solution

NASA Astrophysics Data System (ADS)

Rizzatti, Eduardo O.; Barbosa, Marco Aurélio A.; Barbosa, Marcia C.

2018-02-01

The pressure versus temperature phase diagram of a system of particles interacting through a multiscale shoulder-like potential is exactly computed in one dimension. The N-shoulder potential exhibits N density anomaly regions in the phase diagram if the length scales can be connected by a convex curve. The result is analyzed in terms of the convexity of the Gibbs free energy.

The phase diagram of solid hydrogen at high pressure: A challenge for first principles calculations

NASA Astrophysics Data System (ADS)

Azadi, Sam; Foulkes, Matthew

2015-03-01

We present comprehensive results for the high-pressure phase diagram of solid hydrogen. We focus on the energetically most favorable molecular and atomic crystal structures. To obtain the ground-state static enthalpy and phase diagram, we use semi-local and hybrid density functional theory (DFT) as well as diffusion quantum Monte Carlo (DMC) methods. The closure of the band gap with increasing pressure is investigated utilizing quasi-particle many-body calculations within the GW approximation. The dynamical phase diagram is calculated by adding proton zero-point energies (ZPE) to static enthalpies. Density functional perturbation theory is employed to calculate the proton ZPE and the infra-red and Raman spectra. Our results clearly demonstrate the failure of DFT-based methods to provide an accurate static phase diagram, especially when comparing insulating and metallic phases. Our dynamical phase diagram obtained using fully many-body DMC calculations shows that the molecular-to-atomic phase transition happens at the experimentally accessible pressure of 374 GPa. We claim that going beyond mean-field schemes to obtain derivatives of the total energy and optimize crystal structures at the many-body level is crucial. This work was supported by the UK engineering and physics science research council under Grant EP/I030190/1, and made use of computing facilities provided by HECTOR, and by the Imperial College London high performance computing centre.

Perspective: The Asakura Oosawa model: a colloid prototype for bulk and interfacial phase behavior.

PubMed

Binder, Kurt; Virnau, Peter; Statt, Antonia

2014-10-14

In many colloidal suspensions, the micrometer-sized particles behave like hard spheres, but when non-adsorbing polymers are added to the solution a depletion attraction (of entropic origin) is created. Since 60 years the Asakura-Oosawa model, which simply describes the polymers as ideal soft spheres, is an archetypical description for the statistical thermodynamics of such systems, accounting for many features of real colloid-polymer mixtures very well. While the fugacity of the polymers (which controls their concentration in the solution) plays a role like inverse temperature, the size ratio of polymer versus colloid radii acts as a control parameter to modify the phase diagram: when this ratio is large enough, a vapor-liquid like phase separation occurs at low enough colloid packing fractions, up to a triple point where a liquid-solid two-phase coexistence region takes over. For smaller size ratios, the critical point of the phase separation and the triple point merge, resulting in a single two-phase coexistence region between fluid and crystalline phases (of "inverted swan neck"-topology, with possibly a hidden metastable phase separation). Furthermore, liquid-crystalline ordering may be found if colloidal particles of non-spherical shape (e.g., rod like) are considered. Also interactions of the particles with solid surfaces should be tunable (e.g., walls coated by polymer brushes), and interfacial phenomena are particularly interesting experimentally, since fluctuations can be studied in the microscope on all length scales, down to the particle level. Due to its simplicity this model has become a workhorse for both analytical theory and computer simulation. Recently, generalizations addressing dynamic phenomena (phase separation, crystal nucleation, etc.) have become the focus of studies.

Perspective: The Asakura Oosawa model: A colloid prototype for bulk and interfacial phase behavior

NASA Astrophysics Data System (ADS)

Binder, Kurt; Virnau, Peter; Statt, Antonia

2014-10-01

In many colloidal suspensions, the micrometer-sized particles behave like hard spheres, but when non-adsorbing polymers are added to the solution a depletion attraction (of entropic origin) is created. Since 60 years the Asakura-Oosawa model, which simply describes the polymers as ideal soft spheres, is an archetypical description for the statistical thermodynamics of such systems, accounting for many features of real colloid-polymer mixtures very well. While the fugacity of the polymers (which controls their concentration in the solution) plays a role like inverse temperature, the size ratio of polymer versus colloid radii acts as a control parameter to modify the phase diagram: when this ratio is large enough, a vapor-liquid like phase separation occurs at low enough colloid packing fractions, up to a triple point where a liquid-solid two-phase coexistence region takes over. For smaller size ratios, the critical point of the phase separation and the triple point merge, resulting in a single two-phase coexistence region between fluid and crystalline phases (of "inverted swan neck"-topology, with possibly a hidden metastable phase separation). Furthermore, liquid-crystalline ordering may be found if colloidal particles of non-spherical shape (e.g., rod like) are considered. Also interactions of the particles with solid surfaces should be tunable (e.g., walls coated by polymer brushes), and interfacial phenomena are particularly interesting experimentally, since fluctuations can be studied in the microscope on all length scales, down to the particle level. Due to its simplicity this model has become a workhorse for both analytical theory and computer simulation. Recently, generalizations addressing dynamic phenomena (phase separation, crystal nucleation, etc.) have become the focus of studies.

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.

Nanostructure Formation by controlled dewetting on patterned substrates: A combined theoretical, modeling and experimental study

PubMed Central

Lu, Liang-Xing; Wang, Ying-Min; Srinivasan, Bharathi Madurai; Asbahi, Mohamed; Yang, Joel K. W.; Zhang, Yong-Wei

2016-01-01

We perform systematic two-dimensional energetic analysis to study the stability of various nanostructures formed by dewetting solid films deposited on patterned substrates. Our analytical results show that by controlling system parameters such as the substrate surface pattern, film thickness and wetting angle, a variety of equilibrium nanostructures can be obtained. Phase diagrams are presented to show the complex relations between these system parameters and various nanostructure morphologies. We further carry out both phase field simulations and dewetting experiments to validate the analytically derived phase diagrams. Good agreements between the results from our energetic analyses and those from our phase field simulations and experiments verify our analysis. Hence, the phase diagrams presented here provide guidelines for using solid-state dewetting as a tool to achieve various nanostructures. PMID:27580943

Phase Diagram of the Bose Hubbard Model with Weak Links

NASA Astrophysics Data System (ADS)

Hettiarachchilage, Kalani; Rousseau, Valy; Tam, Ka-Ming; Moreno, Juana; Jarrell, Mark; Sheehy, Daniel

2012-02-01

We study the ground state phase diagram of strongly interacting ultracold Bose gas in a one-dimensional optical lattice with a tunable weak link, by means of Quantum Monte Carlo simulation. This model contains an on-site repulsive interaction (U) and two different near-neighbor hopping terms, J and t, for the weak link and the remainder of the chain, respectively. We show that by reducing the strength of J, a novel intermediate phase develops which is compressible and non-superfluid. This novel phase is identified as a Normal Bose Liquid (NBL) which does not appear in the phase diagram of the homogeneous bosonic Hubbard model. Further, we find a linear variation of the phase boundary of Normal Bose Liquid (NBL) to SuperFluid (SF) as a function of the strength of the weak link. These results may provide a new path to design advanced atomtronic devices in the future.

Experimental Partitioning of As and SB Among Metal, Troilite, Schreibersite, Barringerite, and Metallic Liquid

NASA Astrophysics Data System (ADS)

Jones, J. H.; Casanova, I.

1993-07-01

We have performed a series of experiments to evaluate the behaviors of As and Sb in metallic systems. Because of the reputed chalcophile nature of these elements, we wrongly anticipated that they would follow S and that, compared to the Fe-X systems [1], (solid metal/liquid metal) partition coefficients would be considerably lower in S-bearing systems. Experimental and Analytical: Experiments were performed in sealed silica tubes as in [2]. Starting materials were high-purity metals, natural pyrite, and natural stibnite. Charges were doped either with As or Sb. Experiments were held at either 950 degrees C for six days or 1250 degrees C for three days. Typical experimental assemblages consisted either of taenite and coexisting Fe-Ni-S-X liquid (1250 degrees and 950 degrees C) or an assemblage of troilite, schreibersite, and Fe-Ni-S-P-X liquid (950 degrees C). The schreibersite-bearing, As-doped charge also contained barringerite (Fe,Ni)2P. Charges were mounted in epoxy, polished, and analyzed using a Cameca SX-50 electron microprobe and standard techniques. Results: Phases appeared homogeneous. Our results, along with partition coefficients inferred for the S-free system, are given in Table 1. Table 1 appears here in the hard copy. Discussion: Our results indicate that As behaves as a siderophile element at low temperatures, very analogous to Au. While the siderophility of Sb increases with decreasing temperature, it remains incompatible in solid metal. In this regard Sb is unique. Both As and Sb are very incompatible in troilite. Arsenic is weakly incompatible in schreibersite and strongly compatible in barringerite. Nickel shows no preference for either phosphide. Nickel partition coefficients for metal and schreibersite are similar to those measured previously [3]. On a lnD vs. ln(1-2 alpha X(S)) diagram [4], the data for Sb and As subparallel each other, indicating similar dependencies on S, despite their very different partition coefficients. Arsenic behaves similarly to P. The As and Sb partition coefficients for the S-free system, inferred for kamacite (alpha-iron) from the Fe-As and Fe-Sb phase diagrams [1], are probably not applicable to taenite (gamma-iron). Extrapolation of our data to zero S indicates that the taenite partition coefficients for As and Sb are likely to be much lower than for kamacite. In discussing the fractional crystallization of iron meteorites, Scott [5] originally grouped Au, As, Sb, and Co and assigned them a (solid metal/liquid metal) partition coefficient of about 0.4. This distinguished them from P, which was given a partition coefficient of 0.2. Given the strong decoupling of As and Sb in our experiments, the general coherence of As and Sb in iron meteorites [5] is surprising. To explore this further, we have derived a new equation for the slopes of LogEl vs. LogNi diagrams, which takes into account changes in D. References: [1] Moffatt W. G. (1986) Handbook of Binary Phase Diagrams, Genium. [2] Jones J. H. and Drake M. J. (1983) GCA, 47, 1199. [3] Jones J. H. et al. (1993) GCA, 57, 453-460. [4] Jones J. H. and Malvin D. J. (1990) Metall. Trans., 21B, 697-706. [5] Scott E. R. D. (1972) GCA, 36, 1205.

Lyotropic Phase Behavior of Polybutadiene-Poly(ethylene oxide) Diblock Copolymers in Ionic Liquids

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

Simone, Peter M.; Lodge, Timothy P.

2008-08-26

The lyotropic phase behavior of three poly(1,2-butadiene-b-ethylene oxide) diblock copolymers (PB-PEO) with different monomer volume fractions has been studied in two different ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF{sub 6}]), across the complete concentration range. The ordered microstructures present in the solutions were characterized via small-angle X-ray scattering (SAXS). The phase diagrams for the PB-PEO/ionic liquid solutions include regions corresponding to the classical copolymer microstructures: body-centered-cubic lattices of spheres, hexagonally ordered cylinders, and lamellae. Additionally, the phase diagrams also include wide regions of coexisting microstructures and regions apparently corresponding to a disordered network microstructure. The phase behavior ofmore » the PB-PEO copolymers in both ionic liquids was comparable to their previously reported aqueous solution behavior. The temperature dependence of the phase diagrams was very modest, indicative of a highly segregated system. The level of solvent selectivity was also investigated via cryogenic transmission electron microscopy (cryo-TEM) on dilute solutions. On the basis of the morphology of the dilute solution copolymer aggregate structures in the ionic liquid solvents, and on the structural length scales of the concentrated solutions, it was concluded that for PB-PEO [BMI][PF{sub 6}] behaves as a more selective solvent than [EMI][TFSI].« less

Liquid part of the phase diagram and percolation line for two-dimensional Mercedes-Benz water.

PubMed

Urbic, T

2017-09-01

Monte Carlo simulations and Wertheim's thermodynamic perturbation theory (TPT) are used to predict the phase diagram and percolation curve for the simple two-dimensional Mercedes-Benz (MB) model of water. The MB model of water is quite popular for explaining water properties, but the phase diagram has not been reported till now. In the MB model, water molecules are modeled as two-dimensional Lennard-Jones disks, with three orientation-dependent hydrogen-bonding arms, arranged as in the MB logo. The liquid part of the phase space is explored using grand canonical Monte Carlo simulations and two versions of Wertheim's TPT for associative fluids, which have been used before to predict the properties of the simple MB model. We find that the theory reproduces well the physical properties of hot water but is less successful at capturing the more structured hydrogen bonding that occurs in cold water. In addition to reporting the phase diagram and percolation curve of the model, it is shown that the improved TPT predicts the phase diagram rather well, while the standard one predicts a phase transition at lower temperatures. For the percolation line, both versions have problems predicting the correct position of the line at high temperatures.

Liquid part of the phase diagram and percolation line for two-dimensional Mercedes-Benz water

NASA Astrophysics Data System (ADS)

Urbic, T.

2017-09-01

Monte Carlo simulations and Wertheim's thermodynamic perturbation theory (TPT) are used to predict the phase diagram and percolation curve for the simple two-dimensional Mercedes-Benz (MB) model of water. The MB model of water is quite popular for explaining water properties, but the phase diagram has not been reported till now. In the MB model, water molecules are modeled as two-dimensional Lennard-Jones disks, with three orientation-dependent hydrogen-bonding arms, arranged as in the MB logo. The liquid part of the phase space is explored using grand canonical Monte Carlo simulations and two versions of Wertheim's TPT for associative fluids, which have been used before to predict the properties of the simple MB model. We find that the theory reproduces well the physical properties of hot water but is less successful at capturing the more structured hydrogen bonding that occurs in cold water. In addition to reporting the phase diagram and percolation curve of the model, it is shown that the improved TPT predicts the phase diagram rather well, while the standard one predicts a phase transition at lower temperatures. For the percolation line, both versions have problems predicting the correct position of the line at high temperatures.

Phase Transitions in Model Active Systems

NASA Astrophysics Data System (ADS)

Redner, Gabriel S.

The amazing collective behaviors of active systems such as bird flocks, schools of fish, and colonies of microorganisms have long amazed scientists and laypeople alike. Understanding the physics of such systems is challenging due to their far-from-equilibrium dynamics, as well as the extreme diversity in their ingredients, relevant time- and length-scales, and emergent phenomenology. To make progress, one can categorize active systems by the symmetries of their constituent particles, as well as how activity is expressed. In this work, we examine two categories of active systems, and explore their phase behavior in detail. First, we study systems of self-propelled spherical particles moving in two dimensions. Despite the absence of an aligning interaction, this system displays complex emergent dynamics, including phase separation into a dense active solid and dilute gas. Using simulations and analytic modeling, we quantify the phase diagram and separation kinetics. We show that this nonequilibrium phase transition is analogous to an equilibrium vapor-liquid system, with binodal and spinodal curves and a critical point. We also characterize the dense active solid phase, a unique material which exhibits the structural signatures of a crystalline solid near the crystal-hexatic transition point, as well as anomalous dynamics including superdiffusive motion on intermediate timescales. We also explore the role of interparticle attraction in this system. We demonstrate that attraction drastically changes the phase diagram, which contains two distinct phase-separated regions and is reentrant as a function of propulsion speed. We interpret this complex situation with a simple kinetic model, which builds from the observed microdynamics of individual particles to a full description of the macroscopic phase behavior. We also study active nematics, liquid crystals driven out of equilibrium by energy-dissipating active stresses. The equilibrium nematic state is unstable in these materials, leading to beautiful and surprising behaviors including the spontaneous generation of topological defect pairs which stream through the system and later annihilate, yielding a complex, seemingly chaotic dynamical steady-state. Here, we describe the emergence of order from this chaos in the form of previously unknown broken-symmetry phases in which the topological defects themselves undergo orientational ordering. We have identified these defect-ordered phases in two realizations of an active nematic: first, a suspension of extensile bundles of microtubules and molecular motor proteins, and second, a computational model of extending hard rods. We will describe the defect-stabilized phases that manifest in these systems, our current understanding of their origins, and discuss whether such phases may be a general feature of extensile active nematics.

Phase states and thermomorphologic, thermotropic, and magnetomorphologic properties of lyotropic mesophases: Sodium lauryl sulphate-water-1-decanol liquid-crystalline system

NASA Astrophysics Data System (ADS)

Özden, Pınar; Nesrullajev, Arif; Oktik, Şener

2010-12-01

Phase states in sodium lauryl sulphate-water-1-decanol lyotropic liquid-crystalline system have been investigated for different temperature ranges. The dependence of triangle phase diagram types, phase boundaries, and sequence of lyotropic mesophases vs temperature has been found. The thermomorphologic, thermotropic, and magnetomorphologic properties of hexagonal E, lamellar D, nematic-calamitic NC , nematic-discotic ND , and biaxial nematic Nbx mesophases have been studied in detail. Dynamics of transformations of magnetically induced textures has been investigated. Peculiarities of typical and magnetically induced textures have been investigated in detail. Triangle phase diagrams of sodium lauryl sulphate-water-1-decanol lyotropic liquid-crystalline system for different temperatures and typical and magnetically induced textures of E, D, NC , ND , and Nbx mesophases are presented.

Comparison of forcefields for molecular dynamics simulations of hydrocarbon phase diagrams

NASA Astrophysics Data System (ADS)

Pisarev, V. V.; Zakharov, S. A.

2018-01-01

Molecular dynamics calculations of vapor-liquid equilibrium of methane-n-butane mixture are performed. Three force-field models are tested: the TraPPE-UA united-atom forcefield, LOPLS-AA all-atom forcefield and a fully flexible version of the TraPPE-EH all-atom forcefield. All those forcefields reproduce well the composition of liquid phase in the mixture as a function of pressure at the 300 K isotherm, while significant discrepancies from experimental data are observed in the saturated vapor compositions with OPLS-AA and TraPPE-UA forcefields. The best agreement with the experimental phase diagram is found with TraPPE-EH forcefield which accurately reproduces compositions of both liquid and vapor phase. This forcefield can be recommended for simulation of two-phase hydrocarbon systems.

Anthracene + Pyrene Solid Mixtures: Eutectic and Azeotropic Character

PubMed Central

Rice, James W.; Fu, Jinxia; Suuberg, Eric M.

2010-01-01

To better characterize the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the anthracene (1) + pyrene (2) system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at 404 K at x1 = 0.22. A model based on eutectic formation can be used to predict the enthalpy of fusion associated with the mixture. For mixtures that contain x1 < 0.90, the enthalpy of fusion is near that of pure pyrene. This and X-ray diffraction results indicate that mixtures of anthracene and pyrene have pyrene-like crystal structures and energetics until the composition nears that of pure anthracene. Solid-vapor equilibrium studies show that mixtures of anthracene and pyrene form solid azeotropes at x1 of 0.03 and 0.14. Additionally, mixtures at x1 = 0.99 sublime at the vapor pressure of pure anthracene, suggesting that anthracene behavior is not significantly influenced by x2 = 0.01 in the crystal structure. PMID:21116474

Colloidal gas-liquid condensation of polystyrene latex particles with intermediate kappa a values (5 to 160, a > kappa(-1)).

PubMed

Ishikawa, Masamichi; Kitano, Ryota

2010-02-16

Polystyrene latex particles showed gas-liquid condensation under the conditions of large particle radius (a > kappa(-1)) and intermediate kappa a, where kappa is the Debye-Hückel parameter and a is the particle radius. The particles were dissolved in deionized water containing ethanol from 0 to 77 vol %, settled to the bottom of the glass plate within 1 h, and then laterally moved toward the center of a cell over a 20 h period in reaching a state of equilibrium condensation. All of the suspensions that were 1 and 3 microm in diameter and 0.01-0.20 vol % in concentration realized similar gas-liquid condensation with clear gas-liquid boundaries. In 50 vol % ethanol solvent, additional ethanol was added to enhance the sedimentation force so as to restrict the particles in a monoparticle layer thickness. The coexistence of gas-liquid-solid (crystalline solid) was microscopically recognized from the periphery to the center of the condensates. A phase diagram of the gas-liquid condensation was created as a function of KCl concentration at a particle diameter of 3 microm, 0.10 vol % concentration, and 50:50 water/ethanol solvent at room temperature. The miscibility gap was observed in the concentration range from 1 to 250 microM. There was an upper limit of salt concentration where the phase separation disappeared, showing nearly critical behavior of macroscopic density fluctuation from 250 microM to 1 mM. These results add new experimental evidence to the existence of colloidal gas-liquid condensation and specify conditions of like-charge attraction between particles.

Multicomponent homogeneous alloys and method for making same

DOEpatents

Dutta, Partha S.; Miller, Thomas R.

2003-09-02

The present application discloses a method for preparing a homogeneous ternary or quaternary alloy from a quaternary melt. The method includes providing a family of phase diagrams for the quaternary melt which shows (i) composition/temperature data, (ii) tie lines connecting equilibrium liquid and solid compositions, and (iii) isotherms representing boundaries of a miscibility gap. Based on the family of phase diagrams, a quaternary melt composition and an alloy growth temperature is selected. A quaternary melt having the selected quaternary melt composition is provided and a ternary or quaternary alloy is grown from the quaternary melt at the selected alloy growth temperature. A method for making homogeneous ternary or quaternary alloy from a ternary or quaternary melt is also disclosed, as are homogeneous quaternary single-crystal alloys which are substantially free from crystal defects and which have the formula A.sub.x B.sub.1-x C.sub.y D.sub.1-y, x and y being the same or different and in the range of 0.001 to 0.999.

Melting of Boltzmann particles in different 2D trapping potential

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

Thermodynamic properties of saturated liquid parahydrogen charted for important temperature range

NASA Technical Reports Server (NTRS)

Mc Carty, R. D.; Roder, H. M.

1967-01-01

Six entropy diagrams for parahydrogen in or near the saturated liquid state cover the temperature range from 29.16 degrees to 42.48 degrees R with pressures to 100 psia and mixtures of the liquid and vapor phases to 0.003 quality. The diagrams are printed in color, are 19 by 30 inches in size, and are suitable for wall mounting.

Out-of-equilibrium processes in suspensions of oppositely charged colloids: liquid-to-crystal nucleation and gel formation

NASA Astrophysics Data System (ADS)

Sanz, Eduardo

2009-03-01

We study the kinetics of the liquid-to-crystal transformation and of gel formation in colloidal suspensions of oppositely charged particles. We analyse, by means of both computer simulations and experiments, the evolution of a fluid quenched to a state point of the phase diagram where the most stable state is either a homogeneous crystalline solid or a solid phase in contact with a dilute gas. On the one hand, at high temperatures and high packing fractions, close to an ordered-solid/disordered-solid coexistence line, we find that the fluid-to-crystal pathway does not follow the minimum free energy route. On the other hand, a quench to a state point far from the ordered-crystal/disordered-crystal coexistence border is followed by a fluid-to-solid transition through the minimum free energy pathway. At low temperatures and packing fractions we observe that the system undergoes a gas-liquid spinodal decomposition that, at some point, arrests giving rise to a gel-like structure. Both our simulations and experiments suggest that increasing the interaction range favors crystallization over vitrification in gel-like structures. [4pt] In collaboration with Chantal Valeriani, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands and SUPA, School of Physics, University of Edinburgh, JCMB King's Buildings, Mayfield Road, Edinburgh EH9 3JZ, UK; Teun Vissers, Andrea Fortini, Mirjam E. Leunissen, and Alfons van Blaaderen, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University; Daan Frenke, FOM Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands and Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW, Cambridge, UK; and Marjolein Dijkstra, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University.

Melting curve of SiO2 at multimegabar pressures: implications for gas giants and super-Earths.

PubMed

González-Cataldo, Felipe; Davis, Sergio; Gutiérrez, Gonzalo

2016-05-23

Ultrahigh-pressure phase boundary between solid and liquid SiO2 is still quite unclear. Here we present predictions of silica melting curve for the multimegabar pressure regime, as obtained from first principles molecular dynamics simulations. We calculate the melting temperatures from three high pressure phases of silica (pyrite-, cotunnite-, and Fe2P-type SiO2) at different pressures using the Z method. The computed melting curve is found to rise abruptly around 330 GPa, an increase not previously reported by any melting simulations. This is in close agreement with recent experiments reporting the α-PbO2-pyrite transition around this pressure. The predicted phase diagram indicates that silica could be one of the dominant components of the rocky cores of gas giants, as it remains solid at the core of our Solar System's gas giants. These results are also relevant to model the interior structure and evolution of massive super-Earths.

Melting curve of SiO2 at multimegabar pressures: implications for gas giants and super-Earths

PubMed Central

González-Cataldo, Felipe; Davis, Sergio; Gutiérrez, Gonzalo

2016-01-01

Ultrahigh-pressure phase boundary between solid and liquid SiO2 is still quite unclear. Here we present predictions of silica melting curve for the multimegabar pressure regime, as obtained from first principles molecular dynamics simulations. We calculate the melting temperatures from three high pressure phases of silica (pyrite-, cotunnite-, and Fe2P-type SiO2) at different pressures using the Z method. The computed melting curve is found to rise abruptly around 330 GPa, an increase not previously reported by any melting simulations. This is in close agreement with recent experiments reporting the α-PbO2–pyrite transition around this pressure. The predicted phase diagram indicates that silica could be one of the dominant components of the rocky cores of gas giants, as it remains solid at the core of our Solar System’s gas giants. These results are also relevant to model the interior structure and evolution of massive super-Earths. PMID:27210813

Comparison of a solid SMEDDS and solid dispersion for enhanced stability and bioavailability of clopidogrel napadisilate.

PubMed

Kim, Dong Wuk; Kwon, Min Seok; Yousaf, Abid Mehmood; Balakrishnan, Prabagar; Park, Jong Hyuck; Kim, Dong Shik; Lee, Beom-Jin; Park, Young Joon; Yong, Chul Soon; Kim, Jong Oh; Choi, Han-Gon

2014-12-19

The intention of this study was to compare the physicochemical properties, stability and bioavailability of a clopidogrel napadisilate (CN)-loaded solid dispersion (SD) and solid self-microemulsifying drug delivery system (solid SMEDDS). SD was prepared by a surface attached method using different ratios of Cremophor RH60 (surfactant) and HPMC (polymer), optimized based on their drug solubility. Liquid SMEDDS was composed of oil (peceol), a surfactant (Cremophor RH60) and a co-surfactant (Transcutol HP). A pseudo-ternary phase diagram was constructed to identify the emulsifying domain, and the optimized liquid SMEDDS was spray dried with an inert solid carrier (silicon dioxide), producing the solid SMEDDS. The physicochemical properties, solubility, dissolution, stability and pharmacokinetics were assessed and compared to clopidogrel napadisilate (CN) and bisulfate (CB) powders. In solid SMEDDS, liquid SMEDDS was absorbed or coated inside the pores of silicon dioxide. In SD, hydrophilic polymer and surfactants were adhered onto drug surface. The drug was in crystalline and molecularly dispersed form in SD and solid SMEDDS, respectively. Solid SMEDDS and SD greatly increased the solubility of CN but gave lower drug solubility compared to CB powder. These preparations significantly improved the dissolution of CN, but the latter more increased than the former. Stability under accelerated condition showed that they were more stable compared to CB powder, and SD was more stable than solid SMEDDS. They significantly increased the oral bioavailability of CN powder. Furthermore, SD showed significantly improved oral bioavailability compared to solid SMEDDS and CB powder. Thus, SD with excellent stability and bioavailability is recommended as an alternative for the clopidogrel-based oral formulation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Phase diagrams and crystal growth

NASA Astrophysics Data System (ADS)

Venkrbec, Jan

1980-04-01

Phase diagrams are briefly treated as generalized property-composition relationships, with respect to crystal technology optimization. The treatment is based on mutual interaction of three systems related to semiconductors: (a) the semiconducting material systems, (b0 the data bank, (c) the system of crystallization methods. A model is proposed enabling optimatization on the path from application requirements to the desired material. Further, several examples of the selection as to the composition of LED and laser diode material are given. Some of molten-solution-zone methods are being successfully introduced for this purpose. Common features of these methods, the application of phase diagrams, and their pecularities compared with other crystallization methods are illustrated by schematic diagrams and by examples. LPE methods, particularly the steady-state LPE methods such as Woodall's ISM and Nishizawa's TDM-CVP, and the CAM-S (Crystallization Method Providing Composition Autocontrol in Situ) have been chosen as examples. Another approach of exploiting phase diagrams for optimal material selection and for determination of growth condition before experimentation through a simple calculation is presented on InP-GaP solid solutions. Ternary phase diagrams are visualized in space through calculation and constructions based on the corresponding thermodynamic models and anaglyphs. These make it easy to observe and qualitatively analyze the crystallization of every composition. Phase diagrams can be also used as a powerful tool for the deduction of new crystallization methods. Eutectic crystallization is an example of such an approach where a modified molten-solution-zone method can give a sandwich structure with an abrupt concentration change. The concentration of a component can range from 0 to 100% in the different solid phases.

Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

PubMed

Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

2014-07-23

We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

Mapping coexistence lines via free-energy extrapolation: application to order-disorder phase transitions of hard-core mixtures.

PubMed

Escobedo, Fernando A

2014-03-07

In this work, a variant of the Gibbs-Duhem integration (GDI) method is proposed to trace phase coexistence lines that combines some of the advantages of the original GDI methods such as robustness in handling large system sizes, with the ability of histogram-based methods (but without using histograms) to estimate free-energies and hence avoid the need of on-the-fly corrector schemes. This is done by fitting to an appropriate polynomial function not the coexistence curve itself (as in GDI schemes) but the underlying free-energy function of each phase. The availability of a free-energy model allows the post-processing of the simulated data to obtain improved estimates of the coexistence line. The proposed method is used to elucidate the phase behavior for two non-trivial hard-core mixtures: a binary blend of spheres and cubes and a system of size-polydisperse cubes. The relative size of the spheres and cubes in the first mixture is chosen such that the resulting eutectic pressure-composition phase diagram is nearly symmetric in that the maximum solubility of cubes in the sphere-rich solid (∼20%) is comparable to the maximum solubility of spheres in the cube-rich solid. In the polydisperse cube system, the solid-liquid coexistence line is mapped out for an imposed Gaussian activity distribution, which produces near-Gaussian particle-size distributions in each phase. A terminal polydispersity of 11.3% is found, beyond which the cubic solid phase would not be stable, and near which significant size fractionation between the solid and isotropic phases is predicted.

Optimization of the thermodynamic properties and phase diagrams of P2O5-containing systems

NASA Astrophysics Data System (ADS)

Hudon, Pierre; Jung, In-Ho

2014-05-01

P2O5 is an important oxide component in the late stage products of numerous igneous rocks such as granites and pegmatites. Typically, P2O5 combines with CaO and crystallizes in the form of apatite, while in volatile-free conditions, Ca-whitlockite is formed. In spite of their interest, the thermodynamic properties and phase diagrams of P2O5-containg systems are not well known yet. In the case of the pure P2O5 for example, no experimental thermodynamic data are available for the liquid and the O and O' solid phases. As a result, we re-evaluated all the thermodynamic and phase diagram data of the P2O5 unary system [1]. Optimization of the thermodynamic properties and phase diagrams of the binary P2O5 systems was then performed including the Li2O-, Na2O-, MgO-, CaO-, BaO-, MnO-, FeO-, Fe2O3-, ZnO-, Al2O3-, and SiO2-P2O5 [2] systems. All available thermodynamic and phase equilibrium data were simultaneously reproduced in order to obtain a set of model equations for the Gibbs energies of all phases as functions of temperature and composition. In particular, the Gibbs energy of the liquid solution was described using the Modified Quasichemical Model [3-5] implemented in the FactSage software [6]. Thermodynamic modeling of the Li2O-Na2O-K2O-MgO-CaO-FeO-Fe2O3-Al2O3-SiO2 system, which include many granite-forming minerals such as nepheline, leucite, pyroxene, melilite, feldspar and spinel is currently in progress. [1] Jung, I.-H., Hudon, P. (2012) Thermodynamic assessment of P2O5. J. Am. Ceram. Soc., 95 (11), 3665-3672. [2] Rahman, M., Hudon, P. and Jung, I.-H. (2013) A coupled experimental study and thermodynamic modeling of the SiO2-P2O5 system. Metall. Mater. Trans. B, 44 (4), 837-852. [3] Pelton, A.D. and Blander, M. (1984) Computer-assisted analysis of the thermodynamic properties and phase diagrams of slags. Proc. AIME Symp. Metall. Slags Fluxes, TMS-AIME, 281-294. [4] Pelton, A.D. and Blander, M. (1986) Thermodynamic analysis of ordered liquid solutions by a modified quasichemical approach application to silicate slags. Metall. Trans. B, 17, 805-815. [5] A.D. Pelton, S.A. Decterov, G. Eriksson, C. Robelin and Y. Dessureault (2000) The modified quasichemical model - I Binary solutions. Metall. Mater. Trans. B, 31, 651-660. [6] C.W. Bale, P. Chartrand, S.A. Decterov, G. Eriksson, K. Hack, R. Ben Mahfoud, J. Melançon, A.D. Pelton and S. Petersen. (2002) FactSage Thermochemical Software and Databases. Calphad, 26, 189-228.

Anisotropic phase diagram of the rare-earth hyperkagome system Gd3Ga5O12 (GGG)

NASA Astrophysics Data System (ADS)

Quilliam, Jeffrey; Rousseau, Alexandre; Parent, Jean-Michel

An understanding of the low-temperature properties of the hyperkagome system Gd3Ga5O12 or GGG is a long-standing problem in the field of frustrated magnetism. The origins of spin liquid and exotic spin-glass phases in this material remain mysterious and even its precise magnetic phase diagram is still not firmly established. We have investigated the field-induced phase diagram of this material using the ultrasound velocity and attenuation technique at temperatures as low as 40 mK. Two different field orientations are tested, and give rise to significant quantitative and qualitative differences. Notably, two distinct field-induced antiferromagnetic phases are observed for field parallel to 110, consistent with recent results, whereas only one ordered phase is observed for a 100 orientation. The field dependence of the sound velocity and attenuation is also found to be anisotropic within the low-field spin liquid phase. Research supported by NSERC, FQRNT.

Raman Spectroscopy and Microphysics of Single PSC Precursor Particles Suspended in a Quadrupole Trap

NASA Astrophysics Data System (ADS)

Sonnenfroh, D. M.; Hunter, A. J.; Rawlins, W. T.

2001-12-01

Polar stratospheric clouds (PSCs) consist primarily of solid nitric acid trihydrate (NAT) particles, which are thought to nucleate via HNO3 uptake on background sulfuric acid particles at temperatures below 195 K. The mechanism for this process is uncertain, and depends on whether the sulfuric acid particles are solid or liquid at these temperatures. Previous results from laboratory and field measurements are mixed; our previous single-particle laboratory experiments showed that binary H2SO4/H2O particles at stratospheric compositions are essentially metastable in the liquid phase when cooled to PSC temperatures. Currently, we are investigating the detailed microphysics of binary (H2SO4/H2O) and ternary (HNO3/H2SO4/H2O) single particles suspended in an electrodynamic levitator, using optical elastic scattering and Raman spectroscopy to observe changes in phase and composition. Single-particle Raman spectra for supercooled binary particles exhibit spectral distributions which alter markedly with decreasing temperature down to 190 K. The variations signify increasing dissociation of HSO4(-) to SO4(-2) with decreasing temperature, consistent with measurements for bulk solutions. Upon gradual warming of supercooled liquid binary particles, some of them freeze briefly in a narrow "window" of the phase diagram, near 210 K and 60 weight per cent H2SO4. We will discuss the Raman spectroscopy and microphysical behavior of the liquid and frozen particles for both the binary and ternary systems. This research was supported by the NASA Atmospheric Effects of Aviation Program.

Crystallization process

DOEpatents

Adler, Robert J.; Brown, William R.; Auyang, Lun; Liu, Yin-Chang; Cook, W. Jeffrey

1986-01-01

An improved crystallization process is disclosed for separating a crystallizable material and an excluded material which is at least partially excluded from the solid phase of the crystallizable material obtained upon freezing a liquid phase of the materials. The solid phase is more dense than the liquid phase, and it is separated therefrom by relative movement with the formation of a packed bed of solid phase. The packed bed is continuously formed adjacent its lower end and passed from the liquid phase into a countercurrent flow of backwash liquid. The packed bed extends through the level of the backwash liquid to provide a drained bed of solid phase adjacent its upper end which is melted by a condensing vapor.

Multiphase Equation of State and Strength Properties of Beryllium from AB INITIO and Quantum Molecular Dynamics Calculations.

NASA Astrophysics Data System (ADS)

Robert, G.; Sollier, A.; Legrand, Ph.

2007-12-01

In the framework of density functional theory, static properties and phonon spectra of beryllium have been calculated under high compression (for pressures up to 4 Mbar) for two solid phases: hexagonal compact (hcp) and body-centered cubic (bcc). The melting curve and some isotherms in the liquid phase have been calculated using quantum molecular dynamics. The coupling of these theoretical data to a quasi-harmonic approach (phonon moments) allows us to suggest a new theoretical phase diagram and to build a multiphase equation of state (EOS) valid in a large range of pressure and temperature. The resulting Hugoniot curves as well as the evolution of the longitudinal sound speed with both pressure and temperature are in good agreement with available experimental data.

Thermodynamic Analysis of the Combustion of Metallic Materials

NASA Technical Reports Server (NTRS)

Wilson, D. Bruce; Stoltzfus, Joel M.

2000-01-01

Two types of computer codes are available to assist in the thermodynamic analysis of metallic materials combustion. One type of code calculates phase equilibrium data and is represented by CALPHAD. The other type of code calculates chemical reaction by the Gordon-McBride code. The first has seen significant application for alloy-phase diagrams, but only recently has it been considered for oxidation systems. The Gordon-McBride code has been applied to the combustion of metallic materials. Both codes are limited by their treatment of non-ideal solutions and the fact they are limited to treating volatile and gaseous species as ideal. This paper examines the significance of these limitations for combustion of metallic materials. In addition, the applicability of linear-free energy relationships for solid-phase oxidation and their possible extension to liquid-phase systems is examined.

Microstructural Development during Directional Solidification of Peritectic Alloys

NASA Technical Reports Server (NTRS)

Lograsso, Thomas A.

1996-01-01

A thorough understanding of the microstructures produced through solidification in peritectic systems has yet to be achieved, even though a large number of industrially and scientifically significant materials are in this class. One type of microstructure frequently observed during directional solidification consists of alternating layers of primary solid and peritectic solid oriented perpendicular to the growth direction. This layer formation is usually reported for alloy compositions within the two-phase region of the peritectic isotherm and for temperature gradient and growth rate conditions that result in a planar solid-liquid interface. Layered growth in peritectic alloys has not previously been characterized on a quantitative basis, nor has a mechanism for its formation been verified. The mechanisms that have been proposed for layer formation can be categorized as either extrinsic or intrinsic to the alloy system. The extrinsic mechanisms rely on externally induced perturbations to the system for layer formation, such as temperature oscillations, growth velocity variations, or vibrations. The intrinsic mechanisms approach layer formation as an alternative type of two phase growth that is inherent for certain peritectic systems and solidification conditions. Convective mixing of the liquid is an additional variable which can strongly influence the development and appearance of layers due to the requisite slow growth rate. The first quantitative description of layer formation is a model recently developed by Trivedi based on the intrinsic mechanism of cyclic accumulation and depiction of solute in the liquid ahead of the interface, linked to repeated nucleation events in the absence of convection. The objective of this research is to characterize the layered microstructures developed during ground-based experiments in which external influences have been minimized as much as possible and to compare these results to the current the model. Also, the differences between intrinsic and externally influenced layer formation were explored. The choice of alloy system is critical to a study of the formation of layered microstructures. The ideal system would have a well-characterized phase diagram, equal densities of both elements in the liquid state to minimize compositionally-driven convective flows, a low peritectic temperature to simplify directional solidification and the achievement of a high temperature gradient in the liquid, a broad composition range for the peritectic reaction, and a reasonable hardness at room temperature to facilitate handling and metallographic preparation. The In-Sn system was selected initially due to a very low peritectic temperature and the nearly equal densities of In and Sn in the liquid state. Since the In-rich peritectic reaction had apparently not been utilized previously for solidification research, experiments were conducted to check the phase diagram in the region of interest. The alloys in this system proved to be difficult to handle and prepare in bulk form with the equipment available, so experiments were initiated with the Sn-Cd system. Layered microstructures had been observed previously in Sn-Cd.

Thermodynamic Modeling of Ag-Ni System Combining Experiments and Molecular Dynamic Simulation

NASA Astrophysics Data System (ADS)

Rajkumar, V. B.; Chen, Sinn-wen

2017-04-01

Ag-Ni is a simple and important system with immiscible liquids and (Ag,Ni) phases. Previously, this system has been thermodynamically modeled utilizing certain thermochemical and phase equilibria information based on conjecture. An attempt is made in this study to determine the missing information which are difficult to measure experimentally. The boundaries of the liquid miscibility gap at high temperatures are determined using a pyrometer. The temperature of the liquid ⇌ (Ag) + (Ni) eutectic reaction is measured using differential thermal analysis. Tie-lines of the Ag-Ni system at 1023 K and 1473 K are measured using a conventional metallurgical method. The enthalpy of mixing of the liquid at 1773 K and the (Ag,Ni) at 973 K is calculated by molecular dynamics simulation using a large-scale atomic/molecular massively parallel simulator. These results along with literature information are used to model the Gibbs energy of the liquid and (Ag,Ni) by a calculation of phase diagrams approach, and the Ag-Ni phase diagram is then calculated.

Calcium-aluminum-rich inclusions in the Allende meteorite - Evidence for a liquid origin

NASA Technical Reports Server (NTRS)

Blander, M.; Fuchs, L. H.

1975-01-01

We have made a detailed examination of the mineralogy, textures, and assemblages of six calcium-aluminum-rich inclusions (CAI) in the Allende meteorite. They can be classified into four types - hibonite-bearing, fassaite- and olivine-bearing, feldspathoid-bearing and fassaite-bearing CAI that are hibonite and olivine free. Examples of each type appear to have crystallized from a liquid rather than by agglomeration of solid nebular condensates. Some lines of evidence for a liquid origin are the presence of spherical and ovoid shapes and rims containing minerals that are more refractory than minerals inside the inclusion. Thermodynamic calculations and comparisons with liquidus phase diagrams indicate that the CAI could have been produced by direct condensation to metastable subcooled liquids that subsequently crystallized or by remelting of an equilibrium high-temperature condensate by impact. The diopside rims in some hibonite-bearing CAI and the paucity of metal in fassaite-olivine-bearing CAI are more consistent with direct condensation of a liquid.

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.

Analytical description of the ternary melt and solution crystallization with a non-linear phase diagram

NASA Astrophysics Data System (ADS)

Toropova, L. V.; Alexandrov, D. V.

2018-05-01

The directional solidification of a ternary system with an extended phase transition region is theoretically studied. A mathematical model is developed to describe quasi-stationary solidification, and its analytical solution is constructed with allowance for a nonlinear liquids line equation. We demonstrate that the phase diagram nonlinearity leads to substantial changes of analytical solutions.

Phase diagram of heteronuclear Janus dumbbells

NASA Astrophysics Data System (ADS)

O'Toole, Patrick; Giacometti, Achille; Hudson, Toby

Using Aggregation-Volume-Bias Monte Carlo simulations along with Successive Umbrella Sampling and Histogram Re-weighting, we study the phase diagram of a system of dumbbells formed by two touching spheres having variable sizes, as well as different interaction properties. The first sphere ($h$) interacts with all other spheres belonging to different dumbbells with a hard-sphere potential. The second sphere ($s$) interacts via a square-well interaction with other $s$ spheres belonging to different dumbbells and with a hard-sphere potential with all remaining $h$ spheres. We focus on the region where the $s$ sphere is larger than the $h$ sphere, as measured by a parameter $1\\le \\alpha\\le 2 $ controlling the relative size of the two spheres. As $\\alpha \\to 2$ a simple fluid of square-well spheres is recovered, whereas $\\alpha \\to 1$ corresponds to the Janus dumbbell limit, where the $h$ and $s$ spheres have equal sizes. Many phase diagrams falling into three classes are observed, depending on the value of $\\alpha$. The $1.8 \\le \\alpha \\le 2$ is dominated by a gas-liquid phase separation very similar to that of a pure square-well fluid with varied critical temperature and density. When $1.3 \\le \\alpha \\le 1.8$ we find a progressive destabilization of the gas-liquid phase diagram by the onset of self-assembled structures, that eventually lead to a metastability of the gas-liquid transition below $\\alpha=1.2$.

Mapping Isobaric Aging onto the Equilibrium Phase Diagram.

PubMed

Niss, Kristine

2017-09-15

The linear volume relaxation and the nonlinear volume aging of a glass-forming liquid are measured, directly compared, and used to extract the out-of-equilibrium relaxation time. This opens a window to investigate how the relaxation time depends on temperature, structure, and volume in parts of phase space that are not accessed by the equilibrium liquid. It is found that the temperature dependence of relaxation time is non-Arrhenius even in the isostructural case-challenging the Adam-Gibbs entropy model. Based on the presented data and the idea that aging happens through quasiequilibrium states, we suggest a mapping of the out-of-equilibrium states during isobaric aging to the equilibrium phase diagram. This mapping implies the existence of isostructural lines in the equilibrium phase diagram. The relaxation time is found to depend on the bath temperature, density, and a just single structural parameter, referred to as an effective temperature.

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.

Unified phonon-based approach to the thermodynamics of solid, liquid and gas states

NASA Astrophysics Data System (ADS)

Bolmatov, Dima; Zav'yalov, Dmitry; Zhernenkov, Mikhail; Musaev, Edvard T.; Cai, Yong Q.

2015-12-01

We introduce a unified approach to states of matter (solid, liquid and gas) and describe the thermodynamics of the pressure-temperature phase diagram in terms of phonon excitations. We derive the effective Hamiltonian with low-energy cutoff in two transverse phonon polarizations (phononic band gaps) by breaking the symmetry in phonon interactions. Further, we construct the statistical mechanics of states of aggregation employing the Debye approximation. The introduced formalism covers the Debye theory of solids, the phonon theory of liquids, and thermodynamic limits such as the Dulong-Petit thermodynamic limit (cV = 3kB), the ideal gas limit (cV =3/2 kB) and the new thermodynamic limit (cV = 2kB), dubbed here the Frenkel line thermodynamic limit. We discuss the phonon propagation and localization effects in liquids above and below the Frenkel line, and explain the "fast sound" phenomenon. As a test for our theory we calculate velocity-velocity autocorrelation and pair distribution functions within the Green-Kubo formalism. We show the consistency between dynamics of phonons and pair correlations in the framework of the unified approach. New directions towards advancements in phononic band gaps engineering, hypersound manipulation technologies and exploration of exotic behaviour of fluids relevant to geo- and planetary sciences are discussed. The presented results are equally important both for practical implications and for fundamental research.

Quantitative ionspray liquid chromatographic/tandem mass spectrometric determination of reserpine in equine plasma.

PubMed

Anderson, M A; Wachs, T; Henion, J D

1997-02-01

A method based on ionspray liquid chromatography/tandem mass spectrometry (LC/MS/MS) was developed for the determination of reserpine in equine plasma. A comparison was made of the isolation of reserpine from plasma by liquid-liquid extraction and by solid-phase extraction. A structural analog, rescinnamine, was used as the internal standard. The reconstituted extracts were analyzed by ionspray LC/MS/MS in the selected reaction monitoring (SRM) mode. The calibration graph for reserpine extracted from equine plasma obtained using liquid-liquid extraction was linear from 10 to 5000 pg ml-1 and that using solid-phase extraction from 100 to 5000 pg ml-1. The lower level of quantitation (LLQ) using liquid-liquid and solid-phase extraction was 50 and 200 pg ml-1, respectively. The lower level of detection for reserpine by LC/MS/MS was 10 pg ml-1. The intra-assay accuracy did not exceed 13% for liquid-liquid and 12% for solid-phase extraction. The recoveries for the LLQ were 68% for liquid-liquid and 58% for solid-phase extraction.

Phase relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

USGS Publications Warehouse

Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.

1992-01-01

The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.

Heating-induced glass-glass and glass-liquid transformations in computer simulations of water.

PubMed

Chiu, Janet; Starr, Francis W; Giovambattista, Nicolas

2014-03-21

Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T "phase diagram" for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related, both being associated with the limit of kinetic stability of LDA (HDA).

Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

NASA Astrophysics Data System (ADS)

Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

2014-03-01

Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T "phase diagram" for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related, both being associated with the limit of kinetic stability of LDA (HDA).

Two liquid states of matter: a dynamic line on a phase diagram.

PubMed

Brazhkin, V V; Fomin, Yu D; Lyapin, A G; Ryzhov, V N; Trachenko, K

2012-03-01

It is generally agreed that the supercritical region of a liquid consists of one single state (supercritical fluid). On the other hand, we show here that liquids in this region exist in two qualitatively different states: "rigid" and "nonrigid" liquids. Rigid to nonrigid transition corresponds to the condition τ≈τ(0), where τ is the liquid relaxation time and τ(0) is the minimal period of transverse quasiharmonic waves. This condition defines a new dynamic crossover line on the phase diagram and corresponds to the loss of shear stiffness of a liquid at all available frequencies and, consequently, to the qualitative change in many important liquid properties. We analyze this line theoretically as well as in real and model fluids and show that the transition corresponds to the disappearance of high-frequency sound, to the disappearance of roton minima, qualitative changes in the temperature dependencies of sound velocity, diffusion, viscous flow, and thermal conductivity, an increase in particle thermal speed to half the speed of sound, and a reduction in the constant volume specific heat to 2k(B) per particle. In contrast to the Widom line that exists near the critical point only, the new dynamic line is universal: It separates two liquid states at arbitrarily high pressure and temperature and exists in systems where liquid-gas transition and the critical point are absent altogether. We propose to call the new dynamic line on the phase diagram "Frenkel line".

Critical point analysis of phase envelope diagram

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

Soetikno, Darmadi; Siagian, Ucok W. R.; Kusdiantara, Rudy, E-mail: rkusdiantara@s.itb.ac.id

2014-03-24

Phase diagram or phase envelope is a relation between temperature and pressure that shows the condition of equilibria between the different phases of chemical compounds, mixture of compounds, and solutions. Phase diagram is an important issue in chemical thermodynamics and hydrocarbon reservoir. It is very useful for process simulation, hydrocarbon reactor design, and petroleum engineering studies. It is constructed from the bubble line, dew line, and critical point. Bubble line and dew line are composed of bubble points and dew points, respectively. Bubble point is the first point at which the gas is formed when a liquid is heated. Meanwhile,more » dew point is the first point where the liquid is formed when the gas is cooled. Critical point is the point where all of the properties of gases and liquids are equal, such as temperature, pressure, amount of substance, and others. Critical point is very useful in fuel processing and dissolution of certain chemicals. Here in this paper, we will show the critical point analytically. Then, it will be compared with numerical calculations of Peng-Robinson equation by using Newton-Raphson method. As case studies, several hydrocarbon mixtures are simulated using by Matlab.« less

Kinetic Monte Carlo Simulations of Rod Eutectics and the Surface Roughening Transition in Binary Alloys

NASA Technical Reports Server (NTRS)

Bentz, Daniel N.; Betush, William; Jackson, Kenneth A.

2003-01-01

In this paper we report on two related topics: Kinetic Monte Carlo simulations of the steady state growth of rod eutectics from the melt, and a study of the surface roughness of binary alloys. We have implemented a three dimensional kinetic Monte Carlo (kMC) simulation with diffusion by pair exchange only in the liquid phase. Entropies of fusion are first chosen to fit the surface roughness of the pure materials, and the bond energies are derived from the equilibrium phase diagram, by treating the solid and liquid as regular and ideal solutions respectively. A simple cubic lattice oriented in the {100} direction is used. Growth of the rods is initiated from columns of pure B material embedded in an A matrix, arranged in a close packed array with semi-periodic boundary conditions. The simulation cells typically have dimensions of 50 by 87 by 200 unit cells. Steady state growth is compliant with the Jackson-Hunt model. In the kMC simulations, using the spin-one Ising model, growth of each phase is faceted or nonfaceted phases depending on the entropy of fusion. There have been many studies of the surface roughening transition in single component systems, but none for binary alloy systems. The location of the surface roughening transition for the phases of a eutectic alloy determines whether the eutectic morphology will be regular or irregular. We have conducted a study of surface roughness on the spin-one Ising Model with diffusion using kMC. The surface roughness was found to scale with the melting temperature of the alloy as given by the liquidus line on the equilibrium phase diagram. The density of missing lateral bonds at the surface was used as a measure of surface roughness.

SOLID-LIQUID PHASE TRANSFER CATALYZED SYNTHESIS OF CINNAMYL ACETATE-KINETICS AND ANALYSIS OF FACTORS AFFECTING THE REACTION IN A BATCH REACTOR

EPA Science Inventory

The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...

Polymorphism of phosphoric oxide

USGS Publications Warehouse

Hill, W.L.; Faust, G.T.; Hendricks, S.B.

1943-01-01

The melting points and monotropic relationship of three crystalline forms of phosphoric oxide were determined by the method of quenching. Previous vapor pressure data are discussed and interpreted to establish a pressure-temperature diagram (70 to 600??) for the one-component system. The system involves three triple points, at which solid, liquid and vapor (P4O10) coexist in equilibrium, namely: 420?? and 360 cm., 562?? and 43.7 cm. and 580?? and 55.5 cm., corresponding to the hexagonal, orthorhombic and stable polymorphs, respectively, and at least two distinct liquids, one a stable polymer of the other, which are identified with the melting of the stable form and the hexagonal modification, respectively. Indices of refraction of the polymorphs and glasses were determined. The density and the thermal, hygroscopic and structural properties of the several phases are discussed.

Identification of the states of the processes at liquid cathodes under potentiostatic conditions using semantic diagram models

NASA Astrophysics Data System (ADS)

Smirnov, G. B.; Markina, S. E.; Tomashevich, V. G.

2012-08-01

A technique is described for constructing semantic diagram models of the electrolysis at a liquid cathode in a salt halide melt under potentiostatic conditions that are intended for identifying the static states of this system that correspond to certain combinations of the electrode processes or the processes occurring in the volumes of salt and liquid-metal phases. Examples are given for the discharge of univalent and polyvalent metals.

Theoretical calculation of the melting curve of Cu-Zr binary alloys

DOE PAGES

Gunawardana, K. G.S.H.; Wilson, S. R.; Mendelev, M. I.; ...

2014-11-14

Helmholtz free energies of the dominant binary crystalline solids found in the Cu-Zr system at high temperatures close to the melting curve are calculated. This theoretical approach combines fundamental measure density functional theory (applied to the hard-sphere reference system) and a perturbative approach to include the attractive interactions. The studied crystalline solids are Cu(fcc), Cu 51Zr 14(β), CuZr(B 2), CuZr 2(C11b), Zr(hcp), and Zr(bcc). The calculated Helmholtz free energies of crystalline solids are in good agreement with results from molecular-dynamics (MD) simulations. Using the same perturbation approach, the liquid phase free energies are calculated as a function of composition andmore » temperature, from which the melting curve of the entire composition range of this system can be obtained. Phase diagrams are determined in this way for two leading embedded atom method potentials, and the results are compared with experimental data. Furthermore, theoretical melting temperatures are compared both with experimental values and with values obtained directly from MD simulations at several compositions.« less

Quantum Monte Carlo study of the phase diagram of solid molecular hydrogen at extreme pressures

PubMed Central

Drummond, N. D.; Monserrat, Bartomeu; Lloyd-Williams, Jonathan H.; Ríos, P. López; Pickard, Chris J.; Needs, R. J.

2015-01-01

Establishing the phase diagram of hydrogen is a major challenge for experimental and theoretical physics. Experiment alone cannot establish the atomic structure of solid hydrogen at high pressure, because hydrogen scatters X-rays only weakly. Instead, our understanding of the atomic structure is largely based on density functional theory (DFT). By comparing Raman spectra for low-energy structures found in DFT searches with experimental spectra, candidate atomic structures have been identified for each experimentally observed phase. Unfortunately, DFT predicts a metallic structure to be energetically favoured at a broad range of pressures up to 400 GPa, where it is known experimentally that hydrogen is non-metallic. Here we show that more advanced theoretical methods (diffusion quantum Monte Carlo calculations) find the metallic structure to be uncompetitive, and predict a phase diagram in reasonable agreement with experiment. This greatly strengthens the claim that the candidate atomic structures accurately model the experimentally observed phases. PMID:26215251

Binary nanoparticle superlattices of soft-particle systems

DOE PAGES

Travesset, Alex

2015-08-04

The solid-phase diagram of binary systems consisting of particles of diameter σ A=σ and σ B=γσ (γ≤1) interacting with an inverse p = 12 power law is investigated as a paradigm of a soft potential. In addition to the diameter ratio γ that characterizes hard-sphere models, the phase diagram is a function of an additional parameter that controls the relative interaction strength between the different particle types. Phase diagrams are determined from extremes of thermodynamic functions by considering 15 candidate lattices. In general, it is shown that the phase diagram of a soft repulsive potential leads to the morphological diversitymore » observed in experiments with binary nanoparticles, thus providing a general framework to understand their phase diagrams. In addition, particular emphasis is shown to the two most successful crystallization strategies so far: evaporation of solvent from nanoparticles with grafted hydrocarbon ligands and DNA programmable self-assembly.« less

Effect of solid-meal caloric content on gastric emptying kinetics of solids and liquids.

PubMed

Urbain, J L; Siegel, J A; Mortelmans, L; van Cutsem, E; van den Maegdenbergh, V; de Roo, M

1989-08-01

In this study, we have evaluated the effect of the caloric content of a physiological test meal on the gastric emptying kinetics of solids and liquids. 22 healthy male volunteers were studied in two groups matched for age. After an overnight fast, each volunteer underwent the same test procedure; in the first group (G I), 10 volunteers received a meal consisting of bread, 111In-DTPA water and 1 scrambled egg labeled with 99mTc-labelled sulphur colloid; in the second group (G II) 12 volunteers were given the same meal but with 2 labeled eggs in order to increase the caloric content of the solid phase meal. Simultaneous anterior and posterior images were recorded using a dual-headed gamma camera. Solid and liquid geometric mean data were analyzed to determine the lag phase, the emptying rate and the half-emptying time for both solids and liquids. Solid and liquid gastric half-emptying times were significantly prolonged in G II compared to G I volunteers. For the solid phased, the delay was accounted for by a longer lag phase and a decrease in the equilibrium emptying rate. The emptying rate of the liquid phase was significantly decreased in G II compared to G I. Within each group, no statistically significant difference was observed between solid and liquid emptying rates. We conclude that the caloric content of the solid portion of a meal not only alters the emptying of the solid phase but also affects the emptying of the liquid component of the meal.

The solidification of Al–Pd–Mn studied by high-energy X-ray diffraction from electrostatically levitated samples

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

Quirinale, Dante G.

Here, we report on the results of a high-energy x-ray diffraction study of Al–Pd–Mn to investigate the solidification products obtained during free-cooling using an electrostatic levitation furnace. The primary solidification product from the melt is i-Al–Pd–Mn which coexists with a significant remaining liquid component. As the sample cools further, we find that the solidification pathway is consistent with the liquidus projection and pseudo-binary cut through the ternary phase diagram reported previously. At ambient temperature we have identified the major phase to be the ξ'-phase orthorhombic approximant, along with minor phases identified as Al and, most likely, the R-phase orthorhombic approximant.more » We have also observed a distinct prepeak in the liquid at high temperature, signifying the presence of extended atomic order. Interestingly, this prepeak was not observed in previous neutron diffraction measurements on the Al–Pd–Mn system. No undercooling was observed preceding the solidification of the i-Al–Pd–Mn phase from the melt which may signal the close similarity of the short-range order in the solid and liquid. However, this can not be clearly determined because of the potential for heterogenous nucleation associated with the presence of an Al2O3 impurity at the surface of the sample.« less

Anisotropy of the solid–liquid interface properties of the Ni–Zr B33 phase from molecular dynamics simulation

DOE PAGES

Wilson, S. R.; Mendelev, M. I.

2015-01-08

Solid–liquid interface (SLI) properties of the Ni–Zr B33 phase were determined from molecular dynamics simulations. In order to perform these measurements, a new semi-empirical potential for Ni–Zr alloy was developed that well reproduces the material properties required to model SLIs in the Ni 50.0Zr 50.0 alloy. In particular, the developed potential is shown to provide that the solid phase emerging from the liquid Ni 50.0Zr 50.0alloy is B33 (apart from a small fraction of point defects), in agreement with the experimental phase diagram. The SLI properties obtained using the developed potential exhibit an extraordinary degree of anisotropy. It is observedmore » that anisotropies in both the interfacial free energy and mobility are an order of magnitude larger than those measured to date in any other metallic compound. Moreover, the [0 1 0] interface is shown to play a significant role in the observed anisotropy. Our data suggest that the [0 1 0] interface simultaneously corresponds to the lowest mobility, the lowest free energy and the highest stiffness of all inclinations in B33 Ni–Zr. This finding can be understood by taking into account a rather complicated crystal structure in this crystallographic direction.« less

Modeling of Shock Waves with Multiple Phase Transitions in Condensed Materials

NASA Astrophysics Data System (ADS)

Missonnier, Marc; Heuzé, Olivier

2006-07-01

When a shock wave crosses a solid material and subjects it to solid-solid or solid-liquid phase transition, related phenomena occur: shock splitting, and the corresponding released shock wave after reflection. Modelling of these phenomena raises physical and numerical issues. After shock loading, such materials can reach different kinds of states: single-phase states, binary-phase states, and triple points. The thermodynamic path can be studied and easily understood in the (V,E) or (V,S) planes. In the case of 3 phase tin (β,γ, and liquid) submitted to shock waves, seven states can occur: β,γ, liquid, β-γ, β-liquid, γ-liquid, and β-γ-liquid. After studying the thermodynamic properties with a complete 3-phase Equation of State, we show the existence of these seven states with a hydrodynamic simulation.

Tube Radial Distribution Flow Separation in a Microchannel Using an Ionic Liquid Aqueous Two-Phase System Based on Phase Separation Multi-Phase Flow.

PubMed

Nagatani, Kosuke; Shihata, Yoshinori; Matsushita, Takahiro; Tsukagoshi, Kazuhiko

2016-01-01

Ionic liquid aqueous two-phase systems were delivered into a capillary tube to achieve tube radial distribution flow (TRDF) or annular flow in a microspace. The phase diagram, viscosity of the phases, and TRDF image of the 1-butyl-3-methylimidazolium chloride and NaOH system were examined. The TRDF was formed with inner ionic liquid-rich and outer ionic liquid-poor phases in the capillary tube. The phase configuration was explained using the viscous dissipation principle. We also examined the distribution of rhodamine B in a three-branched microchannel on a microchip with ionic liquid aqueous two-phase systems for the first time.

Cloud Point and Liquid-Liquid Equilibrium Behavior of Thermosensitive Polymer L61 and Salt Aqueous Two-Phase System.

PubMed

Rao, Wenwei; Wang, Yun; Han, Juan; Wang, Lei; Chen, Tong; Liu, Yan; Ni, Liang

2015-06-25

The cloud point of thermosensitive triblock polymer L61, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO), was determined in the presence of various electrolytes (K2HPO4, (NH4)3C6H5O7, and K3C6H5O7). The cloud point of L61 was lowered by the addition of electrolytes, and the cloud point of L61 decreased linearly with increasing electrolyte concentration. The efficacy of electrolytes on reducing cloud point followed the order: K3C6H5O7 > (NH4)3C6H5O7 > K2HPO4. With the increase in salt concentration, aqueous two-phase systems exhibited a phase inversion. In addition, increasing the temperature reduced the concentration of salt needed that could promote phase inversion. The phase diagrams and liquid-liquid equilibrium data of the L61-K2HPO4/(NH4)3C6H5O7/K3C6H5O7 aqueous two-phase systems (before the phase inversion but also after phase inversion) were determined at T = (25, 30, and 35) °C. Phase diagrams of aqueous two-phase systems were fitted to a four-parameter empirical nonlinear expression. Moreover, the slopes of the tie-lines and the area of two-phase region in the diagram have a tendency to rise with increasing temperature. The capacity of different salts to induce aqueous two-phase system formation was the same order as the ability of salts to reduce the cloud point.

Fractionalized Fermi liquids and exotic superconductivity in the Kitaev-Kondo lattice

NASA Astrophysics Data System (ADS)

Seifert, Urban F. P.; Meng, Tobias; Vojta, Matthias

2018-02-01

Fractionalized Fermi liquids (FL*) have been introduced as non-Fermi-liquid metallic phases, characterized by coexisting electron-like charge carriers and local moments which form a fractionalized spin liquid. Here we investigate a Kondo lattice model on the honeycomb lattice with Kitaev interactions among the local moments, a concrete model hosting FL* phases based on Kitaev's Z2 spin liquid. We characterize the FL* phases via perturbation theory, and we employ a Majorana-fermion mean-field theory to map out the full phase diagram. Most remarkably we find nematic triplet superconducting phases which mask the quantum phase transition between fractionalized and conventional Fermi liquid phases. Their pairing structure is inherited from the Kitaev spin liquid; i.e., superconductivity is driven by Majorana glue.

Wetting of heterogeneous substrates. A classical density-functional-theory approach

NASA Astrophysics Data System (ADS)

Yatsyshin, Peter; Parry, Andrew O.; Rascón, Carlos; Duran-Olivencia, Miguel A.; Kalliadasis, Serafim

2017-11-01

Wetting is a nucleation of a third phase (liquid) on the interface between two different phases (solid and gas). In many experimentally accessible cases of wetting, the interplay between the substrate structure, and the fluid-fluid and fluid-substrate intermolecular interactions leads to the appearance of a whole ``zoo'' of exciting interface phase transitions, associated with the formation of nano-droplets/bubbles, and thin films. Practical applications of wetting at small scales are numerous and include the design of lab-on-a-chip devices and superhydrophobic surfaces. In this talk, we will use a fully microscopic approach to explore the phase space of a planar wall, decorated with patches of different hydrophobicity, and demonstrate the highly non-trivial behaviour of the liquid-gas interface near the substrate. We will present fluid density profiles, adsorption isotherms and wetting phase diagrams. Our analysis is based on a formulation of statistical mechanics, commonly known as classical density-functional theory. It provides a computationally-friendly and rigorous framework, suitable for probing small-scale physics of classical fluids and other soft-matter systems. EPSRC Grants No. EP/L027186,EP/K503733;ERC Advanced Grant No. 247031.

Ground-state phase diagram of an anisotropic spin-1/2 model on the triangular lattice

NASA Astrophysics Data System (ADS)

Luo, Qiang; Hu, Shijie; Xi, Bin; Zhao, Jize; Wang, Xiaoqun

2017-04-01

Motivated by a recent experiment on the rare-earth material YbMgGaO4 [Y. Li et al., Phys. Rev. Lett. 115, 167203 (2015), 10.1103/PhysRevLett.115.167203], which found that the ground state of YbMgGaO4 is a quantum spin liquid, we study the ground-state phase diagram of an anisotropic spin-1 /2 model that was proposed to describe YbMgGaO4. Using the density matrix renormalization-group method in combination with the exact-diagonalization method, we calculate a variety of physical quantities, including the ground-state energy, the fidelity, the entanglement entropy and spin-spin correlation functions. Our studies show that in the quantum phase diagram, there is a 120∘ phase and two distinct stripe phases. The transitions from the two stripe phases to the 120∘ phase are of the first order. However, the transition between the two stripe phases is not of the first order, which is different from its classical counterpart. Additionally, we find no evidence for a quantum spin liquid in this model. Our results suggest that additional terms may also be important to model the material YbMgGaO4. These findings will stimulate further experimental and theoretical works in understanding the quantum spin-liquid ground state in YbMgGaO4.

Comparing the catalytic oxidation of ethanol at the solid-gas and solid-liquid interfaces over size-controlled Pt nanoparticles: striking differences in kinetics and mechanism.

PubMed

Sapi, Andras; Liu, Fudong; Cai, Xiaojun; Thompson, Christopher M; Wang, Hailiang; An, Kwangjin; Krier, James M; Somorjai, Gabor A

2014-11-12

Pt nanoparticles with controlled size (2, 4, and 6 nm) are synthesized and tested in ethanol oxidation by molecular oxygen at 60 °C to acetaldehyde and carbon dioxide both in the gas and liquid phases. The turnover frequency of the reaction is ∼80 times faster, and the activation energy is ∼5 times higher at the gas-solid interface compared to the liquid-solid interface. The catalytic activity is highly dependent on the size of the Pt nanoparticles; however, the selectivity is not size sensitive. Acetaldehyde is the main product in both media, while twice as much carbon dioxide was observed in the gas phase compared to the liquid phase. Added water boosts the reaction in the liquid phase; however, it acts as an inhibitor in the gas phase. The more water vapor was added, the more carbon dioxide was formed in the gas phase, while the selectivity was not affected by the concentration of the water in the liquid phase. The differences in the reaction kinetics of the solid-gas and solid-liquid interfaces can be attributed to the molecular orientation deviation of the ethanol molecules on the Pt surface in the gas and liquid phases as evidenced by sum frequency generation vibrational spectroscopy.

40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

Code of Federal Regulations, 2010 CFR

2010-07-01

... solid phases of a material. 227.32 Section 227.32 Protection of Environment ENVIRONMENTAL PROTECTION... MATERIALS Definitions § 227.32 Liquid, suspended particulate, and solid phases of a material. (a) For the... obtained above prior to centrifugation and filtration. The solid phase includes all material settling to...

40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

Code of Federal Regulations, 2011 CFR

2011-07-01

... solid phases of a material. 227.32 Section 227.32 Protection of Environment ENVIRONMENTAL PROTECTION... MATERIALS Definitions § 227.32 Liquid, suspended particulate, and solid phases of a material. (a) For the... obtained above prior to centrifugation and filtration. The solid phase includes all material settling to...

Modes of failure in disordered solids

NASA Astrophysics Data System (ADS)

Roy, Subhadeep; Biswas, Soumyajyoti; Ray, Purusattam

2017-12-01

The two principal ingredients determining the failure modes of disordered solids are the strength of heterogeneity and the length scale of the region affected in the solid following a local failure. While the latter facilitates damage nucleation, the former leads to diffused damage—the two extreme natures of the failure modes. In this study, using the random fiber bundle model as a prototype for disordered solids, we classify all failure modes that are the results of interplay between these two effects. We obtain scaling criteria for the different modes and propose a general phase diagram that provides a framework for understanding previous theoretical and experimental attempts of interpolation between these modes. As the fiber bundle model is a long-standing model for interpreting various features of stressed disordered solids, the general phase diagram can serve as a guiding principle in anticipating the responses of disordered solids in general.

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

Selle, J E

Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussedmore » in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented.« less

Construction of drug-polymer thermodynamic phase diagrams using Flory-Huggins interaction theory: identifying the relevance of temperature and drug weight fraction to phase separation within solid dispersions.

PubMed

Tian, Yiwei; Booth, Jonathan; Meehan, Elizabeth; Jones, David S; Li, Shu; Andrews, Gavin P

2013-01-07

Amorphous drug-polymer solid dispersions have the potential to enhance the dissolution performance and thus bioavailability of BCS class II drug compounds. The principle drawback of this approach is the limited physical stability of amorphous drug within the dispersion. Accurate determination of the solubility and miscibility of drug in the polymer matrix is the key to the successful design and development of such systems. In this paper, we propose a novel method, based on Flory-Huggins theory, to predict and compare the solubility and miscibility of drug in polymeric systems. The systems chosen for this study are (1) hydroxypropyl methylcellulose acetate succinate HF grade (HPMCAS-HF)-felodipine (FD) and (2) Soluplus (a graft copolymer of polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol)-FD. Samples containing different drug compositions were mixed, ball milled, and then analyzed by differential scanning calorimetry (DSC). The value of the drug-polymer interaction parameter χ was calculated from the crystalline drug melting depression data and extrapolated to lower temperatures. The interaction parameter χ was also calculated at 25 °C for both systems using the van Krevelen solubility parameter method. The rank order of interaction parameters of the two systems obtained at this temperature was comparable. Diagrams of drug-polymer temperature-composition and free energy of mixing (ΔG(mix)) were constructed for both systems. The maximum crystalline drug solubility and amorphous drug miscibility may be predicted based on the phase diagrams. Hyper-DSC was used to assess the validity of constructed phase diagrams by annealing solid dispersions at specific drug loadings. Three different samples for each polymer were selected to represent different regions within the phase diagram.

Re-entrant phase behavior for systems with competition between phase separation and self-assembly

NASA Astrophysics Data System (ADS)

Reinhardt, Aleks; Williamson, Alexander J.; Doye, Jonathan P. K.; Carrete, Jesús; Varela, Luis M.; Louis, Ard A.

2011-03-01

In patchy particle systems where there is a competition between the self-assembly of finite clusters and liquid-vapor phase separation, re-entrant phase behavior can be observed, with the system passing from a monomeric vapor phase to a region of liquid-vapor phase coexistence and then to a vapor phase of clusters as the temperature is decreased at constant density. Here, we present a classical statistical mechanical approach to the determination of the complete phase diagram of such a system. We model the system as a van der Waals fluid, but one where the monomers can assemble into monodisperse clusters that have no attractive interactions with any of the other species. The resulting phase diagrams show a clear region of re-entrance. However, for the most physically reasonable parameter values of the model, this behavior is restricted to a certain range of density, with phase separation still persisting at high densities.

Developpement de techniques numeriques pour l'estimation, la modelisation et la prediction de proprietes thermodynamiques et structurales de systems metalliques a fort ordonnancement chimique

NASA Astrophysics Data System (ADS)

Harvey, Jean-Philippe

In this work, the possibility to calculate and evaluate with a high degree of precision the Gibbs energy of complex multiphase equilibria for which chemical ordering is explicitly and simultaneously considered in the thermodynamic description of solid (short range order and long range order) and liquid (short range order) metallic phases is studied. The cluster site approximation (CSA) and the cluster variation method (CVM) are implemented in a new minimization technique of the Gibbs energy of multicomponent and multiphase systems to describe the thermodynamic behaviour of metallic solid solutions showing strong chemical ordering. The modified quasichemical model in the pair approximation (MQMPA) is also implemented in the new minimization algorithm presented in this work to describe the thermodynamic behaviour of metallic liquid solutions. The constrained minimization technique implemented in this work consists of a sequential quadratic programming technique based on an exact Newton’s method (i.e. the use of exact second derivatives in the determination of the Hessian of the objective function) combined to a line search method to identify a direction of sufficient decrease of the merit function. The implementation of a new algorithm to perform the constrained minimization of the Gibbs energy is justified by the difficulty to identify, in specific cases, the correct multiphase assemblage of a system where the thermodynamic behaviour of the equilibrium phases is described by one of the previously quoted models using the FactSage software (ex.: solid_CSA+liquid_MQMPA; solid1_CSA+solid2_CSA). After a rigorous validation of the constrained Gibbs energy minimization algorithm using several assessed binary and ternary systems found in the literature, the CVM and the CSA models used to describe the energetic behaviour of metallic solid solutions present in systems with key industrial applications such as the Cu-Zr and the Al-Zr systems are parameterized using fully consistent thermodynamic an structural data generated from a Monte Carlo (MC) simulator also implemented in the framework of this project. In this MC simulator, the modified embedded atom model in the second nearest neighbour formalism (MEAM-2NN) is used to describe the cohesive energy of each studied structure. A new Al-Zr MEAM-2NN interatomic potential needed to evaluate the cohesive energy of the condensed phases of this system is presented in this work. The thermodynamic integration (TI) method implemented in the MC simulator allows the evaluation of the absolute Gibbs energy of the considered solid or liquid structures. The original implementation of the TI method allowed us to evaluate theoretically for the first time all the thermodynamic mixing contributions (i.e., mixing enthalpy and mixing entropy contributions) of a metallic liquid (Cu-Zr and Al-Zr) and of a solid solution (face-centered cubic (FCC) Al-Zr solid solution) described by the MEAM-2NN. Thermodynamic and structural data obtained from MC and molecular dynamic simulations are then used to parameterize the CVM for the Al-Zr FCC solid solution and the MQMPA for the Al-Zr and the Cu-Zr liquid phase respectively. The extended thermodynamic study of these systems allow the introduction of a new type of configuration-dependent excess parameters in the definition of the thermodynamic function of solid solutions described by the CVM or the CSA. These parameters greatly improve the precision of these thermodynamic models based on experimental evidences found in the literature. A new parameterization approach of the MQMPA model of metallic liquid solutions is presented throughout this work. In this new approach, calculated pair fractions obtained from MC/MD simulations are taken into account as well as configuration-independent volumetric relaxation effects (regular like excess parameters) in order to parameterize precisely the Gibbs energy function of metallic melts. The generation of a complete set of fully consistent thermodynamic, physical and structural data for solid, liquid, and stoichiometric compounds and the subsequent parameterization of their respective thermodynamic model lead to the first description of the complete Al-Zr phase diagram in the range of composition [0 ≤ XZr ≤ 5 / 9] based on theoretical and fully consistent thermodynamic properties. MC and MD simulations are performed for the Al-Zr system to define for the first time the precise thermodynamic behaviour of the amorphous phase for its entire range of composition. Finally, all the thermodynamic models for the liquid phase, the FCC solid solution and the amorphous phase are used to define conditions based on thermodynamic and volumetric considerations that favor the amorphization of Al-Zr alloys.

Investigation of phase diagrams and physical stability of drug-polymer solid dispersions.

PubMed

Lu, Jiannan; Shah, Sejal; Jo, Seongbong; Majumdar, Soumyajit; Gryczke, Andreas; Kolter, Karl; Langley, Nigel; Repka, Michael A

2015-01-01

Solid dispersion technology has been widely explored to improve the solubility and bioavailability of poorly water-soluble compounds. One of the critical drawbacks associated with this technology is the lack of physical stability, i.e. the solid dispersion would undergo recrystallization or phase separation thus limiting a product's shelf life. In the current study, the melting point depression method was utilized to construct a complete phase diagram for felodipine (FEL)-Soluplus® (SOL) and ketoconazole (KTZ)-Soluplus® (SOL) binary systems, respectively, based on the Flory-Huggins theory. The miscibility or solubility of the two compounds in SOL was also determined. The Flory-Huggins interaction parameter χ values of both systems were calculated as positive at room temperature (25 °C), indicating either compound was miscible with SOL. In addition, the glass transition temperatures of both solid dispersion systems were theoretically predicted using three empirical equations and compared with the practical values. Furthermore, the FEL-SOL solid dispersions were subjected to accelerated stability studies for up to 3 months.

Phase diagram of the frustrated J 1 ‑ J 2 transverse field Ising model on the square lattice

NASA Astrophysics Data System (ADS)

Sadrzadeh, M.; Langari, A.

2018-03-01

We study the zero-temperature phase diagram of transverse field Ising model on the J 1 ‑ J 2 square lattice. In zero magnetic field, the model has a classical Néel phase for J 2/J 1 < 0.5 and an antiferromagnetic collinear phase for J 2/J 1 > 0.5. We incorporate harmonic fluctuations by using linear spin wave theory (LSWT) with single spin flip excitations above a magnetic order background and obtain the phase diagram of the model in this approximation. We find that harmonic quantum fluctuations of LSWT fail to lift the large degeneracy at J 2/J 1 = 0.5 and exhibit some inconsistent regions on the phase diagram. However, we show that anharmonic fluctuations of cluster operator approach (COA) resolve the inconsistency of the LSWT, which reveals a string-valence bond solid ordered phase for the highly frustrated region.

Scalability, Scintillation Readout and Charge Drift in a Kilogram Scale Solid Xenon Particle Detector

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

Yoo, J.; Cease, H.; Jaskierny, W. F.

2014-10-23

We report a demonstration of the scalability of optically transparent xenon in the solid phase for use as a particle detector above a kilogram scale. We employ a liquid nitrogen cooled cryostat combined with a xenon purification and chiller system to measure the scintillation light output and electron drift speed from both the solid and liquid phases of xenon. Scintillation light output from sealed radioactive sources is measured by a set of high quantum efficiency photomultiplier tubes suitable for cryogenic applications. We observed a reduced amount of photons in solid phase compared to that in liquid phase. We used amore » conventional time projection chamber system to measure the electron drift time in a kilogram of solid xenon and observed faster electron drift speed in the solid phase xenon compared to that in the liquid phase.« less

Modified-hypernetted-chain determination of the phase diagram of rigid C60 molecules

NASA Astrophysics Data System (ADS)

Caccamo, C.

1995-02-01

The modified-hypernetted-chain theory is applied to the determination of the phase diagram of the Lennard-Jones (LJ) fluid, and of a model of C60 previously investigated [Phys. Rev. Lett. 71, 1200 (1993)] through molecular-dynamics (MD) simulation and a different theoretical approach. In the LJ case the agreement with available MD data is quantitative and superior to other theories. For C60, the phase diagram obtained is in quite good agreement with previous MD results: in particular, the theory confirms the existence of a liquid phase between 1600 and 1920 K, the estimated triple point and critical temperature, respectively.

Floating liquid phase in sedimenting colloid-polymer mixtures.

PubMed

Schmidt, Matthias; Dijkstra, Marjolein; Hansen, Jean-Pierre

2004-08-20

Density functional theory and computer simulation are used to investigate sedimentation equilibria of colloid-polymer mixtures within the Asakura-Oosawa-Vrij model of hard sphere colloids and ideal polymers. When the ratio of buoyant masses of the two species is comparable to the ratio of differences in density of the coexisting bulk (colloid) gas and liquid phases, a stable "floating liquid" phase is found, i.e., a thin layer of liquid sandwiched between upper and lower gas phases. The full phase diagram of the mixture under gravity shows coexistence of this floating liquid phase with a single gas phase or a phase involving liquid-gas equilibrium; the phase coexistence lines meet at a triple point. This scenario remains valid for general asymmetric binary mixtures undergoing bulk phase separation.

Mechanism of Formation of Li 7 P 3 S 11 Solid Electrolytes through Liquid Phase Synthesis

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

Wang, Yuxing; Lu, Dongping; Bowden, Mark

Crystalline Li7P3S11 is a promising solid electrolyte for all solid state lithium/lithium ion batteries. A controllable liquid phase synthesis of Li7P3S11 is more desirable compared to conventional mechanochemical synthesis, but recent attempts suffer from reduced ionic conductivities. Here we elucidate the formation mechanism of crystalline Li7P3S11 synthesized in the liquid phase (acetonitrile, or ACN). We conclude that the crystalline Li7P3S11 forms through a two-step reaction: 1) formation of solid Li3PS4∙ACN and amorphous Li2S∙P2S5 phases in the liquid phase; 2) solid-state conversion of the two phases. The implication of this two-step reaction mechanism to the morphology control and the transport propertiesmore » of liquid phase synthesized Li7P3S11 is identified and discussed.« less

Method for removing solid particulate material from within liquid fuel injector assemblies

DOEpatents

Simandl, R.F.; Brown, J.D.; Andriulli, J.B.; Strain, P.D.

1998-09-08

A method is described for removing residual solid particulate material from the interior of liquid fuel injectors and other fluid flow control mechanisms having or being operatively associated with a flow-regulating fixed or variable orifice. The method comprises the sequential and alternate introduction of columns of a non-compressible liquid phase and columns of a compressed gas phase into the body of a fuel injector whereby the expansion of each column of the gas phase across the orifice accelerates the liquid phase in each trailing column of the liquid phase and thereby generates turbulence in each liquid phase for lifting and entraining the solid particulates for the subsequent removal thereof from the body of the fuel injector. 1 fig.

Method for removing solid particulate material from within liquid fuel injector assemblies

DOEpatents

Simandl, Ronald F.; Brown, John D.; Andriulli, John B.; Strain, Paul D.

1998-01-01

A method for removing residual solid particulate material from the interior of liquid fuel injectors and other fluid flow control mechanisms having or being operatively associated with a flow-regulating fixed or variable orifice. The method comprises the sequential and alternate introduction of columns of a non-compressible liquid phase and columns of a compressed gas phase into the body of a fuel injector whereby the expansion of each column of the gas phase across the orifice accelerates the liquid phase in each trailing column of the liquid phase and thereby generates turbulence in each liquid phase for lifting and entraining the solid particulates for the subsequent removal thereof from the body of the fuel injector.

Phase Diagrams and the Non-Linear Dielectric Constant in the Landau-Type Potential Including the Linear-Quadratic Coupling between Order Parameters

NASA Astrophysics Data System (ADS)

Iwata, Makoto; Orihara, Hiroshi; Ishibashi, Yoshihiro

1997-04-01

The phase diagrams in the Landau-type thermodynamic potential including the linear-quadratic coupling between order parameters p and q, i.e., qp2, which is applicable to the phase transition in the benzil, phospholipid bilayers, and the isotropic-nematic phase transition in liquid crystals, are studied. It was found that the phase diagram in the extreme case has one tricritical point c1, one critical end point e1, and two triple points t1 and t2. The linear and nonlinear dielectric constants in the potential are discussed in the case that the order parameter p is the polarization.

Phase Diagram of Quaternary System NaBr-KBr-CaBr2-H2O at 323 K

NASA Astrophysics Data System (ADS)

Cui, Rui-Zhi; Wang, Wei; Yang, Lei; Sang, Shi-Hua

2018-03-01

The phase equilibria in the system NaBr-KBr-CaBr2-H2O at 323 K were studied using the isothermal dissolution equilibrium method. Using the experimental solubilities of salts data, phase diagram was constructed. The phase diagram have two invariant points, five univariant curves, and four crystallization fields. The equilibrium solid phases in the system are NaBr, NaBr · 2H2O, KBr, and CaBr2 · 4H2O. The solubilities of salts in the system at 323 K were calculated by Pitzer's equation. There is shown that the calculated solubilities agree well with experimental data.

Thermodynamics and Equations of State of Iron to 350 GPa and 6000 K

NASA Astrophysics Data System (ADS)

Dorogokupets, P. I.; Dymshits, A. M.; Litasov, K. D.; Sokolova, T. S.

2017-03-01

The equations of state for solid (with bcc, fcc, and hcp structures) and liquid phases of Fe were defined via simultaneous optimization of the heat capacity, bulk moduli, thermal expansion, and volume at room and higher temperatures. The calculated triple points at the phase diagram have the following parameters: bcc-fcc-hcp is located at 7.3 GPa and 820 K, bcc-fcc-liquid at 5.2 GPa and 1998 K, and fcc-hcp-liquid at 106.5 GPa and 3787 K. At conditions near the fcc-hcp-liquid triple point, the Clapeyron slope of the fcc-liquid curve is dT/dP = 12.8 K/GPa while the slope of the hcp-liquid curve is higher (dT/dP = 13.7 K/GPa). Therefore, the hcp-liquid curve overlaps the metastable fcc-liquid curve at pressures of about 160 GPa. At high-pressure conditions, the metastable bcc-hcp curve is located inside the fcc-Fe or liquid stability field. The density, adiabatic bulk modulus and P-wave velocity of liquid Fe calculated up to 328.9 GPa at adiabatic temperature conditions started from 5882 K (outer/inner core boundary) were compared to the PREM seismological model. We determined the density deficit of hcp-Fe at the inner core boundary (T = 5882 K and P = 328.9 GPa) to be 4.4%.

Thermodynamics and Equations of State of Iron to 350 GPa and 6000 K.

PubMed

Dorogokupets, P I; Dymshits, A M; Litasov, K D; Sokolova, T S

2017-03-06

The equations of state for solid (with bcc, fcc, and hcp structures) and liquid phases of Fe were defined via simultaneous optimization of the heat capacity, bulk moduli, thermal expansion, and volume at room and higher temperatures. The calculated triple points at the phase diagram have the following parameters: bcc-fcc-hcp is located at 7.3 GPa and 820 K, bcc-fcc-liquid at 5.2 GPa and 1998 K, and fcc-hcp-liquid at 106.5 GPa and 3787 K. At conditions near the fcc-hcp-liquid triple point, the Clapeyron slope of the fcc-liquid curve is dT/dP = 12.8 K/GPa while the slope of the hcp-liquid curve is higher (dT/dP = 13.7 K/GPa). Therefore, the hcp-liquid curve overlaps the metastable fcc-liquid curve at pressures of about 160 GPa. At high-pressure conditions, the metastable bcc-hcp curve is located inside the fcc-Fe or liquid stability field. The density, adiabatic bulk modulus and P-wave velocity of liquid Fe calculated up to 328.9 GPa at adiabatic temperature conditions started from 5882 K (outer/inner core boundary) were compared to the PREM seismological model. We determined the density deficit of hcp-Fe at the inner core boundary (T = 5882 K and P = 328.9 GPa) to be 4.4%.

Thermodynamics and Equations of State of Iron to 350 GPa and 6000 K

PubMed Central

Dorogokupets, P. I.; Dymshits, A. M.; Litasov, K. D.; Sokolova, T. S.

2017-01-01

The equations of state for solid (with bcc, fcc, and hcp structures) and liquid phases of Fe were defined via simultaneous optimization of the heat capacity, bulk moduli, thermal expansion, and volume at room and higher temperatures. The calculated triple points at the phase diagram have the following parameters: bcc–fcc–hcp is located at 7.3 GPa and 820 K, bcc–fcc–liquid at 5.2 GPa and 1998 K, and fcc–hcp–liquid at 106.5 GPa and 3787 K. At conditions near the fcc–hcp–liquid triple point, the Clapeyron slope of the fcc–liquid curve is dT/dP = 12.8 K/GPa while the slope of the hcp–liquid curve is higher (dT/dP = 13.7 K/GPa). Therefore, the hcp–liquid curve overlaps the metastable fcc–liquid curve at pressures of about 160 GPa. At high-pressure conditions, the metastable bcc–hcp curve is located inside the fcc-Fe or liquid stability field. The density, adiabatic bulk modulus and P-wave velocity of liquid Fe calculated up to 328.9 GPa at adiabatic temperature conditions started from 5882 K (outer/inner core boundary) were compared to the PREM seismological model. We determined the density deficit of hcp-Fe at the inner core boundary (T = 5882 K and P = 328.9 GPa) to be 4.4%. PMID:28262683

Recent advances in the study of the UO2-PuO2 phase diagram at high temperatures

NASA Astrophysics Data System (ADS)

Böhler, R.; Welland, M. J.; Prieur, D.; Cakir, P.; Vitova, T.; Pruessmann, T.; Pidchenko, I.; Hennig, C.; Guéneau, C.; Konings, R. J. M.; Manara, D.

2014-05-01

Recently, novel container-less laser heating experimental data have been published on the melting behaviour of pure PuO2 and PuO2-rich compositions in the uranium dioxide-plutonium dioxide system. Such data showed that previous data obtained by more traditional furnace heating techniques were affected by extensive interaction between the sample and its containment. It is therefore paramount to check whether data so far used by nuclear engineers for the uranium-rich side of the pseudo-binary dioxide system can be confirmed or not. In the present work, new data are presented both in the UO2-rich part of the phase diagram, most interesting for the uranium-plutonium dioxide based nuclear fuel safety, and in the PuO2 side. The new results confirm earlier furnace heating data in the uranium-dioxide rich part of the phase diagram, and more recent laser-heating data in the plutonium-dioxide side of the system. As a consequence, it is also confirmed that a minimum melting point must exist in the UO2-PuO2 system, at a composition between x(PuO2) = 0.4 and x(PuO2) = 0.7 and 2900 K ⩽ T ⩽ 3000 K. Taking into account that, especially at high temperature, oxygen chemistry has an effect on the reported phase boundary uncertainties, the current results should be projected in the ternary U-Pu-O system. This aspect has been extensively studied here by X-ray diffraction and X-ray absorption spectroscopy. The current results suggest that uncertainty bands related to oxygen behaviour in the equilibria between condensed phases and gas should not significantly affect the qualitative trend of the current solid-liquid phase boundaries.

Comparison of rumen bacteria distribution in original rumen digesta, rumen liquid and solid fractions in lactating Holstein cows.

PubMed

Ji, Shoukun; Zhang, Hongtao; Yan, Hui; Azarfar, Arash; Shi, Haitao; Alugongo, Gibson; Li, Shengli; Cao, Zhijun; Wang, Yajing

2017-01-01

Original rumen digesta, rumen liquid and solid fractions have been frequently used to assess the rumen bacterial community. However, bacterial profiles in rumen original digesta, liquid and solid fractions vary from each other and need to be better established. To compare bacterial profiles in each fraction, samples of rumen digesta from six cows fed either a high fiber diet (HFD) or a high energy diet (HED) were collected via rumen fistulas. Rumen digesta was then squeezed through four layers of cheesecloth to separate liquid and solid fractions. The bacterial profiles of rumen original digesta, liquid and solid fractions were analyzed with High-throughput sequencing technique. Rumen bacterial diversity was mainly affected by diet and individual cow ( P  > 0.05) rather than rumen fraction. Bias distributed bacteria were observed in solid and liquid fractions of rumen content using Venn diagram and LEfSe analysis. Fifteen out of 16 detected biomarkers (using LEfSe analysis) were found in liquid fraction, and these 15 biomarkers contributed the most to the bacterial differences among rumen content fractions. Similar results were found when using samples of original rumen digesta, rumen liquid or solid fractions to assess diversity of rumen bacteria; however, more attention should be draw onto bias distributed bacteria in different ruminal fractions, especially when liquid fraction has been used as a representative sample for rumen bacterial study.

Phase diagrams for sticky rods in bulk and in a monolayer from a lattice free-energy functional for anisotropic particles with depletion attractions

NASA Astrophysics Data System (ADS)

Mortazavifar, M.; Oettel, M.

2017-09-01

A density functional of fundamental measure type for a lattice model of anisotropic particles with hard-core repulsions and effective attractions is derived in the spirit of the Asakura-Oosawa model. Through polymeric lattice particles of various size and shape, effective attractions of different strength and range between the colloids can be generated. The functional is applied to the determination of phase diagrams for sticky rods of length L in two dimensions, in three dimensions, and in a monolayer system on a neutral substrate. In all cases, there is a competition between ordering and gas-liquid transitions. In two dimensions, this gives rise to a tricritical point, whereas in three dimensions, the isotropic-nematic transition crosses over smoothly to a gas-nematic liquid transition. The richest phase behavior is found for the monolayer system. For L =2 , two stable critical points are found corresponding to a standard gas-liquid transition and a nematic liquid-liquid transition. For L =3 , the gas-liquid transition becomes metastable.

Solid-liquid critical behavior of water in nanopores.

PubMed

Mochizuki, Kenji; Koga, Kenichiro

2015-07-07

Nanoconfined liquid water can transform into low-dimensional ices whose crystalline structures are dissimilar to any bulk ices and whose melting point may significantly rise with reducing the pore size, as revealed by computer simulation and confirmed by experiment. One of the intriguing, and as yet unresolved, questions concerns the observation that the liquid water may transform into a low-dimensional ice either via a first-order phase change or without any discontinuity in thermodynamic and dynamic properties, which suggests the existence of solid-liquid critical points in this class of nanoconfined systems. Here we explore the phase behavior of a model of water in carbon nanotubes in the temperature-pressure-diameter space by molecular dynamics simulation and provide unambiguous evidence to support solid-liquid critical phenomena of nanoconfined water. Solid-liquid first-order phase boundaries are determined by tracing spontaneous phase separation at various temperatures. All of the boundaries eventually cease to exist at the critical points and there appear loci of response function maxima, or the Widom lines, extending to the supercritical region. The finite-size scaling analysis of the density distribution supports the presence of both first-order and continuous phase changes between solid and liquid. At around the Widom line, there are microscopic domains of two phases, and continuous solid-liquid phase changes occur in such a way that the domains of one phase grow and those of the other evanesce as the thermodynamic state departs from the Widom line.

"Bligh and Dyer" and Folch Methods for Solid-Liquid-Liquid Extraction of Lipids from Microorganisms. Comprehension of Solvatation Mechanisms and towards Substitution with Alternative Solvents.

PubMed

Breil, Cassandra; Abert Vian, Maryline; Zemb, Thomas; Kunz, Werner; Chemat, Farid

2017-03-27

Bligh and Dyer (B & D) or Folch procedures for the extraction and separation of lipids from microorganisms and biological tissues using chloroform/methanol/water have been used tens of thousands of times and are "gold standards" for the analysis of extracted lipids. Based on the Conductor-like Screening MOdel for realistic Solvatation (COSMO-RS), we select ethanol and ethyl acetate as being potentially suitable for the substitution of methanol and chloroform. We confirm this by performing solid-liquid extraction of yeast ( Yarrowia lipolytica IFP29 ) and subsequent liquid-liquid partition-the two steps of routine extraction. For this purpose, we consider similar points in the ternary phase diagrams of water/methanol/chloroform and water/ethanol/ethyl acetate, both in the monophasic mixtures and in the liquid-liquid miscibility gap. Based on high performance thin-layer chromatography (HPTLC) to obtain the distribution of lipids classes, and gas chromatography coupled with a flame ionisation detector (GC/FID) to obtain fatty acid profiles, this greener solvents pair is found to be almost as effective as the classic methanol-chloroform couple in terms of efficiency and selectivity of lipids and non-lipid material. Moreover, using these bio-sourced solvents as an alternative system is shown to be as effective as the classical system in terms of the yield of lipids extracted from microorganism tissues, independently of their apparent hydrophilicity.

Thermodynamic properties of triangle-well fluids in two dimensions: MC and MD simulations.

PubMed

Reyes, Yuri; Bárcenas, Mariana; Odriozola, Gerardo; Orea, Pedro

2016-11-07

With the aim of providing complementary data of the thermodynamics properties of the triangular well potential, the vapor/liquid phase diagrams for such potential with different interaction ranges were calculated in two dimensions by Monte Carlo and molecular dynamics simulations; also, the vapor/liquid interfacial tension was calculated. As reported for other interaction potentials, it was observed that the reduction of the dimensionality makes the phase diagram to shrink. Finally, with the aid of reported data for the same potential in three dimensions, it was observed that this potential does not follow the principle of corresponding states.

Phase diagrams for the system water/butyric acid/propylene carbonate at T = 293.2-313.2 K and p = 101.3 kPa

NASA Astrophysics Data System (ADS)

Shekarsaraee, Sina; Nahzomi, Hossein Taherpour; Nasiri-Touli, Elham

2017-11-01

Phase diagrams for the system water/butyric acid/propylene carbonate were plotted at T = 293.2, 303.2, 313.2 K and p = 101.3 kPa. Acidimetric titration and refractive index methods were used to determine tie-line data. Solubility data revealed that the studied system exhibits type-1 behavior of liquid-liquid equilibrium. The experimental data were regressed and acceptably correlated using the UNIQUAC and NRTL models. As a result, propylene carbonate is a suitable separating agent for aqueous mixture of butyric acid.

Self-assembled structures of Gaussian nematic particles.

PubMed

Nikoubashman, Arash; Likos, Christos N

2010-03-17

We investigate the stable crystalline configurations of a nematic liquid crystal made of soft parallel ellipsoidal particles interacting via a repulsive, anisotropic Gaussian potential. For this purpose, we use genetic algorithms (GA) in order to predict all relevant and possible solid phase candidates into which this fluid can freeze. Subsequently we present and discuss the emerging novel structures and the resulting zero-temperature phase diagram of this system. The latter features a variety of crystalline arrangements, in which the elongated Gaussian particles in general do not align with any one of the high-symmetry crystallographic directions, a compromise arising from the interplay and competition between anisotropic repulsions and crystal ordering. Only at very strong degrees of elongation does a tendency of the Gaussian nematics to align with the longest axis of the elementary unit cell emerge.

Resveratrol cocrystals with enhanced solubility and tabletability.

PubMed

Zhou, Zhengzheng; Li, Wanying; Sun, Wei-Jhe; Lu, Tongbu; Tong, Henry H Y; Sun, Changquan Calvin; Zheng, Ying

2016-07-25

Two new 1:1 cocrystals of resveratrol (RES) with 4-aminobenzamide (RES-4ABZ) and isoniazid (RES-ISN) were synthesized by liquid assisted grinding (LAG) and rapid solvent removal (RSR) methods using ethanol as solvent. Their physiochemical properties were characterized using PXRD, DSC, solid state and solution NMR, FT-IR, and HPLC. Pharmaceutically relevant properties, including tabletability, solubility, intrinsic dissolution rate, and hygroscopicity, were evaluated. Temperature-composition phase diagram for RES-ISN cocrystal system was constructed from DSC data. Both cocrystals show higher solubility than resveratrol over a broad range of pH. They are phase stable and non-hygroscopic even under high humidity conditions. Importantly, both cocrystals exhibit improved solubility and tabletability compared with RES, which make them more suitable candidates for tablet formulation development. Copyright © 2016 Elsevier B.V. All rights reserved.

Phase diagrams of flux lattices with disorder

NASA Astrophysics Data System (ADS)

Giamarchi, T.; Le Doussal, P.

1997-03-01

We review the prediction, made in a previous work [T. Giamarchi and P. Le Doussal, Phys. Rev. B 52, 1242 (1995)], that the phase diagram of type-II superconductors consists of a topologically ordered Bragg glass phase at low fields undergoing a transition at higher fields into a vortex glass or a liquid. We estimate the position of the phase boundary using a Lindemann criterion. We find that the proposed theory is compatible with recent experiments on superconductors. Further experimental consequences are investigated.

A Direct Experimental Evidence For the New Thermodynamic Boundary in the Supercritical State: Implications for Earth and Planetary Sciences.

NASA Astrophysics Data System (ADS)

Bolmatov, D.

2015-12-01

While scientists have a good theoretical understanding of the heat capacity of both solids and gases, a general theory of the heat capacity of liquids has always remained elusive. Apart from being an awkward hole in our knowledge, heat capacity - the amount of heat needed to change a substance's temperature by a certain amount - is a relevant quantity that it would be nice to be able to predict. I will introduce a phonon-based approach to liquids and supercritical fluids to describe its thermodynamics in terms of sound propagation. I will show that the internal liquid energy has a transverse sound propagation gaps and explain their evolution with temperature variations on the P-T diagram. I will explain how this theoretical framework covers the Debye theory of solids, the phonon theory of liquids, and thermodynamic limits such as the Delong-Petit and the ideal gas thermodynamic limits. As a results, the experimental evidence for the new thermodynamic boundary in the supercritical state (the Frenkel line) on the P-T phase diagram will be demonstrated. Then, I will report on inelastic X-ray scattering experiments combined with the molecular dynamics simulations on deeply supercritical Ar. The presented results unveil the mechanism and regimes of sound propagation in the liquid matter and provide compelling evidence for the adiabatic-to-isothermal longitudinal sound propagation transition. As a result, a universal link will be demonstrated between the positive sound dispersion (PSD) phenomenon and the origin of transverse sound propagation revealing the viscous-to-elastic crossover in compressed liquids. Both can be considered as a universal fingerprint of the dynamic response of a liquid. They can be used then for a signal detection and analysis of a dynamic response in deep water and other fluids which is relevant for describing the thermodynamics of gas giants. The consequences of this finding will be discussed, including a physically justified way to demarcate the interior and the atmosphere in gas giants such as Jupiter and Saturn.

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.; Plummer, Niel; Busenberg, E.

1990-01-01

Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

A review of solid-fluid selection options for optical-based measurements in single-phase liquid, two-phase liquid-liquid and multiphase solid-liquid flows

NASA Astrophysics Data System (ADS)

Wright, Stuart F.; Zadrazil, Ivan; Markides, Christos N.

2017-09-01

Experimental techniques based on optical measurement principles have experienced significant growth in recent decades. They are able to provide detailed information with high-spatiotemporal resolution on important scalar (e.g., temperature, concentration, and phase) and vector (e.g., velocity) fields in single-phase or multiphase flows, as well as interfacial characteristics in the latter, which has been instrumental to step-changes in our fundamental understanding of these flows, and the development and validation of advanced models with ever-improving predictive accuracy and reliability. Relevant techniques rely upon well-established optical methods such as direct photography, laser-induced fluorescence, laser Doppler velocimetry/phase Doppler anemometry, particle image/tracking velocimetry, and variants thereof. The accuracy of the resulting data depends on numerous factors including, importantly, the refractive indices of the solids and liquids used. The best results are obtained when the observational materials have closely matched refractive indices, including test-section walls, liquid phases, and any suspended particles. This paper reviews solid-liquid and solid-liquid-liquid refractive-index-matched systems employed in different fields, e.g., multiphase flows, turbomachinery, bio-fluid flows, with an emphasis on liquid-liquid systems. The refractive indices of various aqueous and organic phases found in the literature span the range 1.330-1.620 and 1.251-1.637, respectively, allowing the identification of appropriate combinations to match selected transparent or translucent plastics/polymers, glasses, or custom materials in single-phase liquid or multiphase liquid-liquid flow systems. In addition, the refractive indices of fluids can be further tuned with the use of additives, which also allows for the matching of important flow similarity parameters such as density and viscosity.

Extended vapor-liquid-solid growth of silicon carbide nanowires.

PubMed

Rajesh, John Anthuvan; Pandurangan, Arumugam

2014-04-01

We developed an alloy catalytic method to explain extended vapor-liquid-solid (VLS) growth of silicon carbide nanowires (SiC NWs) by a simple thermal evaporation of silicon and activated carbon mixture using lanthanum nickel (LaNi5) alloy as catalyst in a chemical vapor deposition process. The LaNi5 alloy binary phase diagram and the phase relationships in the La-Ni-Si ternary system were play a key role to determine the growth parameters in this VLS mechanism. Different reaction temperatures (1300, 1350 and 1400 degrees C) were applied to prove the established growth process by experimentally. Scanning electron microscopy and transmission electron microscopy studies show that the crystalline quality of the SiC NWs increases with the temperature at which they have been synthesized. La-Ni alloyed catalyst particles observed on the top of the SiC NWs confirms that the growth process follows this extended VLS mechanism. The X-ray diffraction and confocal Raman spectroscopy analyses demonstrate that the crystalline structure of the SiC NWs was zinc blende 3C-SiC. Optical property of the SiC NWs was investigated by photoluminescence technique at room temperature. Such a new alloy catalytic method may be extended to synthesis other one-dimensional nanostructures.

Rain and Solid Particle Erosion Damage Mechanisms and Materials Evaluations

DTIC Science & Technology

1986-08-01

intersectiog a laser light beanm just before impact. A schematic diagram of the apparatus is shown in figure 10. A description of the basic gas gun design can be...important, since the collapse of the liquid cavities near a solid boundary produce both shocks and microjets and this adds to the pressures already present

Modified sedimentation-dispersion model for solids in a three-phase slurry column

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

Smith, D.N.; Ruether, J.A.; Shah, Y.T.

1986-03-01

Solids distribution data for a three-phase, batch-fluidized slurry bubble column (SBC) are presented, using air as the gas phase, pure liquids and solutions as the liquid phase, and glass beads and carborundum catalyst powder as the solid phase. Solids distribution data for the three-phase SBC operated in a continuous mode of operation are also presented, using nitrogen as the gas phase, water as the liquid phase, and glass beads as the solid phase. A new model to provide a reasonable approach to predict solids concentration distributions for systems containing polydispersed solids is presented. The model is a modification of standardmore » sedimentation-dispersion model published earlier. Empirical correlations for prediction of hindered settling velocity and solids dispersion coefficient for systems containing polydispersed solids are presented. A new method of evaluating critical gas velocity (CGV) from concentrations of the sample withdrawn at the same port of the SBC is presented. Also presented is a new mapping for CGV which separates the two regimes in the SBC, namely, incomplete fluidization and complete fluidization.« less

Metal Alloy Compositions And Process Background Of The Invention

DOEpatents

Flemings, Merton C.; Martinez-Ayers, Raul A.; de Figueredo, Anacleto M.; Yurko, James A.

2003-11-11

A skinless metal alloy composition free of entrapped gas and comprising primary solid discrete degenerate dendrites homogeneously dispersed within a secondary phase is formed by a process wherein the metal alloy is heated in a vessel to render it a liquid. The liquid is then rapidly cooled while vigorously agitating it under conditions to avoid entrapment of gas while forming solid nuclei homogeneously distributed in the liquid. Agitation then is ceased when the liquid contains a small fraction solid or the liquid-solid alloy is removed from the source of agitation while cooling is continued to form the primary solid discrete degenerate dendrites in liquid secondary phase. The solid-liquid mixture then can be formed such as by casting.

Immobilization of organic radioactive and non-radioactive liquid waste in a composite matrix

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

Galkin, Anatoliy; Gelis, Artem V.; Castiglioni, Andrew J.

A method for immobilizing liquid radioactive waste is provided, the method having the steps of mixing waste with polymer to form a non-liquid waste; contacting the non-liquid waste with a solidifying agent to create a mixture, heating the mixture to cause the polymer, waste, and filler to irreversibly bind in a solid phase, and compressing the solid phase into a monolith. The invention also provides a method for immobilizing liquid radioactive waste containing tritium, the method having the steps of mixing liquid waste with polymer to convert the liquid waste to a non-liquid waste, contacting the non-liquid waste with amore » solidifying agent to create a mixture, heating the mixture to form homogeneous, chemically stable solid phase, and compressing the chemically stable solid phase into a final waste form, wherein the polymer comprises approximately a 9:1 weight ratio mixture of styrene block co-polymers and cross linked co-polymers of acrylamides.« less

COED Transactions, Vol. 8, No. 10, October 1976. The Computer Generation of Thermodynamic Phase Diagrams.

ERIC Educational Resources Information Center

Jolls, Kenneth R.; And Others

A technique is described for the generation of perspective views of three-dimensional models using computer graphics. The technique is applied to models of familiar thermodynamic phase diagrams and the results are presented for the ideal gas and van der Waals equations of state as well as the properties of liquid water and steam from the Steam…

Superclimbing dislocation with a Coulomb-type interaction between jogs

NASA Astrophysics Data System (ADS)

Liu, Longxiang; Kuklov, Anatoly B.

2018-03-01

The main candidate for the superfluid pathways in solid 4He are dislocations with Burgers vector along the hcp symmetry axis. Here we focus on the quantum behavior of a generic edge dislocation which can perform superclimb; that is, it can climb due to the superflow along its core. The role of the long-range elastic interactions between jogs is addressed by Monte Carlo simulations. It is found that such interactions do not change qualitatively the phase diagram found without accounting for the long-range forces. Their main effect consists of renormalizing the effective scale determining the compressibility of the dislocation in the Tomonaga-Luttinger liquid phase. It is also found that the quantum rough phase of the dislocation can be well described within the Gaussian approximation which features off-diagonal long-range order (ODLRO) in one dimension for the superfluid order parameter along the core.

Nuclear fuel alloys or mixtures and method of making thereof

DOEpatents

Mariani, Robert Dominick; Porter, Douglas Lloyd

2016-04-05

Nuclear fuel alloys or mixtures and methods of making nuclear fuel mixtures are provided. Pseudo-binary actinide-M fuel mixtures form alloys and exhibit: body-centered cubic solid phases at low temperatures; high solidus temperatures; and/or minimal or no reaction or inter-diffusion with steel and other cladding materials. Methods described herein through metallurgical and thermodynamics advancements guide the selection of amounts of fuel mixture components by use of phase diagrams. Weight percentages for components of a metallic additive to an actinide fuel are selected in a solid phase region of an isothermal phase diagram taken at a temperature below an upper temperature limit for the resulting fuel mixture in reactor use. Fuel mixtures include uranium-molybdenum-tungsten, uranium-molybdenum-tantalum, molybdenum-titanium-zirconium, and uranium-molybdenum-titanium systems.

Solid-Phase and Oscillating Solution Crystallization Behavior of (+)- and (-)-N-Methylephedrine.

PubMed

Tulashie, Samuel Kofi; Polenske, Daniel; Seidel-Morgenstern, Andreas; Lorenz, Heike

2016-11-01

This work involves the study of the solid-phase and solution crystallization behavior of the N-methylephedrine enantiomers. A systematic investigation of the melt phase diagram of the enantiomeric N-methylephedrine system was performed considering polymorphism. Two monotropically related modifications of the enantiomer were found. Solubilities and the ternary solubility phase diagrams of N-methylephedrine enantiomers in 2 solvents [isopropanol:water, 1:3 (Vol) and (2R, 3R)-diethyl tartrate] were determined in the temperature ranges between 15°C and 25°C, and 25°C and 40°C, respectively. Preferential nucleation and crystallization experiments at higher supersaturation leading to an unusual oscillatory crystallization behavior as well as a successful preferential crystallization experiment at lower supersaturation are presented and discussed. Copyright © 2016. Published by Elsevier Inc.

Study of phase relationships in the Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system. Phase diagram and thermal characteristics of phases

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

Matraszek, Aleksandra, E-mail: aleksandra.matraszek@ue.wroc.pl

2013-07-15

A diagram representing phase relationships in the Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} phosphate system has been developed on the basis of results obtained by thermal analysis (DTA/DSC/TGA) and X-ray diffraction (XRD) methods. One intermediate compound with the formula Sr{sub 3}Ce(PO{sub 4}){sub 3} occurs in the Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system at temperatures exceeding 1045 °C. The compound has a eulytite structure with the following structural parameters: a=b=c=10.1655(8) Å, α=β=γ=90.00°, V=1050.46(6) Å{sup 3}. It's melting point exceeds 1950 °C. A limited solid solution exists in the system, which possesses the structure of a low-temperature form of Sr{sub 3}(PO{sub 4}){sub 2}.more » At 1000 °C the maximal concentration of CePO{sub 4} in the solid solution is below 20 mol%. The solid solution phase field narrows with increased temperature. There is a eutectic point in the (Sr{sub 3}(PO{sub 4}){sub 2}+Sr{sub 3}Ce(PO{sub 4}){sub 3}) phase field at 1765 °C and 15 mol% of CePO{sub 4}. The melting temperature of Sr{sub 3}(PO{sub 4}){sub 2} is 1882±15 °C. - Graphical abstract: The phase diagram of Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system showing the stability ranges of limited solid solution and Sr{sub 3}Ce(PO{sub 4}){sub 3} phases. - Highlights: • Sr{sub 3}(PO{sub 4}){sub 2} melts at 1882 °C. • Phase diagram of Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system has been proposed. • Limited solid solution of CePO{sub 4} in Sr{sub 3}(PO{sub 4}){sub 2} forms in the system. • The Sr{sub 3}Ce(PO{sub 4}){sub 2} phosphate is stable at temperatures above 1045 °C.« less

Thermodynamic Re-modeling of the Sb-Te System Using Associate and Ionic Models

NASA Astrophysics Data System (ADS)

Guo, Cuiping; Li, Changrong; Du, Zhenmin

2014-11-01

The Sb-Te system is re-modeled using the calculation of phase diagram (CALPHAD) technique. The liquid phase is modeled as (Sb, Sb2Te3, Te) using the associate model and as (Sb3+) p (Te2-,Te,Va) q using the ionic model. The solution phases rhom(Sb) and hex(Te) are described as substitutional solutions. Two compounds, delta and gamma, are treated as (Sb)0.4(Sb,Te)0.6 according to their homogeneity ranges, while the compound Sb2Te3 follows a strict stoichiometry. A set of self-consistent thermodynamic parameters is obtained. Using these thermodynamic parameters, the experimental Sb-Te phase diagram, mixing enthalpies of liquid at 911 K and 935 K, activities of Sb and Te in liquid at 911 K and 1023 K, and Gibbs energy of liquid at 911 K, is well reproduced by the calculations. And the calculated enthalpy of formation, enthalpy of fusion, and heat capacity of Sb2Te3 are also in fairly good agreement with all the available experimental data.

Theoretical evidence for a first-order liquid-liquid phase transition in gallium.

PubMed

Carvajal Jara, Diego Alejandro; Fontana Michelon, Mateus; Antonelli, Alex; de Koning, Maurice

2009-06-14

We report on theoretical results that lend support to recent experimental observations suggesting the existence of a first-order liquid-liquid phase transformation (LLPT) in gallium. Using molecular dynamics simulation based on a modified embedded-atom model, we observe a transition from a high-density to a low-density liquid in the supercooled regime. The first-order character of the transition is established through the detection of the release of latent heat and our findings suggest that the LLPT terminates in a critical point that is located in the tensile-strained domain of the metastable phase diagram.

Large Grüneisen Gamma of Dense Silicate Liquids: More Experiments and a First Self- consistent Model

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Mosenfelder, J. L.; Ahrens, T. J.; Sun, D.

2007-12-01

The Grüneisen parameter, γ, of solid materials normally decreases upon compression, approximately as γρq = constant where q=1. However, multiple lines of evidence now indicate the opposite behavior in silicate liquids, in which γ increases upon compression (i.e., q<0). This was observed in shock-melted (Mg,Fe)2SiO4 liquid by Brown et al. [1] via comparison of the Hugoniot and release velocity. We observed the same behavior in Mg2SiO4 liquid (q ≤ -1.5) from comparison of the Hugoniots of forsterite and wadsleyite [2]. First-principles molecular dynamics simulations of MgSiO3 liquid [3] confirm that γ increases with density and show that γ in the liquid phase mimics solids with similar Si coordination state. Hence a continuous increase in γ of silicate liquids to lowermost mantle pressures, well beyond the range where transition to six-coordination of Si is complete, suggests that even higher-coordinated species are forming in the melt and by extension there may be 8- coordinated silicate minerals with stability fields beginning not very far above the Earth's core-mantle boundary pressure [4]. We present new experimental evidence for this behavior in another liquid composition. The Hugoniot of 1400°C anorthite-diopside eutectic liquid was measured at low pressure by Rigden et al. [5] and extended to 110 GPa by our recent work. We collected a Hugoniot point on a solid aggregate of the same composition initially at room temperature, shocked into the melt regime at 133 GPa. The difference in internal energy between this point and the hot liquid Hugoniot allows determination of the γ of this aluminosilicate liquid at 50% compression; the result fits q = -1.85±0.2, entirely consistent with the behavior of enstatite, forsterite, and Fe- bearing olivine liquids. We suggested on the basis of an approximate calculation that the large γ of dense silicate liquids yields a liquid isentrope steeper than the liquidus of a lower mantle magma ocean [2]. Here we show a preliminary self-consistent thermodynamic model of the MgO-SiO2 binary that matches the phase diagrams of MgO, Mg2SiO4, MgSiO3, and SiO2 in the lower mantle, that incorporates negative q in the γ model of the liquid, and that allows calculation of pressure-entropy diagrams showing how model isentropes behave during cooling. We find that for peridotite or chondritic compositions, perovskite crystallization begins at an entropy maximum near 60 GPa. The consequences for geochemical evolution depend on whether these crystals remain turbulently suspended or fractionate [6]; in the case of suspension our model shows that the mush transition affects the entire lower mantle over a rather narrow range in potential temperature. Below this point the solidus does not have a maximum and normal decompression melting behavior is observed. 1. Brown et al., in High-Pressure Research in Mineral Physics, M.H. Manghnani and Y. Syono, Editors. 1987, AGU: Washington, DC. p. 373-384. 2. Mosenfelder et al., J. Geophys. Res., 2007. 112: p. B06208. 3. Stixrude & Karki, Science, 2005. 310(5746): p. 297-299. 4. Akins & Ahrens, Geophys. Res. Lett., 2002. 29(10): 1394-1397. 5. Rigden et al. J. Geophys. Res. 1988. 93(B1): p. 367-382. 6. Solomatov & Stevenson. J. Geophys. Res., 1993. 98(E3): p. 5375-5390.

Liquid?solid helium interface: some conceptual questions

NASA Astrophysics Data System (ADS)

Leggett, A. J.

2003-12-01

I raise, and discuss qualitatively, some conceptual issues concerning the interface between the crystalline solid and superfluid liquid phases of 4He emphasizing, in particular, the fact that the ground-state wave functions of the two phases are prima facie qualitatively quite different, in that the superfluid liquid phase possesses off-diagonal long-range order (ODLRO), while the crystalline solid does not. The fact that the statics and dynamics of the interface do not appear to be particularly sensitive to the presence of ODLRO in the liquid is tentatively explained by the fact that because of a subtlety associated with the Bose statistics obeyed by the atoms, the solid and liquid wave functions are not locally very different.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1999-01-01

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1999-03-30

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

Calculation of electric field–temperature (E, T) phase diagram of a ferroelectric liquid crystal near the SmA–{SmC}}_{\\alpha }^{* } transition

NASA Astrophysics Data System (ADS)

Trabelsi, F.; Dhaouadi, H.; Riahi, O.; Othman, T.

2018-03-01

In this work we perform a theoretical calculation in order to reconstitute the (E–T) phase diagram of a chiral smectic liquid crystal in the vicinity of the SmA–{SmC}}α * transition. This reconstruction is carried out on the basis of a thermodynamic calculation of the slope of the curve joining the {SmC}}α * domain and the unwound SmC*. An empiric correction of the mean field term of Landau De-Gennes development is necessary to accomplish this reconstruction. Thereafter, an experimental validation is performed to verify our calculations.

A thermodynamic recipe for baking the Earth's lower mantle and core as a whole

NASA Astrophysics Data System (ADS)

Tirone, Max; Faak, Kathi

2016-04-01

A rigorous understanding of the thermal and dynamic evolution of the core and the interaction with the silicate mantle cannot preclude a non-empirical petrological description of the problem which takes the form of a thermodynamic model. Because the Earth's core is predominantly made of iron such model may seem relatively straightforward, simply delivering a representation of the phase transformations in the P,T space. However due to well known geophysical considerations, a certain amount of light elements should be added. With the Occam's razor principle in mind, potential candidates could be the most abundant and easily accessible elements in the mantle, O, Si and Mg. Given these premises, the challenging problems on developing this type of model are: - a thermodynamic formulation should not simply describe phase equilibrium relations at least in the Fe-Si-O system (a formidable task itself) but should be also consistently applicable to evaluate thermophysical properties of liquid components and solids phases at extreme conditions (P=500-2000 kbar, T=1000-5000 K). Presently these properties are unknown for certain mineral and liquid components or partially available from scattered sources. - experimental data on the phase relations for iron rich liquid are extremely difficult to obtain and could not cover the entire P,T,X spectrum. - interaction of the outer core with the silicate mantle requires a melt model that is capable of describing a vast range of compositions ranging from metal-rich liquids to silicate liquids. The compound energy formalism for liquids with variable tendency to ionization developed by Hillert and coworkers is a sublattice model with varying stoichiometry that includes vacancies and neutral species in one site. It represents the ideal candidate for the task in hand. The thermodynamic model unfortunately is rather complex and a detailed description of the formulation for practical applications like chemical equilibrium calculations is nowhere to be found, while the model is only accessible on few commercial thermodynamic programs. The latest developments regarding all these related issues will be discussed in this contribution. In particular some self-consistent but preliminary results will be presented addressing the following topics: - some details regarding the implementation of the liquid model for Gibbs free energy minimizations, - the physically consistent behavior of thermodynamic properties of certain solid phases like (Fe,O,Si) BCC, FCC, HCP and liquid components, - selected phase diagrams at core conditions in the system Fe-Si-O, - derived geotherms linking the inner-outer core with the core-mantle boundary. - brief outline of the future geodynamic applications.

Global phase diagram and quantum spin liquids in a spin- 1 2 triangular antiferromagnet

DOE PAGES

Gong, Shou-Shu; Zhu, Wei; Zhu, Jianxin; ...

2017-08-09

For this research, we study the spin-1/2 Heisenberg model on the triangular lattice with the nearest-neighbor J 1 > 0 , the next-nearest-neighobr J 2 > 0 Heisenberg interactions, and the additional scalar chiral interaction Jχ (more » $$\\vec{S}$$ i × $$\\vec{S}$$ j ) · $$\\vec{S}$$ k for the three spins in all the triangles using large-scale density matrix renormalization group calculation on cylinder geometry. With increasing J 2 (J 2 / J 1 ≤ 0.3 ) and Jχ (Jχ / J 1 ≤ 1.0 ) interactions, we establish a quantum phase diagram with the magnetically ordered 120°, stripe, and noncoplanar tetrahedral phase. In between these magnetic order phases, we find a chiral spin liquid (CSL) phase, which is identified as a ν = 1/2 bosonic fractional quantum Hall state with possible spontaneous rotational symmetry breaking. By switching on the chiral interaction, we find that the previously identified spin liquid in the J 1 - J 2 triangular model (0.08 ≲ J 2 / J 1 ≲ 0.15) shows a phase transition to the CSL phase at very small Jχ. We also compute the spin triplet gap in both spin liquid phases, and our finite-size results suggest a large gap in the odd topological sector but a small or vanishing gap in the even sector. Lastly, we discuss the implications of our results on the nature of the spin liquid phases.« less

Dynamical properties of nematic liquid crystals subjected to shear flow and magnetic fields: tumbling instability and nonequilibrium fluctuations.

PubMed

Fatriansyah, Jaka Fajar; Orihara, Hiroshi

2013-07-01

We investigate the dynamical properties of monodomain nematic liquid crystals under shear flow and magnetic fields on the basis of the Ericksen-Leslie theory. Stable and unstable states appear depending on the magnetic field and the shear rate. The trajectory of the unstable state shows tumbling motion. The phase diagram of these states is plotted as a function of the three components of the magnetic field at a constant shear rate. The phase diagram changes depending on the viscous properties of different types of nematic liquid crystals. In this nonequilibrium steady state, we calculate the correlation function of director fluctuations and the response function, and discuss the nonequilibrium fluctuations and the modified fluctuation-dissipation relation in connection with nonconservative forces due to shear flow.

Spinodal decomposition in amorphous metal-silicate thin films: Phase diagram analysis and interface effects on kinetics

NASA Astrophysics Data System (ADS)

Kim, H.; McIntyre, P. C.

2002-11-01

Among several metal silicate candidates for high permittivity gate dielectric applications, the mixing thermodynamics of the ZrO2-SiO2 system were analyzed, based on previously published experimental phase diagrams. The driving force for spinodal decomposition was investigated in an amorphous silicate that was treated as a supercooled liquid solution. A subregular model was used for the excess free energy of mixing of the liquid, and measured invariant points were adopted for the calculations. The resulting simulated ZrO2-SiO2 phase diagram matched the experimental results reasonably well and indicated that a driving force exists for amorphous Zr-silicate compositions between approx40 mol % and approx90 mol % SiO2 to decompose into a ZrO2-rich phase (approx20 mol % SiO2) and SiO2-rich phase (>98 mol % SiO2) through diffusional phase separation at a temperature of 900 degC. These predictions are consistent with recent experimental reports of phase separation in amorphous Zr-silicate thin films. Other metal-silicate systems were also investigated and composition ranges for phase separation in amorphous Hf, La, and Y silicates were identified from the published bulk phase diagrams. The kinetics of one-dimensional spinodal decomposition normal to the plane of the film were simulated for an initially homogeneous Zr-silicate dielectric layer. We examined the effects that local stresses and the capillary driving force for component segregation to the interface have on the rate of spinodal decomposition in amorphous metal-silicate thin films.

RH-temperature phase diagrams of hydrate forming deliquescent crystalline ingredients.

PubMed

Allan, Matthew; Mauer, Lisa J

2017-12-01

Several common deliquescent crystalline food ingredients (including glucose and citric acid) are capable of forming crystal hydrate structures. The propensity of such crystals to hydrate/dehydrate or deliquesce is dependent on the environmental temperature and relative humidity (RH). As an anhydrous crystal converts to a crystal hydrate, water molecules internalize into the crystal structure resulting in different physical properties. Deliquescence is a solid-to-solution phase transformation. RH-temperature phase diagrams of the food ingredients alpha-d-glucose and citric acid, along with sodium sulfate, were produced using established and newly developed methods. Each phase diagram included hydrate and anhydrate deliquescence boundaries, the anhydrate-hydrate phase boundary, and the peritectic temperature (above which the hydrate was no longer stable). This is the first report of RH-temperature phase diagrams of glucose and citric acid, information which is beneficial for selecting storage and processing conditions to promote or avoid hydrate formation or loss and/or deliquescence. Copyright © 2017 Elsevier Ltd. All rights reserved.

Liquid-phase and solid-phase microwave irradiations for reduction of graphite oxide

NASA Astrophysics Data System (ADS)

Zhao, Na; Wen, Chen-Yu; Zhang, David Wei; Wu, Dong-Ping; Zhang, Zhi-Bin; Zhang, Shi-Li

2014-12-01

In this paper, two microwave irradiation methods: (i) liquid-phase microwave irradiation (MWI) reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and (ii) solid-phase MWI reduction of graphite oxide powder have been successfully carried out to reduce graphite oxide. The reduced graphene oxide products are thoroughly characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectral analysis, Raman spectroscopy, UV-Vis absorption spectral analysis, and four-point probe conductivity measurements. The results show that both methods can efficiently remove the oxygen-containing functional groups attached to the graphite layers, though the solid-phase MWI reduction method can obtain far more efficiently a higher quality-reduced graphene oxide with fewer defects. The I(D)/I(G) ratio of the solid-phase MWI sample is as low as 0.46, which is only half of that of the liquid-phase MWI samples. The electrical conductivity of the reduced graphene oxide by the solid method reaches 747.9 S/m, which is about 25 times higher than that made by the liquid-phase method.

What Is a Simple Liquid?

NASA Astrophysics Data System (ADS)

Ingebrigtsen, Trond S.; Schrøder, Thomas B.; Dyre, Jeppe C.

2012-01-01

This paper is an attempt to identify the real essence of simplicity of liquids in John Locke’s understanding of the term. Simple liquids are traditionally defined as many-body systems of classical particles interacting via radially symmetric pair potentials. We suggest that a simple liquid should be defined instead by the property of having strong correlations between virial and potential-energy equilibrium fluctuations in the NVT ensemble. There is considerable overlap between the two definitions, but also some notable differences. For instance, in the new definition simplicity is not a direct property of the intermolecular potential because a liquid is usually only strongly correlating in part of its phase diagram. Moreover, not all simple liquids are atomic (i.e., with radially symmetric pair potentials) and not all atomic liquids are simple. The main part of the paper motivates the new definition of liquid simplicity by presenting evidence that a liquid is strongly correlating if and only if its intermolecular interactions may be ignored beyond the first coordination shell (FCS). This is demonstrated by NVT simulations of the structure and dynamics of several atomic and three molecular model liquids with a shifted-forces cutoff placed at the first minimum of the radial distribution function. The liquids studied are inverse power-law systems (r-n pair potentials with n=18,6,4), Lennard-Jones (LJ) models (the standard LJ model, two generalized Kob-Andersen binary LJ mixtures, and the Wahnstrom binary LJ mixture), the Buckingham model, the Dzugutov model, the LJ Gaussian model, the Gaussian core model, the Hansen-McDonald molten salt model, the Lewis-Wahnstrom ortho-terphenyl model, the asymmetric dumbbell model, and the single-point charge water model. The final part of the paper summarizes properties of strongly correlating liquids, emphasizing that these are simpler than liquids in general. Simple liquids, as defined here, may be characterized in three quite different ways: (1) chemically by the fact that the liquid’s properties are fully determined by interactions from the molecules within the FCS, (2) physically by the fact that there are isomorphs in the phase diagram, i.e., curves along which several properties like excess entropy, structure, and dynamics, are invariant in reduced units, and (3) mathematically by the fact that throughout the phase diagram the reduced-coordinate constant-potential-energy hypersurfaces define a one-parameter family of compact Riemannian manifolds. No proof is given that the chemical characterization follows from the strong correlation property, but we show that this FCS characterization is consistent with the existence of isomorphs in strongly correlating liquids’ phase diagram. Finally, we note that the FCS characterization of simple liquids calls into question the physical basis of standard perturbation theory, according to which the repulsive and attractive forces play fundamentally different roles for the physics of liquids.

Vortex phase diagram of the layered superconductor Cu0.03TaS2 for H \\parallel c

NASA Astrophysics Data System (ADS)

Zhu, X. D.; Lu, J. C.; Sun, Y. P.; Pi, L.; Qu, Z.; Ling, L. S.; Yang, Z. R.; Zhang, Y. H.

2010-12-01

The magnetization and anisotropic electrical transport properties have been measured in high quality Cu0.03TaS2 single crystals. A pronounced peak effect has been observed, indicating that high quality and homogeneity are vital to the peak effect. A kink has been observed in the magnetic field, H, dependence of the in-plane resistivity ρab for H\\parallel c , which corresponds to a transition from activated to diffusive behavior of the vortex liquid phase. In the diffusive regime of the vortex liquid phase, the in-plane resistivity ρab is proportional to H0.3, which does not follow the Bardeen-Stephen law for free flux flow. Finally, a simplified vortex phase diagram of Cu0.03TaS2 for H \\parallel c is given.

Electroepitaxy of multicomponent systems - Ternary and quarternary compounds

NASA Technical Reports Server (NTRS)

Bryskiewicz, T.; Lagowski, J.; Gatos, H. C.

1980-01-01

A theoretical model is presented which accounts for the electroepitaxial growth kinetics and composition of multicomponent compounds in terms of mass transport in the liquid and phase diagram relationships. The mass transport in the interface is dominated by electromigration in the absence of convection and by diffusion in the presence of convection. The composition of the solid is controlled by the Peltier effect at the growth interface and by the diffusion and mobility constants of the solute components and the growth velocity (current density). Thus, for a given solution composition, the composition of the solid can be varied by varying the current density. For a given current density the composition remains constant even in the case of relatively thick epitaxial layers. All aspects of the model were found to be in good agreement with the growth and composition characteristics of Ga/x-1/Al/x/As layers.

Predicting Microstructure and Microsegregation in Multicomponent Aluminum Alloys

NASA Astrophysics Data System (ADS)

Yan, Xinyan; Ding, Ling; Chen, ShuangLin; Xie, Fanyou; Chu, M.; Chang, Y. Austin

Accurate predictions of microstructure and microsegregation in metallic alloys are highly important for applications such as alloy design and process optimization. Restricted assumptions concerning the phase diagram could easily lead to erroneous predictions. The best approach is to couple microsegregation modeling with phase diagram computations. A newly developed numerical model for the prediction of microstructure and microsegregation in multicomponent alloys during dendritic solidification was introduced. The micromodel is directly coupled with phase diagram calculations using a user-friendly and robust phase diagram calculation engine-PANDAT. Solid state back diffusion, undercooling and coarsening effects are included in this model, and the experimentally measured cooling curves are used as the inputs to carry out the calculations. This model has been used to predict the microstructure and microsegregation in two multicomponent aluminum alloys, 2219 and 7050. The calculated values were confirmed using results obtained from directional solidification.

Quantum phases of quadrupolar Fermi gases in coupled one-dimensional systems

NASA Astrophysics Data System (ADS)

Huang, Wen-Min; Lahrz, M.; Mathey, L.

2014-01-01

Following the recent proposal to create quadrupolar gases [Bhongale et al., Phys. Rev. Lett. 110, 155301 (2013), 10.1103/PhysRevLett.110.155301], we investigate what quantum phases can be created in these systems in one dimension. We consider a geometry of two coupled one-dimensional (1D) systems, and derive the quantum phase diagram of ultracold fermionic atoms interacting via quadrupole-quadrupole interactions within a Tomonaga-Luttinger-liquid framework. We map out the phase diagram as a function of the distance between the two tubes and the angle between the direction of the tubes and the quadrupolar moments. The latter can be controlled by an external field. We show that there are two magic angles θB,1c and θB,2c between 0 and π /2, where the intratube quadrupolar interactions vanish and change signs. Adopting a pseudospin language with regard to the two 1D systems, the system undergoes a spin-gap transition and displays a zigzag density pattern, above θB,2c and below θB,1c. Between the two magic angles, we show that polarized triplet superfluidity and a planar spin-density-wave order compete with each other. The latter corresponds to a bond-order solid in higher dimensions. We demonstrate that this order can be further stabilized by applying a commensurate periodic potential along the tubes.

Simultaneous estimation of liquid and solid gastric emptying using radiolabelled egg and water in supine normal subjects.

PubMed

Kris, M G; Yeh, S D; Gralla, R J; Young, C W

1986-01-01

To develop an additional method for the measurement of gastric emptying in supine subjects, 10 normal subjects were given a test meal containing 99Tc-labelled scrambled egg as the "solid" phase marker and 111In in tapwater as the marker for the "liquid" phase. The mean time for emptying 50% of the "solid" phase (t1/2) was 85 min and 29 min for the "liquid" phase. Three individuals were restudied with a mean difference between the two determinations of 10.8% for the "solid" phase and 6.5% for the "liquid" phase. Twenty-six additional studies attempted have been successfully completed in symptomatic patients with advanced cancer. This method provides a simple and reproducible procedure for the determination of gastric emptying that yields results similar to those reported for other test meals and can be used in debilitated patients.

Solid oxygen revisited

NASA Astrophysics Data System (ADS)

Freiman, Yu. A.; Jodl, H. J.; Crespo, Yanier

2018-05-01

The paper provides an up-to-date review of the experimental and theoretical works on solid oxygen published over the past decade. The most important results presented in this review are the following: Detection of magnetic collapse in neutron studies under the delta-epsilon transition. Identification of the lattice structure of the ɛ phase. In this structure the O2 molecules retain their individuality, but there is an additional link leading to the formation of clusters of molecular quartets with the structural formula (O2)4. Discovery of the unique magnetic properties of the delta phase, which hosts three different magnetic structures in the domain of the same crystallographic structure. The extension of the phase diagram to the high-pressure high-temperature region which was previously beyond the reach for experiment; the molecular η and η‧ phases were found and their structures were identified. Behavior of the melting line up to 60 GPa (1750 K). Discovery of a new molecular θ phase in ultrahigh magnetic fields up to over 190 T and the construction of the thermodynamical magnetic-field-temperature H- T phase diagram on the base of the ultrahigh-field magnetization, optical magneto-transmission, and adiabatic magnetocaloric effect measurements. Prediction of the persistence of the molecular state of solid oxygen up to the pressure of 1.9 TPa which is significantly higher than the corresponding limits in solid hydrogen and nitrogen, other generic molecular solids.

Effects of elongation on the phase behavior of the Gay-Berne fluid

NASA Astrophysics Data System (ADS)

Brown, Julian T.; Allen, Michael P.; Martín del Río, Elvira; Miguel, Enrique De

1998-06-01

In this paper we present a computer simulation study of the phase behavior of the Gay-Berne liquid crystal model, concentrating on the effects of varying the molecular elongation κ. We study a range of length-to-width parameters 3<=κ<=4, using a variety of molecular dynamics and Monte Carlo techniques, obtaining a guide to the phase behavior for each shape studied. We observe vapor (V), isotropic liquid (I), nematic (N), smectic-A (SA) and smectic-B (SB) liquid crystal phases. Within the small range of elongation studied, the phase diagram shows significant changes. On increasing κ, the liquid-vapor critical point moves to lower temperature until it falls below the I-SB coexistence line, around κ=3.4, where liquid-vapor coexistence proves hard to establish. The liquid-vapor critical point seems to be completely absent at κ=4.0. Another dramatic effect is the growth of a stable SA ``island'' in the phase diagram at elongations slightly above κ=3.0. The SA range extends to both higher and lower temperatures as κ is increased. Also as κ is increased, the I-N transition is seen to move to lower density (and pressure) at given temperature. The lowest temperature at which the nematic phase is stable does not vary dramatically with κ. On cooling, no SB-crystal transition can be identified in the equation of state for any of these elongations; we suggest that, on the basis of simulation evidence, SB and crystal are really the same phase for these models.

Predicting mixture phase equilibria and critical behavior using the SAFT-VRX approach.

PubMed

Sun, Lixin; Zhao, Honggang; Kiselev, Sergei B; McCabe, Clare

2005-05-12

The SAFT-VRX equation of state combines the SAFT-VR equation with a crossover function that smoothly transforms the classical equation into a nonanalytical form close to the critical point. By a combinination of the accuracy of the SAFT-VR approach away from the critical region with the asymptotic scaling behavior seen at the critical point of real fluids, the SAFT-VRX equation can accurately describe the global fluid phase diagram. In previous work, we demonstrated that the SAFT-VRX equation very accurately describes the pvT and phase behavior of both nonassociating and associating pure fluids, with a minimum of fitting to experimental data. Here, we present a generalized SAFT-VRX equation of state for binary mixtures that is found to accurately predict the vapor-liquid equilibrium and pvT behavior of the systems studied. In particular, we examine binary mixtures of n-alkanes and carbon dioxide + n-alkanes. The SAFT-VRX equation accurately describes not only the gas-liquid critical locus for these systems but also the vapor-liquid equilibrium phase diagrams and thermal properties in single-phase regions.

Binary Colloidal Alloy Test-3 and 4: Critical Point

NASA Technical Reports Server (NTRS)

Weitz, David A.; Lu, Peter J.

2007-01-01

Binary Colloidal Alloy Test - 3 and 4: Critical Point (BCAT-3-4-CP) will determine phase separation rates and add needed points to the phase diagram of a model critical fluid system. Crewmembers photograph samples of polymer and colloidal particles (tiny nanoscale spheres suspended in liquid) that model liquid/gas phase changes. Results will help scientists develop fundamental physics concepts previously cloaked by the effects of gravity.

The viscous to brittle transition in eruptions of clay suspensions

NASA Astrophysics Data System (ADS)

Schmid, Diana; Scheu, Bettina; Wadsworth, Fabian B.; Kennedy, Ben; Jolly, Art; Dingwell, Donald B.

2017-04-01

The research is motivated by the early 2013 activity of White Island, New Zealand, which was characterized by frequent small phreatic activity through a fine grained mud rich shallow crater lake. Field observations demonstrate that the small eruptions were driven by bubble-burst events. Additionally, during the ongoing eruption, water vigorously evaporated, causing a shift in rheology of the crater lake liquid-solid suspension. Yet, the effect of water content on the eruptive behaviour of clay-bearing liquid suspensions is poorly understood. Here we investigate the influence of the solid to water ratio of the clay material erupted on the eruption characteristics. Kaolin was used as an analogue for the clay and was mixed with water in different proportions. We conducted experiments with different kaolin/water mixtures held at 120°C, in which they were decompressed from 2-4 bars to ambient conditions in a few milliseconds. During an experimental eruption, the velocity of the ejected material decreased, resulting in shifts in behaviour. Based on our experimental observations we established five different regimes that depend on the particle velocity relative to the gas velocity, and on the kaolin to water ratio of the mixture. In all experiments and for all kaolin to water ratios, regime 1 is one in which particles are ejected rapidly in an expanding high velocity gas jet. In the liquid-dominated system (low kaolin to water ratios), the jet phase evolves to the ejection of elongate fluidal structures (regime 2) and then to discrete droplets (regime 3) as the ejection velocity wanes. Contrastingly, in the solid-dominated system, the jet phase (regime 1) transitions to a mixed solid-fluid structures (regime 4) and then to individual angular ejecta (regime 5). On the basis of high speed image analysis, we establish a phase diagram separating these regimes based on kaolin/water mixing rations and the ejecta velocities observed. The dominant transition between fluidal and solid-like behaviour is a viscous to brittle transition and occurs between a kaolin mass fraction of 0.48 and 0.65, which is consistent with previous observations of the liquid and plastic rheological limits, respectively. We find that a Stokes' number balances the timescale of flow with the timescale of particle motion opposing flow. We suggest that the transition from regime 1 to regime 2 occurs when the relative velocity between the ejected material and the gas phase increases and the Stokes' number exceeds 1, leading to decoupling and shear-stresses at the ejected fluid interfaces. A capillary number characterizes the transition from elongated liquid structures (regime 2) to individual droplets (regime 3) in the liquid-dominated system when the relative velocity drops to a value at which surface tension can restore the droplets to spherical. Our results emphasize that the different rheology of muddy material exhibit different characteristic eruption styles and offers a way to classify them.

Phase Diagram of an Ethylene Glycol-Hexamethylphosphorotriamide System

NASA Astrophysics Data System (ADS)

Solonina, I. A.; Rodnikova, M. N.; Kiselev, M. R.; Khoroshilov, A. V.

2018-02-01

The phase diagram of an ethylene glycol (EG)-hexamethylphosphorotriamide (HMPT) system is studied over two wide temperature intervals (+25°C…-90°C…+40°C) and (-150°C…+40°C) by means of differential scanning calorimetry using INTERTECH DSC Q100 and METTLER TA4000 DSC instruments (Switzerland) in the DSC30 mode with variable cooling/heating rates. Substantial overcooling of the liquid phase, a glass transition, and different types of interaction are observed in the system. No thermal effects are observed in intermediate range of concentrations during the slow cooling/heating processes, and the system remains liquid until the glass transition. The presence of such a metastable phase is attributed to a sharp rise in the viscosity of the system due to different kinds of interaction between the components. HMPT: 2EG and HMPT: EG compounds with crystallization temperatures of +5 and -0.5°C, respectively, are observed upon rapid cooling and slow heating. Changes in enthalpy are calculated for all of the observed thermal effects. The distinction from the phase diagram of H2O-HMFT (literary data) is explained by the difference in the interactions between system components and by the structural differences between EG and H2O.

Electron drift in a large scale solid xenon

DOE PAGES

Yoo, J.; Jaskierny, W. F.

2015-08-21

A study of charge drift in a large scale optically transparent solid xenon is reported. A pulsed high power xenon light source is used to liberate electrons from a photocathode. The drift speeds of the electrons are measured using a 8.7 cm long electrode in both the liquid and solid phase of xenon. In the liquid phase (163 K), the drift speed is 0.193 ± 0.003 cm/μs while the drift speed in the solid phase (157 K) is 0.397 ± 0.006 cm/μs at 900 V/cm over 8.0 cm of uniform electric fields. Furthermore, it is demonstrated that a factor twomore » faster electron drift speed in solid phase xenon compared to that in liquid in a large scale solid xenon.« less

Solid - solid and solid - liquid phase transitions of iron and iron alloys under laser shock compression

NASA Astrophysics Data System (ADS)

Harmand, M.; Krygier, A.; Appel, K.; Galtier, E.; Hartley, N.; Konopkova, Z.; Lee, H. J.; McBride, E. E.; Miyanishi, K.; Nagler, B.; Nemausat, R.; Vinci, T.; Zhu, D.; Ozaki, N.; Fiquet, G.

2017-12-01

An accurate knowledge of the properties of iron and iron alloys at high pressures and temperatures is crucial for understanding and modelling planetary interiors. While Earth-size and Super-Earth Exoplanets are being discovered in increasingly large numbers, access to detailed information on liquid properties, melting curves and even solid phases of iron and iron at the pressures and temperatures of their interiors is still strongly limited. In this context, XFEL sources coupled with high-energy lasers afford unique opportunities to measure microscopic structural properties at far extreme conditions. Also the achievable time resolution allows the shock history and phase transition mechanisms to be followed during laser compression, improving our understanding of the high pressure and high strain experiments. Here we present recent studies devoted to investigate the solid-solid and solid-liquid transition in laser-shocked iron and iron alloys (Fe-Si, Fe-C and Fe-O alloys) using X-ray diffraction and X-ray diffuse scattering. Experiment were performed at the MEC end-station of the LCLS facility at SLAC (USA). Detection of the diffuse scattering allowed the identification of the first liquid peak position along the Hugoniot, up to 4 Mbar. The time resolution shows ultrafast (between several tens and several hundreds of picoseconds) solid-solid and solid-liquid phase transitions. Future developments at XFEL facilities will enable detailed studies of the solid and liquid structures of iron and iron alloys as well as out-of-Hugoniot studies.

Pascal Liquid Phase in Electronic Waveguides

NASA Astrophysics Data System (ADS)

Tomczyk, M.; Briggeman, M.; Tylan-Tyler, A.; Huang, M.; Tian, B.; Pekker, D.; Lee, J.-W.; Lee, H.; Eom, C.-B.; Levy, J.

Clean one-dimensional electron transport has been observed in very few material systems. The development of exceptionally clean electron waveguides formed at the interface between complex oxides LaAlO3 and SrTiO3 enables low-dimensional transport to be explored with newfound flexibility. This material system not only supports ballistic 1D transport, but possesses a rich phase diagram and strong attractive electron-electron interactions which are not present in other solid-state systems. Here we report an unusual phenomenon in which quantized conductance increases by steps that themselves increase sequentially in multiples of e2 / h . The overall conductance exhibits a Pascal-like sequence: 1, 3, 6, 10... e2 / h , which we ascribe to ballistic transport of 1, 2, 3, 4 ... bunches of electrons. We will discuss how subband degeneracies can occur in non-interacting models that have carefully tuned parameters. Strong attractive interactions are required, however, for these subbands to lock together. This Pascal liquid phase provides a striking example of the consequences of strong attractive interactions in low-dimensional environments. We gratefully acknowledge financial support from AFOSR (FA9550-12-1- 0057 (JL) and FA9550-12-1-0342 (CBE)), ONR N00014-15-1-2847 (JL), and NSF DMR-1234096 (CBE).

Snakes on a plane: modeling flexible active nematics

NASA Astrophysics Data System (ADS)

Selinger, Robin

Active soft matter systems of self-propelled rod-shaped particles exhibit ordered phases and collective behavior that are remarkably different from their passive analogs. In nature, many self-propelled rod-shaped particles, such as gliding bacteria and kinesin-driven microtubules, are flexible and can bend. We model these ``living liquid crystals'' to explore their phase behavior, dynamics, and pattern formation. We model particles as short polymers via molecular dynamics with a Langevin thermostat and various types of activity, substrate, and environments. For self-propelled polar particles gliding on a solid substrate, we map out the phase diagram as a function of particle density and flexibility. We compare simulated defect structures to those observed in colonies of gliding myxobacteria; compare spooling behavior to that observed in microtubule gliding assays; and analyze emergence of nematic and polar order. Next we explore pattern formation of self-propelled polar particles under flexible encapsulation, and on substrates with non-uniform Gaussian curvature. Lastly, we impose an activity mechanism that mimics extensile shear, study flexible particles both on solid substrates and coupled to a lipid membrane, and discuss comparisons to relevant experiments. Work performed in collaboration with Michael Varga (Kent State) and Luca Giomi (Universiteit Leiden.) Work supported by NSF DMR-1409658.

Pair Potential That Reproduces the Shape of Isochrones in Molecular Liquids.

PubMed

Veldhorst, Arno A; Schrøder, Thomas B; Dyre, Jeppe C

2016-08-18

Many liquids have curves (isomorphs) in their phase diagrams along which structure, dynamics, and some thermodynamic quantities are invariant in reduced units. A substantial part of their phase diagrams is thus effectively one dimensional. The shapes of these isomorphs are described by a material-dependent function of density, h(ρ), which for real liquids is well approximated by a power law, ρ(γ). However, in simulations, a power law is not adequate when density changes are large; typical models, such as Lennard-Jones liquids, show that γ(ρ) ≡ d ln h(ρ)/d ln ρ is a decreasing function of density. This article presents results from computer simulations using a new pair potential that diverges at a nonzero distance and can be tuned to give a more realistic shape of γ(ρ). Our results indicate that the finite size of molecules is an important factor to take into account when modeling liquids over a large density range.

Encapsulated Solid-Liquid Phase Change Nanoparticles as Thermal Barcodes for Highly Sensitive Detections of Multiple Lung Cancer Biomarkers

DTIC Science & Technology

2012-10-01

5e. TASK NUMBER LC90061 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT...transduction mechanism based on solid- liquid phase change nanoparticles works for the detection of multiple proteins. A series of metal and alloy...early stage. With the support from DOD-LCRP, we have proved the new signal transduction mechanism based on solid-liquid phase change nanoparticles works

Thermochemical properties of silver tellurides including empressite (AgTe) and phase diagrams for Ag-Te and Ag-Te-O

NASA Astrophysics Data System (ADS)

Voronin, Mikhail V.; Osadchii, Evgeniy G.; Brichkina, Ekaterina A.

2017-10-01

This study compiles original experimental and literature data on the thermodynamic properties (ΔfG°, S°, ΔfH°) of silver tellurides (α-Ag2Te, β-Ag2Te, Ag1.9Te, Ag5Te3, AgTe) obtained by the method of solid-state galvanic cell with the RbAg4I5 and AgI solid electrolytes. The thermodynamic data for empressite (AgTe, pure fraction from Empress Josephine Mine, Colorado USA) have been obtained for the first time by the electrochemical experiment with the virtual reaction Ag + Te = AgTe. The Ag-Te phase diagrams in the T - x and log fTe2 (gas) - 1/ T coordinates have been refined, and the ternary Ag-Te-O diagrams with Ag-Te-TeO2 (paratellurite) composition range have been calculated.

A Simple Approach to Characterize Gas-Aqueous Liquid Two-phase Flow Configuration Based on Discrete Solid-Liquid Contact Electrification.

PubMed

Choi, Dongwhi; Lee, Donghyeon; Kim, Dong Sung

2015-10-14

In this study, we first suggest a simple approach to characterize configuration of gas-aqueous liquid two-phase flow based on discrete solid-liquid contact electrification, which is a newly defined concept as a sequential process of solid-liquid contact and successive detachment of the contact liquid from the solid surface. This approach exhibits several advantages such as simple operation, precise measurement, and cost-effectiveness. By using electric potential that is spontaneously generated by discrete solid-liquid contact electrification, the configurations of the gas-aqueous liquid two-phase flow such as size of a gas slug and flow rate are precisely characterized. According to the experimental and numerical analyses on parameters that affect electric potential, gas slugs have been verified to behave similarly to point electric charges when the measuring point of the electric potential is far enough from the gas slug. In addition, the configuration of the gas-aqueous liquid two-phase microfluidic system with multiple gas slugs is also characterized by using the presented approach. For a proof-of-concept demonstration of using the proposed approach in a self-triggered sensor, a gas slug detector with a counter system is developed to show its practicality and applicability.

Molybdenum-titanium phase diagram evaluated from ab initio calculations

NASA Astrophysics Data System (ADS)

Barzilai, Shmuel; Toher, Cormac; Curtarolo, Stefano; Levy, Ohad

2017-07-01

The design of next generation β -type titanium implants requires detailed knowledge of the relevant stable and metastable phases at temperatures where metallurgical heat treatments can be performed. Recently, a standard specification for surgical implant applications was established for Mo-Ti alloys. However, the thermodynamic properties of this binary system are not well known and two conflicting descriptions of the β -phase stability have been presented in the literature. In this study, we use ab initio calculations to investigate the Mo-Ti phase diagram. These calculations predict that the β phase is stable over a wide concentration range, in qualitative agreement with one of the reported phase diagrams. In addition, they predict stoichiometric compounds, stable at temperatures below 300 ∘C , which have not yet been detected by experiments. The resulting solvus, which defines the transition to the β -phase solid solution, therefore occurs at lower temperatures and is more complex than previously anticipated.

Nonergodicity in binary alloys

NASA Astrophysics Data System (ADS)

Son, Leonid; Sidorov, Valery; Popel, Pjotr; Shulgin, Dmitry

2015-09-01

For binary liquids with limited miscibility of the components, we provide the corrections to the equation of state which arise from the nonergogic diffusivity. It is shown that these corrections result in lowering of critical miscibility point. In some cases, it may result in a bifurcation of miscibility curve: the mixtures near 50% concentration which are homogeneous at the microscopic level, occur to be too stable to provide a quasi - eutectic triple point. These features provide a new look on the phase diagrams of some binary systems. In present work, we discuss Ga-Pb, Fe-Cu, and Cu-Zr alloys. Our investigation corresponds their complex behavior in liquid state to the shapes of their phase diagrams.

Compression Limit of Two-Dimensional Water Constrained in Graphene Nanocapillaries.

PubMed

Zhu, YinBo; Wang, FengChao; Bai, Jaeil; Zeng, Xiao Cheng; Wu, HengAn

2015-12-22

Evaluation of the tensile/compression limit of a solid under conditions of tension or compression is often performed to provide mechanical properties that are critical for structure design and assessment. Algara-Siller et al. recently demonstrated that when water is constrained between two sheets of graphene, it becomes a two-dimensional (2D) liquid and then is turned into an intriguing monolayer solid with a square pattern under high lateral pressure [ Nature , 2015 , 519 , 443 - 445 ]. From a mechanics point of view, this liquid-to-solid transformation characterizes the compression limit (or metastability limit) of the 2D monolayer water. Here, we perform a simulation study of the compression limit of 2D monolayer, bilayer, and trilayer water constrained in graphene nanocapillaries. At 300 K, a myriad of 2D ice polymorphs (both crystalline-like and amorphous) are formed from the liquid water at different widths of the nanocapillaries, ranging from 6.0 to11.6 Å. For monolayer water, the compression limit is typically a few hundred MPa, while for the bilayer and trilayer water, the compression limit is 1.5 GPa or higher, reflecting the ultrahigh van der Waals pressure within the graphene nanocapillaries. The compression-limit (phase) diagram is obtained at the nanocapillary width versus pressure (h-P) plane, based on the comprehensive molecular dynamics simulations at numerous thermodynamic states as well as on the Clapeyron equation. Interestingly, the compression-limit curves exhibit multiple local minima.

Determining phase diagrams of gas-liquid systems using a microfluidic PVT.

PubMed

Mostowfi, Farshid; Molla, Shahnawaz; Tabeling, Patrick

2012-11-07

A novel microfluidic device designed for analyzing phase diagrams of gas-liquid systems (PVT or pressure-volume-temperature measurements) is described. The method mimics the phase transition of a reservoir fluid as it travels through the wellbore from the formation to the surface. The device consists of a long serpentine microchannel etched in a silicon substrate. The local pressure inside the channel is measured using membrane-based optical pressure sensors positioned along the channel. Geometrical restrictions are placed along the microchannel in order to nucleate bubbles when nucleation conditions are met, thus preventing the development of a supersaturation state in the channel. We point out that a local equilibrium state between gas and liquid phases is achieved, which implies that equilibrium properties can be directly measured on the chip. We analyze different mixtures of hydrocarbon systems and, consistently with the preceding analysis, obtain excellent agreement between our technique and conventional measurements. From a practical viewpoint (important for the relevance of the technology), we observe that the measurement time of thermodynamic properties of gas-liquid systems is reduced from hours to minutes with the present device without compromising the measurement accuracy.

An Indirect Method for Vapor Pressure and Phase Change Enthalpy Determination by Thermogravimetry

NASA Astrophysics Data System (ADS)

Giani, Samuele; Riesen, Rudolf; Schawe, Jürgen E. K.

2018-07-01

Vapor pressure is a fundamental property of a pure substance. This property is the pressure of a compound's vapor in thermodynamic equilibrium with its condensed phase (solid or liquid). When phase equilibrium condition is met, phase coexistence of a pure substance involves a continuum interplay of vaporization or sublimation to gas and condensation back to their liquid or solid form, respectively. Thermogravimetric analysis (TGA) techniques are based on mass loss determination and are well suited for the study of such phenomena. In this work, it is shown that TGA method using a reference substance is a suitable technique for vapor pressure determination. This method is easy and fast because it involves a series of isothermal segments. In contrast to original Knudsen's approach, where the use of high vacuum is mandatory, adopting the proposed method a given experimental setup is calibrated under ambient pressure conditions. The theoretical framework of this method is based on a generalization of Langmuir equation of free evaporation: The real strength of the proposed method is the ability to determine the vapor pressure independently of the molecular mass of the vapor. A demonstration of this method has been performed using the Clausius-Clapeyron equation of state to derive the working equation. This algorithm, however, is adaptive and admits the use of other equations of state. The results of a series of experiments with organic molecules indicate that the average difference of the measured and the literature vapor pressure amounts to about 5 %. Vapor pressure determined in this study spans from few mPa up to several kPa. Once the p versus T diagram is obtained, phase transition enthalpy can additionally be calculated from the data.

Characterization of rhamnolipids by liquid chromatography/mass spectrometry after solid-phase extraction.

PubMed

Behrens, Beate; Engelen, Jeannine; Tiso, Till; Blank, Lars Mathias; Hayen, Heiko

2016-04-01

Rhamnolipids are surface-active agents with a broad application potential that are produced in complex mixtures by bacteria of the genus Pseudomonas. Analysis from fermentation broth is often characterized by laborious sample preparation and requires hyphenated analytical techniques like liquid chromatography coupled to mass spectrometry (LC-MS) to obtain detailed information about sample composition. In this study, an analytical procedure based on chromatographic method development and characterization of rhamnolipid sample material by LC-MS as well as a comparison of two sample preparation methods, i.e., liquid-liquid extraction and solid-phase extraction, is presented. Efficient separation was achieved under reversed-phase conditions using a mixed propylphenyl and octadecylsilyl-modified silica gel stationary phase. LC-MS/MS analysis of a supernatant from Pseudomonas putida strain KT2440 pVLT33_rhlABC grown on glucose as sole carbon source and purified by solid-phase extraction revealed a total of 20 congeners of di-rhamnolipids, mono-rhamnolipids, and their biosynthetic precursors 3-(3-hydroxyalkanoyloxy)alkanoic acids (HAAs) with different carbon chain lengths from C8 to C14, including three rhamnolipids with uncommon C9 and C11 fatty acid residues. LC-MS and the orcinol assay were used to evaluate the developed solid-phase extraction method in comparison with the established liquid-liquid extraction. Solid-phase extraction exhibited higher yields and reproducibility as well as lower experimental effort.

Determination of solid- and liquid-phase gastric emptying half times in cats by use of nuclear scintigraphy.

PubMed

Costello, M; Papasouliotis, K; Barr, F J; Gruffydd-Jones, T J; Caney, S M

1999-10-01

To use nuclear scintigraphy to establish a range of gastric emptying half times (t1/2) following a liquid or solid meal in nonsedated cats. 12 clinically normal 3-year-old domestic shorthair cats. A test meal of 75 g of scrambled eggs labeled with technetium Tc 99m tin colloid was fed to 10 of the cats, and solid-phase gastric emptying t1/2 were determined by use of nuclear scintigraphy. In a separate experiment, 8 of these cats plus an additional 2 cats were fed 18 ml (n = 5) or 36 ml (n = 5) of a nutrient liquid meal labeled with technetium Tc 99m pentetate. Liquid-phase gastric emptying t1/2 then were determined by use of scintigraphy. Solid-phase gastric emptying t1/2 were between 210 and 769 minutes (median, 330 minutes). Median liquid-phase gastric emptying t1/2 after ingestion of 18 or 36 ml of the test meal were 67 minutes (range, 60 to 96 minutes) and 117 minutes (range, 101 to 170 minutes), respectively. The median t1/2 determined for cats receiving 18 ml of the radiolabeled liquid was significantly less than that determined for cats receiving 36 ml of the test meal. The protocol was tolerated by nonsedated cats. Solid-phase gastric emptying t1/2 were prolonged, compared with liquid-phase t1/2, and a major factor governing the emptying rate of liquids was the volume consumed. Nuclear scintigraphy may prove useful in assessing gastric motility disorders in cats.

Phase Diagram of the Ethylene Glycol-Dimethylsulfoxide System

NASA Astrophysics Data System (ADS)

Solonina, I. A.; Rodnikova, M. N.; Kiselev, M. R.; Khoroshilov, A. V.; Shirokova, E. V.

2018-05-01

The phase diagram of ethylene glycol (EG)-dimethylsulfoxide (DMSO) system is studied in the temperature range of +25 to -140°C via differential scanning calorimetry. It is established that the EG-DMSO system is characterized by strong overcooling of the liquid phase, a glass transition at -125°C, and the formation of a compound with the composition of DMSO · 2EG. This composition has a melting temperature of -60°C, which is close to those of neighboring eutectics (-75 and -70°C). A drop in the baseline was observed in the temperature range of 8 to -5°C at DMSO concentrations of 5-50 mol %, indicating the existence of a phase separation area in the investigated system. The obtained data is compared to the literature data on the H2O-DMSO phase diagram.

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

NASA Technical Reports Server (NTRS)

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

1996-01-01

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

Determining the phase diagram of lithium via ab initio calculation and ramp compression

NASA Astrophysics Data System (ADS)

Shulenburger, Luke; Seagle, Chris; Haill, Thomas; Harding, Eric

2015-06-01

Diamond anvil cell experiments have shown elemental lithium to have an extraordinarily complex phase diagram under pressure exhibiting numerous solid phases at pressures below 1 Mbar, as well as a complicated melting behavior. We explore this phase diagram utilizing a combination of quantum mechanical calculations and ramp compression experiments performed on Sandia National Laboratories' Z-machine. We aim to extend our knowledge of the high pressure behavior to moderate temperatures at pressures above 50 GPa with a specific focus on the melt line above 70 GPa. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the US Dept of Energy's Natl. Nuclear Security Administration under Contract DE-AC04-94AL85000.

Self-consistent phonon theory of the crystallization and elasticity of attractive hard spheres.

PubMed

Shin, Homin; Schweizer, Kenneth S

2013-02-28

We propose an Einstein-solid, self-consistent phonon theory for the crystal phase of hard spheres that interact via short-range attractions. The approach is first tested against the known behavior of hard spheres, and then applied to homogeneous particles that interact via short-range square well attractions and the Baxter adhesive hard sphere model. Given the crystal symmetry, packing fraction, and strength and range of attractive interactions, an effective harmonic potential experienced by a particle confined to its Wigner-Seitz cell and corresponding mean square vibrational amplitude are self-consistently calculated. The crystal free energy is then computed and, using separate information about the fluid phase free energy, phase diagrams constructed, including a first-order solid-solid phase transition and its associated critical point. The simple theory qualitatively captures all the many distinctive features of the phase diagram (critical and triple point, crystal-fluid re-entrancy, low-density coexistence curve) as a function of attraction range, and overall is in good semi-quantitative agreement with simulation. Knowledge of the particle localization length allows the crystal shear modulus to be estimated based on elementary ideas. Excellent predictions are obtained for the hard sphere crystal. Expanded and condensed face-centered cubic crystals are found to have qualitatively different elastic responses to varying attraction strength or temperature. As temperature increases, the expanded entropic solid stiffens, while the energy-controlled, fully-bonded dense solid softens.

Vortex phase diagram of the layered superconductor Cu0.03TaS2 for H is parallel to c.

PubMed

Zhu, X D; Lu, J C; Sun, Y P; Pi, L; Qu, Z; Ling, L S; Yang, Z R; Zhang, Y H

2010-12-22

The magnetization and anisotropic electrical transport properties have been measured in high quality Cu(0.03)TaS(2) single crystals. A pronounced peak effect has been observed, indicating that high quality and homogeneity are vital to the peak effect. A kink has been observed in the magnetic field, H, dependence of the in-plane resistivity ρ(ab) for H is parallel to c, which corresponds to a transition from activated to diffusive behavior of the vortex liquid phase. In the diffusive regime of the vortex liquid phase, the in-plane resistivity ρ(ab) is proportional to H(0.3), which does not follow the Bardeen-Stephen law for free flux flow. Finally, a simplified vortex phase diagram of Cu(0.03)TaS(2) for H is parallel to c is given.

Classical dimer model with anisotropic interactions on the square lattice

NASA Astrophysics Data System (ADS)

Otsuka, Hiromi

2009-07-01

We discuss phase transitions and the phase diagram of a classical dimer model with anisotropic interactions defined on a square lattice. For the attractive region, the perturbation of the orientational order parameter introduced by the anisotropy causes the Berezinskii-Kosterlitz-Thouless transitions from a dimer-liquid to columnar phases. According to the discussion by Nomura and Okamoto for a quantum-spin chain system [J. Phys. A 27, 5773 (1994)], we proffer criteria to determine transition points and also universal level-splitting conditions. Subsequently, we perform numerical diagonalization calculations of the nonsymmetric real transfer matrices up to linear dimension specified by L=20 and determine the global phase diagram. For the repulsive region, we find the boundary between the dimer-liquid and the strong repulsion phases. Based on the dispersion relation of the one-string motion, which exhibits a twofold “zero-energy flat band” in the strong repulsion limit, we give an intuitive account for the property of the strong repulsion phase.

A multiphysics and multiscale model for low frequency electromagnetic direct-chill casting

NASA Astrophysics Data System (ADS)

Košnik, N.; Guštin, A. Z.; Mavrič, B.; Šarler, B.

2016-03-01

Simulation and control of macrosegregation, deformation and grain size in low frequency electromagnetic (EM) direct-chill casting (LFEMC) is important for downstream processing. Respectively, a multiphysics and multiscale model is developed for solution of Lorentz force, temperature, velocity, concentration, deformation and grain structure of LFEMC processed aluminum alloys, with focus on axisymmetric billets. The mixture equations with lever rule, linearized phase diagram, and stationary thermoelastic solid phase are assumed, together with EM induction equation for the field imposed by the coil. Explicit diffuse approximate meshless solution procedure [1] is used for solving the EM field, and the explicit local radial basis function collocation method [2] is used for solving the coupled transport phenomena and thermomechanics fields. Pressure-velocity coupling is performed by the fractional step method [3]. The point automata method with modified KGT model is used to estimate the grain structure [4] in a post-processing mode. Thermal, mechanical, EM and grain structure outcomes of the model are demonstrated. A systematic study of the complicated influences of the process parameters can be investigated by the model, including intensity and frequency of the electromagnetic field. The meshless solution framework, with the implemented simplest physical models, will be further extended by including more sophisticated microsegregation and grain structure models, as well as a more realistic solid and solid-liquid phase rheology.

Development of a solid self-microemulsifying drug delivery system (SMEDDS) for solubility enhancement of naproxen.

PubMed

Čerpnjak, Katja; Zvonar, Alenka; Vrečer, Franc; Gašperlin, Mirjana

2015-01-01

Comparative evaluation of liquid and solid self-microemulsifying drug delivery systems (SMEDDS) as promising approaches for solubility enhancement. The aim of this work was to develop, characterize, and evaluate a solid SMEDDS prepared via spray-drying of a liquid SMEDDS based on Gelucire® 44/14 to improve the solubility and dissolution rate of naproxen. Various oils and co-surfactants in combination with Gelucire® 44/14 were evaluated during excipient selection study, solubility testing, and construction of (pseudo)ternary diagrams. The selected system was further evaluated for naproxen solubility, self-microemulsification ability, and in vitro dissolution of naproxen. In addition, its transformation into a solid SMEDDS by spray-drying using maltodextrin as a solid carrier was performed. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) were used to evaluate the physical characteristics of the solid SMEDDS obtained. The selected formulation of SMEDDS was comprised of Miglyol 812®, Peceol™, Gelucire® 44/14, and Solutol® HS 15. The liquid and solid SMEDDS formed a microemulsion after dilution with comparable average droplet size and exhibited uniform droplet size distribution. In the solid SMEDDS, liquid SMEDDS was adsorbed onto the surface of maltodextrin and formed smooth granular particles with the encapsulated drug predominantly in a dissolved state and partially in an amorphous state. Overall, incorporation of naproxen in SMEDDS, either liquid or solid, resulted in improved solubility and dissolution rate compared to pure naproxen. This study indicates that a liquid and solid SMEDDS is a strategy for solubility enhancement in the future development of orally delivered dosage forms.

A review of lithium and non-lithium based solid state batteries

NASA Astrophysics Data System (ADS)

Kim, Joo Gon; Son, Byungrak; Mukherjee, Santanu; Schuppert, Nicholas; Bates, Alex; Kwon, Osung; Choi, Moon Jong; Chung, Hyun Yeol; Park, Sam

2015-05-01

Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks, including expensive sealing agents and inherent hazards of fire and leakages. All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used, and a detailed literature review of various important advances made in research. The paper exhaustively studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium based systems. Non-lithium based solid state batteries are attaining widespread commercial applications, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.

Ultra-low temperature (≤300 °C) growth of Ge-rich SiGe by solid-liquid-coexisting annealing of a-GeSn/c-Si structures

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

Sadoh, Taizoh, E-mail: sadoh@ed.kyushu-u.ac.jp; Chikita, Hironori; Miyao, Masanobu

2015-09-07

Ultra-low temperature (≤300 °C) growth of Ge-rich SiGe on Si substrates is strongly desired to realize advanced electronic and optical devices, which can be merged onto Si large-scale integrated circuits (LSI). To achieve this, annealing characteristics of a-GeSn/c-Si structures are investigated under wide ranges of the initial Sn concentrations (0%–26%) and annealing conditions (300–1000 °C, 1 s–48 h). Epitaxial growth triggered by SiGe mixing is observed after annealing, where the annealing temperatures necessary for epitaxial growth significantly decrease with increasing initial Sn concentration and/or annealing time. As a result, Ge-rich (∼80%) SiGe layers with Sn concentrations of ∼2% are realized by ultra-low temperature annealingmore » (300 °C, 48 h) for a sample with the initial Sn concentration of 26%. The annealing temperature (300 °C) is in the solid-liquid coexisting temperature region of the phase diagram for Ge-Sn system. From detailed analysis of crystallization characteristics and composition profiles in grown layers, it is suggested that SiGe mixing is generated by a liquid-phase reaction even at ultra-low temperatures far below the melting temperature of a-GeSn. This ultra-low-temperature growth technique of Ge-rich SiGe on Si substrates is expected to be useful to realize next-generation LSI, where various multi-functional devices are integrated on Si substrates.« less

Role of quantum fluctuations on spin liquids and ordered phases in the Heisenberg model on the honeycomb lattice

NASA Astrophysics Data System (ADS)

Merino, Jaime; Ralko, Arnaud

2018-05-01

Motivated by the rich physics of honeycomb magnetic materials, we obtain the phase diagram and analyze magnetic properties of the spin-1 /2 and spin-1 J1-J2-J3 Heisenberg model on the honeycomb lattice. Based on the SU(2) and SU(3) symmetry representations of the Schwinger boson approach, which treats disordered spin liquids and magnetically ordered phases on an equal footing, we obtain the complete phase diagrams in the (J2,J3) plane. This is achieved using a fully unrestricted approach which does not assume any pre-defined Ansätze. For S =1 /2 , we find a quantum spin liquid (QSL) stabilized between the Néel, spiral, and collinear antiferromagnetic phases in agreement with previous theoretical work. However, by increasing S from 1 /2 to 1, the QSL is quickly destroyed due to the weakening of quantum fluctuations indicating that the model already behaves as a quasiclassical system. The dynamical structure factors and temperature dependence of the magnetic susceptibility are obtained in order to characterize all phases in the phase diagrams. Moreover, motivated by the relevance of the single-ion anisotropy, D , to various S =1 honeycomb compounds, we have analyzed the destruction of magnetic order based on an SU(3) representation of the Schwinger bosons. Our analysis provides a unified understanding of the magnetic properties of honeycomb materials realizing the J1-J2-J3 Heisenberg model from the strong quantum spin regime at S =1 /2 to the S =1 case. Neutron scattering and magnetic susceptibility experiments can be used to test the destruction of the QSL phase when replacing S =1 /2 by S =1 localized moments in certain honeycomb compounds.

A metastable liquid melted from a crystalline solid under decompression

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

TES buffer-induced phase separation of aqueous solutions of several water-miscible organic solvents at 298.15 K: phase diagrams and molecular dynamic simulations.

PubMed

Taha, Mohamed; Lee, Ming-Jer

2013-06-28

Water and the organic solvents tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone are completely miscible in all proportions at room temperature. Here, we present new buffering-out phase separation systems that the above mentioned organic aqueous solutions can be induced to form two liquid phases in the presence of a biological buffer 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]ethanesulfonic acid (TES). The lower liquid phase is rich in water and buffer, and the upper phase is organic rich. This observation has both practical and mechanistic interests. The phase diagrams of these systems were constructed by experimental measurements at ambient conditions. Molecular dynamic (MD) simulations were performed for TES + water + THF system to understand the interactions between TES, water, and organic solvent at molecular level. Several composition-sets for this system, beyond and inside the liquid-liquid phase-splitting region, have been simulated. Interestingly, the MD simulation for compositions inside the phase separation region showed that THF molecules are forced out from the water network to start forming a new liquid phase. The hydrogen-bonds, hydrogen-bonds lifetimes, hydrogen-bond energies, radial distribution functions, coordination numbers, the electrostatic interactions, and the van der Waals interactions between the different pairs have been calculated. Additionally, MD simulations for TES + water + tert-butanol∕acetonitrile∕acetone phase separation systems were simulated. The results from MD simulations provide an explanation for the buffering-out phenomena observed in [TES + water + organic solvent] systems by a mechanism controlled by the competitive interactions of the buffer and the organic solvent with water. The molecular mechanism reported here is helpful for designing new benign separation materials.

Thermodynamic functions, freezing transition, and phase diagram of dense carbon-oxygen mixtures in white dwarfs

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

Iyetomi, H.; Ogata, S.; Ichimaru, S.

1989-07-01

Equations of state for dense carbon-oxygen (C-O) binary-ionic mixtures (BIM's) appropriate to the interiors of white dwarfs are investigated through Monte Carlo simulations, by solution of relevant integral equations andvariational calculations in the density-functional formalism. It is thereby shown that the internal energies of the C-O BIM solids and fluids both obey precisely the linear mixing formulas. We then present an accurate calculation of the phase diagram associated with freezing transitions in such BIM materials, resulting in a novel prediction of an azeotropic diagram. Discontinuities of the mass density across the azeotropic phase boundaries areevaluated numerically for application to amore » study of white-dwarf evolution.« less

Liquid gallium-lead mixture phase diagram, surface tension near the critical mixing point, and prewetting transition.

PubMed

Osman, S M; Grosdidier, B; Ali, I; Abdellah, A Ben

2013-06-01

Quite recently, we reported a semianalytical equation of state (EOS) for the Ga-Pb alloy [Phys. Rev. B 78, 024205 (2008)], which was based on the first-order perturbation theory of fluid mixtures, within the simplified random phase approximation, in conjunction with the Grosdidier et al. model pair potentials for Ga-Ga and Pb-Pb with a suitable nonadditive pair potential between Ga-Pb unlike pairs. In the present work, we employ the present EOS to calculate the Ga-Pb phase diagram along the immiscibility gap region. The accuracy of the EOS is tested by consulting the empirical binodal curve. A statistical-mechanical-based theory for the surface tension is employed to obtain an analytical expression for the alloy surface tension. We calculated the surface tension along the bimodal curve and at extreme conditions of temperatures and pressures. The surface tension exhibits reasonably well the prewetting transition of Pb atoms at the surface of the Ga-rich liquid alloy and could qualitatively explain the prewetting phenomena occurring in the Ga-rich side of the phase diagram. The predicted prewetting line and wetting temperature qualitatively agree with the empirical measurements.

Competition between Chaotic and Nonchaotic Phases in a Quadratically Coupled Sachdev-Ye-Kitaev Model.

PubMed

Chen, Xin; Fan, Ruihua; Chen, Yiming; Zhai, Hui; Zhang, Pengfei

2017-11-17

The Sachdev-Ye-Kitaev (SYK) model is a concrete solvable model to study non-Fermi liquid properties, holographic duality, and maximally chaotic behavior. In this work, we consider a generalization of the SYK model that contains two SYK models with a different number of Majorana modes coupled by quadratic terms. This model is also solvable, and the solution shows a zero-temperature quantum phase transition between two non-Fermi liquid chaotic phases. This phase transition is driven by tuning the ratio of two mode numbers, and a nonchaotic Fermi liquid sits at the critical point with an equal number of modes. At a finite temperature, the Fermi liquid phase expands to a finite regime. More intriguingly, a different non-Fermi liquid phase emerges at a finite temperature. We characterize the phase diagram in terms of the spectral function, the Lyapunov exponent, and the entropy. Our results illustrate a concrete example of the quantum phase transition and critical behavior between two non-Fermi liquid phases.

A Demonstration of the Continuous Phase (Second-Order) Transition of a Binary Liquid System in the Region around Its Critical Point

ERIC Educational Resources Information Center

Johnson, Michael R.

2006-01-01

In most general chemistry and introductory physical chemistry classes, critical point is defined as that temperature-pressure point on a phase diagram where the liquid-gas interface disappears, a phenomenon that generally occurs at relatively high temperatures or high pressures. Two examples are: water, with a critical point at 647 K (critical…

Isolation and recovery of selected polybrominated diphenyl ethers from human serum and sheep serum: coupling reversed-phase solid-phase disk extraction and liquid-liquid extraction techniques with a capillary gas chromatographic electron capture negative ion mass spectrometric determinative technique.

PubMed

Loconto, Paul R; Isenga, David; O'Keefe, Michael; Knottnerus, Mark

2008-01-01

Polybrominated diphenyl ethers (PBDEs) are isolated and recovered with acceptable percent recoveries from human serum via liquid-liquid extraction and column chromatographic cleanup and fractionation with quantitation using capillary gas chromatography-mass spectrometry with electron capture negative ion and selected ion monitoring. PBDEs are found in unspiked serum. An alternative sample preparation approach is developed using sheep serum that utilizes a formic acid pre-treatment followed by reversed-phase solid-phase disk extraction and normal-phase solid-phase cleanup using acidified silica gel that yields>50% recoveries. When these percent recoveries are combined with a minimized phase ratio for human serum and very low instrument detection limits, method detection limits below 500 parts-per-trillion are realized.

Corrosion and Mechanical Properties of Al-5 At. Pct Cr Produced by Cryomilling and Subsequent Consolidation at Various Temperatures

NASA Astrophysics Data System (ADS)

Esquivel, J.; Darling, K. A.; Murdoch, H. A.; Gupta, R. K.

2018-04-01

An Al-5 at. pct Cr alloy was produced by high-energy ball milling at liquid nitrogen temperature followed by consolidation using equal-channel axial extrusion at 200 °C, 300 °C and 450 °C. The microstructure and corrosion response were compared with a cast alloy of the same composition. Rather than the intermetallics expected by the phase diagram and seen in the cast alloy, consolidated HEBM alloys exhibited extended solid solubility of Cr in the aluminum matrix in addition to a finely dispersed Cr-rich phase. This led to improvement in the corrosion behavior as investigated via potentiodynamic polarization and constant immersion tests in NaCl solution. Hardness and tensile tests were performed to evaluate the mechanical properties. The highest consolidation temperature (450 °C) contributed to significant grain growth and Cr diffusion, lessening the beneficial effects of processing with HEBM.

Ab Initio Investigations of High-Pressure Melting of Dense Lithium

NASA Astrophysics Data System (ADS)

Clay, Raymond; Morales, Miguel; Bonev, Stanimir

Lithium at ambient conditions is the simplest alkali metal and exhibits textbook nearly-free electron behavior. As the density is increased, however, significant core/valence overlap leads to surprisingly complex chemistry. We have systematically investigated the phase diagram of lithium at pressures ranging between two and six million atmospheres. Through a combination of density functional theory based path-integral and classical molecular dynamics simulations, we have investigated the impact of both nuclear quantum effects and anharmonicity on the melting line and solid phase boundaries. We also investigate how the inclusion of nuclear quantum effects and approximations in the treatment of electronic exchange-correlation impact the robustness of previous predictions of tetrahedral clustering in dense liquid Li. Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Metastable phase equilibria in co-deposited Ni(1-x)Zr(x) thin films

NASA Astrophysics Data System (ADS)

Rubin, J. B.; Schwarz, R. B.

We determine the glass forming range (GFR) of co-deposited Ni(1-x)Zr(x) (0 less than x less than 1) thin films by measuring their electrical resistance during in situ constant-heating-rate anneals. The measured GFR is continuous for 0.10 less than x less than 0.87. We calculate the GFR of Ni-Zr melts as a function of composition and cooling rate using homogeneous nucleation theory and a published CALPHAD-type thermodynamic modeling of the equilibrium phase diagram. Assuming that the main competition to the retention of the amorphous structure during the cooling of the liquid comes from the partitionless crystallization of the terminal solid solutions, we calculate that for dT/dt = 10(exp 12) K/s, the GFR extends to x = 0.05 and x = 0.96. Better agreement with the measured values is obtained assuming a lower effective cooling rate during the condensation of the films.

Quantum Spin Ice under a [111] Magnetic Field: From Pyrochlore to Kagome

NASA Astrophysics Data System (ADS)

Bojesen, Troels Arnfred; Onoda, Shigeki

2017-12-01

Quantum spin ice, modeled for magnetic rare-earth pyrochlores, has attracted great interest for hosting a U(1) quantum spin liquid, which involves spin-ice monopoles as gapped deconfined spinons, as well as gapless excitations analogous to photons. However, the global phase diagram under a [111] magnetic field remains open. Here we uncover by means of unbiased quantum Monte Carlo simulations that a supersolid of monopoles, showing both a superfluidity and a partial ionization, intervenes the kagome spin ice and a fully ionized monopole insulator, in contrast to classical spin ice where a direct discontinuous phase transition takes place. We also show that on cooling, kagome spin ice evolves towards a valence-bond solid similar to what appears in the associated kagome lattice model [S. V. Isakov et al., Phys. Rev. Lett. 97, 147202 (2006), 10.1103/PhysRevLett.97.147202]. Possible relevance to experiments is discussed.

Enthalpy-based multiple-relaxation-time lattice Boltzmann method for solid-liquid phase-change heat transfer in metal foams.

PubMed

Liu, Qing; He, Ya-Ling; Li, Qing

2017-08-01

In this paper, an enthalpy-based multiple-relaxation-time (MRT) lattice Boltzmann (LB) method is developed for solid-liquid phase-change heat transfer in metal foams under the local thermal nonequilibrium (LTNE) condition. The enthalpy-based MRT-LB method consists of three different MRT-LB models: one for flow field based on the generalized non-Darcy model, and the other two for phase-change material (PCM) and metal-foam temperature fields described by the LTNE model. The moving solid-liquid phase interface is implicitly tracked through the liquid fraction, which is simultaneously obtained when the energy equations of PCM and metal foam are solved. The present method has several distinctive features. First, as compared with previous studies, the present method avoids the iteration procedure; thus it retains the inherent merits of the standard LB method and is superior to the iteration method in terms of accuracy and computational efficiency. Second, a volumetric LB scheme instead of the bounce-back scheme is employed to realize the no-slip velocity condition in the interface and solid phase regions, which is consistent with the actual situation. Last but not least, the MRT collision model is employed, and with additional degrees of freedom, it has the ability to reduce the numerical diffusion across the phase interface induced by solid-liquid phase change. Numerical tests demonstrate that the present method can serve as an accurate and efficient numerical tool for studying metal-foam enhanced solid-liquid phase-change heat transfer in latent heat storage. Finally, comparisons and discussions are made to offer useful information for practical applications of the present method.

Enthalpy-based multiple-relaxation-time lattice Boltzmann method for solid-liquid phase-change heat transfer in metal foams

NASA Astrophysics Data System (ADS)

Liu, Qing; He, Ya-Ling; Li, Qing

2017-08-01

In this paper, an enthalpy-based multiple-relaxation-time (MRT) lattice Boltzmann (LB) method is developed for solid-liquid phase-change heat transfer in metal foams under the local thermal nonequilibrium (LTNE) condition. The enthalpy-based MRT-LB method consists of three different MRT-LB models: one for flow field based on the generalized non-Darcy model, and the other two for phase-change material (PCM) and metal-foam temperature fields described by the LTNE model. The moving solid-liquid phase interface is implicitly tracked through the liquid fraction, which is simultaneously obtained when the energy equations of PCM and metal foam are solved. The present method has several distinctive features. First, as compared with previous studies, the present method avoids the iteration procedure; thus it retains the inherent merits of the standard LB method and is superior to the iteration method in terms of accuracy and computational efficiency. Second, a volumetric LB scheme instead of the bounce-back scheme is employed to realize the no-slip velocity condition in the interface and solid phase regions, which is consistent with the actual situation. Last but not least, the MRT collision model is employed, and with additional degrees of freedom, it has the ability to reduce the numerical diffusion across the phase interface induced by solid-liquid phase change. Numerical tests demonstrate that the present method can serve as an accurate and efficient numerical tool for studying metal-foam enhanced solid-liquid phase-change heat transfer in latent heat storage. Finally, comparisons and discussions are made to offer useful information for practical applications of the present method.

Phase behavior of casein micelles/exocellular polysaccharide mixtures: Experiment and theory

NASA Astrophysics Data System (ADS)

Tuinier, R.; de Kruif, C. G.

1999-05-01

Dispersions of casein micelles and an exocellular polysaccharide (EPS), obtained from Lactococcus lactis subsp. cremoris NIZO B40 EPS, show a phase separation. The phase separation is of the colloidal gas-liquid type. We have determined a phase diagram that describes the separation of skim milk with EPS into a casein-micelle rich phase and an EPS rich phase. We compare the phase diagram with those calculated from theories developed by Vrij, and by Lekkerkerker and co-workers, showing that the experimental phase boundary can be predicted quite well. From dynamic light scattering measurements of the self-diffusion of the casein micelles in the presence of EPS the spinodal could be located and it corresponds with the experimental phase boundary.

Phase-field model of vapor-liquid-solid nanowire growth

NASA Astrophysics Data System (ADS)

Wang, Nan; Upmanyu, Moneesh; Karma, Alain

2018-03-01

We present a multiphase-field model to describe quantitatively nanowire growth by the vapor-liquid-solid (VLS) process. The free-energy functional of this model depends on three nonconserved order parameters that distinguish the vapor, liquid, and solid phases and describe the energetic properties of various interfaces, including arbitrary forms of anisotropic γ plots for the solid-vapor and solid-liquid interfaces. The evolution equations for those order parameters describe basic kinetic processes including the rapid (quasi-instantaneous) equilibration of the liquid catalyst to a droplet shape with constant mean curvature, the slow incorporation of growth atoms at the droplet surface, and crystallization within the droplet. The standard constraint that the sum of the phase fields equals unity and the conservation of the number of catalyst atoms, which relates the catalyst volume to the concentration of growth atoms inside the droplet, are handled via separate Lagrange multipliers. An analysis of the model is presented that rigorously maps the phase-field equations to a desired set of sharp-interface equations for the evolution of the phase boundaries under the constraint of force balance at three-phase junctions (triple points) given by the Young-Herring relation that includes torque term related to the anisotropy of the solid-liquid and solid-vapor interface excess free energies. Numerical examples of growth in two dimensions are presented for the simplest case of vanishing crystalline anisotropy and the more realistic case of a solid-liquid γ plot with cusped minima corresponding to two sets of (10 ) and (11 ) facets. The simulations reproduce many of the salient features of nanowire growth observed experimentally, including growth normal to the substrate with tapering of the side walls, transitions between different growth orientations, and crawling growth along the substrate. They also reproduce different observed relationships between the nanowire growth velocity and radius depending on the growth condition. For the basic normal growth mode, the steady-state solid-liquid interface tip shape consists of a main facet intersected by two truncated side facets ending at triple points. The ratio of truncated and main facet lengths are in quantitative agreement with the prediction of sharp-interface theory that is developed here for faceted nanowire growth in two dimensions.

Understanding the bond-energy, hardness, and adhesive force from the phase diagram via the electron work function

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

Lu, Hao; Huang, Xiaochen; Li, Dongyang, E-mail: dongyang.li@ualberta.ca

2014-11-07

Properties of metallic materials are intrinsically determined by their electron behavior. However, relevant theoretical treatment involving quantum mechanics is complicated and difficult to be applied in materials design. Electron work function (EWF) has been demonstrated to be a simple but fundamental parameter which well correlates properties of materials with their electron behavior and could thus be used to predict material properties from the aspect of electron activities in a relatively easy manner. In this article, we propose a method to extract the electron work functions of binary solid solutions or alloys from their phase diagrams and use this simple approachmore » to predict their mechanical strength and surface properties, such as adhesion. Two alloys, Fe-Ni and Cu-Zn, are used as samples for the study. EWFs extracted from phase diagrams show same trends as experimentally observed ones, based on which hardness and surface adhesive force of the alloys are predicted. This new methodology provides an alternative approach to predict material properties based on the work function, which is extractable from the phase diagram. This work may also help maximize the power of phase diagram for materials design and development.« less

Liquid phase stabilization versus bubble formation at a nanoscale curved interface

NASA Astrophysics Data System (ADS)

Schiffbauer, Jarrod; Luo, Tengfei

2018-03-01

We investigate the nature of vapor bubble formation near a nanoscale-curved convex liquid-solid interface using two models: an equilibrium Gibbs model for homogenous nucleation, and a nonequilibrium dynamic van der Waals-diffuse-interface model for phase change in an initially cool liquid. Vapor bubble formation is shown to occur for sufficiently large radius of curvature and is suppressed for smaller radii. Solid-fluid interactions are accounted for and it is shown that liquid-vapor interfacial energy, and hence Laplace pressure, has limited influence over bubble formation. The dominant factor is the energetic cost of creating the solid-vapor interface from the existing solid-liquid interface, as demonstrated via both equilibrium and nonequilibrium arguments.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1997-01-01

A solid/liquid process for the separation and recovery of TcO.sub.4.sup.-1 ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO.sub.4.sup.-1 ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO.sub.4.sup.-1 ions in such an aqueous solution that is free from MoO.sub.4.sup.-2 ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Stirring-controlled solidified floating solid-liquid drop microextraction as a new solid phase-enhanced liquid-phase microextraction method by exploiting magnetic carbon nanotube-nickel hybrid.

PubMed

Ghazaghi, Mehri; Mousavi, Hassan Zavvar; Shirkhanloo, Hamid; Rashidi, Alimorad

2017-01-25

A specific technique is introduced to overcome limitations of classical solidification of floating organic drop microextraction, such as tedious and time-consuming centrifuge step and using disperser solvent, by facile and efficient participation of solid and liquid phases. In this proposed method of stirring-controlled solidified floating solid-liquid drop microextraction (SC-SF-SLDME), magnetic carbon nanotube-nickel hybrid (MNi-CNT) as a solid part of the extractors are dispersed ultrasonically in sample solution, and the procedure followed by dispersion of liquid phase (1-undecanol) through high-rate stirring and easily recollection of MNi-CNT in organic solvent droplets through hydrophobic force. With the reduction in speed of stirring, one solid-liquid drop is formed on top of the solution. MNi-CNT acts as both extractor and the coalescence helper between organic droplets for a facile recollection. MNi-CNT was prepared by spray pyrolysis of nickel oleate/toluene mixture at 1000 °C. Four tyrosine kinase inhibitors were selected as model analytes and the effecting parameters were investigated. The results confirmed that magnetic nanoadsorbent has an important role in the procedure and complete collection of dispersed solvent is not achieved in the absence of the solid phase. Also, short extraction time exhibited success of the proposed method and effect of dispersed solid/liquid phases. The limits of quantification (LOQs) for imatinib, sunitinib, erlotinib, and nilotinib were determined to be as low as 0.7, 1.7, 0.6, and 1.0 μg L -1 , respectively. The intra-day precisions (RSDs) were lower than 4.5%. Method performance was investigated by determination of mentioned tyrosine kinase inhibitors (TKIs) in human serum and cerebrospinal fluid samples with good recoveries in the range of 93-98%. Copyright © 2016 Elsevier B.V. All rights reserved.

Iron-carbide cluster thermal dynamics for catalyzed carbon nanotube growth

NASA Astrophysics Data System (ADS)

Ding, Feng; Bolton, Kim; Rosén, Arne

2004-07-01

Molecular dynamics simulations have been used to study the thermal behavior of FeN-mCm clusters where N, the total number of atoms, extends up to 2400. Comparison of the computed results with experimental data shows that the simulations yield the correct trends for the liquid-solid region of the iron-carbide phase diagram as well as the correct dependence of cluster melting point as a function of cluster size. The calculation indicates that, when carbon nanotubes (CNTs) are grown on large (>3-4 nm) catalyst particles at low temperatures (<1200 K), the catalyst particles are not completely molten. It is argued that the mechanism of CNT growth under these conditions may be governed by the surface melting of the cluster. .

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Phase diagrams of orientational transitions in absorbing nematic liquid crystals

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

Zolot’ko, A. S., E-mail: zolotko@lebedev.ru; Ochkin, V. N.; Smayev, M. P.

2015-05-15

A theory of orientational transitions in nematic liquid crystals (NLCs), which employs the expansion of optical torques acting on the NLC director with respect to the rotation angle, has been developed for NLCs with additives of conformationally active compounds under the action of optical and low-frequency electric and magnetic fields. Phase diagrams of NLCs are constructed as a function of the intensity and polarization of the light field, the strength of low-frequency electric field, and a parameter that characterizes the feedback between the rotation of the NLC director and optical torque. Conditions for the occurrence of first- and second-order transitionsmore » are determined. The proposed theory agrees with available experimental data.« less

Field-temperature phase diagram and entropy landscape of CeAuSb 2

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

Zhao, Lishan; Yelland, Edward A.; Bruin, Jan A. N.

2016-05-12

Here, we report a field-temperature phase diagram and an entropy map for the heavy-fermion compound CeAuSb 2. CeAuSb 2 orders antiferromagnetically below T N = 6.6 K and has two metamagnetic transitions, at 2.8 and 5.6 T. The locations of the critical end points of the metamagnetic transitions, which may play a strong role in the putative quantum criticality of CeAuSb 2 and related compounds, are identified. The entropy map reveals an apparent entropy balance with Fermi-liquid behavior, implying that above the Neel transition the Ce moments are incorporated into the Fermi liquid. High-field data showing that the magnetic behaviormore » is remarkably anisotropic are also reported.« less

A thermodynamic database for tellurium-bearing systems relevant to nuclear technology

NASA Astrophysics Data System (ADS)

Chattopadhyay, G.; Juneja, J. M.

1993-06-01

A thermodynamic database for tellurium-bearing condensed phases and gaseous species which are relevant to nuclear technology is presented. It contains phase diagrams of the binary systems, PdTe, RhTe, PuTe, SmTe, CsTe, ZrTe, of the ternary systems, ZrTeO, MoTeO, AgTeO, UTeO, CsTeO, BaTeO as well as thermodynamic data for crystalline and liquid Te, for the solid phases Cs 2Te, Ag 2Te, SnTe, BaTe, CeTe, SmTe, RuTe 2, ZrTe 2, Fe 0.53Te 0.47, Mo 0.43Te 0.57, Cr 0.43Te 0.57, Ni 0.5Te 0.4, Cs 2TeO 3 and for the gaseous species, Te, Te 2, TeO, TeO 2, TeO(OH) 2, H 2Te, TeI, TeI 2, TeI 4, TeOI 2, SnTe, Sn 2Te 2, SnTe 2.

Mono- and polynucleation, atomistic growth, and crystal phase of III-V nanowires under varying group V flow

NASA Astrophysics Data System (ADS)

Dubrovskii, V. G.

2015-05-01

We present a refined model for the vapor-liquid-solid growth and crystal structure of Au-catalyzed III-V nanowires, which revisits several assumptions used so far and is capable of describing the transition from mononuclear to polynuclear regime and ultimately to regular atomistic growth. We construct the crystal phase diagrams and calculate the wurtzite percentages, elongation rates, critical sizes, and polynucleation thresholds of Au-catalyzed GaAs nanowires depending on the As flow. We find a non-monotonic dependence of the crystal phase on the group V flow, with the zincblende structure being preferred at low and high group V flows and the wurtzite structure forming at intermediate group V flows. This correlates with most of the available experimental data. Finally, we discuss the atomistic growth picture which yields zincblende crystal structure and should be very advantageous for fabrication of ternary III-V nanowires with well-controlled composition and heterointerfaces.

Investigating the Retention Mechanisms of Liquid Chromatography Using Solid-Phase Extraction Cartridges

ERIC Educational Resources Information Center

O'Donnell, Mary E.; Musial, Beata A.; Bretz, Stacey Lowery; Danielson, Neil D.; Ca, Diep

2009-01-01

Liquid chromatography (LC) experiments for the undergraduate analytical laboratory course often illustrate the application of reversed-phase LC to solve a separation problem, but rarely compare LC retention mechanisms. In addition, a high-performance liquid chromatography instrument may be beyond what some small colleges can purchase. Solid-phase…

A Simple Approach to Characterize Gas-Aqueous Liquid Two-phase Flow Configuration Based on Discrete Solid-Liquid Contact Electrification

PubMed Central

Choi, Dongwhi; Lee, Donghyeon; Sung Kim, Dong

2015-01-01

In this study, we first suggest a simple approach to characterize configuration of gas-aqueous liquid two–phase flow based on discrete solid-liquid contact electrification, which is a newly defined concept as a sequential process of solid-liquid contact and successive detachment of the contact liquid from the solid surface. This approach exhibits several advantages such as simple operation, precise measurement, and cost-effectiveness. By using electric potential that is spontaneously generated by discrete solid–liquid contact electrification, the configurations of the gas-aqueous liquid two-phase flow such as size of a gas slug and flow rate are precisely characterized. According to the experimental and numerical analyses on parameters that affect electric potential, gas slugs have been verified to behave similarly to point electric charges when the measuring point of the electric potential is far enough from the gas slug. In addition, the configuration of the gas-aqueous liquid two-phase microfluidic system with multiple gas slugs is also characterized by using the presented approach. For a proof-of-concept demonstration of using the proposed approach in a self-triggered sensor, a gas slug detector with a counter system is developed to show its practicality and applicability. PMID:26462437

Phase transition detection by surface photo charge effect in liquid crystals

NASA Astrophysics Data System (ADS)

Ivanov, O.; Petrov, M.; Naradikian, H.; Perez-Diaz, J. L.

2018-05-01

The surface photo charge effect (SPCE) was applied for the first time at structure and phase transitions study of hydrogen bonded in dimer liquid crystals (HBDLCs). Due to the high sensitivity of this method, besides first-order phase transitions, characteristic for the p,n-octyloxibenzoic acids (8OBA), an order transition was definitely detected within the nematic range. We state that the SPCE, arising at the solid-HBDLCs interface due to the double electrical layer, is invariably concomitant with solid surface-liquid interfaces, and indicates that the changes of the characteristics of this layer, under incident optical irradiation, induce surface charge rearrangement and alternating potential difference. A mechanism of induction of the SPCE at the interface of solid surface-anisotropic liquids is proposed. We also indicate that this mechanism can be adapted for solid surface-isotropic liquid interface, including colloids (milk) and fog (aerosols)-condensed medium.

Nickel-Silver Monotectic in Alumina Crucible for Use with Contact Thermometry

NASA Astrophysics Data System (ADS)

Gotoh, M.; Dedyulin, S. N.

2017-07-01

Previously, the authors have published work describing a pure Ni fixed point within alumina crucibles. The success of this study stimulated working with the Ni-Ag monotectic point in alumina crucibles. Similar to eutectic points, the Ni-Ag monotectic temperature is an invariant point but it differs from a eutectic reaction in such a way that the monotectic phase change takes place from Ni-Ag liquid solution to Ni-Ag solid solution and Ag rich Ni-Ag liquid solution. In the phase diagram references, the Ni-Ag monotectic phase transition temperature is assigned to be about 20°C below the pure Ni melting/freezing point. As is the case for pure Ni, mechanical stability is one of the concerns. Therefore, proper cell design is necessary to avoid breakage of the alumina crucible. The techniques used for the fabrication and measurement of the pure Ni cell were applied to the Ni-Ag cell as well. The cells have been successfully fabricated and the temperature measurement at the fixed point was carried out for more than 20 thermal cycles in total. A Pt/Pd thermocouple was used to measure the temperature and was calibrated from the tin point to the gold point to measure the ITS-90. Freezing plateaus are realized with the technique of "recurrent offset freezing method with reserved solid". The duration of each freezing plateau is a minimum of 30 min. The monotectic transformation temperature for the best performed cell is determined as 1428.27°C with a combined uncertainty of ±0.06°C ({k}=1).

Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192

NASA Astrophysics Data System (ADS)

Acree, William; Chickos, James S.

2017-03-01

The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state.

Electrical resistivity of the UAs 1- xSex solid solutions

NASA Astrophysics Data System (ADS)

Breandon, C.; Bartholin, H.; Tchapoutian, R.; Therond, P. G.; Schoenes, J.; Vogt, O.

1987-01-01

The electrical resistivity ϱ of UAs 1- xSex solid solutions has been measured between 13 K and room temperature. The magnetic phase diagram has been deduced. Effects of uniaxial stress on ϱ allow to understand some results and to reveal anisotropy of ϱ.

Phase Stability for the Pd-Si System. First-Principles, Experiments, and Solution-Based Modeling

DOE PAGES

Zhou, S. H.; Huo, Y.; Napolitano, Ralph E.

2015-11-05

Relative stabilities of the compounds in the binary Pd-Si system were assessed using first-principles calculations and experimental methods. Calculations of lattice parameters and enthalpy of formation indicate that Pd 5Si-μ, Pd 9Si 2-α, Pd 3 Si-β, Pd 2 Si-γ, and PdSi-δ are the stable phases at 0 K (-273 °C). X-ray diffraction analyses (XRD) and electron probe microanalysis (EPMA) of the as-solidified and heat-treated samples support the computational findings, except that the PdSi-δ phase was not observed at low temperature. Considering both experimental data and first-principles results, the compounds Pd 5 Si-μ, Pd 9 Si 2-α, Pd 3Si-β, and Pdmore » 2Si-γ are treated as stable phases down to 0 K (-273 °C), while the PdSi-δ is treated as being stable over a limited range, exhibiting a lower bound. Using these findings, a comprehensive solution-based thermodynamic model is formulated for the Pd-Si system, permitting phase diagram calculation. Moreover, the liquid phase is described using a three-species association model and other phases are treated as solid solutions, where a random substitutional model is adopted for Pd-fcc and Si-dia, and a two-sublattice model is employed for Pd 5Si-μ, Pd 9Si 2-α, Pd 3Si-β, Pd 2Si-γ, and PdSi-δ. Model parameters are fitted using available experimental data and first-principles data, and the resulting phase diagram is reported over the full range of compositions.« less

Phase Stability for the Pd-Si System. First-Principles, Experiments, and Solution-Based Modeling

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

Zhou, S. H.; Huo, Y.; Napolitano, Ralph E.

Relative stabilities of the compounds in the binary Pd-Si system were assessed using first-principles calculations and experimental methods. Calculations of lattice parameters and enthalpy of formation indicate that Pd 5Si-μ, Pd 9Si 2-α, Pd 3 Si-β, Pd 2 Si-γ, and PdSi-δ are the stable phases at 0 K (-273 °C). X-ray diffraction analyses (XRD) and electron probe microanalysis (EPMA) of the as-solidified and heat-treated samples support the computational findings, except that the PdSi-δ phase was not observed at low temperature. Considering both experimental data and first-principles results, the compounds Pd 5 Si-μ, Pd 9 Si 2-α, Pd 3Si-β, and Pdmore » 2Si-γ are treated as stable phases down to 0 K (-273 °C), while the PdSi-δ is treated as being stable over a limited range, exhibiting a lower bound. Using these findings, a comprehensive solution-based thermodynamic model is formulated for the Pd-Si system, permitting phase diagram calculation. Moreover, the liquid phase is described using a three-species association model and other phases are treated as solid solutions, where a random substitutional model is adopted for Pd-fcc and Si-dia, and a two-sublattice model is employed for Pd 5Si-μ, Pd 9Si 2-α, Pd 3Si-β, Pd 2Si-γ, and PdSi-δ. Model parameters are fitted using available experimental data and first-principles data, and the resulting phase diagram is reported over the full range of compositions.« less

AsS melt under pressure: one substance, three liquids.

PubMed

Brazhkin, V V; Katayama, Y; Kondrin, M V; Hattori, T; Lyapin, A G; Saitoh, H

2008-04-11

An in situ high-temperature--high-pressure study of liquid chalcogenide AsS by x-ray diffraction, resistivity measurements, and quenching from melt is presented. The obtained data provide direct evidence for the existence in the melt under compression of two transformations: one is from a moderate-viscosity molecular liquid to a high-viscosity nonmetallic polymerized liquid at P approximately 1.6-2.2 GPa; the other is from the latter to a low-viscosity metallic liquid at P approximately 4.6-4.8 GPa. Upon rapid cooling, molecular and metallic liquids crystallize to normal and high-pressure phases, respectively, while a polymerized liquid is easily quenched to a new AsS glass. General aspects of multiple phase transitions in liquid AsS, including relations to the phase diagram of the respective crystalline, are discussed.

As-Cast Icosashedral Quasicrystals in Ti-Zr-Ni Alloys

NASA Astrophysics Data System (ADS)

Lee, Geun Woo; Gangopadhyay, Anup K.; Kelton, Kenneth F.

2002-03-01

Most Ti-based icosahedral quasicrystals (i-phase) obtained by rapid quenching from the melt are metastable and disordered. In contrast, the Ti-Zr-Ni i-phase prepared by low temperature annealing is stable and better ordered. This i-phase is formed by a solid-state transformation from C14 Laves phase and α (Ti/Zr) solid-solution phase. It has not been possible previously to grow this i-phase directly from the liquid. Here, the nucleation and growth of the i-phase from the liquid in as-cast Ti-Zr-Ni alloys is reported. Pentagonal growth ledges in as-cast Ti-Zr-Ni ingots are clearly observed. Transmission electron microscopy and x-ray diffraction studies confirm the phase identity. Differential scanning calorimetry measurements show an endothermic transformation from the i-phase to a phase mixture of the C14 Laves and solid-solution phases, demonstrating that this i-phase is also stable. The short time that the liquid remains in the Laves phase-forming-field and the higher nucleation rate of the i-phase, owing to the presumed similarity between the local atomic structures of the i-phase and liquid, allows the i-phase to nucleate and grow directly from the liquid. Container-less solidification studies using electrostatic levitation (ESL) techniques support this conclusion.

The ammonia-water phase diagram and its implications for icy satellites

NASA Technical Reports Server (NTRS)

Johnson, M. L.; Nicol, M.

1986-01-01

A Holzapfel-type diamond anvil cell is used to determine the NH3 - H2O phase diagram in the region from 0 to 33 mole percent NH3, 240 to 370 K, and 0 to 5 GPa. The following phases were identified: liquid; water ices Ih, III, V, VI, VII, and VIII; ammonia monohydrate, NH3.H2O; and ammonia dihydrate NH3.2H2O. Ammonia dihydrate becomes prominent at moderate pressures (less than 1 GPa), with planetologically significant implications, including the possibility of layering in Titan's magma ocean.

The ammonia-water phase diagram and its implications for icy satellites

NASA Technical Reports Server (NTRS)

Johnson, Mary L.; Nicol, Malcolm

1987-01-01

A Holzapfel-type diamond anvil cell is used to determine the NH3 - H2O phase diagram in the region from 0 to 33 mole percent NH3, 240 to 370 K, and 0 to 5 GPa. The following phases were identified: liquid; water ices Ih, III, V, VI, VII, and VIII; ammonia monohydrate, NH3.H2O; and ammonia dihydrate NH3.2H2O. Ammonia dihydrate becomes prominent at moderate pressures (less than 1 GPa), with planetologically significant implications, including the possibility of layering in Titan's magma ocean.

Effect of Alcohols on the Phase Behavior and Emulsification of a Sucrose Fatty Acid Ester/Water/Edible Oil System.

PubMed

Matsuura, Tsutashi; Ogawa, Akihiro; Ohara, Yukari; Nishina, Shogo; Nakanishi, Maho; Gohtani, Shoichi

2018-02-01

The effect of alcohols (ethanol, 1-propanol, propylene glycol, glycerin, sucrose) on the phase behavior and emulsification of sucrose stearic acid ester (SSE)/water/edible vegetable oil (EVO) systems was investigated. Adding sucrose, propylene glycol, and glycerin narrowed the oil-separated two-phase region in the phase diagram of the SSE/water/EVO systems, whereas adding ethanol and 1-propanol expanded the oil-separated two-phase region. Changing the course of emulsification in the phase diagram showed that the size of the oil-droplet particle typically decreased in a system with a narrowed oil-separated region. The emulsification properties of the systems varied with respect to changes in the phase diagram. The microstructure of the systems was examined using small-angle X-ray scattering, and the ability to retain the oil in the lamellar structure of the SSEs was suggested as an important role in emulsification, because the mechanism of the systems was the same as that for the liquid crystal emulsification method.

Understanding the Phase Behavior of Tetrahydrofuran + Carbon Dioxide, + Methane, and + Water Binary Mixtures from the SAFT-VR Approach.

PubMed

Míguez, J M; Piñeiro, M M; Algaba, J; Mendiboure, B; Torré, J P; Blas, F J

2015-11-05

The high-pressure phase diagrams of the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) mixtures are examined using the SAFT-VR approach. Carbon dioxide molecule is modeled as two spherical segments tangentially bonded, water is modeled as a spherical segment with four associating sites to represent the hydrogen bonding, methane is represented as an isolated sphere, and tetrahydrofuran is represented as a chain of m tangentially bonded spherical segments. Dispersive interactions are modeled using the square-well intermolecular potential. In addition, two different molecular model mixtures are developed to take into account the subtle balance between water-tetrahydrofuran hydrogen-bonding interactions. The polar and quadrupolar interactions present in water, tetrahydrofuran, and carbon dioxide are treated in an effective way via square-well potentials of variable range. The optimized intermolecular parameters are taken from the works of Giner et al. (Fluid Phase Equil. 2007, 255, 200), Galindo and Blas (J. Phys. Chem. B 2002, 106, 4503), Patel et al. (Ind. Eng. Chem. Res. 2003, 42, 3809), and Clark et al. (Mol. Phys. 2006, 104, 3561) for tetrahydrofuran, carbon dioxide, methane, and water, respectively. The phase diagrams of the binary mixtures exhibit different types of phase behavior according to the classification of van Konynenburg and Scott, ranging from types I, III, and VI phase behavior for the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) binary mixtures, respectively. This last type is characterized by the presence of a Bancroft point, positive azeotropy, and the so-called closed-loop curves that represent regions of liquid-liquid immiscibility in the phase diagram. The system exhibits lower critical solution temperatures (LCSTs), which denote the lower limit of immiscibility together with upper critical solution temperatures (UCSTs). This behavior is explained in terms of competition between the incompatibility with the alkyl parts of the tetrahydrofuran ring chain and the hydrogen bonding between water and the ether group. A minimum number of unlike interaction parameters are fitted to give the optimal representation of the most representative features of the binary phase diagrams. In the particular case of tetrahydrofuran(1) + water(2), two sets of intermolecular potential model parameters are proposed to describe accurately either the hypercritical point associated with the closed-loop liquid-liquid immiscibility region or the location of the mixture lower- and upper-critical end-points. The theory is not only able to predict the type of phase behavior of each mixture, but also provides a reasonably good description of the global phase behavior whenever experimental data are available.

Unsteady numerical analysis of solid-liquid two-phase flow in stirred tank with double helical ribbon impeller

NASA Astrophysics Data System (ADS)

Bai, He; Chen, Xiangshan; Zhao, Guangyu; Xiao, Chenglei; Li, Chen; Zhong, Cheng; Chen, Yu

2017-08-01

In order to enhance the mixing process of soil contaminated by oil and water, one kind of double helical ribbon (DHR) impeller was developed. In this study, the unsteady simulation analysis of solid-liquid two-phase flow in stirring tank with DHR impeller was conducted by the the computational fluid dynamics and the multi-reference frame (MRF) method. It was found that at 0-3.0 s stage, the rate of liquid was greater than the rate of solid particles, while the power consumption was 5-6 times more than the smooth operation. The rates of the liquid and the solid particles were almost the same, and the required power was 32 KW at t > 3.0 s. The flow of the solid particles in the tank was a typical axial circle flow, and the dispersed sequence of the solid that was accumulated at the bottom of the tank was: the bottom loop region, the annular region near the wall of the groove and finally the area near axial center. The results show that the DHR impeller was suitable for the mixing of liquid-solid two-phase.

Triclinic-monoclinic-orthorhombic (T-M-O) structural transitions in phase diagram of FeVO4-CrVO4 solid solutions

NASA Astrophysics Data System (ADS)

Bera, Ganesh; Reddy, V. R.; Rambabu, P.; Mal, P.; Das, Pradip; Mohapatra, N.; Padmaja, G.; Turpu, G. R.

2017-09-01

Phase diagram of FeVO4-CrVO4 solid solutions pertinent with structural and magnetic phases is presented with unambiguous experimental evidences. Solid solutions Fe1-xCrxVO4 (0 ≤ x ≤ 1.0) were synthesized through the standard solid state route and studied by X-ray diffraction, scanning electron microscopy, energy dispersive spectra of X-rays, Raman spectroscopy, d.c. magnetization, and 57Fe Mössbauer spectroscopic studies. FeVO4 and CrVO4 were found to be in triclinic (P-1 space group) and orthorhombic structures (Cmcm space group), respectively. Cr incorporation into the FeVO4 lattice leads to the emergence of a new monoclinic phase dissimilar to the both end members of the solid solutions. In Fe1-xCrxVO4 up to x = 0.10, no discernible changes in the triclinic structure were found. A new structural monoclinic phase (C2/m space group) emerges within the triclinic phase at x = 0.125, and with the increase in Cr content, it gets stabilized with clear single phase signatures in the range of x = 0.175-0.25 as evidenced by the Rietveld analysis of the structures. Beyond x = 0.33, orthorhombic phase similar to CrVO4 (Cmcm space group) emerges and coexists with a monoclinic structure up to x = 0.85, which finally tends to stabilize in the range of x = 0.90-1.00. The Raman spectroscopic studies also confirm the structural transition. FeVO4 Raman spectra show the modes related to three nonequivalent V ions in the triclinic structure, where up to 42 Raman modes are observed in the present study. With the stabilization of structures having higher symmetry, the number of Raman modes decreases and the modes related to symmetry inequivalent sites collate into singular modes from the doublet structure. A systematic crossover from two magnetic transitions in FeVO4, at 21.5 K and 15.4 K to single magnetic transition in CrVO4, at 71 K (antiferromagnetic transition), is observed in magnetization studies. The intermediate solid solution with x = 0.15 shows two magnetic transitions, whereas in the compound with x = 0.33 one of the magnetic transitions disappears. 57Fe Mössbauer spectroscopic studies show a finger print evidence for disappearance of non-equivalent sites of Fe as the structure changes from Triclinic-Monoclinic-Orthorhombic phases with the increasing Cr content in Fe1-xCrxVO4. Comprehensive studies related to the structural changes in Fe1-xCrxVO4 solid solutions lead us to detailed phase diagrams which shall be characteristic for room temperature structural and temperature dependent magnetic transitions in these solid solutions, respectively.

Self-healing liquid/solid state battery

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

Burke, Paul J.; Chung, Brice H.V.; Phadke, Satyajit R.

A battery system that exchanges energy with an external device is provided. The battery system includes a positive electrode having a first metal or alloy, a negative electrode having a second metal or alloy, and an electrolyte including a salt of the second metal or alloy. The positive electrode, the negative electrode, and the electrolyte are in a liquid phase at an operating temperature during at least one portion of operation. The positive electrode is entirely in a liquid phase in one charged state and includes a solid phase in another charged state. The solid phase of the positive electrodemore » includes a solid intermetallic formed by the first and the second metals or alloys. Methods of storing electrical energy from an external circuit using such a battery system are also provided.« less

Further insight into the mechanism of heavy metals partitioning in stormwater runoff.

PubMed

Djukić, Aleksandar; Lekić, Branislava; Rajaković-Ognjanović, Vladana; Veljović, Djordje; Vulić, Tatjana; Djolić, Maja; Naunovic, Zorana; Despotović, Jovan; Prodanović, Dušan

2016-03-01

Various particles and materials, including pollutants, deposited on urban surfaces are washed off by stormwater runoff during rain events. The interactions between the solid and dissolved compounds in stormwater runoff are phenomena of importance for the selection and improvement of optimal stormwater management practices aimed at minimizing pollutant input to receiving waters. The objective of this research was to further investigate the mechanisms responsible for the partitioning of heavy metals (HM) between the solid and liquid phases in urban stormwater runoff. The research involved the collection of samples from urban asphalt surfaces, chemical characterization of the bulk liquid samples, solids separation, particle size distribution fractionation and chemical and physico-chemical characterization of the solid phase particles. The results revealed that a negligible fraction of HM was present in the liquid phase (less than 3% by weight), while there was a strong correlation between the total content of heavy metals and total suspended solids. Examinations of surface morphology and mineralogy revealed that the solid phase particles consist predominantly of natural macroporous materials: alpha quartz (80%), magnetite (11.4%) and silicon diphosphate (8.9%). These materials have a low surface area and do not have significant adsorptive capacity. These materials have a low surface area and do not have significant adsorptive capacity. The presence of HM on the surface of solid particles was not confirmed by scanning electron microscopy and energy dispersive X-ray microanalyses. These findings, along with the results of the liquid phase sample characterization, indicate that the partitioning of HM between the liquid and solid phases in the analyzed samples may be attributed to precipitation processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1997-02-18

A solid/liquid process for the separation and recovery of TcO{sub 4}{sup {minus}1} ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO{sub 4}{sup {minus}1} ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO{sub 4}{sup {minus}1} ions in such an aqueous solution that is free from MoO{sub 4}{sup {minus}2} ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 15 figs.

Numerical simulation analysis of four-stage mutation of solid-liquid two-phase grinding

NASA Astrophysics Data System (ADS)

Li, Junye; Liu, Yang; Hou, Jikun; Hu, Jinglei; Zhang, Hengfu; Wu, Guiling

2018-03-01

In order to explore the numerical simulation of solid-liquid two-phase abrasive grain polishing and abrupt change tube, in this paper, the fourth order abrupt change tube was selected as the research object, using the fluid mechanics software to simulate,based on the theory of solid-liquid two-phase flow dynamics, study on the mechanism of AFM micromachining a workpiece during polishing.Analysis at different inlet pressures, the dynamic pressure distribution pipe mutant fourth order abrasive flow field, turbulence intensity, discuss the influence of the inlet pressure of different abrasive flow polishing effect.

Effect of proximal vagotomy and Roux-en-Y diversion on gastric emptying kinetics in asymptomatic patients.

PubMed

Urbain, J L; Penninckx, F; Siegel, J A; Vandenborre, P; Van Cutsem, E; Vandenmaegdenbergh, V; De Roo, M

1990-10-01

The role of the distal stomach in gastric emptying was studied. Ten patients with proximal gastric vagotomy (PV) and 10 age-matched patients with Roux-en-Y gastro-jejunostomy (R-Y) were compared with 10 healthy controls. Gastric emptying of solids and liquids was determined by the use of Tc-99m SC scrambled eggs and In-111 DTPA. In PV, gastric emptying of both solids and liquids was delayed; the prolongation with solids was mainly accounted for by an abnormal lag phase. In R-Y patients, no lag phase was observed, and the solid emptying curve pattern was characterized by early rapid emptying followed by very slow emptying. Both the solid and liquid phases were prolonged. The lag phase is affected by proximal vagotomy and is mainly determined by the distal stomach, which appears to be essential for normal emptying.

PROGRESS ON THE STUDY OF THE URANIUM-ALUMINUM-IRON CONSTITUTION DIAGRAM FOR THE PERIOD APRIL 1-AUGUST 31, 1963

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

Russell, R.B.

Progress is reported of a research program on deterinining the U--Al-- Fe constitution diagram up to approximates 1000 ppm each of Al and Fe. Results are reported of metallographic examinations of U--Al, U--Fe, and U--Al--Fe alloys, and tentative phase diagrams are given for all three systems. Lattice parameters and electrical resistances were measured in an effort to determine the solid solubilities of Al and Fe in U. (D.L.C.)

Quantification of VX Nerve Agent in Various Food Matrices by Solid-Phase Extraction Ultra-Performance Liquid ChromatographyTime-of-Flight Mass Spectrometry

DTIC Science & Technology

2016-04-01

QUANTIFICATION OF VX NERVE AGENT IN VARIOUS FOOD MATRICES BY SOLID-PHASE EXTRACTION ULTRA-PERFORMANCE...TITLE AND SUBTITLE Quantification of VX Nerve Agent in Various Food Matrices by Solid-Phase Extraction Ultra-Performance Liquid Chromatography... food matrices. The mixed-mode cation exchange (MCX) sorbent and Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods were used for

The phase diagram and transport properties of MgO from theory and experiment

NASA Astrophysics Data System (ADS)

Shulenburger, Luke

2013-06-01

Planetary structure and the formation of terrestrial planets have received tremendous interest due to the discovery of so called super-earth exoplanets. MgO is a major constituent of Earth's mantle, the rocky cores of gas giants and is a likely component of the interiors of many of these exoplanets. The high pressure - high temperature behavior of MgO directly affects equation of state models for planetary structure and formation. In this work, we examine MgO under extreme conditions using experimental and theoretical methods to determine its phase diagram and transport properties. Using plate impact experiments on Sandia's Z facility the solid-solid phase transition from B1 to B2 is clearly determined. The melting transition, on the other hand, is subtle, involving little to no signal in us-up space. Theoretical work utilizing density functional theory (DFT) provides a complementary picture of the phase diagram. The solid-solid phase transition is identified through a series of quasi-harmonic phonon calculations and thermodynamic integration, while the melt boundary is found using phase coexistence calculations. One issue of particular import is the calculation of reflectivity along the Hugoniot and the influence of the ionic structure on the transport properties. Particular care is necessary because of the underestimation of the band gap and attendant overestimation of transport properties due to the use of semi-local density functional theory. We will explore the impact of this theoretical challenge and its potential solutions in this talk. The integrated use of DFT simulations and high-accuracy shock experiments together provide a comprehensive understanding of MgO under extreme conditions. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the U.S. DOE's National Nuclear Security Administration under contract DE-AC04-94AL85000.

[Gastric emptying of a solid-liquid meal in normal subjects: validity of the labeling (99mTc) of chicken liver by a multipuncture technic].

PubMed

Hostein, J; Capony, P; Busquet, G; Bost, R; Fournet, J

1985-04-01

For gastric emptying studies of a solid-liquid meal by the scintigraphic method, a valid isotope labeling method for each phase of the meal must be obtained. The aim of this study was to validate a simple chicken liver labeling method in normal subjects by multipuncture technic with 99mtechnetium. Labeling according to Meyer's method was chosen as a reference. Simultaneously, a study of the quality of liquid phase labeling by 111indium was done. The labeling process quality for each phase of the meal was assessed: a) in vitro, after incubation of the meal with human gastric juice (n = 12); b) in vivo, after meal ingestion and sequential collection of gastric contents by aspiration (n = 4). Furthermore, in 8 healthy volunteers, gastric emptying curves of the solid and liquid phases of the meal were determined scintigraphically and compared. Our results showed: a) for the solid phase: a good specificity of the marker, which was assessed in vitro and in vivo, after liver labeling with multipuncture technique (89 p. 100 and 92 p. 100 after 180 min, respectively); b) for the liquid phase: a good specificity of the marker in vitro and a poor specificity in vivo (82 p. 100 and 27 p. 100 after 180 min, respectively); c) similar half-gastric emptying times and cumulative percentages for the solid and liquid phases with both liver labeling methods. In conclusion, the multipuncture technique for chicken liver labeling may be used for gastric emptying studies in humans.

Analysis of the heat capacity for pure CH4 and CH4/CCl4 on graphite near the melting point and calculation of the T-X phase diagram for (CH3)CCl3 + CCl4

NASA Astrophysics Data System (ADS)

Yurtseven, Hamit; Yılmaz, Aygül

2016-06-01

We study the temperature dependence of the heat capacity Cp for the pure CH4 and the coadsorbed CH4/CCl4 on graphite near the melting point. The heat capacity peaks are analyzed using the experimental data from the literature by means of the power-law formula. The critical exponents for the heat capacity are deduced below and above the melting point for CH4 (Tm = 104.8 K) and CH4/CCl4 (Tm = 99.2 K). Our exponent values are larger as compared with the predicted values of some theoretical models exhibiting second order transition. Our analyses indicate that the pure methane shows a nearly second order (weak discontinuity in the heat capacity peak), whereas the transition in coadsorbed CH4/CCl4 is of first order (apparent discontinuity in Cp). We also study the T - X phase diagram of a two-component system of CH3CCl3+CCl4 using the Landau phenomenological model. Phase lines of the R+L (rhombohedral+liquid) and FCC+L (face-centred cubic + liquid) are calculated using the observed T - X phase diagram of this binary mixture. Our results show that the Landau mean field theory describes the observed behavior of CH3CCl3+CCl4 adequately. From the calculated T - X phase diagram, critical behavior of some thermodynamic quantities can be predicted at various temperatures and concentrations (CCl4) for a binary mixture of CH3CCl3+CCl4.

On the Fluctuations that Order and Frustrate Liquid Water

NASA Astrophysics Data System (ADS)

Limmer, David Tyler

At ambient conditions, water sits close to phase coexistence with its crystal. More so than in many other materials, this fact is manifested in the fluctuations that maintain a large degree of local order in the liquid. These fluctuations and how they result in long-ranged order, or its absence, are emergent features of many interacting molecules. Their study therefore requires using the tools of statistical mechanics for their their systematic understanding. In this dissertation we develop such an understanding. In particular, we focus on collective behavior that emerges in liquid and solid water. At room temperatures, the thermophysical properties of water are quantified and rationalized with simple molecular models. A key feature of these models is the correct characterization of the competition between entropic forces of packing and the energetic preference for tetrahedral order. At cold temperatures, the properties of ice surfaces are studied with statistical field theory. The theory we develop for the long wavelength features of ice interfaces allows us to explain the existence of a premelting layer on the surface of ice and the stability of ice in confinement. In between these extremes, the dynamics of supercooled water are considered. A detailed theory for the early stages of coarsening is developed and used to explain the peculiar observation of a transient second liquid state of water. When coarsening dynamics are arrested, the result is the formation of a glassy states of water. We show that out-of-equilibrium the phase diagram for supercooled water exhibits a rich amount of structure, including a triple point between two glass phases of water and the liquid. At the end, we explore possible technological implications for the interplay between ordering and frustration in studies of water at metal interfaces.

Two-dimensional solid-phase extraction strategy for the selective enrichment of aminoglycosides in milk.

PubMed

Shen, Aijin; Wei, Jie; Yan, Jingyu; Jin, Gaowa; Ding, Junjie; Yang, Bingcheng; Guo, Zhimou; Zhang, Feifang; Liang, Xinmiao

2017-03-01

An orthogonal two-dimensional solid-phase extraction strategy was established for the selective enrichment of three aminoglycosides including spectinomycin, streptomycin, and dihydrostreptomycin in milk. A reversed-phase liquid chromatography material (C 18 ) and a weak cation-exchange material (TGA) were integrated in a single solid-phase extraction cartridge. The feasibility of two-dimensional clean-up procedure that experienced two-step adsorption, two-step rinsing, and two-step elution was systematically investigated. Based on the orthogonality of reversed-phase and weak cation-exchange procedures, the two-dimensional solid-phase extraction strategy could minimize the interference from the hydrophobic matrix existing in traditional reversed-phase solid-phase extraction. In addition, high ionic strength in the extracts could be effectively removed before the second dimension of weak cation-exchange solid-phase extraction. Combined with liquid chromatography and tandem mass spectrometry, the optimized procedure was validated according to the European Union Commission directive 2002/657/EC. A good performance was achieved in terms of linearity, recovery, precision, decision limit, and detection capability in milk. Finally, the optimized two-dimensional clean-up procedure incorporated with liquid chromatography and tandem mass spectrometry was successfully applied to the rapid monitoring of aminoglycoside residues in milk. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A metastable liquid melted from a crystalline solid under decompression

DOE PAGES

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

2017-01-23

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

A metastable liquid melted from a crystalline solid under decompression

PubMed Central

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

2017-01-01

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

Structural ordering at solid-liquid interfaces in Al-Sm system: A molecular-dynamics study

DOE PAGES

Sun, Yang; Zhang, Feng; Ye, Zhuo; ...

2016-07-12

The structural ordering at solid-liquid interfaces far from equilibrium is studied with molecular dynamics simulations for the Al-Sm system. Using the van-Hove self-correlation function as the criterion to identify attachment/detachment events that occur at the interface, we are able to determine the time-dependent interface position, and characterize the detailed interfacial structure ordering surrounding the attached atoms. For the interface between an undercooled Al90Sm10 liquid and a metastable cubic structure, the solid induces the crystalline order of the cubic phase in the liquid layers, promoting the continuous growth of the crystal phase. When the same liquid is put in contact withmore » f.c.c. Al, Sm from the liquid can still attach to the solid interface despite its insolubility in the Al lattice. Non-f.c.c. order is revealed surrounding the attached Sm atoms. Lastly, we show that the local structure ordering at interface is highly correlated to solid packing and liquid ordering.« less

Universality away from critical points in a thermostatistical model

NASA Astrophysics Data System (ADS)

Lapilli, C. M.; Wexler, C.; Pfeifer, P.

Nature uses phase transitions as powerful regulators of processes ranging from climate to the alteration of phase behavior of cell membranes to protect cells from cold, building on the fact that thermodynamic properties of a solid, liquid, or gas are sensitive fingerprints of intermolecular interactions. The only known exceptions from this sensitivity are critical points. At a critical point, two phases become indistinguishable and thermodynamic properties exhibit universal behavior: systems with widely different intermolecular interactions behave identically. Here we report a major counterexample. We show that different members of a family of two-dimensional systems —the discrete p-state clock model— with different Hamiltonians describing different microscopic interactions between molecules or spins, may exhibit identical thermodynamic behavior over a wide range of temperatures. The results generate a comprehensive map of the phase diagram of the model and, by virtue of the discrete rotors behaving like continuous rotors, an emergent symmetry, not present in the Hamiltonian. This symmetry, or many-to-one map of intermolecular interactions onto thermodynamic states, demonstrates previously unknown limits for macroscopic distinguishability of different microscopic interactions.

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

X-Ray Diffraction on NIF

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

Eggert, J H; Wark, J

2012-02-15

The National Ignition Facility (NIF) is currently a 192 beam, 1.6 MJ laser. NIF Ramp-Compression Experiments have already made the relevant exo-planet pressure range from 1 to 50 Mbar accessible. We Proposed to Study Carbon Phases by X-Ray Diffraction on NIF. Just a few years ago, ultra-high pressure phase diagrams for materials were very 'simple'. New experiments and theories point out surprising and decidedly complex behavior at the highest pressures considered. High pressures phases of aluminum are also predicted to be complex. Recent metadynamics survey of carbon proposed a dynamic pathway among multiple phases. We need to develop diagnostics andmore » techniques to explore this new regime of highly compressed matter science. X-Ray Diffraction - Understand the phase diagram/EOS/strength/texture of materials to 10's of Mbar. Strategy and physics goals: (1) Powder diffraction; (2) Begin with diamond; (3) Continue with metals etc.; (4) Explore phase diagrams; (5) Develop liquid diffraction; and (6) Reduce background/improve resolution.« less

Multinary alloy electrodes for solid state batteries I. A phase diagram approach for the selection and storage properties determination of candidate electrode materials

NASA Astrophysics Data System (ADS)

Anani, A.; Huggins, R. A.

The desire to produce high specific energy rechargeable batteries has led to the investigation of ternary alloy systems for use as negative electrode components in lithium-based cells. The addition of a third component to a binary alloy electrode could result in a significant change in the thermodynamic and/or kinetic behavior of the electrode material, depending on the relevant phase diagram and the crystal structures of the phases present. The influence of ternary phase diagram characteristics upon the thermodynamic properties and specific energies of multi-component electrodes is discussed with lithiumsilicon-based systems as an illustration. It is shown that the electrode potentials (and thus specific energies of the ensuing cell) as well as the theoretical lithium capacities of electrodes based on these ternary alloy modifications can be significantly increased with respect to their present day binary counterpart.

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.

Prediction of binary nanoparticle superlattices from soft potentials

DOE PAGES

Horst, Nathan; Travesset, Alex

2016-01-07

Driven by the hypothesis that a sufficiently continuous short-ranged potential is able to account for shell flexibility and phonon modes and therefore provides a more realistic description of nanoparticle interactions than a hard sphere model, we compute the solid phase diagram of particles of different radii interacting with an inverse power law potential. From a pool of 24 candidate lattices, the free energy is optimized with respect to additional internal parameters and the p-exponent, determining the short-range properties of the potential, is varied between p = 12 and p = 6. The phase diagrams contain the phases found in ongoingmore » self-assembly experiments, including DNA programmable self-assembly and nanoparticles with capping ligands assembled by evaporation from an organic solvent. Thus, the resulting phase diagrams can be mapped quantitatively to existing experiments as a function of only two parameters: Nanoparticle radius ratio (γ) and softness asymmetry.« less

Prediction of Binary Nanoparticle Superlattices from Soft Potentials

NASA Astrophysics Data System (ADS)

Horst, Nathan; Travesset, Alex

Driven by the hypothesis that a sufficiently continuous short-ranged potential is able to account for shell flexibility and phonon modes and therefore provides a more realistic description of nanoparticle interactions than a hard sphere model, we compute the solid phase diagram of particles of different radii interacting with an inverse power law potential. We explore 24 candidate lattices where the p-exponent, determining the short-range properties of the potential, is varied between p=12 and p=6, and optimize the free energy with respect to additional internal parameters. The phase diagrams contain the phases found in ongoing self-assembly experiments, including DNA programmable self-assembly and nanoparticles with capping ligands assembled by evaporation from an organic solvent. The resulting phase diagrams can be mapped quantitatively to existing experiments as a function of only two parameters: nanoparticle radius ratio (γ) and softness asymmetry (SA). Supported by DOE under Contract Number DE-AC02-07CH11358.

Prediction of binary nanoparticle superlattices from soft potentials

NASA Astrophysics Data System (ADS)

Horst, Nathan; Travesset, Alex

2016-01-01

Driven by the hypothesis that a sufficiently continuous short-ranged potential is able to account for shell flexibility and phonon modes and therefore provides a more realistic description of nanoparticle interactions than a hard sphere model, we compute the solid phase diagram of particles of different radii interacting with an inverse power law potential. From a pool of 24 candidate lattices, the free energy is optimized with respect to additional internal parameters and the p-exponent, determining the short-range properties of the potential, is varied between p = 12 and p = 6. The phase diagrams contain the phases found in ongoing self-assembly experiments, including DNA programmable self-assembly and nanoparticles with capping ligands assembled by evaporation from an organic solvent. The resulting phase diagrams can be mapped quantitatively to existing experiments as a function of only two parameters: Nanoparticle radius ratio (γ) and softness asymmetry.

Kinetics and equilibria of lysozyme precipitation and crystallization in concentrated ammonium sulfate solutions.

PubMed

Cheng, Yu-Chia; Lobo, Raul F; Sandler, Stanley I; Lenhoff, Abraham M

2006-05-05

The kinetics and thermodynamics of lysozyme precipitation in ammonium sulfate solutions at pH 4 and 8 and room temperature were studied. X-ray powder diffraction (XRD) was used to characterize the structure of lysozyme precipitates. It was found that, if sufficient time was allowed, microcrystals developed following an induction period after initial lysozyme precipitation, even up to ionic strengths of 8 m and at acidic pH, where lysozyme is refractory to crystallization in ammonium sulfate. The full set of precipitation and crystallization data allowed construction of a phase diagram of lysozyme, showing the ammonium sulfate dependence. It suggests that precipitation may reflect a frustrated metastable liquid-liquid phase separation, which would allow this process to be understood within the framework of the generic phase diagram for proteins. The results also demonstrate that XRD, more frequently used for characterizing inorganic and organic polycrystalline materials, is useful both in characterizing the presence of crystals in the dense phase and in verifying the crystal form of proteins.

Indirect measurement of the solid/liquid interface using the minimization technique

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

Choi, H.; Chun, M.

1985-11-01

The phenomenon of solidification of a flowing fluid in a vertical tube is closely related to the relocation dynamics of molten nuclear fuels in hypothetical core-disruptive accidents of a liquid-metal fast breeder reactor. The knowledge of the transient shape and the position of the liquid/solid interface is of practical importance in analysis of phase change processes. Sparrow and Broadbent directly measured the solid liquid interface via experiments, whereas Viskanta observed the solid/liquid interface motion via a photographic method. In this paper, a new method to predict the transient position of the solid/liquid interface is developed. This method is based onmore » the minimization technique. To use this method one needs the temperature of the wall on which the phase change is to take place. The new technique is useful, in particular, for the case of inward solidification of a flowing fluid in a tube where direct measurement of the solid/liquid interface is not possible, whereas the tube wall temperature measurement is relatively easy.« less

Wetting phenomenon in the liquid-vapor phase coexistence of a partially miscible Lennard-Jones binary mixture

NASA Astrophysics Data System (ADS)

Ramírez-Santiago, Guillermo; Díaz-Herrera, Enrique; Moreno Razo, José A.

2004-03-01

We have carried out extensive equilibrium MD simulations to study wetting phenomena in the liquid-vapor phase coexistence of a partially miscible binary LJ mixture. We find that in the temperature range 0.60 ≤ T^* < 0.80, the system separates forming a liquid A-liquid B interface in coexistence with the vapor phase. At higher temperatures, 0.80 ≤ T^* < 1.25 the liquid phases are wet by the vapor phase. By studying the behavior of the surface tension as a function of temperature we estimate the wetting transition temperature (WTT) to be T^*_w≃ 0.80. The adsorption of molecules at the liquid-liquid interface shows a discontinuity at about T^*≃ 0.79 suggesting that the wetting transition is a first order phase transition. These results are in agreement with some experiments carried out in fluid binary mixtures. In addition, we estimated the consolute temperature to be T^* _cons≃ 1.25. The calculated phase diagram of the mixture suggest the existence of a tricritical point.

Syntax diagrams for body wave nomenclature, with generalizations for terrestrial planets

NASA Astrophysics Data System (ADS)

Knapmeyer, M.

2003-04-01

The Apollo network on the Moon constitutes the beginning of planetary seismology. In the next few decades, we may see seismometers deployed on the Moon again, on Mars, and perhaps on other terrestrial planets or satellites. Any seismological software for computation of body wave travel times on other planets should be highly versatile and be prepared for a huge variety of velocity distributions and internal structures. A suite of trial models for a planet might, for example, contain models with and without solid inner cores. It would then be useful if the software could detect physically meaningless phase names automatically without actually carrying out any computation. It would also be useful if the program were prepared to deal with features like fully solid cores, internal oceans, and varying depths of mineralogical phase changes like the olivine-spinel transition. Syntax diagrams are a standard method to describe the syntax of programming languages. They represent a graphical way to define which letter or phrase is allowed to follow a given sequence of letters. Syntax diagrams may be stored in data structures that allow automatic evaluation of a given letter sequence. Such diagrams are presented here for a generalized body wave nomenclature. Generalizations are made to overcome earth-specific notations which incorporate discontinuity depths into phase names or to distinguish olivine transitions from ice-ice transitions (as expected on the Galilean Satellites).

Metallic hydrogen

NASA Astrophysics Data System (ADS)

Silvera, Isaac F.; Dias, Ranga

2018-06-01

Hydrogen is the simplest and most abundant element in the Universe. There are two pathways for creating metallic hydrogen under high pressures. Over 80 years ago Wigner and Huntington predicted that if solid molecular hydrogen was sufficiently compressed in the T  =  0 K limit, molecules would dissociate to form atomic metallic hydrogen (MH). We have observed this transition at a pressure of 4.95 megabars. MH in this form has probably never existed on Earth or in the Universe; it may be a room temperature superconductor and is predicted to be metastable. If metastable it will have an important technological impact. Liquid metallic hydrogen can also be produced at intermediate pressures and high temperatures and is believed to make up ~90% of the planet Jupiter. We have observed this liquid–liquid transition, also known as the plasma phase transition, at pressures of ~1–2 megabar and temperatures ~1000–2000 K. However, in this paper we shall focus on the Wigner–Huntington transition. We shall discuss the methods used to observe metallic hydrogen at extreme conditions of static pressure in the laboratory, extending our understanding of the phase diagram of the simplest atom in the periodic table.

Soluble 1:1 complexes and insoluble 3:2 complexes - Understanding the phase-solubility diagram of hydrocortisone and γ-cyclodextrin.

PubMed

Schönbeck, Christian; Madsen, Tobias L; Peters, Günther H; Holm, René; Loftsson, Thorsteinn

2017-10-15

The molecular mechanisms underlying the drug-solubilizing properties of γ-cyclodextrin were explored using hydrocortisone as a model drug. The B S -type phase-solubility diagram of hydrocortisone with γ-cyclodextrin was thoroughly characterized by measuring the concentrations of hydrocortisone and γ-cyclodextrin in solution and the solid phase. The drug-solubilizer interaction was also studied by isothermal titration calorimetry from which a precise value of the 1:1 binding constant (K 11 =4.01mM -1 at 20°C) was obtained. The formation of water-soluble 1:1 complexes is responsible for the initial increase in hydrocortisone solubility while the precipitation of entities with a 3:2 ratio of γ-cyclodextrin:hydrocortisone is responsible for the plateau and the ensuing strong decrease in solubility once all solid hydrocortisone is used up. The complete phase-solubility diagram is well accounted for by a model employing the 1:1 binding constant and the solubility product of the precipitating 3:2 entity (K 32 S =5.51 mM 5 ). For such systems, a small surplus of γ-cyclodextrin above the optimum concentration may result in a significant decrease in drug solubility, and the implications for drug formulations are briefly discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

FAST TRACK COMMUNICATION: A closer look at arrested spinodal decomposition in protein solutions

NASA Astrophysics Data System (ADS)

Gibaud, Thomas; Schurtenberger, Peter

2009-08-01

Concentrated aqueous solutions of the protein lysozyme undergo a liquid-solid transition upon a temperature quench into the unstable spinodal region below a characteristic arrest temperature of Tf = 15 °C. We use video microscopy and ultra-small angle light scattering in order to investigate the arrested structures as a function of initial concentration, quench temperature and rate of the temperature quench. We find that the solid-like samples show all the features of a bicontinuous network that is formed through an arrested spinodal decomposition process. We determine the correlation length ξ and demonstrate that ξ exhibits a temperature dependence that closely follows the critical scaling expected for density fluctuations during the early stages of spinodal decomposition. These findings are in agreement with an arrest scenario based on a state diagram where the arrest or gel line extends far into the unstable region below the spinodal line. Arrest then occurs when during the early stage of spinodal decomposition the volume fraction phi2 of the dense phase intersects the dynamical arrest threshold phi2,Glass, upon which phase separation gets pinned into a space-spanning gel network with a characteristic length ξ.

Solid-liquid surface tensions of critical nuclei and nucleation barriers from a phase-field-crystal study of a model binary alloy using finite system sizes.

PubMed

Choudhary, Muhammad Ajmal; Kundin, Julia; Emmerich, Heike; Oettel, Martin

2014-08-01

Phase-field-crystal (PFC) modeling has emerged as a computationally efficient tool to address crystal growth phenomena on atomistic length and diffusive time scales. We use a two-dimensional phase-field-crystal model for a binary system based on Elder et al. [Phys. Rev. B 75, 064107 (2007)] to study critical nuclei and their liquid-solid phase boundaries, in particular the nucleus size dependence of the liquid-solid interface tension as well as of the nucleation barrier. Critical nuclei are stabilized in finite systems of various sizes, however, the extracted interface tension as function of the nucleus radius r is independent of system size. We suggest a phenomenological expression to describe the dependence of the extracted interface tension on the nucleus radius r for the liquid-solid system. Moreover, the numerical PFC results show that this dependency can not be fully described by the nonclassical Tolman formula.

Investigating Planetesimal Evolution by Experiments with Fe-Ni Metallic Melts: Light Element Composition Effects on Trace Element Partitioning Behavior

NASA Astrophysics Data System (ADS)

Chabot, N. L.

2017-12-01

As planetesimals were heated up in the early Solar System, the formation of Fe-Ni metallic melts was a common occurrence. During planetesimal differentiation, the denser Fe-Ni metallic melts separated from the less dense silicate components, though some meteorites suggest that their parent bodies only experienced partial differentiation. If the Fe-Ni metallic melts did form a central metallic core, the core eventually crystallized to a solid, some of which we sample as iron meteorites. In all of these planetesimal evolution processes, the composition of the Fe-Ni metallic melt influenced the process and the resulting trace element chemical signatures. In particular, the metallic melt's "light element" composition, those elements present in the metallic melt in a significant concentration but with lower atomic masses than Fe, can strongly affect trace element partitioning. Experimental studies have provided critical data to determine the effects of light elements in Fe-Ni metallic melts on trace element partitioning behavior. Here I focus on combining numerous experimental results to identify trace elements that provide unique insight into constraining the light element composition of early Solar System Fe-Ni metallic melts. Experimental studies have been conducted at 1 atm in a variety of Fe-Ni systems to investigate the effects of light elements on trace element partitioning behavior. A frequent experimental examination of the effects of light elements in metallic systems involves producing run products with coexisting solid metal and liquid metal phases. Such solid-metal-liquid-metal experiments have been conducted in the Fe-Ni binary system as well as Fe-Ni systems with S, P, and C. Experiments with O-bearing or Si-bearing Fe-Ni metallic melts do not lend themselves to experiments with coexisting solid metal and liquid metal phases, due to the phase diagrams of these elements, but experiments with two immiscible Fe-Ni metallic melts have provided insight into the qualitative effects of O and Si relative to the well-determined effects of S. Together, these experimental studies provide a robust dataset to identify key elements that are predicted to produce distinct chemical signatures as a function of different Fe-Ni metallic melt compositions during planetesimal evolution processes.

Ionic-liquid-based dispersive liquid-liquid microextraction combined with magnetic solid-phase extraction for the determination of aflatoxins B1 , B2 , G1 , and G2 in animal feeds by high-performance liquid chromatography with fluorescence detection.

PubMed

Zhao, Jiao; Zhu, Yan; Jiao, Yang; Ning, Jinyan; Yang, Yaling

2016-10-01

A novel two-step extraction technique combining ionic-liquid-based dispersive liquid-liquid microextraction with magnetic solid-phase extraction was developed for the preconcentration and separation of aflatoxins in animal feedstuffs before high-performance liquid chromatography coupled with fluorescence detection. In this work, ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate was used as the extractant in dispersive liquid-liquid microextraction, and hydrophobic pelargonic acid modified Fe 3 O 4 magnetic nanoparticles as an efficient adsorbent were applied to retrieve the aflatoxins-containing ionic liquid. Notably, the target of magnetic nanoparticles was the ionic liquid rather than the aflatoxins. Because of the rapid mass transfer associated with the dispersive liquid-liquid microextraction and magnetic solid phase steps, fast extraction could be achieved. The main parameters affecting the extraction recoveries of aflatoxins were investigated and optimized. Under the optimum conditions, vortexing at 2500 rpm for 1 min in the dispersive liquid-liquid microextraction and magnetic solid-phase extraction and then desorption by sonication for 2 min with acetonitrile as eluent. The recoveries were 90.3-103.7% with relative standard deviations of 3.2-6.4%. Good linearity was observed with correlation coefficients ranged from 0.9986 to 0.9995. The detection limits were 0.632, 0.087, 0.422 and 0.146 ng/mL for aflatoxins B 1 , B2, G1, and G2, respectively. The results were also compared with the pretreatment method carried out by conventional immunoaffinity columns. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Field-induced phase transitions in chiral smectic liquid crystals studied by the constant current method

NASA Astrophysics Data System (ADS)

H, Dhaouadi; R, Zgueb; O, Riahi; F, Trabelsi; T, Othman

2016-05-01

In ferroelectric liquid crystals, phase transitions can be induced by an electric field. The current constant method allows these transition to be quickly localized and thus the (E,T) phase diagram of the studied product can be obtained. In this work, we make a slight modification to the measurement principles based on this method. This modification allows the characteristic parameters of ferroelectric liquid crystal to be quantitatively measured. The use of a current square signal highlights a phenomenon of ferroelectric hysteresis with remnant polarization at null field, which points out an effect of memory in this compound.

Kerr-AdS analogue of triple point and solid/liquid/gas phase transition

NASA Astrophysics Data System (ADS)

Altamirano, Natacha; Kubizňák, David; Mann, Robert B.; Sherkatghanad, Zeinab

2014-02-01

We study the thermodynamic behavior of multi-spinning d = 6 Kerr-anti de Sitter black holes in the canonical ensemble of fixed angular momenta J1 and J2. We find, dependent on the ratio q = J2/J1, qualitatively different interesting phenomena known from the ‘every day thermodynamics’ of simple substances. For q = 0 the system exhibits recently observed reentrant large/small/large black hole phase transitions, but for 0 < q ≪ 1 we find an analogue of a ‘solid/liquid’ phase transition. Furthermore, for q ∈ (0.00905, 0.0985) the system displays the presence of a large/intermediate/small black hole phase transition with two critical and one triple (or tricritical) points. This behavior is reminiscent of the solid/liquid/gas phase transition except that the coexistence line of small and intermediate black holes does not continue for an arbitrary value of pressure (similar to the solid/liquid coexistence line) but rather terminates at one of the critical points. Finally, for q > 0.0985 we observe the ‘standard liquid/gas behavior’ of the Van der Waals fluid.

Phase diagrams and physicochemical properties of Li+,K+(Rb+)//borate-H2O systems at 323 K

NASA Astrophysics Data System (ADS)

Feng, Shan; Yu, Xudong; Cheng, Xinglong; Zeng, Ying

2017-11-01

The phase and physicochemical properties diagrams of Li+,K+(Rb+)//borate-H2O systems at 323 K were constructed using the experimentally measured solubilities, densities, and refractive indices. The Schreinemakers' wet residue method and the X-ray diffraction were used for the determination of the compositions of solid phase. Results show that these two systems belong to the hydrate I type, with no solid solution or double salt formation. The borate phases formed in our experiments are RbB5O6(OH)4 · 2H2O, Li2B4O5(OH)4 · H2O, and K2B4O5(OH)4 · 2H2O. Comparison between the stable phase diagrams of the studied system at 288, 323, and 348 K show that in this temperature range, the crystallization form of salts do not changed. With the increase in temperature, the crystallization field of Li2B4O5(OH)4 · H2O salt at 348 K is obviously larger than that at 288 K. In the Li+,K+(Rb+)//borate-H2O systems, the densities and refractive indices of the solutions (at equilibrium) increase along with the mass fraction of K2B4O7 (Rb2B4O7), and reach the maximum values at invariant point E.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

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.

Triple points and phase diagrams in the extended phase space of charged Gauss-Bonnet black holes in AdS space

NASA Astrophysics Data System (ADS)

Wei, Shao-Wen; Liu, Yu-Xiao

2014-08-01

We study the triple points and phase diagrams in the extended phase space of the charged Gauss-Bonnet black holes in d-dimensional anti-de Sitter space, where the cosmological constant appears as a dynamical pressure of the system and its conjugate quantity is the thermodynamic volume of the black holes. Employing the equation of state T=T(v,P), we demonstrate that the information of the phase transition and behavior of the Gibbs free energy are potential encoded in the T-v (T-rh) line with fixed pressure P. We get the phase diagrams for the charged Gauss-Bonnet black holes with different values of the charge Q and dimension d. The result shows that the small/large black hole phase transitions appear for any d, which is reminiscent of the liquid/gas transition of a Van der Waals type. Moreover, the interesting thermodynamic phenomena, i.e., the triple points and the small/intermediate/large black hole phase transitions are observed for d=6 and Q ∈(0.1705,0.1946).

Efficient chemical potential evaluation with kinetic Monte Carlo method and non-uniform external potential: Lennard-Jones fluid, liquid, and solid

NASA Astrophysics Data System (ADS)

Ustinov, E. A.

2017-07-01

The aim of this paper is to present a method of a direct evaluation of the chemical potential of fluid, liquid, and solid with kinetic Monte Carlo simulation. The method is illustrated with the 12-6 Lennard-Jones (LJ) system over a wide range of density and temperature. A distinctive feature of the methodology used in the present study is imposing an external potential on the elongated simulation box to split the system into two equilibrium phases, one of which is substantially diluted. This technique provides a reliable direct evaluation of the chemical potential of the whole non-uniform system (including that of the uniformly distributed dense phase in the central zone of the box), which, for example, is impossible in simulation of the uniform crystalline phase. The parameters of the vapor-liquid, liquid-solid, and fluid-solid transitions have been reliably determined. The chemical potential and the pressure are defined as thermodynamically consistent functions of density and temperature separately for the liquid and the solid (FCC) phases. It has been shown that in two-phase systems separated by a flat interface, the crystal melting always occurs at equilibrium conditions. It is also proved that in the limit of zero temperature, the specific heat capacity of an LJ crystal at constant volume is exactly 3Rg (where Rg is the gas constant) without resorting to harmonic oscillators.

Studies of nuclei under the extreme conditions of density, temperature, isospin asymmetry and the phase diagram of hadronic matter

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

Mekjian, Aram

2016-10-18

The main emphasis of the entire project is on issues having to do with medium energy and ultra-relativistic energy and heavy ion collisions. A major goal of both theory and experiment is to study properties of hot dense nuclear matter under various extreme conditions and to map out the phase diagram in density or chemical potential and temperature. My studies in medium energy nuclear collisions focused on the liquid-gas phase transition and cluster yields from such transitions. Here I developed both the statistical model of nuclear multi-fragmentation and also a mean field theory.

Quick connect coupling

NASA Technical Reports Server (NTRS)

Lomax, Curtis (Inventor); Webbon, Bruce (Inventor)

1995-01-01

A cooling apparatus includes a container filled with a quantity of coolant fluid initially cooled to a solid phase, a cooling loop disposed between a heat load and the container, a pump for circulating a quantity of the same type of coolant fluid in a liquid phase through the cooling loop, and a pair of couplings for communicating the liquid phase coolant fluid into the container in a direct interface with the solid phase coolant fluid.

Dispersed bubble reactor for enhanced gas-liquid-solids contact and mass transfer

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

Vimalchand, Pannalal; Liu, Guohai; Peng, WanWang

An apparatus to promote gas-liquid contact and facilitate enhanced mass transfer. The dispersed bubble reactor (DBR) operates in the dispersed bubble flow regime to selectively absorb gas phase constituents into the liquid phase. The dispersion is achieved by shearing the large inlet gas bubbles into fine bubbles with circulating liquid and additional pumped liquid solvent when necessary. The DBR is capable of handling precipitates that may form during absorption or fine catalysts that may be necessary to promote liquid phase reactions. The DBR can be configured with multistage counter current flow sections by inserting concentric cylindrical sections into the risermore » to facilitate annular flow. While the DBR can absorb CO.sub.2 in liquid solvents that may lead to precipitates at high loadings, it is equally capable of handling many different types of chemical processes involving solids (precipitates/catalysts) along with gas and liquid phases.« less

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high-performance liquid chromatography.

PubMed

Wang, Zhibing; He, Mengyu; Jiang, Chunzhu; Zhang, Fengqing; Du, Shanshan; Feng, Wennan; Zhang, Hanqi

2015-12-01

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High-performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid-phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid-phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion-pairing agent (NH4 PF6 ), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3-13.4 μg/kg. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase-field crystal simulation facet and branch crystal growth

NASA Astrophysics Data System (ADS)

Chen, Zhi; Wang, Zhaoyang; Gu, Xinrui; Chen, Yufei; Hao, Limei; de Wit, Jos; Jin, Kexin

2018-05-01

Phase-field crystal model with one mode is introduced to describe morphological transition. The relationship between growth morphology and smooth density distribution was investigated. The results indicate that the pattern selection of dendrite growth is caused by the competition between interface energy anisotropy and interface kinetic anisotropy based on the 2D phase diagram. When the calculation time increases, the crystal grows to secondary dendrite at the dimensionless undercooling equal to - 0.4. Moreover, when noise is introduced in the growth progress, the symmetry is broken in the growth mode, and there becomes irregular fractal-like growth morphology. Furthermore, the single crystal shape develops into polycrystalline when the noise amplitude is large enough. When the dimensionless undercooling is less than - 0.3, the noise has a significant effect on the growth shape. In addition, the growth velocity of crystal near to liquid phase line is slow, while the shape far away from the liquid adapts to fast growth. Based on the simulation results, the method was proved to be effective, and it can easily obtain different crystal shapes by choosing the different points in 2D phase diagram.

Spin-one bilinear-biquadratic model on a star lattice

NASA Astrophysics Data System (ADS)

Lee, Hyun-Yong; Kawashima, Naoki

2018-05-01

We study the ground-state phase diagram of the S =1 bilinear-biquadratic model (BLBQ) on the star lattice with the state-of-art tensor network algorithms. The system has four phases: the ferromagnetic, antiferromagnetic, ferroquadrupolar, and spin-liquid phases. The phases and their phase boundaries are determined by examining various local observables, correlation functions, and transfer matrices exhaustively. The spin-liquid phase, which is the first quantum disordered phase found in the two-dimensional BLBQ model, is gapped and devoid of any conventional long-range order. It is also characterized by fixed-parity virtual bonds in the tensor network formalism, analogous to the Haldane phase, while the parity varies depending on the location of the bond.

Phase behavior and formation of o/w nano-emulsion in vegetable oil/ mixture of polyglycerol polyricinoleate and polyglycerin fatty acid ester/water systems.

PubMed

Wakisaka, Satoshi; Nakanishi, Masami; Gohtani, Shoichi

2014-01-01

It is reported that mixing polyglycerol polyricinoleate (PGPR) and polyglycerol laurilester has a great emulsifying capacity, and consequently fine oil-in-water (o/w) emulsions can be formed. However, the role of PGPR is not clear. The objective of this research is to investigate the phase behavior of vegetable oil/mixture of PGPR and polyglycerol fatty acid ester/water systems, and to clarify the role of PGPR in making a fine emulsion. Phase diagrams were constructed to elucidate the optimal process for preparing fine emulsions. In all the systems examined in this study, the phases, including the liquid crystal phase (L(c)) and sponge phase (L(3)), spread widely in the phase diagrams. We examined droplet size of the emulsions prepared from each phase and found that o/w nano-emulsions with droplet sizes as small as 50 nm were formed by emulsifying either from a single L(3) phase or a two-phase region, L(c) + L(3). These results indicate that a sponge phase L(3) or liquid crystal phase L(c) or both is necessary to form an o/w nano-emulsion whose average droplet diameter is less than 50 nm for PGPR and polyglycerin fatty acid ester mixtures used as surfactant.

Role of Precursor-Conversion Chemistry in the Crystal-Phase Control of Catalytically Grown Colloidal Semiconductor Quantum Wires.

PubMed

Wang, Fudong; Buhro, William E

2017-12-26

Crystal-phase control is one of the most challenging problems in nanowire growth. We demonstrate that, in the solution-phase catalyzed growth of colloidal cadmium telluride (CdTe) quantum wires (QWs), the crystal phase can be controlled by manipulating the reaction chemistry of the Cd precursors and tri-n-octylphosphine telluride (TOPTe) to favor the production of either a CdTe solute or Te, which consequently determines the composition and (liquid or solid) state of the Bi x Cd y Te z catalyst nanoparticles. Growth of single-phase (e.g., wurtzite) QWs is achieved only from solid catalysts (y ≪ z) that enable the solution-solid-solid growth of the QWs, whereas the liquid catalysts (y ≈ z) fulfill the solution-liquid-solid growth of the polytypic QWs. Factors that affect the precursor-conversion chemistry are systematically accounted for, which are correlated with a kinetic study of the composition and state of the catalyst nanoparticles to understand the mechanism. This work reveals the role of the precursor-reaction chemistry in the crystal-phase control of catalytically grown colloidal QWs, opening the possibility of growing phase-pure QWs of other compositions.

Characterization of van der Waals type bimodal,- lambda,- meta- and spinodal phase transitions in liquid mixtures, solid suspensions and thin films.

PubMed

Rosenholm, Jarl B

2018-03-01

The perfect gas law is used as a reference when selecting state variables (P, V, T, n) needed to characterize ideal gases (vapors), liquids and solids. Van der Waals equation of state is used as a reference for models characterizing interactions in liquids, solids and their mixtures. Van der Waals loop introduces meta- and unstable states between the observed gas (vapor)-liquid P-V transitions at low T. These intermediate states are shown to appear also between liquid-liquid, liquid-solid and solid-solid phase transitions. First-order phase transitions are characterized by a sharp discontinuity of first-order partial derivatives (P, S, V) of Helmholtz and Gibbs free energies. Second-order partial derivatives (K T , B, C V , C P , E) consist of a static contribution relating to second-order phase transitions and a relaxation contribution representing the degree of first-order phase transitions. Bimodal (first-order) and spinodal (second-order) phase boundaries are used to separate stable phases from metastable and unstable phases. The boundaries are identified and quantified by partial derivatives of molar Gibbs free energy or chemical potentials with respect to P, S, V and composition (mole fractions). Molecules confined to spread Langmuir monolayers or adsorbed Gibbs monolayers are characterized by equation of state and adsorption isotherms relating to a two-dimensional van der Waals equation of state. The basic work of two-dimensional wetting (cohesion, adsorption, spreading, immersion), have to be adjusted by a horizontal surface pressure in the presence of adsorbed vapor layers. If the adsorption is extended to liquid films a vertical surface pressure (Π) may be added to account for the lateral interaction, thus restoring PV = ΠAh dependence of thin films. Van der Waals attraction, Coulomb repulsion and structural hydration forces contribute to the vertical surface pressure. A van der Waals type coexistence of ordered (dispersed) and disordered (aggregated) phases is shown to exist when liquid vapor is confined in capillaries (condensation-liquefaction-evaporation and flux). This pheno-menon can be experimentally illustrated with suspended nano-sized particles (flocculation-coagulation-peptisation of colloidal sols) being confined in sample holders of varying size. The self-assembled aggregates represent critical self-similar equilibrium structures corres-ponding to rate determining complexes in kinetics. Overall, a self-consistent thermodynamic framework is established for the characterization of two- and three-dimensional phase separations in one-, two- and three-component systems. Copyright © 2018 Elsevier B.V. All rights reserved.

ICPP: Charge and Density Coupling in Nonideal Plasmas

NASA Astrophysics Data System (ADS)

Fortov, V. E.

2000-10-01

Plasmas with Strong Coulomb Interaction (SCI) are found in astrophysics, planetary physics, inertial confinement fusion, advanced energetics and elsewhere[1]. SCI plasmas can be achieved in: I Dusty plasmas, II Shock-compressed plasmas. I. SCI in low-density dusty (colloidal) plasmas arises from the high charge of micron-size macroparticles[2]. Experiments use glow and inductive RF discharges, combustion flames of gas and solid propellant, ultraviolet light beams, and radioactive decay fluxes. Liquid- and solid-like structures are seen, and phase diagrams and transitions investigated by experiment and simulation. Zero-g experiments on space station Mir and in aircraft clarified the gravity effect on plasma crystal formation. II. Plasma SCI can arise in shock compression of solid and porous metals, noble gases, hydrogen, sulphur, and iodine at megabar pressures [3,4], using high explosive drive. Phase diagram regions were examined, where thermal and pressure ionization exist. Multiple-shock-compressed hydrogen can show metal-like conductivity from pressure ionization. The ``metal-to-dielectric" transition in shock-compressed lithium at 0.5 Mbar was detected and analyzed. Thermodynamics, equation of state, plasma composition, electrical and radiative properties show SCI suppression of discrete electron spectra and strong lowering of ionization potentials, evoking the ``confined-atom" model[5] for SCI and other models[6]. [1] V.E.Fortov, I.T.Yakubov, Physics of Nonideal Plasmas, Hemisphere, N.Y.-London (1989). [2] V.E.Fortov, A.P.Nefedov, O.F.Petrov, Soviet Physics-Uspekhy, 167(1997)1215. [3] V.Gryaznov, I.Iosilevsky, V.Fortov, Contrib. Plasma Physics, 39(1999)89. [4] V.Ya.Temovoi, A.S. Filimonov, V.E.Fortov et al. Proc. XXXVI EHPRG Meeting, Catania, Italy (1998). [5] V.K.Gryaznov, M.V.Zhernokletov et al. Zh. Exp. Teor. Fiz. (Soviet JETP) 78(1980) 573. [6] V.Ebeling, A.Foerster, V.Fortov et al. Thermodynamical Properties of Hot Dense Plasmas, Teubner Verlaggeselschaft , Berlin-Stuttgart, 1991.

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

Chen, Jing-Yuan, E-mail: chjy@uchicago.edu; Stanford Institute for Theoretical Physics, Stanford University, CA 94305; Son, Dam Thanh, E-mail: dtson@uchicago.edu

We develop an extension of the Landau Fermi liquid theory to systems of interacting fermions with non-trivial Berry curvature. We propose a kinetic equation and a constitutive relation for the electromagnetic current that together encode the linear response of such systems to external electromagnetic perturbations, to leading and next-to-leading orders in the expansion over the frequency and wave number of the perturbations. We analyze the Feynman diagrams in a large class of interacting quantum field theories and show that, after summing up all orders in perturbation theory, the current–current correlator exactly matches with the result obtained from the kinetic theory.more » - Highlights: • We extend Landau’s kinetic theory of Fermi liquid to incorporate Berry phase. • Berry phase effects in Fermi liquid take exactly the same form as in Fermi gas. • There is a new “emergent electric dipole” contribution to the anomalous Hall effect. • Our kinetic theory is matched to field theory to all orders in Feynman diagrams.« less

COMPARISON OF TWO DIFFERENT SOLID PHASE EXTRACTION/LARGE VOLUME INJECTION PROCEDURES FOR METHOD 8270

EPA Science Inventory

Two solid phase (SPE) and one traditional continuous liquid-liquid extraction method are compared for analysis of Method 8270 SVOCs. Productivity parameters include data quality, sample volume, analysis time and solvent waste.

One SPE system, unique in the U.S., uses aut...

Flow Effects on the Flammability Diagrams of Solid Fuels

NASA Technical Reports Server (NTRS)

Cordova, J. L.; Ceamanos, J.; Fernandez-Pello, A. C.; Long, R. T.; Torero, J. L.; Quintiere, J. G.

1997-01-01

A research program is currently underway with the final objective of developing a fundamental understanding of the controlling mechanisms underlying the flammability diagrams of solid combustible materials and their derived fire properties. Given that there is a high possibility of an accidental fire occurring in a space-based facility, understanding the fire properties of materials that will be used in such facilities is of critical importance. With this purpose, the flammability diagrams of the materials, as those produced by the Lateral Ignition and Flame Spread Test (LIFT) apparatus and by a new forced flow device, the Forced Flow Ignition and Flame Spread Test (FIST) apparatus, will be obtained. The specific objective of the program is to apply the new flammability apparatus, which will more accurately reflect the potential ambient conditions of space-based environments, to the characterization of the materials for space applications. This paper presents a parametric study of oxidizer flow effects on the ignition curve of the flammability diagrams of PMMA. The dependence of the ignition delay time on the external radiant flux and either the sample width (LIFT) or the flow velocity (FIST) has been studied. Although preliminary, the results indicate that natural and forced convection flow changes, affect the characteristics of the ignition curves of the flammability diagrams. The major effect on the ignition time appears to be due to convective transfer variations at the fuel surface. At high radiant fluxes or high flow velocities, however, it appears that gas phase processes become increasingly important, affecting the overall ignition delay time. A numerical analysis of the solid fuel heating and pyrolysis has also been developed. The theoretical predictions approximate the experiments well for conditions in which the gas phase induction time is negligible.

Experimental study of the Ca-Mg-Zn system using diffusion couples and key alloys

NASA Astrophysics Data System (ADS)

Zhang, Yi-Nan; Kevorkov, Dmytro; Bridier, Florent; Medraj, Mamoun

2011-03-01

Nine diffusion couples and 32 key samples were prepared to map the phase diagram of the Ca-Mg-Zn system. Phase relations and solubility limits were determined for binary and ternary compounds using scanning electron microscopy, electron probe microanalysis and x-ray diffraction (XRD). The crystal structure of the ternary compounds was studied by XRD and electron backscatter diffraction. Four ternary intermetallic (IM) compounds were identified in this system: Ca3MgxZn15-x (4.6<=x<=12 at 335 °C, IM1), Ca14.5Mg15.8Zn69.7 (IM2), Ca2Mg5Zn13 (IM3) and Ca1.5Mg55.3Zn43.2 (IM4). Three binary compounds were found to have extended solid solubility into ternary systems: CaZn11, CaZn13 and Mg2Ca form substitutional solid solutions where Mg substitutes for Zn atoms in the first two compounds, and Zn substitutes for both Ca and Mg atoms in Mg2Ca. The isothermal section of the Ca-Mg-Zn phase diagram at 335 °C was constructed on the basis of the obtained experimental results. The morphologies of the diffusion couples in the Ca-Mg-Zn phase diagram at 335 °C were studied. Depending on the terminal compositions of the diffusion couples, the two-phase regions in the diffusion zone have either a tooth-like morphology or contain a matrix phase with isolated and/or dendritic precipitates.

Control of disinfection by-products in canned vegetables caused by water used in their processing.

PubMed

Cardador, Maria Jose; Gallego, Mercedes

2017-01-01

Canned vegetables come into contact with sanitizers and/or treated water in industry during several steps (namely washing, sanitising, blanching and filling with sauces or brine solutions) and therefore they can contain disinfection by-products - DBPs). This study focused on the occurrence of trihalomethanes (THMs) and haloacetic acids (HAAs) in a wide variety of canned vegetables (75 samples). For each vegetable, the edible solid and liquid phases of the package were separated and analysed individually. DBPs can be present in both solid (up to eight species) and liquid (up to 11 species) phases, their levels being higher in liquid ones. Volatile THMs predominate in the edible solid phase (up to four species), while HAAs do so in the liquid phase (up to five species) according to their ionic and non-volatile nature. The lowest concentrations of DBPs were found in tomatoes because they were often preserved in their own juice, without water.

Gravitational Role in Liquid Phase Sintering

NASA Technical Reports Server (NTRS)

Upadhyaya, Anish; Iacocca, Ronald G.; German, Randall M.

1998-01-01

To comprehensively understand the gravitational effects on the evolution of both the microstructure and the macrostructure during liquid phase sintering, W-Ni-Fe alloys with W content varying from 35 to 98 wt.% were sintered in microgravity. Compositions that slump during ground-based sintering also distort when sintered under microgravity. In ground-based sintering, low solid content alloys distort with a typical elephant-foot profile, while in microgravity, the compacts tend to spheroidize. This study shows that microstructural segregation occurs in both ground-based as well as microgravity sintering. In ground-based experiments, because of the density difference between the solid and the liquid phase, the solid content increases from top to the bottom of the sample. In microgravity, the solid content increases from periphery to the center of the samples. This study also shows that the pores during microgravity sintering act as a stable phase and attain anomalous shapes.

PROGRESS ON THE STUDY OF THE URANIUM-ALUMINUM-IRON CONSTITUTION DIAGRAM FOR THE PERIOD SEPTEMBER 1-DECEMBER 31, 1963

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

Russell, R.B.

The U--Al--Fe constitution diagram up to about 1000 ppm each of aluminum and iron is sthdied. The techniques used for this study include optical, electron, and x-ray metallography; microprobe analysis, electric conductivity, and hardness measurements. A combination of techniques are giving evidence of the amount of solid solubility of aluminum and iron in alpha, beta, and gamma uranium at selected higher temperatures. The U-Al and U-Fe phase diagrams are also being determined. (N.W.R.)

Electric-field induced phase transitions of dielectric colloids: Impact of multiparticle effects

NASA Astrophysics Data System (ADS)

Wood, Jeffery A.; Docoslis, Aristides

2012-05-01

The thermodynamic framework for predicting the electric-field induced fluid like-solid like phase transition of dielectric colloids developed by Khusid and Acrivos [Phys. Rev. E. 54, 5428 (1996)] is extended to examine the impact of multiscattering/multiparticle effects on the resulting phase diagrams. This was accomplished using effective permittivity models suitable both over the entire composition region for hard spheres (0≤c

Suppressing the cellular breakdown in silicon supersaturated with titanium

NASA Astrophysics Data System (ADS)

Liu, Fang; Prucnal, S.; Hübner, R.; Yuan, Ye; Skorupa, W.; Helm, M.; Zhou, Shengqiang

2016-06-01

Hyper doping Si with up to 6 at.% Ti in solid solution was performed by ion implantation followed by pulsed laser annealing and flash lamp annealing. In both cases, the implanted Si layer can be well recrystallized by liquid phase epitaxy and solid phase epitaxy, respectively. Cross-sectional transmission electron microscopy of Ti-implanted Si after liquid phase epitaxy shows the so-called growth interface breakdown or cellular breakdown owing to the occurrence of constitutional supercooling in the melt. The appearance of cellular breakdown prevents further recrystallization. However, the out-diffusion and cellular breakdown can be effectively suppressed by solid phase epitaxy during flash lamp annealing due to the high velocity of amorphous-crystalline interface and the low diffusion velocity for Ti in the solid phase.

High pressure and high temperature in situ X-ray diffraction studies in the Paris-Edinburgh cell using a laboratory X-ray source†

NASA Astrophysics Data System (ADS)

Toulemonde, Pierre; Goujon, Céline; Laversenne, Laetitia; Bordet, Pierre; Bruyère, Rémy; Legendre, Murielle; Leynaud, Olivier; Prat, Alain; Mezouar, Mohamed

2014-04-01

We have developed a new laboratory experimental set-up to study in situ the pressure-temperature phase diagram of a given pure element or compound, its associated phase transitions, or the chemical reactions involved at high pressure and high temperature (HP-HT) between different solids and liquids. This new tool allows laboratory studies before conducting further detailed experiments using more brilliant synchrotron X-ray sources or before kinetic studies. This device uses the diffraction of X-rays produced by a quasi-monochromatic micro-beam source operating at the silver radiation (λ(Ag)Kα 1, 2≈0.56 Å). The experimental set-up is based on a VX Paris-Edinburgh cell equipped with tungsten carbide or sintered diamond anvils and uses standard B-epoxy 5 or 7 mm gaskets. The diffracted signal coming from the compressed (and heated) sample is collected on an image plate. The pressure and temperature calibrations were performed by diffraction, using conventional calibrants (BN, NaCl and MgO) for determination of the pressure, and by crossing isochores of BN, NaCl, Cu or Au for the determination of the temperature. The first examples of studies performed with this new laboratory set-up are presented in the article: determination of the melting point of germanium and magnesium under HP-HT, synthesis of MgB2 or C-diamond and partial study of the P, T phase diagram of MgH2.

Water: A Tale of Two Liquids.

PubMed

Gallo, Paola; Amann-Winkel, Katrin; Angell, Charles Austen; Anisimov, Mikhail Alexeevich; Caupin, Frédéric; Chakravarty, Charusita; Lascaris, Erik; Loerting, Thomas; Panagiotopoulos, Athanassios Zois; Russo, John; Sellberg, Jonas Alexander; Stanley, Harry Eugene; Tanaka, Hajime; Vega, Carlos; Xu, Limei; Pettersson, Lars Gunnar Moody

2016-07-13

Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambient conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid-liquid critical point, LLCP. On approaching this LLCP from the one-phase region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. Some of the possible experimental lines of research that are essential to complete this picture are explored.

Manifestation of hopping conductivity and granularity within phase diagrams of LaO1-x F x BiS2, Sr1-x La x FBiS2 and related BiS2-based compounds

NASA Astrophysics Data System (ADS)

Arouca, R.; Silva Neto, M. B.; Chaves, C. M.; Nagao, M.; Watauchi, S.; Tanaka, I.; ElMassalami, M.

2017-09-01

Layered BiS 2 -based series, such as LaO 1-x F x BiS 2 and Sr 1-x La x FBiS 2 , offer ideal examples for studying normal and superconducting phase diagram of a solid solution that evolves from a nonmagnetic band-insulator parent. We constructed typical x-T phase diagrams of these systems based on events occurring in thermal evolution of their electrical resistivity, ρ(x, T) . Overall evolution of these diagrams can be rationalized in terms of (i) Mott-Efros-Shklovskii scenario which, within the semiconducting x regime (x_MIT = Mott metal-insulator transition), describes the doping influence on the thermally activated hopping conductivity. (ii) A granular metal (superconductor) scenario which, within x_MIT< x < x_solubility , describes the evolution of normal and superconducting properties in terms of conductance g, Coulomb charging energy E c and Josephson coupling J; their joint influence is usually captured within a g-\\frac{gE_c}{J}-T phase diagram. Based on analysis of the granular character of ρ(x, T) , we converted the x-T diagrams into projected g - T diagrams which, being fundamental, allow a better understanding of evolution of various granular-related properties (in particular the hallmarks of normal-state \\partialρ/\\partial T<0 feature and superconductor-insulator transition) and how such properties are influenced by x, pressure or heat treatment.

Physicochemical properties and solubility of alkyl-(2-hydroxyethyl)-dimethylammonium bromide.

PubMed

Domańska, Urszula; Bogel-Łukasik, Rafał

2005-06-23

Quaternary ammonium salts, which are precursors of ionic liquids, have been prepared from N,N-dimethylethanolamine as a substrate. The paper includes specific basic characterization of synthesized compounds via the following procedures: nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectra, water content, mass spectroscopy (MS) spectra, temperatures of decompositions, basic thermodynamic properties of pure ionic liquids (the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition), and the difference in the solute heat capacity between the liquid and solid at the melting temperature determined by differential scanning calorimetry (DSC). The (solid + liquid) phase equilibria of binary mixtures containing (quaternary ammonium salt + water, or + 1-octanol) has been measured by a dynamic method over wide range of temperatures, from 230 K to 560 K. These data were correlated by means of the UNIQUAC ASM and modified nonrandom two-liquid NRTL1 equations utilizing parameters derived from the (solid + liquid) equilibrium. The partition coefficient of ionic liquid in the 1-octanol/water binary system has been calculated from the solubility results. Experimental partition coefficients (log P) were negative at three temperatures.

Crystal Structures and Phase Relationships of 2 Polymorphs of 1,4-Diazabicyclo[3.2.2]nonane-4-Carboxylic Acid 4-Bromophenyl Ester Fumarate, A Selective α-7 Nicotinic Receptor Partial Agonist.

PubMed

Robert, Benoît; Perrin, Marc-Antoine; Barrio, Maria; Tamarit, Josep-Lluis; Coquerel, Gérard; Ceolin, René; Rietveld, Ivo B

2016-01-01

Two polymorphs of the 1:1 fumarate salt of 1,4-diazabicyclo[3.2.2]nonane-4-carboxylic acid 4-bromophenyl ester, developed for the treatment of cognitive symptoms of schizophrenia and Alzheimer disease, have been characterized. The 2 crystal structures have been solved, and their phase relationships have been established. The space group of form I is P2₁/c with a unit-cell volume of 1811.6 (5) Å(3) with Z = 4. The crystals of form I were 2-component nonmerohedral twins. The space group of form II is P2₁/n with a unit-cell volume of 1818.6 (3) Å(3) with Z = 4. Relative stabilities have been inferred from experimental and topological P-T diagrams exhibiting an overall enantiotropic relationship between forms I and II although the solid-solid transition has never been observed. The slope of the I-II equilibrium in the P-T diagram is negative, form II is the stable phase below the solid-solid transition temperature of 371 K, and form I exhibits a stable melting equilibrium. The I-II transition temperature has been obtained from the intersection of the sublimation curves of the 2 solid forms. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Gas-liquid phase coexistence and crossover behavior of binary ionic fluids with screened Coulomb interactions.

PubMed

Patsahan, O

2014-06-01

We study the effects of an interaction range on the gas-liquid phase diagram and the crossover behavior of a simple model of ionic fluids: an equimolar binary mixture of equisized hard spheres interacting through screened Coulomb potentials which are repulsive between particles of the same species and attractive between particles of different species. Using the collective variables theory, we find explicit expressions for the relevant coefficients of the effective φ{4} Ginzburg-Landau Hamiltonian in a one-loop approximation. Within the framework of this approximation, we calculate the critical parameters and gas-liquid phase diagrams for varying inverse screening length z. Both the critical temperature scaled by the Yukawa potential contact value and the critical density rapidly decrease with an increase of the interaction range (a decrease of z) and then for z<0.05 they slowly approach the values found for a restricted primitive model (RPM). We find that gas-liquid coexistence region reduces with an increase of z and completely vanishes at z≃2.78. Our results clearly show that an increase in the interaction range leads to a decrease of the crossover temperature. For z≃0.01, the crossover temperature is the same as for the RPM.

P-T phase diagram and structural transformations of molten P2O5 under pressure

NASA Astrophysics Data System (ADS)

Brazhkin, V. V.; Katayama, Y.; Lyapin, A. G.; Saitoh, H.

2014-03-01

The P2O5 compound is an archetypical glass-forming oxide with a record high hygroscopicity, which makes its study extremely difficult. We present the in situ x-ray diffraction study of the pressure-temperature phase diagram of P2O5 and, particularly, of the liquid P2O5 structure under high pressure up to 10 GPa. Additionally, quenching from the melt has been used to extend the melting curve up to 15 GPa. We found that structural transformation in the liquid P2O5 under pressure is unique and includes three stages: first, the disappearance of the intermediate range order of the melt together with a slow increase in the average first-coordination number (P-O and O-P neighbors) up to 4 GPa; second, the "normal" compression almost without structural modification at higher pressures up to 8-9 GPa; and, finally, the abrupt change of the short-range order structure of the liquid with the jumplike increase at 9-10 GPa. The last stage correlates with the melting curve maximum (≈1250 °C) at ≈10 GPa and can be interpreted as a transformation to the liquid phase with entirely fivefold-coordinated phosphorus and twofold-coordinated oxygen atoms.

Pressure-temperature phase diagram of a charge-ordered organic conductor studied by C13 NMR

NASA Astrophysics Data System (ADS)

Itou, T.; Miyagawa, K.; Nakamura, J.; Kanoda, K.; Hiraki, K.; Takahashi, T.

2014-07-01

We performed C13 NMR measurements on the quasi-one-dimensional (Q1D) charge-ordered system (DI-DCNQI)2Ag under ambient and applied pressure to clarify the pressure-temperature phase diagram. For pressures up to 15 kbar, the NMR spectra exhibit complicated splitting at low temperatures, indicating a "generalized 3D Wigner crystal" state. In this pressure region, we find that increased pressure causes a decrease in the charge disproportionation ratio, along with a decrease in the transition temperature of the generalized 3D Wigner crystal. In the high-pressure region, near 20 kbar, where a 1D confined liquid crosses over to a 3D Fermi liquid at high temperatures, the ground state is replaced by a nonmagnetic insulating state that is qualitatively different from the generalized 3D Wigner crystal.

A contribution to the knowledge of HMX decomposition and application of results. [at atmospheric pressure

NASA Technical Reports Server (NTRS)

Kraeutle, K. J.

1980-01-01

The decomposition of cyclotramethylenetetranitramine (HMX) in the solid and liquid phase was studied by isothermal and nonisothermal heating at atmospheric pressure. Decomposition rates of solid HMX changed with sample size and gaseous environment. Kinetic parameters were obtained from weight loss measurements in the temperature range 229 C - 269 C. These tests also yielded highly porous solid residues. Qualitative aspects of solid and liquid phase decomposition of HMX with additives were also investigated in isothermal and nonisothermal tests.

New Density Functional Approach for Solid-Liquid-Vapor Transitions in Pure Materials

NASA Astrophysics Data System (ADS)

Kocher, Gabriel; Provatas, Nikolas

2015-04-01

A new phase field crystal (PFC) type theory is presented, which accounts for the full spectrum of solid-liquid-vapor phase transitions within the framework of a single density order parameter. Its equilibrium properties show the most quantitative features to date in PFC modeling of pure substances, and full consistency with thermodynamics in pressure-volume-temperature space is demonstrated. A method to control either the volume or the pressure of the system is also introduced. Nonequilibrium simulations show that 2- and 3-phase growth of solid, vapor, and liquid can be achieved, while our formalism also allows for a full range of pressure-induced transformations. This model opens up a new window for the study of pressure driven interactions of condensed phases with vapor, an experimentally relevant paradigm previously missing from phase field crystal theories.

The competition of hydrogen-like and isotropic interactions on polymer collapse

NASA Astrophysics Data System (ADS)

Krawczyk, J.; Owczarek, A. L.; Prellberg, T.

2007-09-01

We investigate a lattice model of polymers where the nearest neighbour monomer monomer interaction strengths differ according to whether the local configurations have so-called 'hydrogen-like' formations or not. If the interaction strengths are all the same then the classical θ-point collapse transition occurs on lowering the temperature, and the polymer enters the isotropic liquid drop phase known as the collapsed globule. On the other hand, strongly favouring the hydrogen-like interactions gives rise to an anisotropic folded (solid-like) phase on lowering the temperature. We use Monte Carlo simulations up to a length of 256 to map out the phase diagram in the plane of parameters and determine the order of the associated phase transitions. We discuss the connections to semi-flexible polymers and other polymer models. Importantly, we demonstrate that for a range of energy parameters, two phase transitions occur on lowering the temperature, the second being a transition from the globule state to the crystal state. We argue from our data that this globule-to-crystal transition is continuous in two dimensions in accord with field-theory arguments concerning Hamiltonian walks, but is first order in three dimensions.

Experimental Phase Equilibria Studies of the Pb-Fe-O System in Air, in Equilibrium with Metallic Lead and at Intermediate Oxygen Potentials

NASA Astrophysics Data System (ADS)

Shevchenko, M.; Jak, E.

2017-12-01

The phase equilibria information on the Pb-Fe-O system is of practical importance for the improvement of the existing thermodynamic database of lead-containing slag systems (Pb-Zn-Fe-Cu-Si-Ca-Al-Mg-O). Phase equilibria of the Pb-Fe-O system have been investigated: (a) in air at temperatures between 1053 K and 1373 K (780 °C and 1100 °C); (b) in equilibrium with metallic lead at temperatures between 1053 K and 1373 K (780 °C and 1100 °C); and (c) at intermediate oxidation conditions for the liquid slag in equilibrium with two solids (spinel + magnetoplumbite), at temperatures between 1093 K and 1373 K (820 °C and 1100 °C). The high-temperature equilibration/quenching/electron probe X-ray microanalysis technique has been used to accurately determine the compositions of the phases in equilibrium in the system. The Pb and Fe concentrations in the phases were determined directly; preliminary thermodynamic modeling with FactSage was used to estimate the ferrous-to-ferric ratios and to present the results in the ternary diagram.

Solid coatings deposited from liquid methyl methacrylate via Plasma Polymerization

NASA Astrophysics Data System (ADS)

Wurlitzer, Lisa; Maus-Friedrichs, Wolfgang; Dahle, Sebastian

2016-09-01

The polymerization of methyl methacrylate via plasma discharges is well known today. Usually, plasma-enhanced chemical vapor deposition (PECVD) is used to deposit polymer coatings. Solid coatings are formed out of the liquid phase from methyl methacrylate via dielectric barrier discharge. The formation of the coating proceeds in the gas and the liquid phase. To learn more about the reactions in the two phases, the coatings from MMA monomer will be compared to those from MMA resin. Finally, attenuated total reflection infrared spectroscopy, confocal laser scanning microscopy and X-ray photoelectron spectroscopy are employed to characterize the solid coatings. In conclusion, the plasma enhanced chemical solution deposition is compared to the classical thermal polymerization of MMA.

Effect of temperature gradient on liquid-liquid phase separation in a polyolefin blend.

PubMed

Jiang, Hua; Dou, Nannan; Fan, Guoqiang; Yang, Zhaohui; Zhang, Xiaohua

2013-09-28

We have investigated experimentally the structure formation processes during phase separation via spinodal decomposition above and below the spinodal line in a binary polymer blend system exposed to in-plane stationary thermal gradients using phase contrast optical microscopy and temperature gradient hot stage. Below the spinodal line there is a coupling of concentration fluctuations and thermal gradient imposed by the temperature gradient hot stage. Also under the thermal gradient annealing phase-separated domains grow faster compared with the system under homogeneous temperature annealing on a zero-gradient or a conventional hot stage. We suggest that the in-plane thermal gradient accelerates phase separation through the enhancement in concentration fluctuations in the early and intermediate stages of spinodal decomposition. In a thermal gradient field, the strength of concentration fluctuation close to the critical point (above the spinodal line) is strong enough to induce phase separation even in one-phase regime of the phase diagram. In the presence of a temperature gradient the equilibrium phase diagrams are no longer valid, and the systems with an upper critical solution temperature can be quenched into phase separation by applying the stationary temperature gradient. The in-plane temperature gradient drives enhanced concentration fluctuations in a binary polymer blend system above and below the spinodal line.

Towards building a robust computational framework to simulate multi-physics problems - a solution technique for three-phase (gas-liquid-solid) interactions

NASA Astrophysics Data System (ADS)

Zhang, Lucy

In this talk, we show a robust numerical framework to model and simulate gas-liquid-solid three-phase flows. The overall algorithm adopts a non-boundary-fitted approach that avoids frequent mesh-updating procedures by defining independent meshes and explicit interfacial points to represent each phase. In this framework, we couple the immersed finite element method (IFEM) and the connectivity-free front tracking (CFFT) method that model fluid-solid and gas-liquid interactions, respectively, for the three-phase models. The CFFT is used here to simulate gas-liquid multi-fluid flows that uses explicit interfacial points to represent the gas-liquid interface and for its easy handling of interface topology changes. Instead of defining different levels simultaneously as used in level sets, an indicator function naturally couples the two methods together to represent and track each of the three phases. Several 2-D and 3-D testing cases are performed to demonstrate the robustness and capability of the coupled numerical framework in dealing with complex three-phase problems, in particular free surfaces interacting with deformable solids. The solution technique offers accuracy and stability, which provides a means to simulate various engineering applications. The author would like to acknowledge the supports from NIH/DHHS R01-2R01DC005642-10A1 and the National Natural Science Foundation of China (NSFC) 11550110185.

Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface.

PubMed

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2018-04-06

We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface-controlled by a crossover in how methane is supplied from the gas and liquid phases-which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

A microstructure-based model for shape distortion during liquid phase sintering

NASA Astrophysics Data System (ADS)

Upadhyaya, Anish

Tight dimensional control is a major concern in consolidation of alloys via liquid phase sintering. This research demonstrates the role of microstructure in controlling the bulk dimensional changes that occur during liquid phase sintering. The dimensional changes were measured using a coordinate measuring machine and also on a real-time basis using in situ video imaging. To quantify compact distortion, a distortion parameter is formulated which takes into consideration the compact distortion in radial as well as axial directions. The microstructural attributes considered in this study are as follows: solid content, dihedral angle, grain size, grain contiguity and connectivity, and solid-solubility. Sintering experiments were conducted with the W-Ni-Cu, W-Ni-Fe, Mo-Ni-Cu, and Fe-Cu systems. The alloy systems and the compositions were selected to give a range of microstructures during liquid phase sintering. The results show that distortion correlates with the measured microstructural attributes. Systems containing a high solid content, high grain coordination number and contiguity, and large dihedral angle have more structural rigidity. The results show that a minimum two-dimensional grain coordination number of 3.0 is necessary for shape preservation. Based on the experimental observations, a model is derived that relates the critical solid content required for maintaining structural rigidity to the dihedral angle. The critical solid content decreases with an increasing dihedral angle. Consequently, W-Cu alloys, which have a dihedral angle of about 95sp°, can be consolidated without gross distortion with as little as 20 vol.% solid. To comprehensively understand the gravitational effects in the evolution of both the microstructure and the macrostructure during liquid phase sintering, W-Ni-Fe alloys with W content varying from 78 to 93 wt.% were sintered in microgravity. Compositions that slump during ground-based sintering also distort when sintered under microgravity. In ground-based sintering, low solid content alloys distort with a typical elephant-foot profile, while in microgravity, the compacts tend to spheroidize. This study shows that microstructural segregation occurs in both ground-based as well as microgravity sintering. In ground-based experiments, because of the density difference between the solid and the liquid phase, the solid content increases from top to the bottom of the sample. In microgravity, the solid content increases from periphery to the center of the samples. A model is derived to show that grain agglomeration and segregation are energetically favored events and will therefore be inherent to the system, even in the absence of gravity. Real time distortion measurement in alloys having appreciable solid-solubility in the liquid phase, such as W-Ni-Fe and Fe-Cu, show that the bulk of distortion occur within the first 5 min of melt formation. Distortion in such systems can be minimized by presaturating the matrix with the solid phase.

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.

Applications of the Peng-Robinson Equation of State Using MATLAB[R

ERIC Educational Resources Information Center

Nasri, Zakia; Binous, Housam

2009-01-01

A single equation of state (EOS) such as the Peng-Robinson (PR) EOS can accurately describe both the liquid and vapor phase. We present several applications of this equation of state, including estimation of pure component properties and computation of the vapor-liquid equilibrium (VLE) diagram for binary mixtures. We perform high-pressure…

Biofuel production utilizing a dual-phase cultivation system with filamentous cyanobacteria.

PubMed

Aoki, Jinichi; Kawamata, Toru; Kodaka, Asuka; Minakawa, Masayuki; Imamura, Nobukazu; Tsuzuki, Mikio; Asayama, Munehiko

2018-04-17

Biomass yields and biofuel production were examined in a dual (solid and liquid)-phase cultivation system (DuPHA) with the unique filamentous cyanobacteria, Pseudanabaena sp. ABRG 5-3 and Limnothrix sp. SK1-2-1. Continuous circular cultivation was driven under the indoor closed (IC) or indoor opened (IO) conditions and provided biomass yields of approximately 8 to 27 g dry cell weight (DCW) floor m -2 d -1 . Alkanes of heptadecane (C 17 H 36 ) or pentadecane (C 15 H 32 ) as liquid biofuels were also recovered from the lower liquid-phase, in which cyanobacteria were dropped from the upper solid-phase and continuously cultivated with a small amount of medium. After the main cultivation in DuPHA, the upper solid-phase of a cotton cloth on which cyanobacteria grew was dried and directly subjected to a combustion test. This resulted in the thermal power (kJ s -1 ) of the cloth with microalgae increasing approximately 20 to 50% higher than that of the cloth only, suggesting a possibility of using the solid phase with microalgae as solid biofuel. Copyright © 2018. Published by Elsevier B.V.

Enhancement of solubility and oral bioavailability of manidipine by formation of ternary solid dispersion with d-α-tocopherol polyethylene glycol 1000 succinate and copovidone.

PubMed

Chamsai, Benchawan; Limmatvapirat, Sontaya; Sungthongjeen, Srisagul; Sriamornsak, Pornsak

2017-12-01

Low bioavailability of oral manidipine (MDP) is due to its low water solubility. The objective of this study was to increase the solubility and bioavailability of MDP by fabricating ternary solid dispersion (tSD) with d-α-tocopherol polyethyleneglycol-1000-succinate and copovidone. In this study, solid ternary phase diagram was applied in order to check the homogeneity of tSD prepared by melting and solidifying with dry ice. The physicochemical properties of different formulations were determined by differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR) and hot stage microscopy. Their solubility, dissolution, stability and bioavailability were also investigated. The results demonstrated that tSD obtained from ternary phase diagram divided into homogeneous and non-homogeneous regions. In the homogenous region, the transparent characteristics of tSD was observed and considered as a glass solution, which have a higher MDP solubility than that in non-homogenous region. The hot stage microscopy, DSC and PXRD confirmed that solid dispersion was formed in which MDP was molecularly dispersed in the carriers, especially in the homogenous region of phase diagram. FTIR analysis demonstrated strong hydrogen bonding between amine groups of MDP and carbonyl groups of copovidone, which supported a higher solubility and dissolution of tSD. The pharmacokinetic study in Wistar rats showed that the tSD had the greatest effect on oral bioavailability. Immediate hypotensive effect of tSD was also observed in vivo. The improvement of stability, dissolution and oral bioavailability of MDP could be achieved by using tSD technique.

Unexpectedly high pressure for molecular dissociation in liquid hydrogen by electronic simulation.

PubMed

Mazzola, Guglielmo; Yunoki, Seiji; Sorella, Sandro

2014-03-19

The study of the high pressure phase diagram of hydrogen has continued with renewed effort for about one century as it remains a fundamental challenge for experimental and theoretical techniques. Here we employ an efficient molecular dynamics based on the quantum Monte Carlo method, which can describe accurately the electronic correlation and treat a large number of hydrogen atoms, allowing a realistic and reliable prediction of thermodynamic properties. We find that the molecular liquid phase is unexpectedly stable, and the transition towards a fully atomic liquid phase occurs at much higher pressure than previously believed. The old standing problem of low-temperature atomization is, therefore, still far from experimental reach.

Solid-liquid staged combustion space boosters

NASA Technical Reports Server (NTRS)

Culver, D. W.

1990-01-01

NASA has begun to evaluate solid-liquid hybrid propulsion for launch vehicle booster. A three-phase program was outlined to identify, acquire, and demonstrate technology needed to approximate solid and liquid propulsion state of the art. Aerojet has completed a Phase 1 study and recommends a solid-liquid staged combustion concept in which turbopump fed LO2 is burned with fuel-rich solid propellant effluent in aft-mounted thrust chambers.These reasonably sized thrust chambers are LO2 regeneratively cooled, supplemented with fuel-rich barrier cooling. Turbopumps are driven by the resulting GO2 coolant in an expander-bleed-burnoff cycle. Turbine exhaust pressurizes the LO2 tankage directly, and the excess is bled into supersonic nozzle splitlines, where it combusts with the fuel rich boundary layer. Thrust vector control is enhanced by supersonic nozzle movement on flexseal mounts. Every hybrid solid-liquid concept examined improves booster energy management and launch propellant safety compared to current solid boosters. Solid-liquid staged combustion improves hybrid performance by improving both combustion efficiency and combustion stability, especially important for large boosters. These improvements result from careful fluid management and use of smaller combustors. The study shows NASA safety, reliability, cost, and performance criteria are best met with this concept, wherein simple hardware relies on several separate emerging technologies, all of which have been demonstrated successfully.

Thermodynamic Modeling of the Ge-Nd Binary System

NASA Astrophysics Data System (ADS)

Liu, Miao; Li, Changrong; Du, Zhenmin; Guo, Cuiping; Niu, Chunju

The Ge-Nd has been critically assessed by means of the CALculation of PHAse Diagram (CALPHAD) technique. For the liquid phase, the associate model was used with the constituent species Ge, Nd, Ge3Nd5 and Ge1.6Nd in the Ge-Nd system. The terminal solid solution diamond-(Ge), dhcp-(Nd) and bcc_A2-(Nd) in the Ge-Nd system were described using the substitutional model, in which the excess Gibbs energy was formulated with the Redlich-Kister equation. The compounds with homogeneity ranges, α(Ge1.6Nd), β(Ge1.6Nd), (GeNd), (Ge4Nd5) and (Ge3Nd5) were modeled using two sublattices as α(Ge,Nd)1.6Nd, β(Ge,Nd)1.6Nd, (Ge,Nd)Nd, (Ge,Nd)4Nd5 and (Ge,Nd)3Nd5, respectively. A set of self-consistent thermodynamic parameters for each of the Ge-Nd binary systems was obtained. The calculation results agree well with the available experimental data from literatures.

Thermophysical Parameters of Organic PCM Coconut Oil from T-History Method and Its Potential as Thermal Energy Storage in Indonesia

NASA Astrophysics Data System (ADS)

Silalahi, Alfriska O.; Sukmawati, Nissa; Sutjahja, I. M.; Kurnia, D.; Wonorahardjo, S.

2017-07-01

The thermophysical parameters of organic phase change material (PCM) of coconut oil (co_oil) have been studied by analyzing the temperature vs time data during liquid-solid phase transition (solidification process) based on T-history method, adopting the original version and its modified form to extract the values of mean specific heats of the solid and liquid co_oil and the heat of fusion related to phase transition of co_oil. We found that the liquid-solid phase transition occurs rather gradually, which might be due to the fact that co_oil consists of many kinds of fatty acids with the largest amount of lauric acid (about 50%), with relatively small supercooling degree. For this reason, the end of phase transition region become smeared out, although the inflection point in the temperature derivative is clearly observed signifying the drastic temperature variation between the phase transition and solid phase periods. The data have led to the values of mean specific heat of the solid and liquid co_oil that are comparable to the pure lauric acid, while the value for heat of fusion is resemble to those of the DSC result, both from references data. The advantage of co_oil as the potential sensible and latent TES for room-temperature conditioning application in Indonesia is discussed in terms of its rather broad working temperature range due to its mixture composition characteristic.

Water: A Tale of Two Liquids

DOE PAGES

Gallo, Paola; Amann-Winkel, Katrin; Angell, Charles Austen; ...

2016-07-05

Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambientmore » conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid–liquid critical point, LLCP. On approaching this LLCP from the one-phase region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. In conclusion, some of the possible experimental lines of research that are essential to complete this picture are explored.« less

Water: A Tale of Two Liquids

PubMed Central

2016-01-01

Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambient conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid–liquid critical point, LLCP. On approaching this LLCP from the one-phase region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. Some of the possible experimental lines of research that are essential to complete this picture are explored. PMID:27380438

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

Salud, J.; Lopez, D.O.; Barrio, M.

The experimental two-component phase diagram between the orientationally disordered crystals 2-amino-2-methyl-1,3-propanediol (AMP) and 1,1,1-tris(hydroxymethyl)propane (PG) has been established from room temperature to the liquid state using thermal analysis and X-ray powder diffraction techniques. The intermolecular interactions in the orientationally disordered mixed crystals of the mentioned system and other related two-component systems are discussed by analyzing the evolution of the packing coefficient as a function of the composition. A thermodynamic analysis of the presented phase diagram and the redetermined AMP/NPG (2,2-dimethyl-1,3-propanediol) is reported on the basis of the enthalpy-entropy compensation theory.

Isomorphism and solid solutions among Ag- and Au-selenides

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

Palyanova, Galina A.; Seryotkin, Yurii V.; Novosibirsk State University

Au-Ag selenides were synthesized by heating stoichiometric mixtures of elementary substances of initial compositions Ag{sub 2−x}Au{sub x}Se with a step of x=0.25 (0≤x≤2) to 1050 °C and annealing at 500 °C. Scanning electron microscopy, optical microscopy, electron microprobe analysis and X-ray powder diffraction methods have been applied to study synthesized samples. Results of studies of synthesized products revealed the existence of three solid solutions with limited isomorphism Ag↔Au: naumannite Ag{sub 2}Se – Ag{sub 1.94}Au{sub 0.06}Se, fischesserite Ag{sub 3}AuSe{sub 2} - Ag{sub 3.2}Au{sub 0.8}Se{sub 2} and gold selenide AuSe - Au{sub 0.94}Ag{sub 0.06}Se. Solid solutions and AgAuSe phases were added tomore » the phase diagram of Ag-Au-Se system. Crystal-chemical interpretation of Ag-Au isomorphism in selenides was made on the basis of structural features of fischesserite, naumannite, and AuSe. - Highlights: • Au-Ag selenides were synthesized. • Limited Ag-Au isomorphism in the selenides is affected by structural features. • Some new phases were introduced to the phase diagram Ag-Au-Se.« less

Decaying shock studies of phase transitions in MgO-SiO2 systems: implications for the Super-Earths' interiors

NASA Astrophysics Data System (ADS)

Bolis, R.; Morard, G.; Vinci, T.; Ravasio, A.; Bambrink, E.; Guarguaglini, M.; Koenig, M.; Musella, R.; Françoise, R.; Bouchet, J.; Ozaki, N.; Miyanishi, K.; Sekine, T.; Sakawa, Y.; Sano, T.; Kodama, R.; Guyot, F. J.; Benuzzi, A.

2016-12-01

Mantles of telluric exoplanets, so-called Earth-like and Super-Earths, are expected to be mainly composed of different type of oxides, such as periclase (MgO), enstatite (MgSiO3) and forsterite (Mg2SiO4). Determining the phase diagrams, melting curves and liquid properties of these compounds under extreme pressure (0.2-1 TPa) is crucial to model the internal dynamic of these exoplanets, as the melting of mantle components controls planetary temperature profiles [6]. Experimentally, these planetary thermodynamic states can be achieved with laser-shock compression. Here we present laser-driven decaying shock experiments on MgO, MgSiO3 and Mg2SiO4 samples performed at LULI and GEKKO laser facilities, where we focused 1.2-2.5 ns laser pulses with an intensity between 3-8 1013 W/cm2 exploring pressures between 0.2 and 1 TPa and temperature between 5000 and 30000 K. We determined the thermodynamic states using rear side optical diagnostics. We observed a single transition for MgO associated to melting (at 0.47 TPa ± 0.04 and 9863 ± 812 K) and no evidence of a liquid-liquid transition, dissociation or melting for all the other compounds in the range 150-500 Gpa and 200-800 Gpa respectively for MgSiO3 and Mg2SiO4. Some implications are presented comparing our data experimental and theoretical data found in literature [1, 2, 3, 4, 5]. In particular these results represent a key input to solve the controversy on a possible MgSiO3 liquid-liquid phase transition. Moreover we propose a revision of the phase diagram of MgO, with a lower melting line which results in a lower temperature profile for super-Earths. Finally our data evidence the presence of a poor electrically conducting liquid in the phase diagram of all the studied material, with implications for the modelling of magnetic field generation via dynamo mechanism.[1] McWilliams et al., Science 338 (2012): 1330-1333. [2] Spaulding et al., Physical Review Letters108 (2012): 065701. [3] Root et al., Physical Review Letters 115 (2015): 198501. [4] Miyanishi et al., Physical Review E 92 (2015): 023103. [5] Militzer, High Energy Density Physics 9 (2013): 152-157. [6] Stixrude, Philos. Trans. R. Soc. A 372 (2014): 20130076.

Absence of magnetic ordering and field-induced phase diagram in the gadolinium aluminum garnet

NASA Astrophysics Data System (ADS)

Florea, O.; Lhotel, E.; Jacobsen, H.; Knee, C. S.; Deen, P. P.

2017-12-01

The robustness of spin liquids with respect to small perturbations, and the way magnetic frustration can be lifted by slight changes in the balance between competing magnetic interactions, remains a rich and open issue. We address this question through the study of the gadolinium aluminum garnet Gd3Al5O12 , a related compound to the extensively studied Gd3Ga5O12 . We report on its magnetic properties at very low temperatures. We show that despite a freezing at about 300 mK, no magnetic transition is observed, suggesting the presence of a spin-liquid state down to the lowest temperatures, similarly to Gd3Ga5O12 , in spite of a larger ratio between exchange and dipolar interactions. Finally, the phase diagram as a function of field and temperature is strongly reminiscent of the one reported in Gd3Ga5O12 . This study reveals the robust nature of the spin-liquid phase for Gd ions on the garnet lattice, in stark contrast to Gd ions on the pyrochlore lattice for which a slight perturbation drives the compound into a range of magnetically ordered states.

Electrical and thermal transport properties of the electron-doped cuprate Sm2-x Ce x CuO4-y system

NASA Astrophysics Data System (ADS)

Scanderbeg, D. J.; Taylor, B. J.; Baumbach, R. E.; Paglione, J.; Maple, M. B.

2016-12-01

Electrical and thermal transport measurements were performed on thin films of the electron-doped superconductor Sm2-x Ce x CuO4-y (x  =  0.13  -  0.19) in order to study the evolving nature of the charge carriers from the under-doped to over-doped regime. A temperature versus cerium content (T  -  x) phase diagram has been constructed from the electrical transport measurements, yielding a superconducting region similar to that found for other electron-doped superconductors. Thermopower measurements show a dramatic change from the underdoped region (x  <  0.15) to the overdoped region (x  >  0.15). Application of the Fisher-Fisher-Huse (FFH) vortex glass scaling model to the magnetoresistance data was found to be insufficient to describe the data in the region of the vortex-solid to vortex-liquid transition. It was found instead that the modified vortex glass scaling model of Rydh, Rapp, and Anderson provided a good description of the data, indicating the importance of the applied field on the pinning landscape. A magnetic field versus temperature (H  -  T) phase diagram has also been constructed for the films with x≥slant 0.14 , displaying the evolution of the vortex glass melting lines H g (T) across the superconducting regime.

Determination of endocrine-disrupting compounds in water samples by magnetic nanoparticle-assisted dispersive liquid-liquid microextraction combined with gas chromatography-tandem mass spectrometry.

PubMed

Pérez, Rosa Ana; Albero, Beatriz; Tadeo, José Luis; Sánchez-Brunete, Consuelo

2016-11-01

A rapid extraction procedure is presented for the determination of five endocrine-disrupting compounds, estrone, ethinylestradiol, bisphenol A, triclosan, and 2-ethylhexylsalicylate, in water samples. The analysis involves a two-step extraction procedure that combines dispersive liquid-liquid microextraction (DLLME) with dispersive micro-solid phase extraction (D-μ-SPE), using magnetic nanoparticles, followed by in situ derivatization in the injection port of a gas chromatograph coupled to triple quadrupole mass spectrometry. The use of uncoated or oleate-coated Fe 3 O 4 nanoparticles as sorbent in the extraction process was evaluated and compared. The main parameters involved in the extraction process were optimized applying experimental designs. Uncoated Fe 3 O 4 nanoparticles were selected in order to simplify and make more cost-effective the procedure. DLLME was carried out at pH 3, during 2 min, followed by the addition of the nanoparticles for D-μ-SPE employing 1 min in the extraction. Analysis of spiked water samples of different sources gave satisfactory recovery results for all the compounds with detection limits ranging from 7 to 180 ng l -1 . Finally, the procedure was applied in tap, well, and river water. Graphical abstract Diagram of the extraction method using magnetic nanoparticles (MNPs).

Metallic Hydrogen

NASA Astrophysics Data System (ADS)

Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

2015-03-01

Hydrogen is the simplest and most abundant element in the Universe. At high pressure it is predicted to transform to a metal with remarkable properties: room temperature superconductivity, a metastable metal at ambient conditions, and a revolutionary rocket propellant. Both theory and experiment have been challenged for almost 80 years to determine its condensed matter phase diagram, in particular the insulator-metal transition. Hydrogen is predicted to dissociate to a liquid atomic metal at multi-megabar pressures and T =0 K, or at megabar pressures and very high temperatures. Thus, its predicted phase diagram has a broad field of liquid metallic hydrogen at high pressure, with temperatures ranging from thousands of degrees to zero Kelvin. In a bench top experiment using static compression in a diamond anvil cell and pulsed laser heating, we have conducted measurements on dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K. We observe a first-order phase transition in the liquid phase, as well as sharp changes in optical transmission and reflectivity when this phase is entered. The optical signature is that of a metal. The mapping of the phase line of this transition is in excellent agreement with recent theoretical predictions for the long-sought plasma phase transition to metallic hydrogen. Research supported by the NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H.

Navigating at Will on the Water Phase Diagram

NASA Astrophysics Data System (ADS)

Pipolo, S.; Salanne, M.; Ferlat, G.; Klotz, S.; Saitta, A. M.; Pietrucci, F.

2017-12-01

Despite the simplicity of its molecular unit, water is a challenging system because of its uniquely rich polymorphism and predicted but yet unconfirmed features. Introducing a novel space of generalized coordinates that capture changes in the topology of the interatomic network, we are able to systematically track transitions among liquid, amorphous, and crystalline forms throughout the whole phase diagram of water, including the nucleation of crystals above and below the melting point. Our approach, based on molecular dynamics and enhanced sampling or free energy calculation techniques, is not specific to water and could be applied to very different structural phase transitions, paving the way towards the prediction of kinetic routes connecting polymorphic structures in a range of materials.

A classical model for closed-loop diagrams of binary liquid mixtures

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

Schnitzler, J.v.; Prausnitz, J.M.

1994-03-01

A classical lattice model for closed-loop temperature-composition phase diagrams has been developed. It considers the effect of specific interactions, such as hydrogen bonding, between dissimilar components. This van Laar-type model includes a Flory-Huggins term for the excess entropy of mixing. It is applied to several liquid-liquid equilibria of nonelectrolytes, where the molecules of the two components differ in size. The model is able to represent the observed data semi-quantitatively, but in most cases it is not flexible enough to predict all parts of the closed loop quantitatively. The ability of the model to represent different binary systems is discussed. Finally,more » attention is given to a correction term, concerning the effect of concentration fluctuations near the upper critical solution temperature.« less

Spin Bose-metal phase in a spin- (1)/(2) model with ring exchange on a two-leg triangular strip

NASA Astrophysics Data System (ADS)

Sheng, D. N.; Motrunich, Olexei I.; Fisher, Matthew P. A.

2009-05-01

Recent experiments on triangular lattice organic Mott insulators have found evidence for a two-dimensional (2D) spin liquid in close proximity to the metal-insulator transition. A Gutzwiller wave function study of the triangular lattice Heisenberg model with a four-spin ring exchange term appropriate in this regime has found that the projected spinon Fermi sea state has a low variational energy. This wave function, together with a slave particle-gauge theory analysis, suggests that this putative spin liquid possesses spin correlations that are singular along surfaces in momentum space, i.e., “Bose surfaces.” Signatures of this state, which we will refer to as a “spin Bose metal” (SBM), are expected to manifest in quasi-one-dimensional (quasi-1D) ladder systems: the discrete transverse momenta cut through the 2D Bose surface leading to a distinct pattern of 1D gapless modes. Here, we search for a quasi-1D descendant of the triangular lattice SBM state by exploring the Heisenberg plus ring model on a two-leg triangular strip (zigzag chain). Using density matrix renormalization group (DMRG) supplemented by variational wave functions and a bosonization analysis, we map out the full phase diagram. In the absence of ring exchange the model is equivalent to the J1-J2 Heisenberg chain, and we find the expected Bethe-chain and dimerized phases. Remarkably, moderate ring exchange reveals a new gapless phase over a large swath of the phase diagram. Spin and dimer correlations possess singular wave vectors at particular “Bose points” (remnants of the 2D Bose surface) and allow us to identify this phase as the hoped for quasi-1D descendant of the triangular lattice SBM state. We use bosonization to derive a low-energy effective theory for the zigzag spin Bose metal and find three gapless modes and one Luttinger parameter controlling all power law correlations. Potential instabilities out of the zigzag SBM give rise to other interesting phases such as a period-3 valence bond solid or a period-4 chirality order, which we discover in the DMRG. Another interesting instability is into a spin Bose-metal phase with partial ferromagnetism (spin polarization of one spinon band), which we also find numerically using the DMRG.

Quantitative tomographic measurements of opaque multiphase flows

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

GEORGE,DARIN L.; TORCZYNSKI,JOHN R.; SHOLLENBERGER,KIM ANN

2000-03-01

An electrical-impedance tomography (EIT) system has been developed for quantitative measurements of radial phase distribution profiles in two-phase and three-phase vertical column flows. The EIT system is described along with the computer algorithm used for reconstructing phase volume fraction profiles. EIT measurements were validated by comparison with a gamma-densitometry tomography (GDT) system. The EIT system was used to accurately measure average solid volume fractions up to 0.05 in solid-liquid flows, and radial gas volume fraction profiles in gas-liquid flows with gas volume fractions up to 0.15. In both flows, average phase volume fractions and radial volume fraction profiles from GDTmore » and EIT were in good agreement. A minor modification to the formula used to relate conductivity data to phase volume fractions was found to improve agreement between the methods. GDT and EIT were then applied together to simultaneously measure the solid, liquid, and gas radial distributions within several vertical three-phase flows. For average solid volume fractions up to 0.30, the gas distribution for each gas flow rate was approximately independent of the amount of solids in the column. Measurements made with this EIT system demonstrate that EIT may be used successfully for noninvasive, quantitative measurements of dispersed multiphase flows.« less

Solid phase pegylation of hemoglobin.

PubMed

Suo, Xiaoyan; Zheng, Chunyang; Yu, Pengzhan; Lu, Xiuling; Ma, Guanghui; Su, Zhiguo

2009-01-01

A solid phase conjugation process was developed for attachment of polyethylene glycol to hemoglobin molecule. Bovine hemoglobin was loaded onto an ion exchange chromatography column and adsorbed by the solid medium. Succinimidyl carbonate mPEG was introduced in the mobile phase after the adsorption. Pegylation took place between the hemoglobin on the solid phase, and the pegylation reagent in the liquid phase. A further elution was carried out to separate the pegylated and the unpegylated protein. Analysis by HPSEC, SDS-PAGE, and MALLS demonstrated that the fractions eluted from the solid phase contained well-defined components. Pegylated hemoglobin with one PEG chain was obtained with the yield of 75%, in comparison to the yield of 30% in the liquid phase pegylation. The P(50) values of the mono-pegylated hemoglobin, prepared with SC-mPEG 5 kDa, 10 kDa and 20 kDa, were 19.97, 20.23 and 20.54 mmHg, which were much closer to the value of red blood cells than that of pegylated hemoglobin prepared with the conventional method.

Development and kinetic analysis of cobalt gradient formation in WC-Co composites

NASA Astrophysics Data System (ADS)

Guo, Jun

2011-12-01

Functionally graded cemented tungsten carbide (FG WC-Co) is one of the main research directions in the field of WC-Co over decades. Although it has long been recognized that FG WC-Co could outperform conventional homogeneous WC-Co owing to its potentially superior combinations of mechanical properties, until recently there has been a lack of effective and economical methods to make such materials. The lack of the technology has prevented the manufacturing and industrial applications of FG WC-Co from becoming a reality. This dissertation is a comprehensive study of an innovative atmosphere heat treatment process for producing FG WC-Co with a surface cobalt compositional gradient. The process exploited a triple phase field in W-C-Co phase diagram among three phases (solid WC, solid Co, and liquid Co) and the dependence of the migration of liquid Co on temperature and carbon content. WC-Co with a graded surface cobalt composition can be achieved by controlling the diffusion of carbon transported from atmosphere during sintering or during postsintering heat treatment. The feasibility of the process was validated by the successful preparations of FG WC-Co via both carburization and decarburization process following conventional liquid phase sintering. A study of the carburization process was undertaken to further understand and quantitatively modeled this process. The effects of key processing parameters (including heat treating temperature, atmosphere, and time) and key materials variables (involving Co content, WC grain size, and addition of grain growth inhibitors) on the formation of Co gradients were examined. Moreover, a carbon-diffusion controlled kinetic model was developed for simulating the formation of the gradient during the process. The parameters involved in this model were determined by thermodynamic calculations and regression-fit of simulation results with experimental data. In summary, this research first demonstrated the principle of the approach. Second, a model was developed to predict the gradients produced by the carbon-controlled atmosphere heat treatment process, which is useful for manufacturing WC-Co with designed gradients. FG WC-Co materials produced using this method are expected to exhibit superior performance in many applications and to have a profound impact on the manufacturing industries that use tungsten carbide tools.

Column Liquid Chromatography.

ERIC Educational Resources Information Center

Majors, Ronald E.; And Others

1984-01-01

Reviews literature covering developments of column liquid chromatography during 1982-83. Areas considered include: books and reviews; general theory; columns; instrumentation; detectors; automation and data handling; multidimensional chromatographic and column switching techniques; liquid-solid chromatography; normal bonded-phase, reversed-phase,…

Resolving Discrepancies in the Measurements of the Interfacial Tension for the CO2 + H2O Mixture by Computer Simulation.

PubMed

Müller, Erich A; Mejía, Andrés

2014-04-03

Literature values regarding the pressure dependence of the interfacial tension of the system of carbon dioxide (CO2) + water (H2O) show an unexplained divergence and scatter at the transition between low-pressure gas-liquid equilibrium and the high-pressure liquid-liquid equilibrium. We employ the Statistical Associating Fluid Theory (SAFT) and canonical molecular dynamics simulations based on the corresponding coarse grained force field to map out the phase diagram of the mixture and the interfacial tension for this system. We showcase how at ambient temperatures a triple point (gas-liquid-liquid) is expected and detail the implications that the appearance of the third phase has on the interfacial tensions of the system.

Fluorous tagging strategy for solution-phase synthesis of small molecules, peptides and oligosaccharides

PubMed Central

Zhang, Wei

2005-01-01

The purification of reaction mixtures is a slow process in organic synthesis, especially during the production of large numbers of analogs and compound libraries. Phase-tag methods such as solid-phase synthesis and fluorous synthesis, provide efficient ways of addressing the separation issue. Fluorous synthesis employs functionalized perfluoroalkyl groups attached to substrates or reagents. The separation of the resulting fluorous molecules can be achieved using strong and selective fluorous liquid-liquid extraction, fluorous silica gel-based solid-phase extraction or high-performance liquid chromatography. Fluorous technology is a novel solution-phase method, which has the advantages of fast reaction times in homogeneous environments, being readily adaptable to literature conditions, having easy intermediate analysis, and having flexibility in reaction scale and scope. In principle, any synthetic methods that use a solid-support could be conducted in solution-phase by replacing the polymer linker with a corresponding fluorous tag. This review summarizes the progress of fluorous tags in solution-phase synthesis of small molecules, peptides and oligosaccharides. PMID:15595439

A three-dimensional phase field model for nanowire growth by the vapor-liquid-solid mechanism

NASA Astrophysics Data System (ADS)

Wang, Yanming; Ryu, Seunghwa; McIntyre, Paul C.; Cai, Wei

2014-07-01

We present a three-dimensional multi-phase field model for catalyzed nanowire (NW) growth by the vapor-liquid-solid (VLS) mechanism. The equation of motion contains both a Ginzburg-Landau term for deposition and a diffusion (Cahn-Hilliard) term for interface relaxation without deposition. Direct deposition from vapor to solid, which competes with NW crystal growth through the molten catalyst droplet, is suppressed by assigning a very small kinetic coefficient at the solid-vapor interface. The thermodynamic self-consistency of the model is demonstrated by its ability to reproduce the equilibrium contact angles at the VLS junction. The incorporation of orientation dependent gradient energy leads to faceting of the solid-liquid and solid-vapor interfaces. The model successfully captures the curved shape of the NW base and the Gibbs-Thomson effect on growth velocity.

Predicting phase equilibria in one-component systems

NASA Astrophysics Data System (ADS)

Korchuganova, M. R.; Esina, Z. N.

2015-07-01

It is shown that Simon equation coefficients for n-alkanes and n-alcohols can be modeled using critical and triple point parameters. Predictions of the phase liquid-vapor, solid-vapor, and liquid-solid equilibria in one-component systems are based on the Clausius-Clapeyron relation, Van der Waals and Simon equations, and the principle of thermodynamic similarity.

First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

NASA Astrophysics Data System (ADS)

Bechtel, Jonathon S.; Van der Ven, Anton

2018-04-01

Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.

Phase-field-crystal model for magnetocrystalline interactions in isotropic ferromagnetic solids

NASA Astrophysics Data System (ADS)

Faghihi, Niloufar; Provatas, Nikolas; Elder, K. R.; Grant, Martin; Karttunen, Mikko

2013-09-01

An isotropic magnetoelastic phase-field-crystal model to study the relation between morphological structure and magnetic properties of pure ferromagnetic solids is introduced. Analytic calculations in two dimensions were used to determine the phase diagram and obtain the relationship between elastic strains and magnetization. Time-dependent numerical simulations in two dimensions were used to demonstrate the effect of grain boundaries on the formation of magnetic domains. It was shown that the grain boundaries act as nucleating sites for domains of reverse magnetization. Finally, we derive a relation for coercivity versus grain misorientation in the isotropic limit.

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

Travesset, Alex

An extensive characterization of the low temperature phase diagram of particles interacting with power law or Lennard-Jones potentials is provided from Lattice Dynamical Theory. For power law systems, only two lattice structures are stable for certain values of the exponent (or softness) (A15, body centered cube (bcc)) and two more (face centered cubic (fcc), hexagonal close packed (hcp)) are always stable. Among them, only the fcc and bcc are equilibrium states. For Lennard-Jones systems, the equilibrium states are either hcp or fcc, with a coexistence curve in pressure and temperature that shows reentrant behavior. The hcp solid never coexists withmore » the liquid. In all cases analyzed, for both power law and Lennard-Jones potentials, the fcc crystal has higher entropy than the hcp. The role of anharmonic terms is thoroughly analyzed and a general thermodynamic integration to account for them is proposed.« less

Comparative study on solid self-nanoemulsifying drug delivery and solid dispersion system for enhanced solubility and bioavailability of ezetimibe

PubMed Central

Rashid, Rehmana; Kim, Dong Wuk; Yousaf, Abid Mehmood; Mustapha, Omer; Din, Fakhar ud; Park, Jong Hyuck; Yong, Chul Soon; Oh, Yu-Kyoung; Youn, Yu Seok; Kim, Jong Oh; Choi, Han-Gon

2015-01-01

Background The objective of this study was to compare the physicochemical characteristics, solubility, dissolution, and oral bioavailability of an ezetimibe-loaded solid self-nanoemulsifying drug delivery system (SNEDDS), surface modified solid dispersion (SMSD), and solvent evaporated solid dispersion (SESD) to identify the best drug delivery system with the highest oral bioavailability. Methods For the liquid SNEDDS formulation, Capryol 90, Cremophor EL, and Tween 80 were selected as the oil, surfactant, and cosurfactant, respectively. The nanoemulsion-forming region was sketched using a pseudoternary phase diagram on the basis of reduced emulsion size. The optimized liquid SNEDDS was converted to solid SNEDDS by spray drying with silicon dioxide. Furthermore, SMSDs were prepared using the spray drying technique with various amounts of hydroxypropylcellulose and Tween 80, optimized on the basis of their drug solubility. The SESD formulation was prepared with the same composition of optimized SMSD. The aqueous solubility, dissolution, physicochemical properties, and pharmacokinetics of all of the formulations were investigated and compared with the drug powder. Results The drug existed in the crystalline form in SMSD, but was changed into an amorphous form in SNEDDS and SESD, giving particle sizes of approximately 24, 6, and 11 µm, respectively. All of these formulations significantly improved the aqueous solubility and dissolution in the order of solid SNEDDS ≥ SESD > SMSD, and showed a total higher plasma concentration than did the drug powder. Moreover, SESD gave a higher area under the drug concentration time curve from zero to infinity than did SNEDDS and SMSD, even if they were not significantly different, suggesting more improved oral bioavailability. Conclusion Among the various formulations tested in this study, the SESD system would be strongly recommended as a drug delivery system for the oral administration of ezetimibe with poor water solubility. PMID:26491288

Dynamic X-ray diffraction observation of shocked solid iron up to 170 GPa

PubMed Central

Denoeud, Adrien; Ozaki, Norimasa; Benuzzi-Mounaix, Alessandra; Uranishi, Hiroyuki; Kondo, Yoshihiko; Kodama, Ryosuke; Brambrink, Erik; Ravasio, Alessandra; Bocoum, Maimouna; Boudenne, Jean-Michel; Harmand, Marion; Guyot, François; Mazevet, Stephane; Riley, David; Makita, Mikako; Sano, Takayoshi; Sakawa, Youichi; Inubushi, Yuichi; Gregori, Gianluca; Koenig, Michel; Morard, Guillaume

2016-01-01

Investigation of the iron phase diagram under high pressure and temperature is crucial for the determination of the composition of the cores of rocky planets and for better understanding the generation of planetary magnetic fields. Here we present X-ray diffraction results from laser-driven shock-compressed single-crystal and polycrystalline iron, indicating the presence of solid hexagonal close-packed iron up to pressure of at least 170 GPa along the principal Hugoniot, corresponding to a temperature of 4,150 K. This is confirmed by the agreement between the pressure obtained from the measurement of the iron volume in the sample and the inferred shock strength from velocimetry deductions. Results presented in this study are of the first importance regarding pure Fe phase diagram probed under dynamic compression and can be applied to study conditions that are relevant to Earth and super-Earth cores. PMID:27357672

Statistical Mechanics Model of Solids with Defects

NASA Astrophysics Data System (ADS)

Kaufman, M.; Walters, P. A.; Ferrante, J.

1997-03-01

Previously(M.Kaufman, J.Ferrante,NASA Tech. Memor.,1996), we examined the phase diagram for the failure of a solid under isotropic expansion and compression as a function of stress and temperature with the "springs" modelled by the universal binding energy relation (UBER)(J.H.Rose, J.R.Smith, F.Guinea, J.Ferrante, Phys.Rev.B29, 2963 (1984)). In the previous calculation we assumed that the "springs" failed independently and that the strain is uniform. In the present work, we have extended this statistical model of mechanical failure by allowing for correlations between "springs" and for thermal fluctuations in strains. The springs are now modelled in the harmonic approximation with a failure threshold energy E0, as an intermediate step in future studies to reinclude the full non-linear dependence of the UBER for modelling the interactions. We use the Migdal-Kadanoff renormalization-group method to determine the phase diagram of the model and to compute the free energy.

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.

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

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

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

Ordering-separation phase transitions in a Co3V alloy

NASA Astrophysics Data System (ADS)

Ustinovshchikov, Yu. I.

2017-01-01

The microstructure of the Co3V alloy formed by heat treatment at various temperatures is studied by transmission electron microscopy. Two ordering-separation phase transitions are revealed at temperatures of 400-450 and 800°C. At the high-temperature phase separation, the microstructure consists of bcc vanadium particles and an fcc solid solution; at the low-temperature phase separation, the microstructure is cellular. In the ordering range, the microstructure consists of chemical compound Co3V particles chaotically arranged in the solid solution. The structure of the Co3V alloy is shown not to correspond to the structures indicated in the Co-V phase diagram at any temperatures.

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

Gallo, Paola; Amann-Winkel, Katrin; Angell, Charles Austen

Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambientmore » conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid–liquid critical point, LLCP. On approaching this LLCP from the one-phase region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. In conclusion, some of the possible experimental lines of research that are essential to complete this picture are explored.« less

Thermodynamic modeling of the Ge-La binary system

NASA Astrophysics Data System (ADS)

Liu, Miao; Li, Chang-rong; Du, Zhen-min; Guo, Cui-ping; Niu, Chun-ju

2012-08-01

The Ge-La binary system was critically assessed by means of the calculation of phase diagram (CALPHAD) technique. The associate model was used for the liquid phase containing the constituent species Ge, La, Ge3La5, and Ge1.7La. The terminal solid solution diamond-(Ge) with a small solubility of La was described using the substitutional model, in which the excess Gibbs energy was formulated with the Redlich-Kister equation. The compounds with homogeneity ranges, α(Ge1.7La), β(Ge1.7La), and (GeLa), were modeled using two sublattices as α(Ge,La)1.7La, β(Ge,La)1.7La, and (Ge,La)(Ge,La), respectively. The intermediate phases with no solubility ranges, Ge4La5, Ge3La4, Ge3La5, and GeLa3, were treated as stoichiometric compounds. The three allotropic modifications of La, dhcp-La, fcc-La, and bcc-La, were kept as pure element phases since no solubility of Ge in La was reported. A set of self-consistent thermodynamic parameters of the Ge-La binary system was obtained. The calculation results agree well with the available experimental data from literatures.

Kinetics of diffusional droplet growth in a liquid/liquid two-phase system

NASA Technical Reports Server (NTRS)

Baird, James K.; Cain, Judith B.

1993-01-01

This report contains experimental results for the interdiffusion coefficient of the system, succinonitrile plus water, at a number of compositions and temperatures in the single phase region of the phase diagram. The concentration and temperature dependence of the measured diffusion coefficient has been analyzed in terms of Landau - Ginzburg theory, which assumes that the Gibb free energy is an analytic function of its variables, and can be expanded in a Taylor series about any point in the phase diagram. At most points in the single phase region this is adequate. Near the consolute point (critical point of solution), however, the free energy is non-analytic, and the Landau - Ginzburg theory fails. The solution to this problem dictates that the Landau - Ginzburg form of the free energy be replaced by Widom scaling functions with irrational values for the scaling exponents. As our measurements of the diffusion coefficient near the critical point reflect this non-analytic character, we are preparing for publication in a refereed journal a separate analysis of some of the data contained herein as well as some additional measurements we have just completed. When published, reprints of this article will be furnished to NASA.

Pressure-induced orientational glass phase in molecular para-hydrogen.

PubMed

Schelkacheva, T I; Tareyeva, E E; Chtchelkatchev, N M

2009-02-01

We propose a theoretical description of a possible orientational glass transition in solid molecular para-hydrogen and ortho-deuterium under pressure supposing that they are mixtures of J=0 and J=2 states of molecules. The theory uses the basic concepts and methods of standard spin-glass theory. We expect our orientational glass to correspond to the II' phase of the high-pressure hydrogen phase diagram.

Energy and Resource Saving of Steelmaking Process: Utilization of Innovative Multi-phase Flux During Dephosphorization Process

NASA Astrophysics Data System (ADS)

Matsuura, Hiroyuki; Hamano, Tasuku; Zhong, Ming; Gao, Xu; Yang, Xiao; Tsukihashi, Fumitaka

2014-09-01

An increase in the utilization efficiency of CaO, one of the major fluxing agents used in various steelmaking processes, is required to reduce the amount of discharged slag and energy consumption of the process. The authors have intensively focused on the development of innovative dephosphorization process by using so called "multi-phase flux" composed of solid and liquid phases. This article summarizes the research on the above topic done by the authors, in which the formation mechanisms of P2O5-containing phase during CaO or 2CaO·SiO2 dissolution into molten slag, the phase relationship between solid and liquid phases at equilibrium, and thermodynamic properties of P2O5-containing phase have been clarified. The reactions between solid CaO or 2CaO·SiO2 and molten CaO-FeO x -SiO2-P2O5 slag were observed by dipping solid specimen in the synthesized slag at 1573 K or 1673 K. The formation of the CaO-FeO layer and dual-phase layer of solid 2CaO·SiO2 and FeO x -rich liquid phase was observed around the interface from the solid CaO side toward the bulk slag phase side. Condensation of P2O5 into 2CaO·SiO2 phase as 2CaO·SiO2-3CaO·P2O5 solid solution was observed in both cases of CaO and 2CaO·SiO2 as solid specimens. Measurement of the phase relationship for the CaO-FeO x -SiO2-P2O5 system confirmed the condensation of P2O5 in solid phase at low oxygen partial pressure. The thermodynamics of 2CaO·SiO2-3CaO·P2O5 solid solution are to be clarified to quantitatively simulate the dephosphorization process, and the current results are also introduced. Based on the above results, the reduction of CaO consumption, the discharged slag curtailment, and energy-saving effects have been discussed.

Structure and phase behavior of a confined nanodroplet composed of the flexible chain molecules.

PubMed

Kim, Soon-Chul; Kim, Eun-Young; Seong, Baek-Seok

2011-04-28

A polymer density functional theory has been employed for investigating the structure and phase behaviors of the chain polymer, which is modelled as the tangentially connected sphere chain with an attractive interaction, inside the nanosized pores. The excess free energy of the chain polymer has been approximated as the modified fundamental measure-theory for the hard spheres, the Wertheim's first-order perturbation for the chain connectivity, and the mean-field approximation for the van der Waals contribution. For the value of the chemical potential corresponding to a stable liquid phase in the bulk system and a metastable vapor phase, the flexible chain molecules undergo the liquid-vapor transition as the pore size is reduced; the vapor is the stable phase at small volume, whereas the liquid is the stable phase at large volume. The wide liquid-vapor coexistence curve, which explains the wide range of metastable liquid-vapor states, is observed at low temperature. The increase of temperature and decrease of pore size result in a narrowing of liquid-vapor coexistence curves. The increase of chain length leads to a shift of the liquid-vapor coexistence curve towards lower values of chemical potential. The coexistence curves for the confined phase diagram are contained within the corresponding bulk liquid-vapor coexistence curve. The equilibrium capillary phase transition occurs at a higher chemical potential than in the bulk phase.

On the bad metallicity and phase diagrams of Fe1+δX (X =Te, Se, S, solid solutions): an electrical resistivity study

NASA Astrophysics Data System (ADS)

El Massalami, M.; Deguchi, K.; Machida, T.; Takeya, H.; Takano, Y.

2014-12-01

Based on a systematic analysis of the thermal evolution of the resistivities of Fe-based chalcogenides Fe1+δTe1-xXx (X = Se, S), it is inferred that their often observed nonmetallic resistivities are related to a presence of two resistive channels: one is a high- temperature thermally-activated process while the other is a low-temperature log-in-T process. On lowering temperature, there are often two metal-to-nonmetall crossover events: one from the high-T thermally-activated nonmetallic regime into a metal-like phase and the other from the log-in-T regime into a second metal-like phase. Based on these events, together with the magnetic and superconducting transitions, a phase diagram is constructed for each series. We discuss the origin of both processes as well as the associated crossover events. We also discuss how these resistive processes are being influenced by pressure, intercalation, disorder, doping, or sample condition and, in turn, how these modifications are shaping the associated phase diagrams.

Preparative isolation of flavonoid glycosides from Sphaerophysa salsula using hydrophilic interaction solid-phase extraction coupled with two-dimensional preparative liquid chromatography.

PubMed

Jiao, Lijin; Tao, Yanduo; Wang, Weidong; Shao, Yun; Mei, Lijuan; Wang, Qilan; Dang, Jun

2017-10-01

An offline preparative two-dimensional reversed-phase liquid chromatography/hydrophilic interaction liquid chromatography coupled with hydrophilic interaction solid-phase extraction method was developed for the preparative isolation of flavonoid glycosides from a crude sample of Sphaerophysa salsula. First, the non-flavonoids were removed using an XAmide solid-phase extraction cartridge. Based on the separation results of three different chromatographic stationary phases, the first-dimensional preparation was performed on an XAqua C18 prep column, and 15 fractions were obtained from the 5.2 g target sample. Then, three representative fractions were selected for additional purification on an XAmide preparative column to further isolate the flavonoid glycosides. In all, eight flavonoid glycosides were isolated in purities over 97%. The results demonstrated that the two-dimensional liquid chromatography method used in this study was effective for the preparative separation of flavonoid glycosides from Sphaerophysa salsula. Additionally, this method showed great potential for the separation of flavonoid glycosides from other plant materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Iwamoto, Y.; Shin, S.G.; Matsubara, H.

The grain growth behavior of ceramic materials under the existence of a liquid phase was investigated for Si{sub 3}N{sub 4}-Y{sub 2}O{sub 3}-SiO{sub 2}, TiC-Ni, and WC-Co systems. The kinetics of grain growth behavior of these systems closely fitted to the cubic relation of d{sup 3} - d{sub 0}{sup 3} = Kt. The growth rate of {beta}-Si{sub 3}N{sub 4} grain was approximately one order of magnitude larger in length direction than that in width direction. The growth rate slightly increased with increasing liquid phase content in both these directions of the {beta}-Si{sub 3}N{sub 4} grain. TiC-Ni and WC-Co cermets had amore » peak in growth rate at a certain liquid phase content. The rate constant values of these systems were much smaller by a factor of 10{sup 3}{approximately}10{sup 5} compared to the theoretical values expected from the diffusion-controlled growth model. The experimental growth rates tended to decrease with increasing contiguity of the solid phase. The grain growth behavior of these systems could be explained by the mechanism resulting from the existence of contiguous boundaries of solid phase, which suppressed the movement of solid/liquid interfaces during liquid phase sintering.« less

Effectiveness of Liquid-Liquid Extraction, Solid Phase Extraction, and Headspace Technique for Determination of Some Volatile Water-Soluble Compounds of Rose Aromatic Water

PubMed Central

2017-01-01

Steam distillation is used to isolate scent of rose flowers. Rose aromatic water is commonly used in European cuisine and aromatherapy besides its use in cosmetic industry for its lovely scent. In this study, three different sampling techniques, liquid-liquid extraction (LLE), headspace technique (HS), and solid phase extraction (SPE), were compared for the analysis of volatile water-soluble compounds in commercial rose aromatic water. Some volatile water-soluble compounds of rose aromatic water were also analyzed by gas chromatography mass spectrometry (GCMS). In any case, it was concluded that one of the solid phase extraction methods led to higher recoveries for 2-phenylethyl alcohol (PEA) in the rose aromatic water than the liquid-liquid extraction and headspace technique. Liquid-liquid extraction method provided higher recovery ratios for citronellol, nerol, and geraniol than others. Ideal linear correlation coefficient values were observed by GCMS for quantitative analysis of volatile compounds (r2 ≥ 0.999). Optimized methods showed acceptable repeatability (RSDs < 5%) and excellent recovery (>95%). For compounds such as α-pinene, linalool, β-caryophyllene, α-humulene, methyl eugenol, and eugenol, the best recovery values were obtained with LLE and SPE. PMID:28791049

Use of the Flory-Huggins theory to predict the solubility of nifedipine and sulfamethoxazole in the triblock, graft copolymer Soluplus.

PubMed

Altamimi, Mohammad A; Neau, Steven H

2016-01-01

Drug dispersed in a polymer can improve bioavailability; dispersed amorphous drug undergoes recrystallization. Solid solutions eliminate amorphous regions, but require a measure of the solubility. Use the Flory-Huggins Theory to predict crystalline drugs solubility in the triblock, graft copolymer Soluplus® to provide a solid solution. Physical mixtures of the two drugs with similar melting points but different glass forming ability, sulfamethoxazole and nifedipine, were prepared with Soluplus® using a quick technique. Drug melting point depression (MPD) was measured using differential scanning calorimetry. The Flory-Huggins Theory allowed: (1) interaction parameter, χ, calculation using MPD data to provide a measure of drug-polymer interaction strength and (2) estimation of the free energy of mixing. A phase diagram was constructed with the MPD data and glass transition temperature (Tg) curves. The interaction parameters with Soluplus® and the free energy of mixing were estimated. Drug solubility was calculated by the intersection of solubility equations and that of MPD and Tg curves in the phase diagram. Negative interaction parameters indicated strong drug-polymer interactions. The phase diagram and solubility equations provided comparable solubility estimates for each drug in Soluplus®. Results using the onset of melting rather than the end of melting support the use of the onset of melting. The Flory-Huggins Theory indicates that Soluplus® interacts effectively with each drug, making solid solution formation feasible. The predicted solubility of the drugs in Soluplus® compared favorably across the methods and supports the use of the onset of melting.

Use of the Flory-Huggins theory to predict the solubility of nifedipine and sulfamethoxazole in the triblock, graft copolymer Soluplus.

PubMed

Altamimi, Mohammad A; Neau, Steven H

2016-03-01

Drug dispersed in a polymer can improve bioavailability; dispersed amorphous drug undergoes recrystallization. Solid solutions eliminate amorphous regions, but require a measure of the solubility. Use the Flory-Huggins Theory to predict crystalline drugs solubility in the triblock, graft copolymer Soluplus® to provide a solid solution. Physical mixtures of the two drugs with similar melting points but different glass forming ability, sulfamethoxazole and nifedipine, were prepared with Soluplus® using a quick technique. Drug melting point depression (MPD) was measured using differential scanning calorimetry. The Flory-Huggins Theory allowed: (1) interaction parameter, χ, calculation using MPD data to provide a measure of drug-polymer interaction strength and (2) estimation of the free energy of mixing. A phase diagram was constructed with the MPD data and glass transition temperature (T g ) curves. The interaction parameters with Soluplus® and the free energy of mixing were estimated. Drug solubility was calculated by the intersection of solubility equations and that of MPD and T g curves in the phase diagram. Negative interaction parameters indicated strong drug-polymer interactions. The phase diagram and solubility equations provided comparable solubility estimates for each drug in Soluplus®. Results using the onset of melting rather than the end of melting support the use of the onset of melting. The Flory-Huggins Theory indicates that Soluplus® interacts effectively with each drug, making solid solution formation feasible. The predicted solubility of the drugs in Soluplus® compared favorably across the methods and supports the use of the onset of melting.

Anisotropic phase diagram and spin fluctuations of the hyperkagome magnet Gd3Ga5O12 as revealed by sound velocity measurements

NASA Astrophysics Data System (ADS)

Rousseau, Alexandre; Parent, Jean-Michel; Quilliam, Jeffrey A.

2017-08-01

Sound velocity and attenuation measurements on the frustrated garnet material Gd3Ga5O12 (GGG) are presented as a function of field and temperature, with two different magnetic field orientations: [100 ] and [110 ] . We demonstrate that the phase diagram is highly anisotropic, with two distinct field-induced ordered phases for H ||[110 ] and only one for H ||[100 ] . Extensive lattice softening is found to occur at low fields, which can be associated with spin fluctuations. However, deep within the spin liquid phase a low-temperature stiffening of the lattice and reduced attenuation provide evidence for a spin gap which may be related to short-range antiferromagnetic correlations over minimal ten-spin loops.

CRYOCHEM, Thermodynamic Model for Cryogenic Chemical Systems: Solid-Vapor and Solid-Liquid-Vapor Phase Equilibria Toward Applications on Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.; Adidharma, H.; Marion, G. M.

2014-12-01

Until in-situ measurements can be made regularly on extraterrestrial bodies, thermodynamic models are the only tools to investigate the properties and behavior of chemical systems on those bodies. The resulting findings are often critical in describing physicochemical processes in the atmosphere, surface, and subsurface in planetary geochemistry and climate studies. The extremely cold conditions on Triton, Pluto and other Kuiper Belt Objects, and Titan introduce huge non-ideality that prevents conventional models from performing adequately. At such conditions, atmospheres as a whole—not components individually—are subject to phase equilibria with their equilibrium solid phases or liquid phases or both. A molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, the development of which is still in progress, was shown to reproduce the vertical composition profile of Titan's atmospheric methane measured by the Huygens probe (Tan et al., Icarus 2013, 222, 53). Recently, the model was also used to describe Titan's global circulation where the calculated composition of liquid in Ligeia Mare is consistent with the bathymetry and microwave absorption analysis of T91 Cassini fly-by data (Tan et al., 2014, submitted). Its capability to deal with equilibria involving solid phases has also been demonstrated (Tan et al., Fluid Phase Equilib. 2013, 360, 320). With all those previous works done, our attention is now shifting to the lower temperatures in Titan's tropopause and on Pluto's surface, where much technical development remains for CRYOCHEM to assure adequate performance at low temperatures. In these conditions, solid-vapor equilibrium (SVE) is the dominant phase behavior that determines the composition of the atmosphere and the existing ices. Another potential application is for the subsurface phase equilibrium, which also involves liquid, thus three-phase equilibrium: solid-liquid-vapor (SLV). This presentation will discuss the current state of CRYOCHEM in representing the SVE and SLV of chemical systems at temperatures and pressures relevant to Titan's tropopause and Pluto and the upper crusts of these objects.

Thermodynamics and structural transition of binary atomic Bose-Fermi mixtures in box or harmonic potentials: A path-integral study

NASA Astrophysics Data System (ADS)

Kim, Tom; Chien, Chih-Chun

2018-03-01

Experimental realizations of a variety of atomic binary Bose-Fermi mixtures have brought opportunities for studying composite quantum systems with different spin statistics. The binary atomic mixtures can exhibit a structural transition from a mixture into phase separation as the boson-fermion interaction increases. By using a path-integral formalism to evaluate the grand partition function and the thermodynamic grand potential, we obtain the effective potential of binary Bose-Fermi mixtures. Thermodynamic quantities in a broad range of temperatures and interactions are also derived. The structural transition can be identified as a loop of the effective potential curve, and the volume fraction of phase separation can be determined by the lever rule. For 6Li-7Li and 6Li-41K mixtures, we present the phase diagrams of the mixtures in a box potential at zero and finite temperatures. Due to the flexible densities of atomic gases, the construction of phase separation is more complicated when compared to conventional liquid or solid mixtures where the individual densities are fixed. For harmonically trapped mixtures, we use the local density approximation to map out the finite-temperature density profiles and present typical trap structures, including the mixture, partially separated phases, and fully separated phases.

Free energy change of off-eutectic binary alloys on solidification

NASA Technical Reports Server (NTRS)

Ohsaka, K.; Trinh, E. H.; Lin, J.-C.; Perepezko, J. H.

1991-01-01

A formula for the free energy difference between the undercooled liquid phase and the stable solid phase is derived for off-eutectic binary alloys in which the equilibrium solid/liquid transition takes place over a certain temperature range. The free energy change is then evaluated numerically for a Bi-25 at. pct Cd alloy modeled as a sub-subregular solution.

METHOD 544. DETERMINATION OF MICROCYSTINS AND NODULARIN IN DRINKING WATER BY SOLID PHASE EXTRACTION AND LIQUID CHROMATOGRAPHY/TANDEM MASS SPECTROMETRY (LC/MS/MS)

EPA Science Inventory

Method 544 is an accurate and precise analytical method to determine six microcystins (including MC-LR) and nodularin in drinking water using solid phase extraction and liquid chromatography tandem mass spectrometry (SPE-LC/MS/MS). The advantage of this SPE-LC/MS/MS is its sensi...

Discrete elastic model for two-dimensional melting.

PubMed

Lansac, Yves; Glaser, Matthew A; Clark, Noel A

2006-04-01

We present a network model for the study of melting and liquid structure in two dimensions, the first in which the presence and energy of topological defects (dislocations and disclinations) and of geometrical defects (elemental voids) can be independently controlled. Interparticle interaction is via harmonic springs and control is achieved by Monte Carlo moves which springs can either be orientationally "flipped" between particles to generate topological defects, or can be "popped" in force-free shape, to generate geometrical defects. With the geometrical defects suppressed the transition to the liquid phase occurs via disclination unbinding, as described by the Kosterlitz-Thouless-Halperin-Nelson-Young model and found in soft potential two-dimensional (2D) systems, such as the dipole-dipole potential [H. H. von Grünberg, Phys. Rev. Lett. 93, 255703 (2004)]. By contrast, with topological defects suppressed, a disordering transition, the Glaser-Clark condensation of geometrical defects [M. A. Glaser and N. A. Clark, Adv. Chem. Phys. 83, 543 (1993); M. A. Glaser, (Springer-Verlag, Berlin, 1990), Vol. 52, p. 141], produces a state that accurately characterizes the local liquid structure and first-order melting observed in hard-potential 2D systems, such as hard disk and the Weeks-Chandler-Andersen (WCA) potentials (M. A. Glaser and co-workers, see above). Thus both the geometrical and topological defect systems play a role in melting. The present work introduces a system in which the relative roles of topological and geometrical defects and their interactions can be explored. We perform Monte Carlo simulations of this model in the isobaric-isothermal ensemble, and present the phase diagram as well as various thermodynamic, statistical, and structural quantities as a function of the relative populations of geometrical and topological defects. The model exhibits a rich phase behavior including hexagonal and square crystals, expanded crystal, dodecagonal quasicrystal, and isotropic liquid phases. In this system the geometrical defects effectively control the melting, reducing the solid-liquid transition temperature by a factor of relative to the topological-only case. The local structure of the dense liquid has been investigated and the results are compared to that from simulations of WCA systems.

FAST TRACK COMMUNICATION: Gas liquid phase coexistence in a tetrahedral patchy particle model

NASA Astrophysics Data System (ADS)

Romano, Flavio; Tartaglia, Piero; Sciortino, Francesco

2007-08-01

We evaluate the location of the gas-liquid coexistence line and of the associated critical point for the primitive model for water (PMW), introduced by Kolafa and Nezbeda (1987 Mol. Phys. 61 161). Besides being a simple model for a molecular network forming liquid, the PMW is representative of patchy proteins and novel colloidal particles interacting with localized directional short-range attractions. We show that the gas-liquid phase separation is metastable, i.e. it takes place in the region of the phase diagram where the crystal phase is thermodynamically favoured, as in the case of particles interacting via short-range attractive spherical potentials. We do not observe crystallization close to the critical point. The region of gas-liquid instability of this patchy model is significantly reduced as compared to that from equivalent models of spherically interacting particles, confirming the possibility of observing kinetic arrest in a homogeneous sample driven by bonding as opposed to packing.

Optimized microemulsions and solid microemulsion systems of simvastatin: characterization and in vivo evaluation.

PubMed

Dixit, Rahul P; Nagarsenker, Mangal S

2010-12-01

The study describes development of solid microemulsions (SME) for improved delivery of simvastatin (SMV). Pseudo-ternary phase diagrams were constructed and MEs were optimized for oil and drug content. SMEs were prepared using colloidal silicon dioxide to adsorb the liquid ME. MEs were characterized for mean globule size in aqueous medium and the SMEs were evaluated for powder characteristics, mean globule size after dilution with water, dissolution profile and for in vivo efficacy in rats. X-ray diffraction studies indicated complete amorphization and/or solubilization of SMV in the SMEs. It was supported by scanning electronic microscopic studies, which did not show evidence of precipitation of the drug on the surface of the carrier. Dissolution studies revealed remarkable increase in dissolution of the drug as compared to plain drug. All the formulations provided significant reduction in the total cholesterol levels in hyperlipidemic rats with reference to rats of control group (p < 0.05). The proposed SMEs have potential to deliver water insoluble drugs like SMV by oral route for better efficacy. © 2010 Wiley-Liss, Inc. and the American Pharmacists Association